DEVELOPMENT OF LOW-DIFFUSION FLUX-SPLITTING METHODS FOR DENSE GAS-SOLID FLOWS

EPA Science Inventory

The development of a class of low-diffusion upwinding methods for computing dense gas-solid flows is presented in this work. An artificial compressibility/low-Mach preconditioning strategy is developed for a hyperbolic two-phase flow equation system consisting of separate solids ...

Influence of surface wettability on transport mechanisms governing water droplet evaporation.

PubMed

Pan, Zhenhai; Weibel, Justin A; Garimella, Suresh V

2014-08-19

Prediction and manipulation of the evaporation of small droplets is a fundamental problem with importance in a variety of microfluidic, microfabrication, and biomedical applications. A vapor-diffusion-based model has been widely employed to predict the interfacial evaporation rate; however, its scope of applicability is limited due to incorporation of a number of simplifying assumptions of the physical behavior. Two key transport mechanisms besides vapor diffusion-evaporative cooling and natural convection in the surrounding gas-are investigated here as a function of the substrate wettability using an augmented droplet evaporation model. Three regimes are distinguished by the instantaneous contact angle (CA). In Regime I (CA ≲ 60°), the flat droplet shape results in a small thermal resistance between the liquid-vapor interface and substrate, which mitigates the effect of evaporative cooling; upward gas-phase natural convection enhances evaporation. In Regime II (60 ≲ CA ≲ 90°), evaporative cooling at the interface suppresses evaporation with increasing contact angle and counterbalances the gas-phase convection enhancement. Because effects of the evaporative cooling and gas-phase convection mechanisms largely neutralize each other, the vapor-diffusion-based model can predict the overall evaporation rates in this regime. In Regime III (CA ≳ 90°), evaporative cooling suppresses the evaporation rate significantly and reverses entirely the direction of natural convection induced by vapor concentration gradients in the gas phase. Delineation of these counteracting mechanisms reconciles previous debate (founded on single-surface experiments or models that consider only a subset of the governing transport mechanisms) regarding the applicability of the classic vapor-diffusion model. The vapor diffusion-based model cannot predict the local evaporation flux along the interface for high contact angle (CA ≥ 90°) when evaporative cooling is strong and the temperature gradient along the interface determines the peak local evaporation flux.

Effects of lateral diffusion on morphology and dynamics of a microscopic lattice-gas model of pulsed electrodeposition.

PubMed

Frank, Stefan; Roberts, Daniel E; Rikvold, Per Arne

2005-02-08

The influence of nearest-neighbor diffusion on the decay of a metastable low-coverage phase (monolayer adsorption) in a square lattice-gas model of electrochemical metal deposition is investigated by kinetic Monte Carlo simulations. The phase-transformation dynamics are compared to the well-established Kolmogorov-Johnson-Mehl-Avrami theory. The phase transformation is accelerated by diffusion, but remains in accord with the theory for continuous nucleation up to moderate diffusion rates. At very high diffusion rates the phase-transformation kinetic shows a crossover to instantaneous nucleation. Then, the probability of medium-sized clusters is reduced in favor of large clusters. Upon reversal of the supersaturation, the adsorbate desorbs, but large clusters still tend to grow during the initial stages of desorption. Calculation of the free energy of subcritical clusters by enumeration of lattice animals yields a quasiequilibrium distribution which is in reasonable agreement with the simulation results. This is an improvement relative to classical droplet theory, which fails to describe the distributions, since the macroscopic surface tension is a bad approximation for small clusters.

Determination of diffusion and partition coefficients of model migrants by direct contact and vapour phase transfer from low-density polyethylene films into cake.

PubMed

Paseiro-Cerrato, Rafael; Rodríguez-Bernaldo de Quirós, Ana; Otero-Pazos, Pablo; Sendón, Raquel; Paseiro-Losada, Perfecto

2018-03-01

The aim of the present study was to determine the migration kinetics of one photoinitiator, benzophenone, and two optical brighteners, Uvitex OB and 1,4-diphenyl-1,3-butadiene (DPBD), from low-density polyethylene (LDPE) films into cake. Transfer was assessed by both direct contact and also the vapour phase. To perform the migration tests by direct contact, plastic films enriched with the additives were placed between two cake slices. To evaluate the migration through the gas phase, cake and the fortified LDPE film were placed with no direct contact in a glass container that was hermetically closed. Samples were stored at different time-temperature conditions. Target compounds were extracted from the films with ethanol (70°C, 24 h) and analysed by HPLC-DAD. Relevant parameters such as partition and diffusion coefficients between food and plastic film were calculated. The Arrhenius equation was applied to estimate the diffusion coefficient at any temperature. The data indicate that migration of benzophenone occurs in a significant extent into cake by both direct contact and through the gas phase (no direct contact). Conversely, very little migration occurred for Uvitex OB by direct contact and none through the gas phase. Results for benzophenone suggest that migration through the gas phase should be considered when evaluating migration from food packaging materials into food.

An efficient approach for treating composition-dependent diffusion within organic particles

DOE PAGES

O'Meara, Simon; Topping, David O.; Zaveri, Rahul A.; ...

2017-09-07

Mounting evidence demonstrates that under certain conditions the rate of component partitioning between the gas and particle phase in atmospheric organic aerosol is limited by particle-phase diffusion. To date, however, particle-phase diffusion has not been incorporated into regional atmospheric models. An analytical rather than numerical solution to diffusion through organic particulate matter is desirable because of its comparatively small computational expense in regional models. Current analytical models assume diffusion to be independent of composition and therefore use a constant diffusion coefficient. To realistically model diffusion, however, it should be composition-dependent (e.g. due to the partitioning of components that plasticise, vitrifymore » or solidify). This study assesses the modelling capability of an analytical solution to diffusion corrected to account for composition dependence against a numerical solution. Results show reasonable agreement when the gas-phase saturation ratio of a partitioning component is constant and particle-phase diffusion limits partitioning rate (<10% discrepancy in estimated radius change). However, when the saturation ratio of the partitioning component varies, a generally applicable correction cannot be found, indicating that existing methodologies are incapable of deriving a general solution. Until such time as a general solution is found, caution should be given to sensitivity studies that assume constant diffusivity. Furthermore, the correction was implemented in the polydisperse, multi-process Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) and is used to illustrate how the evolution of number size distribution may be accelerated by condensation of a plasticising component onto viscous organic particles.« less

An efficient approach for treating composition-dependent diffusion within organic particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Meara, Simon; Topping, David O.; Zaveri, Rahul A.

Mounting evidence demonstrates that under certain conditions the rate of component partitioning between the gas and particle phase in atmospheric organic aerosol is limited by particle-phase diffusion. To date, however, particle-phase diffusion has not been incorporated into regional atmospheric models. An analytical rather than numerical solution to diffusion through organic particulate matter is desirable because of its comparatively small computational expense in regional models. Current analytical models assume diffusion to be independent of composition and therefore use a constant diffusion coefficient. To realistically model diffusion, however, it should be composition-dependent (e.g. due to the partitioning of components that plasticise, vitrifymore » or solidify). This study assesses the modelling capability of an analytical solution to diffusion corrected to account for composition dependence against a numerical solution. Results show reasonable agreement when the gas-phase saturation ratio of a partitioning component is constant and particle-phase diffusion limits partitioning rate (<10% discrepancy in estimated radius change). However, when the saturation ratio of the partitioning component varies, a generally applicable correction cannot be found, indicating that existing methodologies are incapable of deriving a general solution. Until such time as a general solution is found, caution should be given to sensitivity studies that assume constant diffusivity. Furthermore, the correction was implemented in the polydisperse, multi-process Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) and is used to illustrate how the evolution of number size distribution may be accelerated by condensation of a plasticising component onto viscous organic particles.« less

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

An Introduction to the Gas Phase

NASA Astrophysics Data System (ADS)

Vallance, Claire

2017-11-01

'An Introduction to the Gas Phase' is adapted from a set of lecture notes for a core first year lecture course in physical chemistry taught at the University of Oxford. The book is intended to give a relatively concise introduction to the gas phase at a level suitable for any undergraduate scientist. After defining the gas phase, properties of gases such as temperature, pressure, and volume are discussed. The relationships between these properties are explained at a molecular level, and simple models are introduced that allow the various gas laws to be derived from first principles. Finally, the collisional behaviour of gases is used to explain a number of gas-phase phenomena, such as effusion, diffusion, and thermal conductivity.

Extinguishment of a Diffusion Flame Over a PMMA Cylinder by Depressurization in Reduced-Gravity

NASA Technical Reports Server (NTRS)

Goldmeer, Jeffrey Scott

1996-01-01

Extinction of a diffusion flame burning over horizontal PMMA (Polymethyl methacrylate) cylinders in low-gravity was examined experimentally and via numerical simulations. Low-gravity conditions were obtained using the NASA Lewis Research Center's reduced-gravity aircraft. The effects of velocity and pressure on the visible flame were examined. The flammability of the burning solid was examined as a function of pressure and the solid-phase centerline temperature. As the solid temperature increased, the extinction pressure decreased, and with a centerline temperature of 525 K, the flame was sustained to 0.1 atmospheres before extinguishing. The numerical simulation iteratively coupled a two-dimensional quasi-steady, gas-phase model with a transient solid-phase model which included conductive heat transfer and surface regression. This model employed an energy balance at the gas/solid interface that included the energy conducted by the gas-phase to the gas/solid interface, Arrhenius pyrolysis kinetics, surface radiation, and the energy conducted into the solid. The ratio of the solid and gas-phase conductive fluxes Phi was a boundary condition for the gas-phase model at the solid-surface. Initial simulations modeled conditions similar to the low-gravity experiments and predicted low-pressure extinction limits consistent with the experimental limits. Other simulations examined the effects of velocity, depressurization rate and Phi on extinction.

Chemistry and Evolution of Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wooden, D. H.; Charnley, S. B.; Ehrenfreund, P.

2003-01-01

In this chapter we describe how elements have been and are still being formed in the galaxy and how they are transformed into the reservoir of materials present at the time of formation of our protosolar nebula. We discuss the global cycle of matter, beginning at its formation site in stars, where it is ejected through winds and explosions into the diffuse interstellar medium. In the next stage of the global cycle occurs in cold, dense molecular clouds, where the complexity of molecules and ices increases relative to the diffuse ISM.. When a protostar forms in a dense core within a molecular cloud, it heats the surrounding infalling matter warms and releases molecules from the solid phase into the gas phase in a warm, dense core, sponsoring a rich gas-phase chemistry. Some material from the cold and warm regions within molecular clouds probably survives as interstellar matter in the protostellar disk. For the diffuse ISM, for cold, dense clouds, and for dense-warm cores, the physio-chemical processes that occur within the gas and solid phases are discussed in detail.

On the Chemistry of Hydrides of N Atoms and O+ Ions

NASA Astrophysics Data System (ADS)

Awad, Zainab; Viti, Serena; Williams, David A.

2016-08-01

Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

High temperature coatings for gas turbines

DOEpatents

Zheng, Xiaoci Maggie

2003-10-21

Coating for high temperature gas turbine components that include a MCrAlX phase, and an aluminum-rich phase, significantly increase oxidation and cracking resistance of the components, thereby increasing their useful life and reducing operating costs. The aluminum-rich phase includes aluminum at a higher concentration than aluminum concentration in the MCrAlX alloy, and an aluminum diffusion-retarding composition, which may include cobalt, nickel, yttrium, zirconium, niobium, molybdenum, rhodium, cadmium, indium, cerium, iron, chromium, tantalum, silicon, boron, carbon, titanium, tungsten, rhenium, platinum, and combinations thereof, and particularly nickel and/or rhenium. The aluminum-rich phase may be derived from a particulate aluminum composite that has a core comprising aluminum and a shell comprising the aluminum diffusion-retarding composition.

Modeling of acetone biofiltration process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsiu-Mu Tang; Shyh-Jye Hwang; Wen-Chuan Wang

1996-12-31

The objective of this research was to investigate the kinetic behavior of the biofiltration process for the removal of acetone 41 which was used as a model compound for highly water soluble gas pollutants. A mathematical model was developed by taking into account diffusion and biodegradation of acetone and oxygen in the biofilm, mass transfer resistance in the gas film, and flow pattern of the bulk gas phase. The simulated results obtained by the proposed model indicated that mass transfer resistance in the gas phase was negligible for this biofiltration process. Analysis of the relative importance of various rate stepsmore » indicated that the overall acetone removal process was primarily limited by the oxygen diffusion rate. 11 refs., 6 figs., 1 tab.« less

DIFFUSIVE EXCHANGE OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS AND POLYCHLORINATED BIPHENYLS ACROSS THE AIR-WATER INTERFACE OF THE CHESAPEAKE BAY. (R825245)

EPA Science Inventory

Dissolved and gas-phase concentrations of nine polycyclic aromatic hydrocarbons and 46 polychlorinated biphenyl congeners were measured at eight sites on the Chesapeake Bay at four different times of the year to estimate net diffusive air-water gas exchange rates. Gaseous PAHs ar...

LABORATORY ASSESSMENT OF THE PERMEABILITY AND DIFFUSION CHARACTERISTICS OF FLORIDA CONCRETES - PHASE I - METHODS DEVELOPMENT AND TESTING

EPA Science Inventory

The report gives results of Phase I of a laboratory assessment of the permeability and diffusion characteristics of Florida concretes. (NOTE: The ability of concrete to permit air flow under pressure (permeability) and the passage of radon gas without any pressure difference (dif...

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

USGS Publications Warehouse

Smith, James A.; Tisdale, Amy K.; Cho, H. Jean

1996-01-01

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Resonant acoustic measurement of vapor phase transport phenomenon in porous media

NASA Astrophysics Data System (ADS)

Schuhmann, Richard; Garrett, Steven

2002-05-01

Diffusion of gases through porous media is commonly described using Fick's law and is characterized by a gas diffusion coefficient modified by a media-specific tortuosity parameter. A phase-locked-loop resonance frequency tracker [J. Acoust. Soc. Am. 108, 2520 (2000)] has been upgraded with an insulated copper resonator and a bellows-sealed piston instrumented with an accelerometer. Average system stability (temperature divided by frequency squared) is about 180 ppm. Glass-bead-filled cores of different lengths are fitted into an o-ring sealed opening at the top of the resonator. The rate at which the tracer gas is replaced by air within the resonator is controlled by the core's diffusion constant. Mean molecular weight of the gas mixture in the resonator is determined in real time from the ratio of the absolute temperature to the square of the fundamental acoustic resonance frequency. Molecular weight of the gas mixture is determined approximately six times per minute. Changes in the gas mixture concentration are exponential in time (within 0.1%) over nearly two decades in concentration. We will report diffusion constants for two different sizes of glass beads, in samples of five different lengths, using two different tracer gases, to establish the validity of this approach. [Work supported by ONR.

Derivation of effective fission gas diffusivities in UO2 from lower length scale simulations and implementation of fission gas diffusion models in BISON

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders David Ragnar; Pastore, Giovanni; Liu, Xiang-Yang

2014-11-07

This report summarizes the development of new fission gas diffusion models from lower length scale simulations and assessment of these models in terms of annealing experiments and fission gas release simulations using the BISON fuel performance code. Based on the mechanisms established from density functional theory (DFT) and empirical potential calculations, continuum models for diffusion of xenon (Xe) in UO 2 were derived for both intrinsic conditions and under irradiation. The importance of the large X eU3O cluster (a Xe atom in a uranium + oxygen vacancy trap site with two bound uranium vacancies) is emphasized, which is a consequencemore » of its high mobility and stability. These models were implemented in the MARMOT phase field code, which is used to calculate effective Xe diffusivities for various irradiation conditions. The effective diffusivities were used in BISON to calculate fission gas release for a number of test cases. The results are assessed against experimental data and future directions for research are outlined based on the conclusions.« less

Uncovering Implicit Assumptions: A Large-Scale Study on Students' Mental Models of Diffusion

ERIC Educational Resources Information Center

Stains, Marilyne; Sevian, Hannah

2015-01-01

Students' mental models of diffusion in a gas phase solution were studied through the use of the Structure and Motion of Matter (SAMM) survey. This survey permits identification of categories of ways students think about the structure of the gaseous solute and solvent, the origin of motion of gas particles, and trajectories of solute particles in…

Longitudinal distribution of ozone and chlorine in the human respiratory tract: simulation of nasal and oral breathing with the single-path diffusion model.

PubMed

Bush, M L; Zhang, W; Ben-Jebria, A; Ultman, J S

2001-06-15

In the single-path model of the respiratory system, gas transport occurs within a conduit of progressively increasing cross-sectional and surface areas by a combination of flow, longitudinal dispersion, and lateral absorption. The purpose of this study was to use bolus inhalation data previously obtained for chlorine (Cl(2)) and for ozone (O(3)) to test the predictive capability of the single-path model and to adjust input parameters for applying the model to other exposure conditions. The data, consisting of uptake fraction as a function of bolus penetration volume, were recorded on 10 healthy nonsmokers breathing orally as well as nasally at alternative air flows of 150, 250, and 1000 ml/s. By employing published data for airway anatomy, gas-phase dispersion coefficients, and gas-phase mass transfer coefficients while neglecting diffusion limitations in the mucus phase, the single-path model was capable of predicting the uptake distribution for O(3) but not the steeper distribution that was observed for Cl(2). To simultaneously explain the data for these two gases, it was necessary to increase gas-phase mass transfer coefficients and to include a finite diffusion resistance of O(3) within the mucous layer. The O(3) reaction rate constants that accounted for this diffusion resistance, 2 x 10(6) s(-1) in the mouth and 8 x 10(6) s(-1) in the nose and lower airways, were much greater than previously reported reactivities of individual substrates found in mucus. Copyright 2001 Academic Press.

Diffusion NMR methods applied to xenon gas for materials study

NASA Technical Reports Server (NTRS)

Mair, R. W.; Rosen, M. S.; Wang, R.; Cory, D. G.; Walsworth, R. L.

2002-01-01

We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. c2002 John Wiley & Sons, Ltd.

Simulation of radiation driven fission gas diffusion in UO 2, ThO 2 and PuO 2

DOE PAGES

Cooper, Michael William D.; Stanek, Christopher Richard; Turnbull, James Anthony; ...

2016-12-01

Below 1000 K it is thought that fission gas diffusion in nuclear fuel during irradiation occurs through atomic mixing due to radiation damage. Here we present a molecular dynamics (MD) study of Xe, Kr, Th, U, Pu and O diffusion due to irradiation. It is concluded that the ballistic phase does not sufficiently account for the experimentally observed diffusion. Thermal spike simulations are used to confirm that electronic stopping remedies the discrepancy with experiment and the predicted diffusivities lie within the scatter of the experimental data. Here, our results predict that the diffusion coefficients are ordered such that D* 0more » > D* Kr > D* Xe > D* U. For all species >98.5% of diffusivity is accounted for by electronic stopping. Fission gas diffusivity was not predicted to vary significantly between ThO 2, UO 2 and PuO 2, indicating that this process would not change greatly for mixed oxide fuels.« less

Chromatographic determination of the diffusion coefficients of light hydrocarbons in polymers

NASA Astrophysics Data System (ADS)

Yakubenko, E. E.; Korolev, A. A.; Chapala, P. P.; Bermeshev, M. V.; Kanat'eva, A. Yu.; Kurganov, A. A.

2017-01-01

Gas-chromatographic determination of the diffusion coefficients that allows for the compressibility of the mobile phase has been suggested. The diffusion coefficients were determined for light hydrocarbons C1-C4 in four polymers with a high free volume, which are candidates for use as gas-separating membranes. The diffusion coefficients calculated from chromatographic data were shown to be one or two orders of magnitude smaller than the values obtained by the membrane method. This may be due to the presence of an additional flow through the membrane caused by the pressure gradient across the membrane in membrane methods.

Numerical and experimental study of the effects of the electrical resistance and diffusivity under clamping pressure on the performance of a metallic gas-diffusion layer in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Tanaka, Shiro; Bradfield, Warwick W.; Legrand, Cloe; Malan, Arnaud G.

2016-10-01

The performance of a perforated metal-sheet gas-diffusion layer incorporated with a microporous layer in a fuel cell is evaluated with fine-pitch channel/land designs for the gas flow field on a bipolar plate. The combination of metal-sheet gas-diffusion layer and microporous layer exhibits significant performance without a large flooding effect. When comparing the performance with wider and narrower land cases, the land width affects the performance. To investigate the roles of the microporous layer, land width, etc. in the fuel cell with the metal-sheet gas-diffusion layer, a single-phase, isothermal, and multi-physics simulation is developed and coupled with electrical, mechanical, electrochemical and fluid dynamics factors. The simulated current-voltage performance is then compared to the experimentally measure performance. These are shown to be in good agreement apart for very high current-density cases i.e. greater than 1.5 A cm-2. This is due the flooding effect predominantly appearing. It is further demonstrated that the microporous layer serves as the key component in facilitating gas diffusion and for preventing flooding. Furthermore, the pressure is found to have a strong impact on the performance, affecting the gas diffusion and electric resistance around the microporous layer.

NMR spin-rotation relaxation and diffusion of methane

NASA Astrophysics Data System (ADS)

Singer, P. M.; Asthagiri, D.; Chapman, W. G.; Hirasaki, G. J.

2018-05-01

The translational diffusion-coefficient and the spin-rotation contribution to the 1H NMR relaxation rate for methane (CH4) are investigated using MD (molecular dynamics) simulations, over a wide range of densities and temperatures, spanning the liquid, supercritical, and gas phases. The simulated diffusion-coefficients agree well with measurements, without any adjustable parameters in the interpretation of the simulations. A minimization technique is developed to compute the angular velocity for non-rigid spherical molecules, which is used to simulate the autocorrelation function for spin-rotation interactions. With increasing diffusivity, the autocorrelation function shows increasing deviations from the single-exponential decay predicted by the Langevin theory for rigid spheres, and the deviations are quantified using inverse Laplace transforms. The 1H spin-rotation relaxation rate derived from the autocorrelation function using the "kinetic model" agrees well with measurements in the supercritical/gas phase, while the relaxation rate derived using the "diffusion model" agrees well with measurements in the liquid phase. 1H spin-rotation relaxation is shown to dominate over the MD-simulated 1H-1H dipole-dipole relaxation at high diffusivity, while the opposite is found at low diffusivity. At high diffusivity, the simulated spin-rotation correlation time agrees with the kinetic collision time for gases, which is used to derive a new expression for 1H spin-rotation relaxation, without any adjustable parameters.

Density-driven transport of gas phase chemicals in unsaturated soils

NASA Astrophysics Data System (ADS)

Fen, Chiu-Shia; Sun, Yong-tai; Cheng, Yuen; Chen, Yuanchin; Yang, Whaiwan; Pan, Changtai

2018-01-01

Variations of gas phase density are responsible for advective and diffusive transports of organic vapors in unsaturated soils. Laboratory experiments were conducted to explore dense gas transport (sulfur hexafluoride, SF6) from different source densities through a nitrogen gas-dry soil column. Gas pressures and SF6 densities at transient state were measured along the soil column for three transport configurations (horizontal, vertically upward and vertically downward transport). These measurements and others reported in the literature were compared with simulation results obtained from two models based on different diffusion approaches: the dusty gas model (DGM) equations and a Fickian-type molar fraction-based diffusion expression. The results show that the DGM and Fickian-based models predicted similar dense gas density profiles which matched the measured data well for horizontal transport of dense gas at low to high source densities, despite the pressure variations predicted in the soil column were opposite to the measurements. The pressure evolutions predicted by both models were in trend similar to the measured ones for vertical transport of dense gas. However, differences between the dense gas densities predicted by the DGM and Fickian-based models were discernible for vertically upward transport of dense gas even at low source densities, as the DGM-based predictions matched the measured data better than the Fickian results did. For vertically downward transport, the dense gas densities predicted by both models were not greatly different from our experimental measurements, but substantially greater than the observations obtained from the literature, especially at high source densities. Further research will be necessary for exploring factors affecting downward transport of dense gas in soil columns. Use of the measured data to compute flux components of SF6 showed that the magnitudes of diffusive flux component based on the Fickian-type diffusion expressions in terms of molar concentration, molar fraction and mass density fraction gradient were almost the same. However, they were greater than the result computed with the mass fraction gradient for > 24% and the DGM-based result for more than one time. As a consequence, the DGM-based total flux of SF6 was in magnitude greatly less than the Fickian result not only for horizontal transport (diffusion-dominating) but also for vertical transport (advection and diffusion) of dense gas. Particularly, the Fickian-based total flux was more than two times in magnitude as much as the DGM result for vertically upward transport of dense gas.

Multimodel analysis of anisotropic diffusive tracer-gas transport in a deep arid unsaturated zone

USGS Publications Warehouse

Green, Christopher T.; Walvoord, Michelle Ann; Andraski, Brian J.; Striegl, Robert G.; Stonestrom, David A.

2015-01-01

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Milestone report: The simulation of radiation driven gas diffusion in UO 2 at low temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, Michael William; Kuganathan, Navaratnarajah; Burr, Patrick A

2016-10-24

Below 1000 K it is thought that fission gas diffusion in nuclear fuel during irradiation occurs through atomic mixing due to radiation damage. This is an important process for nuclear reactor performance as it affects fission gas release, particularly from the periphery of the pellet where such temperatures are normal. Here we present a molecular dynamics study of Xe and Kr diffusion due to irradiation. Thermal spikes and cascades have been used to study the electronic stopping and ballistic phases of damage, respectively. Our results predict that O and Kr exhibit the greatest diffusivity and U the least, while Xemore » lies in between. It is concluded that the ballistic phase does not sufficiently account for the experimentally observed diffusion. Preliminary thermal spike calculations indicate that the electronic stopping phase generates greater fission gas displacement than the ballistic phase, although further calculation must be carried out to confirm this. A good description of the system by the empirical potentials is important over the very wide temperatures induced during thermal spike and damage cascade simulations. This has motivated the development of a parameter set for gas-actinide and gas-oxygen interactions that is complementary for use with a recent many-body potential set. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO 2, ThO 2, UO 2 and PuO 2. These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT binding energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO 2, ThO 2, UO 2 and PuO 2, providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO 2 as well as advanced MOX fuels.« less

Numerical Modelling and Simulation of Chemical Reactions in a Nano-Pulse Discharged Bubble for Water Treatment

NASA Astrophysics Data System (ADS)

He, Yuchen; Satoshi, Uehara; Hidemasa, Takana; Hideya, Nishiyama

2016-09-01

A zero-dimensional model to simulate a nano-pulse-discharged bubble in water was developed. The model consists of gas and liquid phases corresponding to the inside and outside of the bubble, respectively. The diffusions of chemical species from the gas to the liquid phase through the bubble interface was also investigated. The initial gas is Ar, but includes a little H2O and O2 in the bubble. The time evolution of the OH concentration in the liquid phase was mainly investigated as an important species for water treatment. It was shown that OH was generated in the bubble and then diffused into the liquid. With the application of a continuous nano-pulse discharge, more OH radicals were generated as the frequency increased at a low voltage for a given power consumption. supported partially by Japan Society for the Promotion of Science (JSPS) KAKENHI (No. 26249015)

Investigating fuel-cell transport limitations using hydrogen limiting current

DOE PAGES

Spingler, Franz B.; Phillips, Adam; Schuler, Tobias; ...

2017-03-09

Reducing mass-transport losses in polymer-electrolyte fuel cells (PEFCs) is essential to increase their power density and reduce overall stack cost. At the same time, cost also motivates the reduction in expensive precious-metal catalysts, which results in higher local transport losses in the catalyst layers. Here, we use a hydrogen-pump limiting-current setup to explore the gas-phase transport losses through PEFC catalyst layers and various gas-diffusion and microporous layers. It is shown that the effective diffusivity in the gas-diffusion layers is a strong function of liquid saturation. Additionally, it is shown how the catalyst layer unexpectedly contributes significantly to the overall measuredmore » transport resistance. This is especially true for low catalyst loadings. It is also shown how the various losses can be separated into different mechanisms including diffusional processes and mass-dependent and independent ones, where the data suggests that a large part of the transport resistance in catalyst layers cannot be attributed to a gas-phase diffusional process. The technique is promising for deconvoluting transport losses in PEFCs.« less

A Systematic Procedure to Describe Shale Gas Permeability Evolution during the Production Process

NASA Astrophysics Data System (ADS)

Jia, B.; Tsau, J. S.; Barati, R.

2017-12-01

Gas flow behavior in shales is complex due to the multi-physics nature of the process. Pore size reduces as the in-situ stress increases during the production process, which will reduce intrinsic permeability of the porous media. Slip flow/pore diffusion enhances gas apparent permeability, especially under low reservoir pressures. Adsorption not only increases original gas in place but also influences gas flow behavior because of the adsorption layer. Surface diffusion between free gas and adsorption phase enhances gas permeability. Pore size reduction and the adsorption layer both have complex impacts on gas apparent permeability and non-Darcy flow might be a major component in nanopores. Previously published literature is generally incomplete in terms of coupling of all these four physics with fluid flow during gas production. This work proposes a methodology to simultaneously take them into account to describe a permeability evolution process. Our results show that to fully describe shale gas permeability evolution during gas production, three sets of experimental data are needed initially: 1) intrinsic permeability under different in-situ stress, 2) adsorption isotherm under reservoir conditions and 3) surface diffusivity measurement by the pulse-decay method. Geomechanical effects, slip flow/pore diffusion, adsorption layer and surface diffusion all play roles affecting gas permeability. Neglecting any of them might lead to misleading results. The increasing in-situ stress during shale gas production is unfavorable to shale gas flow process. Slip flow/pore diffusion is important for gas permeability under low pressures in the tight porous media. They might overwhelm the geomechanical effect and enhance gas permeability at low pressures. Adsorption layer reduces the gas permeability by reducing the effective pore size, but the effect is limited. Surface diffusion increases gas permeability more under lower pressures. The total gas apparent permeability might keep increasing during the gas production process when the surface diffusivity is larger than a critical value. We believe that our workflow proposed in this study will help describe shale gas permeability evolution considering all the underlying physics altogether.

Effect of grain morphology on gas bubble swelling in UMo fuels – A 3D microstructure dependent Booth model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Shenyang; Burkes, Douglas; Lavender, Curt A.

2016-11-01

A three dimensional microstructure dependent swelling model is developed for studying the fission gas swelling kinetics in irradiated nuclear fuels. The model is extended from the Booth model [1] in order to investigate the effect of heterogeneous microstructures on gas bubble swelling kinetics. As an application of the model, the effect of grain morphology, fission gas diffusivity, and spatial dependent fission rate on swelling kinetics are simulated in UMo fuels. It is found that the decrease of grain size, the increase of grain aspect ratio for the grain having the same volume, and the increase of fission gas diffusivity (fissionmore » rate) cause the increase of swelling kinetics. Other heterogeneities such as second phases and spatial dependent thermodynamic properties including diffusivity of fission gas, sink and source strength of defects could be naturally integrated into the model to enhance the model capability.« less

Modeling diffusion in foamed polymer nanocomposites.

PubMed

Ippalapalli, Sandeep; Ranaprathapan, A Dileep; Singh, Sachchida N; Harikrishnan, G

2013-04-15

Two-way multicomponent diffusion processes in polymeric nanocomposite foams, where the condensed phase is nanoscopically reinforced with impermeable fillers, are investigated. The diffusion process involves simultaneous outward permeation of the components of the dispersed gas phase and inward diffusion of atmospheric air. The transient variation in thermal conductivity of foam is used as the macroscopic property to track the compositional variations of the dispersed gases due to the diffusion process. In the continuum approach adopted, the unsteady-state diffusion process is combined with tortuosity theory. The simulations conducted at ambient temperature reveal distinct regimes of diffusion processes in the nanocomposite foams owing to the reduction in the gas-transport rate induced by nanofillers. Simulations at a higher temperature are also conducted and the predictions are compared with experimentally determined thermal conductivities under accelerated diffusion conditions for polyurethane foams reinforced with clay nanoplatelets of varying individual lamellar dimensions. Intermittent measurements of foam thermal conductivity are performed while the accelerated diffusion proceeded. The predictions under accelerated diffusion conditions show good agreement with experimentally measured thermal conductivities for nanocomposite foams reinforced with low and medium aspect-ratios fillers. The model shows higher deviations for foams with fillers that have a high aspect ratio. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

1988-01-01

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-07-01

Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-03-01

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analyzed by means of X-ray computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Shenyang; Joshi, Vineet; Lavender, Curt A.

Experiments showed that recrystallization dramatically speeds up the gas bubble swelling kinetics in metallic UMo fuels. In this work a recrystallization model is developed to study the effect of microstructures and radiation conditions on recrystallization kinetics. The model integrates the rate theory of intra-granular gas bubble and interstitial loop evolution and a phase field model of recrystallization zone evolution. A fast passage method is employed to describe one dimensional diffusion of interstitials which have diffusivity several order magnitude larger than that of the fission gas Xe. With the model, the effect of grain sizes on recrystallization kinetics is simulated.

Monitoring of tritium

DOEpatents

Corbett, James A.; Meacham, Sterling A.

1981-01-01

The fluid from a breeder nuclear reactor, which may be the sodium cooling fluid or the helium reactor-cover-gas, or the helium coolant of a gas-cooled reactor passes over the portion of the enclosure of a gaseous discharge device which is permeable to hydrogen and its isotopes. The tritium diffused into the discharge device is radioactive producing beta rays which ionize the gas (argon) in the discharge device. The tritium is monitored by measuring the ionization current produced when the sodium phase and the gas phase of the hydrogen isotopes within the enclosure are in equilibrium.

A Gas-Kinetic Method for Hyperbolic-Elliptic Equations and Its Application in Two-Phase Fluid Flow

NASA Technical Reports Server (NTRS)

Xu, Kun

1999-01-01

A gas-kinetic method for the hyperbolic-elliptic equations is presented in this paper. In the mixed type system, the co-existence and the phase transition between liquid and gas are described by the van der Waals-type equation of state (EOS). Due to the unstable mechanism for a fluid in the elliptic region, interface between the liquid and gas can be kept sharp through the condensation and evaporation process to remove the "averaged" numerical fluid away from the elliptic region, and the interface thickness depends on the numerical diffusion and stiffness of the phase change. A few examples are presented in this paper for both phase transition and multifluid interface problems.

Nucleation and growth constraints and outcome in the natural gas hydrate system

NASA Astrophysics Data System (ADS)

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

2016-12-01

Hydrate formation processes are functions of energy distribution constrained by physical and kinetic parameters. The generation of energy and energy derivative plots of a constrained growth crucible are used to demonstrate nucleation probability zones (phase origin(s)). Nucleation sets the stage for growth by further constraining the pathways through changes in heat capacity, heat flow coefficient, and enthalpy which in turn modify the mass and energy flow into the hydrate formation region. Nucleation events result from the accumulation of materials and energy relative to pressure, temperature, and composition. Nucleation induction is predictive (a frequency parameter) rather than directly dependent on time. Growth, as mass tranfer into a new phase, adds time as a direct parameter. Growth has direct feedback on phase transfer, energy dynamics, and mass export/import rates. Many studies have shown that hydrate growth is largely an equilibrium process controlled by either mass or energy flows. Subtle changes in the overall energy distribution shift the equilibrium in a predictable fashion. We will demonstrate the localization of hydrate nucleation in a reservoir followed by likely evolution of growth in a capped, sand filled environment. The gas hydrate stability zone (GHSZ) can be characterized as a semi-batch crystallizer in which nucleation and growth of natural gas hydrate (NGH) is a continuous process that may result in very large concentrations of NGH. Gas flux, or the relative concentration of hydrate-forming gas is the critical factor in a GHSZ. In an open groundwater system in which flow rate exceeds diffusion transport rate, dissolved natural gas is transported into and through the GHSZ. In a closed system, such as a geological trap, diffusion of hydrate-forming gas from a free gas zone below the GHSZ is the primary mechanism for movement of gas reactants. Because of the lower molecular weight of methane, where diffusion is the principal transport mechanism, the natural system can be a purification process for formation of increasingly pure NGH from a mixed gas solution over time.

Controlled surface diffusion in plasma-enhanced chemical vapor deposition of GaN nanowires.

PubMed

Hou, Wen Chi; Hong, Franklin Chau-Nan

2009-02-04

This study investigates the growth of GaN nanowires by controlling the surface diffusion of Ga species on sapphire in a plasma-enhanced chemical vapor deposition (CVD) system. Under nitrogen-rich growth conditions, Ga has a tendency to adsorb on the substrate surface diffusing to nanowires to contribute to their growth. The significance of surface diffusion on the growth of nanowires is dependent on the environment of the nanowire on the substrate surface as well as the gas phase species and compositions. Under nitrogen-rich growth conditions, the growth rate is strongly dependent on the surface diffusion of gallium, but the addition of 5% hydrogen in nitrogen plasma instantly diminishes the surface diffusion effect. Gallium desorbs easily from the surface by reaction with hydrogen. On the other hand, under gallium-rich growth conditions, nanowire growth is shown to be dominated by the gas phase deposition, with negligible contribution from surface diffusion. This is the first study reporting the inhibition of surface diffusion effects by hydrogen addition, which can be useful in tailoring the growth and characteristics of nanowires. Without any evidence of direct deposition on the nanowire surface, gallium and nitrogen are shown to dissolve into the catalyst for growing the nanowires at 900 degrees C.

Transport of gases between the environment and alveoli – theoretical foundations

PubMed Central

Butler, James P.; Tsuda, Akira

2015-01-01

The transport of oxygen and carbon dioxide in the gas phase from the ambient environment to and from the alveolar gas/blood interface is accomplished through the tracheobronchial tree, and involves mechanisms of bulk or convective transport and diffusive net transport. The geometry of the airway tree and the fluid dynamics of these two transport processes combine in such a way that promotes a classical fractionation of ventilation into dead space and alveolar ventilation respectively. This simple picture continues to capture much of the essence of gas phase transport. On the other hand, a more detailed look at the interaction of convection and diffusion leads to significant new issues, many of which remain open questions. These are associated with parallel and serial inhomogeneities especially within the distal acinar units, velocity profiles in distal airways and terminal spaces subject to moving boundary conditions, and the serial transport of respiratory gases within the complex acinar architecture. This chapter focuses specifically on the theoretical foundations of gas transport, addressing two broad areas. The first deals with the reasons why the classical picture of alveolar and dead space ventilation is so successful; the second examines the underlying assumptions within current approximations to convective and diffusive transport, and how they interact to effect net gas exchange. PMID:23733643

Diffuse CO2 degassing at Vesuvio, Italy

NASA Astrophysics Data System (ADS)

Frondini, Francesco; Chiodini, Giovanni; Caliro, Stefano; Cardellini, Carlo; Granieri, Domenico; Ventura, Guido

2004-10-01

At Vesuvio, a significant fraction of the rising hydrothermal-volcanic fluids is subjected to a condensation and separation process producing a CO2-rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic-hydrothermal CO2 discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d-1. The steam associated with the CO2 output, computed assuming that the original H2O/CO2 ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d-1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×1012 J d-1 (17 MW). The location of the CO2 and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO2 degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO2 flux, can constitute a useful tool to monitor volcanic activity.

Calculation of the Rate of Combustion of a Metallized Composite Solid Propellant with Allowance for the Size Distribution of Agglomerates

NASA Astrophysics Data System (ADS)

Poryazov, V. A.; Krainov, A. Yu.

2016-05-01

A physicomathematical model of combustion of a metallized composite solid propellant based on ammonium perchlorate has been presented. The model takes account of the thermal effect of decomposition of a condensed phase (c phase), convection, diffusion, the exothermal chemical reaction in a gas phase, the heating and combustion of aluminum particles in the gas flow, and the velocity lag of the particles behind the gas. The influence of the granulometric composition of aluminum particles escaping from the combustion surface on the linear rate of combustion has been investigated. It has been shown that information not only on the kinetics of chemical reactions in the gas phase, but also on the granulometric composition of aluminum particles escaping from the surface of the c phase into the gas, is of importance for determination of the linear rate of combustion.

Development and validation of a portable gas phase standard generation and calibration system for volatile organic compounds

Treesearch

P. Veres; J. B. Gilman; J. M. Roberts; W. C. Kuster; C. Warneke; I. R. Burling; J. de Gouw

2010-01-01

We report on the development of an accurate, portable, dynamic calibration system for volatile organic compounds (VOCs). The Mobile Organic Carbon Calibration System (MOCCS) combines the production of gas-phase VOC standards using permeation or diffusion sources with quantitative total organic carbon (TOC) conversion on a palladium surface to CO2 in the presence of...

Gas Phase Spectroscopy of Cold PAH Ions: Contribution to the Interstellar Extinction and the Diffuse Interstellar Bands

NASA Technical Reports Server (NTRS)

Biennier, L.; Salama, F.; Allamandola, L. J.; Scherer, J. J.; OKeefe, A.

2002-01-01

Polycyclic Aromatic Hydrocarbon molecules (PAHs) are ubiquitous in the interstellar medium (ISM) and constitute the building blocks of interstellar dust grains. Despite their inferred important role in mediating the energetic and chemical processes in thc ISM, their exact contribution to the interstellar extinction, and in particular to the diffuse interstellar bands (DIBs) remains unclear. The DIBs are spectral absorption features observed in the line of sight of stars that are obscured by diffuse interstellar clouds. More than 200 bands have been reported to date spanning from the near UV to the near IR with bandwidths ranging from 0.4 to 40 Angstroms (Tielens & Snow 1995). The present consensus is that the DIBs arise from free flying, gas-phase, organic molecules and/or ions that are abundant under the typical conditions reigning in the diffuse ISM. PAHs have been proposed as possible carriers (Allamandola et al. 1985; Leger & DHendecourt 1985). The PAH hypothesis is consistent with the cosmic abundance of Carbon and Hydrogen and with the required photostability of the DIB carriers against the strong VUV radiation field in the diffuse interstellar clouds. A significant fraction of PAHs is expected to be ionized in the diffuse ISM.

Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

USGS Publications Warehouse

Molins, S.; Mayer, K.U.

2007-01-01

The two‐way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate‐rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

Scaling Relations for Viscous and Gravitational Flow Instabilities in Multiphase Multicomponent Compressible Flow

NASA Astrophysics Data System (ADS)

Moortgat, J.; Amooie, M. A.; Soltanian, M. R.

2016-12-01

Problems in hydrogeology and hydrocarbon reservoirs generally involve the transport of solutes in a single solvent phase (e.g., contaminants or dissolved injection gas), or the flow of multiple phases that may or may not exchange mass (e.g., brine, NAPL, oil, gas). Often, flow is viscously and gravitationally unstable due to mobility and density contrasts within a phase or between phases. Such instabilities have been studied in detail for single-phase incompressible fluids and for two-phase immiscible flow, but to a lesser extent for multiphase multicomponent compressible flow. The latter is the subject of this presentation. Robust phase stability analyses and phase split calculations, based on equations of state, determine the mass exchange between phases and the resulting phase behavior, i.e., phase densities, viscosities, and volumes. Higher-order finite element methods and fine grids are used to capture the small-scale onset of flow instabilities. A full matrix of composition dependent coefficients is considered for each Fickian diffusive phase flux. Formation heterogeneity can have a profound impact and is represented by realistic geostatistical models. Qualitatively, fingering in multiphase compositional flow is different from single-phase problems because 1) phase mobilities depend on rock wettability through relative permeabilities, and 2) the initial density and viscosity ratios between phases may change due to species transfer. To quantify mixing rates in different flow regimes and for varying degrees of miscibility and medium heterogeneities, we define the spatial variance, scalar dissipation rate, dilution index, skewness, and kurtosis of the molar density of introduced species. Molar densities, unlike compositions, include compressibility effects. The temporal evolution of these measures shows that, while transport at the small-scale (cm) is described by the classical advection-diffusion-dispersion relations, scaling at the macro-scale (> 10 m) shows transitions between advective, diffusive, ballistic, sub-diffusive, and non-Fickian diffusive behavior. These scaling relations can be used to improve the predictive powers of field-scale reservoir simulations that cannot resolve the complexities of unstable flow and transport at cm-m scales.

Can the Lyman Continuum Leaked Out of H II Regions Explain Diffuse Ionized Gas?

NASA Astrophysics Data System (ADS)

Seon, Kwang-Il

2009-09-01

We present an attempt to explain the diffuse Hα emission of a face-on galaxy M 51 with the "standard" photoionization model, in which the Lyman continuum (Lyc) escaping from H II regions propagates large distances into the diffuse interstellar medium (ISM). The diffuse Hα emission of M 51 is analyzed using thin slab models and exponential disk models in the context of the "on-the-spot" approximation. The scale height of the ionized gas needed to explain the diffuse Hα emission with the scenario is found to be of the order of ~1-2 kpc, consistent with those of our Galaxy and edge-on galaxies. The model also provides a vertical profile, when the galaxy is viewed edge-on, consisting of two-exponential components. However, it is found that an incredibly low absorption coefficient of κ0 ≈ 0.4-0.8 kpc-1 at the galactic plane, or, equivalently, an effective cross section as low as σeff ~ 10-5 of the photoionization cross section at 912 Å is required to allow the stellar Lyc photons to travel through the H I disk. Such a low absorption coefficient is out of accord with the properties of the ISM. Furthermore, we found that even the model that has the diffuse ionized gas (DIG) phase only and no H I gas phase shows highly concentrated Hα emissions around H II regions, and can account for only lsim26% of the Hα luminosity of the DIG. This result places a strong constraint on the ionizing source of the DIG. We also report that the Hα intensity distribution functions not only of the DIG, but also of H II regions in M 51, appear to be lognormal.

Diffuse cloud chemistry. [in interstellar matter

NASA Technical Reports Server (NTRS)

Van Dishoeck, Ewine F.; Black, John H.

1988-01-01

The current status of models of diffuse interstellar clouds is reviewed. A detailed comparison of recent gas-phase steady-state models shows that both the physical conditions and the molecular abundances in diffuse clouds are still not fully understood. Alternative mechanisms are discussed and observational tests which may discriminate between the various models are suggested. Recent developments regarding the velocity structure of diffuse clouds are mentioned. Similarities and differences between the chemistries in diffuse clouds and those in translucent and high latitude clouds are pointed out.

Investigating Phase-Change-Induced Flow in Gas Diffusion Layers in Fuel Cells with X-ray Computed Tomography

DOE PAGES

Shum, Andrew D.; Parkinson, Dilworth Y.; Xiao, Xianghui; ...

2017-10-07

The performance of polymer-electrolyte fuel cells is heavily dependent on proper management of liquid water. One particular reason is that liquid water can collect in the gas diffusion layers (GDLs) blocking the reactant flow to the catalyst layer. This results in increased mass-transport losses. At higher temperatures, evaporation of water becomes a dominant water-removal mechanism and specifically phase-change-induced (PCI) flow is present due to thermal gradients. This study used synchrotron based micro X-ray computed tomography (CT) to visualize and quantify the water distribution within gas diffusion layers subject to a thermal gradient. Plotting saturation as a function of through-plane distancemore » quantitatively shows water redistribution, where water evaporates at hotter locations and condenses in colder locations. The morphology of the 2 GDLs on the micro-scale, as well as evaporating water clusters, are resolved, indicating that the GDL voids are slightly prolate, whereas water clusters are oblate. From the mean radii of water distributions and visual inspection, it is observed that larger water clusters evaporate faster than smaller ones.« less

Tracking Water Diffusion Fronts in a Highly Viscous Aerosol Particle

NASA Astrophysics Data System (ADS)

Bastelberger, Sandra; Krieger, Ulrich; Peter, Thomas

2016-04-01

Field measurements indicate that atmospheric secondary aerosol particles can be present in a highly viscous, glassy state [1]. In contrast to liquid state particles, the gas phase equilibration is kinetically limited and governed by condensed phase diffusion. In recent water diffusion experiments on highly viscous single aerosol particles levitated in an electrodynamic balance (EDB) we observed a characteristic shift behavior of the Mie whispering gallery modes (WGM) indicative of the changing radial structure of the particle, thus providing us with an experimental method to track the diffusion process inside the particle. When a highly viscous, homogeneous particle is exposed to an abrupt increase in relative humidity, the rapid gas phase diffusion and strong concentration dependence of the diffusion coefficient in the condensed phase lead to extremely steep water concentration gradients inside the particle, reminiscent of diffusion fronts. The resulting quasi step-like concentration profile motivates the introduction of a simple core-shell model describing the morphology of the non-equilibrium particle during humidification. The subsequent particle growth and reduction of the shell refractive index can be observed as red and blueshift behavior of the WGM, respectively. The shift pattern can be attributed to a core-shell radius ratio and particle radius derived from model calculations [2]. If supplemented with growth information obtained from the WGM redshift and thermodynamic equilibrium data, we can infer a comprehensive picture of the time evolution of the diffusion fronts in the framework of our core-shell model. The measured time dependent concentration profile is then compared with simulations solving the non-linear diffusion equation [3] [1] Virtanen, A., et al., Nature, 467, 824-827, 2010 [2] Kaiser, T., Schweiger, G., Computers in Physics, Vol. 7, No. 6, 682-686, Nov/Dec 1993 [3] Zobrist, B., Soonsin, V., Luo, B.P., Peter, T. et al., Phys. Chem. Chem. Phys., 13,3514-3526, 2011

Resonant Acoustic Measurement of Vapor Phase Transport Phenomenon

NASA Astrophysics Data System (ADS)

Schuhmann, R. J.; Garrett, S. L.; Matson, J. V.

2002-12-01

A major impediment to accurate non steady-state diffusion measurements is the ability to accurately measure and track a rapidly changing gas concentration without disturbing the system. Non-destructive methods that do not interfere with system dynamics have been developed in the past. These methods, however, have tended to be cumbersome or inaccurate at low concentrations. A new experimental approach has been developed to measure gaseous diffusion in free air and through porous materials. The method combines the traditional non steady-state laboratory methodology with resonant acoustic gas analysis. A phase-locked-loop (PLL) resonance frequency tracker is combined with a thermally insulated copper resonator. A piston sealed with a metal bellows excites the fundamental standing wave resonance of the resonator. The PLL maintains a constant phase difference (typically 90§) between the accelerometer mounted on the piston and a microphone near the piston to track the resonance frequency in real time. A capillary or glass bead filled core is fitted into an o-ring sealed opening at the end of the resonator opposite the bellows. The rate at which the tracer gas is replaced by air within the resonator is controlled by the diffusion coefficient of the gas in free air through the capillary (DA) or by the effective diffusion coefficient of the gas through the core (De). The mean molecular weight of the gas mixture in the resonator is directly determined six times each minute from the ratio of the absolute temperature to the square of the fundamental acoustic resonance frequency. Average system stability (temperature divided by frequency squared) is better than 350 ppm. DA values for a 0.3-inch diameter capillary were in excellent agreement with published values. De values for porous media samples (0.5 mm glass beads) of four different lengths (1 through 4 inches) using three different tracer gases (He, CH4, Kr) will be reported. Comments will be offered regarding tracer gas selection and device orientation and their effect on experimental results. [Work supported by the Office of Naval Research.

Improving estimates of subsurface gas transport in unsaturated fractured media using experimental Xe diffusion data and numerical methods

NASA Astrophysics Data System (ADS)

Ortiz, J. P.; Ortega, A. D.; Harp, D. R.; Boukhalfa, H.; Stauffer, P. H.

2017-12-01

Gas transport in unsaturated fractured media plays an important role in a variety of applications, including detection of underground nuclear explosions, transport from volatile contaminant plumes, shallow CO2 leakage from carbon sequestration sites, and methane leaks from hydraulic fracturing operations. Gas breakthrough times are highly sensitive to uncertainties associated with a variety of hydrogeologic parameters, including: rock type, fracture aperture, matrix permeability, porosity, and saturation. Furthermore, a couple simplifying assumptions are typically employed when representing fracture flow and transport. Aqueous phase transport is typically considered insignificant compared to gas phase transport in unsaturated fracture flow regimes, and an assumption of instantaneous dissolution/volatilization of radionuclide gas is commonly used to reduce computational expense. We conduct this research using a twofold approach that combines laboratory gas experimentation and numerical modeling to verify and refine these simplifying assumptions in our current models of gas transport. Using a gas diffusion cell, we are able to measure air pressure transmission through fractured tuff core samples while also measuring Xe gas breakthrough measured using a mass spectrometer. We can thus create synthetic barometric fluctuations akin to those observed in field tests and measure the associated gas flow through the fracture and matrix pore space for varying degrees of fluid saturation. We then attempt to reproduce the experimental results using numerical models in PLFOTRAN and FEHM codes to better understand the importance of different parameters and assumptions on gas transport. Our numerical approaches represent both single-phase gas flow with immobile water, as well as full multi-phase transport in order to test the validity of assuming immobile pore water. Our approaches also include the ability to simulate the reaction equilibrium kinetics of dissolution/volatilization in order to identify when the assumption of instantaneous equilibrium is reasonable. These efforts will aid us in our application of such models to larger, field-scale tests and improve our ability to predict gas breakthrough times.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

NASA Astrophysics Data System (ADS)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix-a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30-47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3-35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.

Static SPME sampling of VOCs emitted from indoor building materials: prediction of calibration curves of single compounds for two different emission cells.

PubMed

Mocho, Pierre; Desauziers, Valérie

2011-05-01

Solid-phase microextraction (SPME) is a powerful technique, easy to implement for on-site static sampling of indoor VOCs emitted by building materials. However, a major constraint lies in the establishment of calibration curves which requires complex generation of standard atmospheres. Thus, the purpose of this paper is to propose a model to predict adsorption kinetics (i.e., calibration curves) of four model VOCs. The model is based on Fick's laws for the gas phase and on the equilibrium or the solid diffusion model for the adsorptive phase. Two samplers (the FLEC® and a home-made cylindrical emission cell), coupled to SPME for static sampling of material emissions, were studied. A good agreement between modeling and experimental data is observed and results show the influence of sampling rate on mass transfer mode in function of sample volume. The equilibrium model is adapted to quite large volume sampler (cylindrical cell) while the solid diffusion model is dedicated to small volume sampler (FLEC®). The limiting steps of mass transfer are the diffusion in gas phase for the cylindrical cell and the pore surface diffusion for the FLEC®. In the future, this modeling approach could be a useful tool for time-saving development of SPME to study building material emission in static mode sampling.

The narrow pulse approximation and long length scale determination in xenon gas diffusion NMR studies of model porous media

NASA Technical Reports Server (NTRS)

Mair, R. W.; Sen, P. N.; Hurlimann, M. D.; Patz, S.; Cory, D. G.; Walsworth, R. L.

2002-01-01

We report a systematic study of xenon gas diffusion NMR in simple model porous media, random packs of mono-sized glass beads, and focus on three specific areas peculiar to gas-phase diffusion. These topics are: (i) diffusion of spins on the order of the pore dimensions during the application of the diffusion encoding gradient pulses in a PGSE experiment (breakdown of the narrow pulse approximation and imperfect background gradient cancellation), (ii) the ability to derive long length scale structural information, and (iii) effects of finite sample size. We find that the time-dependent diffusion coefficient, D(t), of the imbibed xenon gas at short diffusion times in small beads is significantly affected by the gas pressure. In particular, as expected, we find smaller deviations between measured D(t) and theoretical predictions as the gas pressure is increased, resulting from reduced diffusion during the application of the gradient pulse. The deviations are then completely removed when water D(t) is observed in the same samples. The use of gas also allows us to probe D(t) over a wide range of length scales and observe the long time asymptotic limit which is proportional to the inverse tortuosity of the sample, as well as the diffusion distance where this limit takes effect (approximately 1-1.5 bead diameters). The Pade approximation can be used as a reference for expected xenon D(t) data between the short and the long time limits, allowing us to explore deviations from the expected behavior at intermediate times as a result of finite sample size effects. Finally, the application of the Pade interpolation between the long and the short time asymptotic limits yields a fitted length scale (the Pade length), which is found to be approximately 0.13b for all bead packs, where b is the bead diameter. c. 2002 Elsevier Sciences (USA).

The narrow pulse approximation and long length scale determination in xenon gas diffusion NMR studies of model porous media.

PubMed

Mair, R W; Sen, P N; Hürlimann, M D; Patz, S; Cory, D G; Walsworth, R L

2002-06-01

We report a systematic study of xenon gas diffusion NMR in simple model porous media, random packs of mono-sized glass beads, and focus on three specific areas peculiar to gas-phase diffusion. These topics are: (i) diffusion of spins on the order of the pore dimensions during the application of the diffusion encoding gradient pulses in a PGSE experiment (breakdown of the narrow pulse approximation and imperfect background gradient cancellation), (ii) the ability to derive long length scale structural information, and (iii) effects of finite sample size. We find that the time-dependent diffusion coefficient, D(t), of the imbibed xenon gas at short diffusion times in small beads is significantly affected by the gas pressure. In particular, as expected, we find smaller deviations between measured D(t) and theoretical predictions as the gas pressure is increased, resulting from reduced diffusion during the application of the gradient pulse. The deviations are then completely removed when water D(t) is observed in the same samples. The use of gas also allows us to probe D(t) over a wide range of length scales and observe the long time asymptotic limit which is proportional to the inverse tortuosity of the sample, as well as the diffusion distance where this limit takes effect (approximately 1-1.5 bead diameters). The Padé approximation can be used as a reference for expected xenon D(t) data between the short and the long time limits, allowing us to explore deviations from the expected behavior at intermediate times as a result of finite sample size effects. Finally, the application of the Padé interpolation between the long and the short time asymptotic limits yields a fitted length scale (the Padé length), which is found to be approximately 0.13b for all bead packs, where b is the bead diameter. c. 2002 Elsevier Sciences (USA).

Free molecular collision cross section calculation methods for nanoparticles and complex ions with energy accommodation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larriba, Carlos, E-mail: clarriba@umn.edu; Hogan, Christopher J.

2013-10-15

The structures of nanoparticles, macromolecules, and molecular clusters in gas phase environments are often studied via measurement of collision cross sections. To directly compare structure models to measurements, it is hence necessary to have computational techniques available to calculate the collision cross sections of structural models under conditions matching measurements. However, presently available collision cross section methods contain the underlying assumption that collision between gas molecules and structures are completely elastic (gas molecule translational energy conserving) and specular, while experimental evidence suggests that in the most commonly used background gases for measurements, air and molecular nitrogen, gas molecule reemission ismore » largely inelastic (with exchange of energy between vibrational, rotational, and translational modes) and should be treated as diffuse in computations with fixed structural models. In this work, we describe computational techniques to predict the free molecular collision cross sections for fixed structural models of gas phase entities where inelastic and non-specular gas molecule reemission rules can be invoked, and the long range ion-induced dipole (polarization) potential between gas molecules and a charged entity can be considered. Specifically, two calculation procedures are described detail: a diffuse hard sphere scattering (DHSS) method, in which structures are modeled as hard spheres and collision cross sections are calculated for rectilinear trajectories of gas molecules, and a diffuse trajectory method (DTM), in which the assumption of rectilinear trajectories is relaxed and the ion-induced dipole potential is considered. Collision cross section calculations using the DHSS and DTM methods are performed on spheres, models of quasifractal aggregates of varying fractal dimension, and fullerene like structures. Techniques to accelerate DTM calculations by assessing the contribution of grazing gas molecule collisions (gas molecules with altered trajectories by the potential interaction) without tracking grazing trajectories are further discussed. The presented calculation techniques should enable more accurate collision cross section predictions under experimentally relevant conditions than pre-existing approaches, and should enhance the ability of collision cross section measurement schemes to discern the structures of gas phase entities.« less

Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roldin, P.; Eriksson, A. C.; Nordin, E. Z.

2014-08-11

We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3)more » and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.« less

Particle transport characteristics of the RT-1 magnetospheric plasma using gas-puffing modulation technique

NASA Astrophysics Data System (ADS)

Kenmochi, Naoki; Nishiura, Masaki; Yoshida, Zensho; Sugata, Tetsuya; Nakamura, Kaori; Katsura, Shotaro

2017-10-01

The Ring Trap 1 (RT-1) device creates a laboratory magnetosphere that is realized by a levitated superconducting ring magnet in vacuum. The RT-1 experiment has demonstrated the self-organization of a plasma clump with a steep density gradient; a peaked density distribution is spontaneously created through `inward diffusion'. In order to evaluate particle transport characteristics in the RT-1 magnetospheric plasmas which cause these inward diffusion, density modulation experiments were performed in the RT-1. Density modulation is a powerful method for estimating a diffusion coefficient D and a convection velocity V by puffing a periodic neutral gas. The gas puff modulation causes the change in the electron density measured by two chords of microwave interferometer (the radial positions r = 60 and 70 cm, vertical chord). In the case of 2 Hz gas puff modulation, the phase delay and the modulation-amplitude decay at the chord r = 60 cm are obtained with 15 degree and 0.8, respectively, with respect to the phase and the amplitude at r = 70 cm. The particle balance equations are solved on the assumption of profile shapes for D to evaluate D, V and particle source rate. The result suggests the inward convection in high beta magnetospheric plasmas.

Modeling Ignition of HMX with the Gibbs Formulation

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott

2017-06-01

We present a HMX model with the Gibbs formulation in which stress tensor and temperature are assumed to be in local equilibrium, but phase/chemical changes are not assumed to be in equilibrium. We assume multi-components for HMX including beta- and delta-phase, liquid, and gas phase of HMX and its gas products. Isotropic small strain solid model, modified Fried Howard liquid EOS, and ideal gas EOS are used for its relevant component. Phase/chemical changes are characterized as reactions and are in individual reaction rate. Maxwell-Stefan model is used for diffusion. Excited gas products in the local domain lead unreacted HMX solid to the ignition event. Density of the mixture, stress, strain, displacement, mass fractions, and temperature are considered in 1D domain with time histories. Office of Naval Research and Air Force Office of Scientific Research.

Effects of Gas-Phase Radiation and Detailed Kinetics on the Burning and Extinction of a Solid Fuel

NASA Technical Reports Server (NTRS)

Rhatigan, Jennifer L.

2001-01-01

This is the first attempt to analyze both radiation and detailed kinetics on the burning and extinction of a solid fuel in a stagnation-point diffusion flame. We present a detailed and comparatively accurate computational model of a solid fuel flame along with a quantitative study of the kinetics mechanism, radiation interactions, and the extinction limits of the flame. A detailed kinetics model for the burning of solid trioxane (a trimer of formaldehyde) is coupled with a narrowband radiation model, with carbon dioxide, carbon monoxide, and water vapor as the gas-phase participating media. The solution of the solid trioxane diffusion flame over the flammable regime is presented in some detail, as this is the first solution of a heterogeneous trioxane flame. We identify high-temperature and low-temperature reaction paths for the heterogeneous trioxane flame. We then compare the adiabatic solution to solutions that include Surface radiation only and gas-phase and surface radiation using a black surface model. The analysis includes discussion of detailed flame chemistry over the flammable regime and, in particular, at the low stretch extinction limit. We emphasize the low stretch regime of the radiatively participating flame, since this is the region representative of microgravity flames. When only surface radiation is included, two extinction limits exist (the blow-off limit, and the low stretch radiative limit), and the burning rate and maximum flame temperatures are lower, as expected. With the inclusion of surface and gas-phase radiation, results show that, while flame temperatures are lower, the burning rate of the trioxane diffusion flame may actually increase at low stretch rate due to radiative feedback from the flame to the surface.

Attenuation in gas-charged magma

NASA Astrophysics Data System (ADS)

Collier, L.; Neuberg, J. W.; Lensky, N.; Lyakhovsky, V.; Navon, O.

2006-05-01

Low frequency seismic events observed on volcanoes, such as Soufriere Hills Volcano, Montserrat, are thought to be caused by a resonating system. The modelling of seismic waves in gas-charged magma is critical for the understanding of seismic resonance effects in conduits, dykes and cracks. Seismic attenuation, which depends mainly on magma viscosity, gas and crystal content, is an essential factor in such modelling attempts. So far only two-phase gas-melt systems with the assumption of no diffusion and transport of volatiles between the melt and the gas bubbles have been considered. In this study, we develop a method of quantifying attenuation within gas-charged magma, including the effects of diffusion and exsolution of gas into the bubbles. The results show that by including such bubble growth processes attenuation levels are increased within magma. The resulting complex behaviour of attenuation with pressure and frequency indicates that two factors are controlling attenuation, the first due to viscous hindrance or the melt, and the second due diffusion processes. The level of attenuation within a gas-charged magma conduit suggests an upper limit on the length of a resonating conduit section of just a few hundred meters.

Near-critical fluid boiling: overheating and wetting films.

PubMed

Hegseth, J; Oprisan, A; Garrabos, Y; Lecoutre-Chabot, C; Nikolayev, V S; Beysens, D

2008-08-01

The heating of coexisting gas and liquid phases of pure fluid through its critical point makes the fluid extremely compressible, expandable, slows the diffusive transport, and decreases the contact angle to zero (perfect wetting by the liquid phase). We have performed experiments on near-critical fluids in a variable volume cell in the weightlessness of an orbiting space vehicle, to suppress buoyancy-driven flows and gravitational constraints on the liquid-gas interface. The high compressibility, high thermal expansion, and low thermal diffusivity lead to a pronounced adiabatic heating called the piston effect. We have directly visualized the near-critical fluid's boundary layer response to a volume quench when the external temperature is held constant. We have found that when the system's temperature T is increased at a constant rate past the critical temperature T(c), the interior of the fluid gains a higher temperature than the hot wall (overheating). This extends previous results in temperature quenching experiments in a similarly prepared system when the gas is clearly isolated from the wall. Large elliptical wetting film distortions are also seen during these ramps. By ray tracing through the elliptically shaped wetting film, we find very thick wetting film on the walls. This wetting film is at least one order of magnitude thicker than films that form in the Earth's gravity. The thick wetting film isolates the gas bubble from the wall allowing gas overheating to occur due to the difference in the piston effect response between gas and liquid. Remarkably, this overheating continues and actually increases when the fluid is ramped into the single-phase supercritical phase.

I. Excitonic Phase Diagram in Silicon: Evidence for Two Condensed Phases. I. Motion of Photoexcited Carriers in GALLIUM-ARSENIDE/ALUMINUM(X)GALLIUM(1-X)ARSENIDE Multiple Quantum Wells-Anomalous Confinement at High Densities.

NASA Astrophysics Data System (ADS)

Smith, Leigh Morris

This thesis describes work on the thermodynamics and transport properties of photoexcited carriers in bulk and two-dimensional semiconductors. Two major topics are addressed. I. Photoluminescence experiments of excitons in unstressed silicon are presented which indicate the existence of a new non-degenerate condensed phase of plasma. This new liquid has a density one-tenth that of the ground state electron-hole liquid and is observed both above and below the liquid-gas critical point (~24.5K). A new phase diagram of excitons in silicon is presented which includes these two condensed plasmas. Consistent with the Gibbs phase rule, a triple point at 18.5 K is inferred from the luminescence data as the only temperature where the exciton gas, condensed plasma (CP) and electron-hole liquid (EHL) coexist. The low density condensed plasma persists up to a second critical point at 45 +/- 5K, above which the photoexcited carriers are observed to continuously decay into a partially ionized excitonic gas. II. We have measured the in-plane motion of photoexcited carriers in semiconductor quantum wells with 5 μm spatial and 10 ps temporal resolution and have discovered several surprising results. The effective diffusivity of the carriers at densities below n = 2 times 10^{11}cm ^{-2} is found to depend upon excitation level, possibly indicating defect-limited diffusion or phonon-wind effects. Above this density the spatial profiles exhibit two distinct components with widely differing diffusivities. This remarkable behavior may be understood with consideration of the interactions of non-equilibrium phonons with the photoexcited carriers. We postulate that the slowly diffusing component represents carriers which are "thermally confined" to a phonon hot spot, while the rapidly moving component is driven by the flux of non-equilibrium phonons away from the excitation region.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Gas phase hydrogen permeation in alpha titanium and carbon steels

NASA Technical Reports Server (NTRS)

Johnson, D. L.; Shah, K. K.; Reeves, B. H.; Gadgeel, V. L.

1980-01-01

Commercially pure titanium and heats of Armco ingot iron and steels containing from 0.008-1.23 w/oC were annealed or normalized and machined into hollow cylinders. Coefficients of diffusion for alpha-Ti and alpha-Fe were determined by the lag-time technique. Steady state permeation experiments yield first power pressure dependence for alpha-Ti and Sievert's law square root dependence for Armco iron and carbon steels. As in the case of diffusion, permeation data confirm that alpha-titanium is subject to at least partial phase boundary reaction control while the steels are purely diffusion controlled. The permeation rate in steels also decreases as the carbon content increases. As a consequence of Sievert's law, the computed hydrogen solubility decreases as the carbon content increases. This decreases in explained in terms of hydrogen trapping at carbide interfaces. Oxidizing and nitriding the surfaces of alpha-titanium membranes result in a decrease in the permeation rate for such treatment on the gas inlet surfaces but resulted in a slight increase in the rate for such treatment on the gas outlet surfaces. This is explained in terms of a discontinuous TiH2 layer.

Methane Hydrate Formation in Thick Sand Reservoirs: Long-range Gas Transport or Short-range Methane Diffusion?

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2016-12-01

We developed two 2-D numerical models to simulate hydrate formation by long range methane gas transport and short-range methane diffusion. We interpret that methane hydrates in thick sands are most likely formed by long range gas transport where methane gas is transported upward into the hydrate stability zone (HSZ) under buoyancy and locally forms hydrate to its stability limit. In short-range methane diffusion, methane is generated locally by biodegradation of organic matter in mud and diffused into bounding sands where it forms hydrate. We could not simulate enough methane transport by diffusion to account for its observed concentration in thick sands. In our models, we include the capillary effect on dissolved methane solubility and on the hydrate phase boundary, sedimentation and different compaction in sand and mud, fracture generation as well as the fully coupled multiphase flow and multicomponent transport. We apply our models to a 12 meter-thick hydrate-bearing sand layer at Walker Ridge 313, Northern Gulf of Mexico. With the long-range gas transport, hydrate saturation is greater than 90% and salinity is increased from seawater to about 8 wt.% through the entire sand. With short-range diffusion, hydrate saturation is more than 90% at the sand base and is less than 10% in the overlying section; salinity is close to seawater when sand is deposited to 800 meter below seafloor by short-range methane diffusion. With short-range diffusion, the amount of hydrate formed is much less than that interpreted from the well log data. Two transient gas layers separated by a hydrate layer are formed from short-range diffusion caused by capillary effect. This could be interpreted as a double bottom simulating reflector. This study provides further insights into different hydrate formation mechanisms, and could serve as a base to confirm the hydrate formation mechanism in fields.

Multiscale simulation of xenon diffusion and grain boundary segregation in UO₂

DOE PAGES

Andersson, David A.; Tonks, Michael R.; Casillas, Luis; ...

2015-07-01

In light water reactor fuel, gaseous fission products segregate to grain boundaries, resulting in the nucleation and growth of large intergranular fission gas bubbles. The segregation rate is controlled by diffusion of fission gas atoms through the grains and interaction with the boundaries. Based on the mechanisms established from earlier density functional theory (DFT) and empirical potential calculations, diffusion models for xenon (Xe), uranium (U) vacancies and U interstitials in UO₂ have been derived for both intrinsic (no irradiation) and irradiation conditions. Segregation of Xe to grain boundaries is described by combining the bulk diffusion model with a model formore » the interaction between Xe atoms and three different grain boundaries in UO₂ (Σ5 tilt, Σ5 twist and a high angle random boundary), as derived from atomistic calculations. The present model does not attempt to capture nucleation or growth of fission gas bubbles at the grain boundaries. The point defect and Xe diffusion and segregation models are implemented in the MARMOT phase field code, which is used to calculate effective Xe and U diffusivities as well as to simulate Xe redistribution for a few simple microstructures.« less

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

PubMed Central

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-01-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release. PMID:27306967

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE PAGES

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-16

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Air sparging: Air-water mass transfer coefficients

NASA Astrophysics Data System (ADS)

Braida, Washington J.; Ong, Say Kee

1998-12-01

Experiments investigating the mass transfer of several dissolved volatile organic compounds (VOCs) across the air-water interface were conducted using a single-air- channel air-sparging system. Three different porous media were used in the study. Air velocities ranged from 0.2 cm s-1 to 2.5 cm s-1. The tortuosity factor for each porous medium and the air-water mass transfer coefficients were estimated by fitting experimental data to a one-dimensional diffusion model. The estimated mass transfer coefficients KG ranged from 1.79 × 10-3 cm min-1 to 3.85 × 10-2 cm min-1. The estimated lumped gas phase mass transfer coefficients KGa were found to be directly related to the air diffusivity of the VOC, air velocity, and particle size, and inversely related to the Henry's law constant of the VOCs. Of the four parameters investigated, the parameter that controlled or had a dominant effect on the lumped gas phase mass transfer coefficient was the air diffusivity of the VOC. Two empirical models were developed by correlating the Damkohler and the modified air phase Sherwood numbers with the air phase Peclet number, Henry's law constant, and the reduced mean particle size of porous media. The correlation developed in this study may be used to obtain better predictions of mass transfer fluxes for field conditions.

Is the kinetic equation for turbulent gas-particle flows ill posed?

PubMed

Reeks, M; Swailes, D C; Bragg, A D

2018-02-01

This paper is about the kinetic equation for gas-particle flows, in particular its well-posedness and realizability and its relationship to the generalized Langevin model (GLM) probability density function (PDF) equation. Previous analyses, e.g. [J.-P. Minier and C. Profeta, Phys. Rev. E 92, 053020 (2015)PLEEE81539-375510.1103/PhysRevE.92.053020], have concluded that this kinetic equation is ill posed, that in particular it has the properties of a backward heat equation, and as a consequence, its solution will in the course of time exhibit finite-time singularities. We show that this conclusion is fundamentally flawed because it ignores the coupling between the phase space variables in the kinetic equation and the time and particle inertia dependence of the phase space diffusion tensor. This contributes an extra positive diffusion that always outweighs the negative diffusion associated with the dispersion along one of the principal axes of the phase space diffusion tensor. This is confirmed by a numerical evaluation of analytic solutions of these positive and negative contributions to the particle diffusion coefficient along this principal axis. We also examine other erroneous claims and assumptions made in previous studies that demonstrate the apparent superiority of the GLM PDF approach over the kinetic approach. In so doing, we have drawn attention to the limitations of the GLM approach, which these studies have ignored or not properly considered, to give a more balanced appraisal of the benefits of both PDF approaches.

Gradient complex protective coatings for single-crystal turbine blades of high-heat gas turbine engines

NASA Astrophysics Data System (ADS)

Kuznetsov, V. P.; Lesnikov, V. P.; Muboyadzhyan, S. A.; Repina, O. V.

2007-05-01

Complex diffusion-condensation protective coatings characterized by gradient distribution of alloying elements over the thickness due to formation of a diffusion barrier layer on the surface of blades followed by deposition of condensation alloyed layers based on the Ni-Co-Cr-Al-Y system and an external layer based on a NiAl alloyed β-phase and a ZrO2: Y2O3 ceramics are presented. A complex gradient coating possessing unique protective properties at t = 1100-1200°C for single-crystal blades from alloy ZhS36VI for advanced gas turbine engines with gas temperature of 1550°C at the inlet to the turbine is described.

Analysis of flame spread over multicomponent combustibles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohtani, H.; Sato, J.

1985-01-01

A theoretical model of volatile component diffusion in the condensed phase is carried out in order to form a basis for predicting the flame spread rate in thermally thick multicomponent combustibles in a non-fluid condensed phase. The fuels could be, e.g., crude oil, heavy oil, or light oil. Mass transfer occurs only by diffusion so the gas phase volatile concentration at the surface is estimated from the condensed phase volatile concentration and the surface temperature, which increases close to the leading flame edge. The flame spread rate is assumed steady. The velocity of the flame spread is shown to bemore » a function of the initial condensed phase temperature and the temperature at the leading flame edge.« less

INTEGRATED AND REAL-TIME DIFFUSION DENUDER SAMPLE FOR PM2.5. (R825367)

EPA Science Inventory

Abstract

Particulate matter (PM) is a complex mixture of stable condensed phases, adsorbed or dissolved gases, and semi-volatile materials, i.e. compounds that transfer between the gas and condensed phases. Fine particles in both rural and urban environments contain su...

Variations in Gas and Water Pulses at an Arctic Seep: Fluid Sources and Methane Transport

NASA Astrophysics Data System (ADS)

Hong, W.-L.; Torres, M. E.; Portnov, A.; Waage, M.; Haley, B.; Lepland, A.

2018-05-01

Methane fluxes into the oceans are largely dependent on the methane phase as it migrates upward through the sediments. Here we document decoupled methane transport by gaseous and aqueous phases in Storfjordrenna (offshore Svalbard) and propose a three-stage evolution model for active seepage in the region where gas hydrates are present in the shallow subsurface. In a preactive seepage stage, solute diffusion is the primary transport mechanism for methane in the dissolved phase. Fluids containing dissolved methane have high 87Sr/86Sr ratios due to silicate weathering in the microbial methanogenesis zone. During the active seepage stage, migration of gaseous methane results in near-seafloor gas hydrate formation and vigorous seafloor gas discharge with a thermogenic fingerprint. In the postactive seepage stage, the high concentration of dissolved lithium points to the contribution of a deeper-sourced aqueous fluid, which we postulate advects upward following cessation of gas discharge.

Irradiation of FeS: Implications for the Lifecycle of Sulfur in the Interstellar Medium and Presolar FeS Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Loeffler, M. J.; Christoffersen, R.; Dukes, C.; Rahman, Z.; Baragiola, R.

2010-01-01

Fe(Ni) sulfides are ubiquitous in chondritic meteorites and cometary samples where they are the dominant host of sulfur. Despite their abundance in these early solar system materials, their presence in interstellar and circumstellar environments is poorly understood. Fe-sulfides have been reported from astronomical observations of pre- and post-main sequence stars [1, 2] and occur as inclusions in bonafide circumstellar silicate grains [3, 4]. In cold, dense molecular cloud (MC) environments, sulfur is highly depleted from the gas phase [e.g. 5], yet observations of sulfur-bearing molecules in dense cores find a total abundance that is only a small fraction of the sulfur seen in diffuse regions [6], therefore the bulk of the depletion must reside in an abundant unobserved phase. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium (ISM) [7-9], indicating that little sulfur is incorporated into solid grains in this environment. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. The main destruction mechanism is sputtering due to supernova shocks in the warm, diffuse ISM [10]. This process involves the reduction of Fe-sulfide with the production of Fe metal as a by-product and returning S to the gas phase. In order to test this hypothesis, we irradiated FeS and analyzed the resulting material using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

Analysis and Modeling of a Two-Phase Jet Pump of a Flow Boiling Test Facility for Aerospace Applications

NASA Technical Reports Server (NTRS)

Sherif, S. A.; Steadham, Justin M.

1996-01-01

Jet pumps are devices capable of pumping fluids to a higher pressure employing a nozzle/diffuser/mixing chamber combination. A primary fluid is usually allowed to pass through a converging-diverging nozzle where it can accelerate to supersonic speeds at the nozzle exit. The relatively high kinetic energy that the primary fluid possesses at the nozzle exit is accompanied by a low pressure region in order to satisfy Bernoulli's equation. The low pressure region downstream of the nozzle exit permits a secondary fluid to be entrained into and mixed with the primary fluid in a mixing chamber located downstream of the nozzle. Several combinations may exist in terms of the nature of the primary and secondary fluids in so far as whether they are single or two-phase fluids. Depending on this, the jet pump may be classified as gas/gas, gas/liquid, liquid/liquid, two-phase/liquid, or similar combinations. The mixing chamber serves to create a homogeneous single-phase or two-phase mixture which enters a diffuser where the high kinetic energy of the fluid is converted into pressure energy. If the fluid mixture entering the diffuser is in the supersonic flow regime, a normal shock wave usually develops inside the diffuser. If the fluid mixture is one that can easily change phase, a condensation shock would normally develop. Because of the overall rise in pressure in the diffuser as well as the additional rise in pressure across the shock layer, condensation becomes more likely. Associated with the pressure rise across the shock is a velocity reduction from the supersonic to the subsonic range. If the two-phase flow entering the diffuser is predominantly gaseous with liquid droplets suspended in it, it will transform into a predominantly liquid flow containing gaseous bubbles (bubbly flow) somewhere in the diffuser. While past researchers have been able to model the two-phase flow jet pump using the one-dimensional assumption with no shock waves and no phase change, there is no research known to the authors apart from that of Anand (1992) which accounted for condensation shocks. One of the objectives of this research effort is to develop a comprehensive model in which the effects of phase slip and inter-phase heat transfer as well as the wall friction and shock waves are accounted for. While this modeling effort is predominantly analytical in nature and is primarily intended to provide a parametric understanding of the jet pump performance under different operating scenarios, another parallel effort employing a commercial CFD code is also implemented. The latter effort is primarily intended to model an axisymmetric counterpart of the problem in question. The viability of using the CFD code to model a two-phase flow jet pump will be assessed by attempting to recreate some of the existing performance data of similar jet pumps. The code will eventually be used to generate the jet pump performance characteristics of several scenarios involving jet pump geometries as well as flow regimes in order to be able to determine an optimum design which would be suitable for a two-phase flow boiling test facility at NASA-Marshall. Because of the extensive nature of the analytical model developed, the following section will only provide very brief highlights of it, while leaving the details to a more complete report submitted to the NASA colleague. This report will also contain some of the simulation results obtained using the CFD code.

Numerical Simulation of Permeation from Deposited Droplets: Model Expansion

DTIC Science & Technology

1992-04-01

This is primarily due to the low vapor pressures of chemical agent simulants, which minimize the driving forces for diffusion through the gas-phase...was presented at the November 1990 CRDEC Scientific Conference on Chemical Defense Research (4]. Previous work in this area also includes a substantial...most of the overall chemical poten- tial driving force is dissipated in the gas, not the membrane phase). 1.0 l 0.9-0 A 0 0.8 - 0.7 C 0.6,, 0.00 0.25

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

NASA Astrophysics Data System (ADS)

Wang, Yun; Chen, Ken S.

2016-05-01

In the present work, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Analysis is performed on a dimensionless parameter Da0 introduced in our previous paper [Y. Wang and K. S. Chen, Chemical Engineering Science 66 (2011) 3557-3567] and the parameter is further evaluated in a realistic fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

DOE PAGES

Wang, Yun; Chen, Ken S.

2016-03-21

In the present study, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Here, analysis is performed on a dimensionless parameter Da 0 introduced in our previous paper and the parameter is further evaluated in a realisticmore » fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da 0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.« less

Accurate measurements of the thermal diffusivity of thin filaments by lock-in thermography

NASA Astrophysics Data System (ADS)

Salazar, Agustín; Mendioroz, Arantza; Fuente, Raquel; Celorrio, Ricardo

2010-02-01

In lock-in (modulated) thermography the lateral thermal diffusivity can be obtained from the slope of the linear relation between the phase of the surface temperature and the distance to the heating spot. However, this slope is greatly affected by heat losses, leading to an overestimation of the thermal diffusivity, especially for thin samples of poor thermal conducting materials. In this paper, we present a complete theoretical model to calculate the surface temperature of filaments heated by a focused and modulated laser beam. All heat losses have been included: conduction to the gas, convection, and radiation. Monofilaments and coated wires have been studied. Conduction to the gas has been identified as the most disturbing effect preventing from the direct use of the slope method to measure the thermal diffusivity. As a result, by keeping the sample in vacuum a slope method combining amplitude and phase can be used to obtain the accurate diffusivity value. Measurements performed in a wide variety of filaments confirm the validity of the conclusion. On the other hand, in the case of coated wires, the slope method gives an effective thermal diffusivity, which verifies the in-parallel thermal resistor model. As an application, the slope method has been used to retrieve the thermal conductivity of thin tubes by filling them with a liquid of known thermal properties.

Feasibility study of tungsten as a diffusion barrier between nickel-chromium-aluminum and Gamma/Gamma prime - Delta eutectic alloys

NASA Technical Reports Server (NTRS)

Young, S. G.; Zellars, G. R.

1978-01-01

Coating systems proposed for potential use on eutectic alloy components in high-temperature gas turbine engines were studied with emphasis on deterioration of such systems by diffusion. A 1-mil thick W sheet was placed between eutectic alloys and a NiCrAl layer. Layered test specimens were aged at 1100 C for as long as long as 500 hours. Without the W barrier, the delta phase of the eutectic deteriorated by diffusion of Nb into the NiCrAl. Insertion of the W barrier stopped the diffusion of Nb from delta. Chromium diffusion from the NiCrAl into the gamma/gamma prime phase of the eutectic was greatly reduced by the barrier. However, the barrier thickness decreased with time; and W diffused into both the NiCrAl and the eutectic. When the delta platelets were alined parallel to the NiCrAl layer, rather than perpendicular, diffusion into the eutectic was reduced.

Modelling of soot formation in laminar diffusion flames using a comprehensive CFD-PBE model with detailed gas-phase chemistry

NASA Astrophysics Data System (ADS)

Akridis, Petros; Rigopoulos, Stelios

2017-01-01

A discretised population balance equation (PBE) is coupled with an in-house computational fluid dynamics (CFD) code in order to model soot formation in laminar diffusion flames. The unsteady Navier-Stokes, species and enthalpy transport equations and the spatially-distributed discretised PBE for the soot particles are solved in a coupled manner, together with comprehensive gas-phase chemistry and an optically thin radiation model, thus yielding the complete particle size distribution of the soot particles. Nucleation, surface growth and oxidation are incorporated into the PBE using an acetylene-based soot model. The potential of the proposed methodology is investigated by comparing with experimental results from the Santoro jet burner [Santoro, Semerjian and Dobbins, Soot particle measurements in diffusion flames, Combustion and Flame, Vol. 51 (1983), pp. 203-218; Santoro, Yeh, Horvath and Semerjian, The transport and growth of soot particles in laminar diffusion flames, Combustion Science and Technology, Vol. 53 (1987), pp. 89-115] for three laminar axisymmetric non-premixed ethylene flames: a non-smoking, an incipient smoking and a smoking flame. Overall, good agreement is observed between the numerical and the experimental results.

Cooling of a microchannel with thin evaporating liquid film sheared by dry gas flow

NASA Astrophysics Data System (ADS)

Kabova, Yu O.; Kuznetsov, V. V.

2017-11-01

A joint motion of thin liquid film and dry gas in a microchannel is investigated numerically at different values of initial concentration of the liquid vapor in the gas phase, taking into account the evaporation process. Major factors affecting the temperature distribution in the liquid and the gas phases are as follows: transfer of heat by liquid and gas flows, heat loses due to evaporation, diffusion heat exchange. Comparisons of the numerical results for the case of the dry gas and for the case of equilibrium concentration of vapor in the gas have been carried out. It is shown that use of dry gas enhances the heat dissipation from the heater. It is found out that not only intense evaporation occurs near the heating areas, but also in both cases vapor condensation takes place below the heater in streamwise direction.

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

2003-01-01

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

Solid phase microextraction for active or passive sampling of methyl bromide during fumigations

USDA-ARS?s Scientific Manuscript database

The high diffusivity and volatility of methyl bromide make it an ideal compound for Solid Phase Micro Extraction (SPME)-based sampling of air prior to gas-chromatographic quantifications. SPME fibers can be used as active methyl bromide samplers, with high capacities and an equilibrium time of 1-2 m...

Lateral gas phase diffusion length of boron atoms over Si/B surfaces during CVD of pure boron layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammadi, V., E-mail: V.Mohammadi@tudelft.nl; Nihtianov, S.

The lateral gas phase diffusion length of boron atoms, L{sub B}, along silicon and boron surfaces during chemical vapor deposition (CVD) using diborane (B{sub 2}H{sub 6}) is reported. The value of L{sub B} is critical for reliable and uniform boron layer coverage. The presented information was obtained experimentally and confirmed analytically in the boron deposition temperature range from 700 °C down to 400 °C. For this temperature range the local loading effect of the boron deposition is investigated on the micro scale. A L{sub B} = 2.2 mm was determined for boron deposition at 700 °C, while a L{sub B}more » of less than 1 mm was observed at temperatures lower than 500 °C.« less

Flow Distribution Control Characteristics in Marine Gas Turbine Waste-Heat Recovery Systems. Phase I. Flow Distribution Characteristics and Control in Diffusers.

DTIC Science & Technology

1981-08-01

provide the lowest rate of momentum outflow and thus yield maximum diffuser efficiency. In their study, Wolf and Johnston (Ref. 1.12) used screens made...other words, the uniform velocity at the diffuser exit implies the lowest exit velocity attainable for a given flow rate and lowest rate of momentum ... momentum , and energy and the equation of state. The procedures of manipulating these partial differential iations into an analytical model for analyzing

Standing waves, clustering, and phase waves in 1D simulations of kinetic relaxation oscillations in NO+NH 3 on Pt(1 0 0) coupled by diffusion

NASA Astrophysics Data System (ADS)

Uecker, Hannes

2004-04-01

The Lombardo-Imbihl-Fink (LFI) ODE model of the NO+NH 3 reaction on a Pt(1 0 0) surface shows stable relaxation oscillations with very sharp transitions for temperatures T between 404 and 433 K. Here we study numerically the effect of linear diffusive coupling of these oscillators in one spatial dimension. Depending on the parameters and initial conditions we find a rich variety of spatio-temporal patterns which we group into four main regimes: bulk oscillations (BOs), standing waves (SW), phase clusters (PC), and phase waves (PW). Two key ingredients for SW and PC are identified, namely the relaxation type of the ODE oscillations and a nonlocal (and nonglobal) coupling due to relatively fast diffusion of the kinetically slaved variables NH 3 and H. In particular, the latter replaces the global coupling through the gas phase used to obtain SW and PC in models of related surface reactions. The PW exist only under the assumption of (relatively) slow diffusion of NH 3 and H.

High-temperature protection of steel goods from gas corrosion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerasimov, V.V.; Porfir`eva, R.T.; Peskov, A.V.

The feasibility of using phosphorus-containing compounds to activate the thermal diffusion impregnation of steels with aluminum was explored and substantiated by experiment. Volatile phosphorus formed from the thermal destruction of the phosphorus-containing substances and the resulting Al/P-type complexes, which provide a gas-transportation medium to take the aluminum to the article surface, were instrumental in the mechanism. The resultant thermal diffusion coatings enabled steel to be safely protected from gas corrosion at a temperature of 950{degrees}C. As a result of research on the structure of the protective layer using electron microscopy and X-ray phase analysis, coatings formed using a mixture containingmore » 1 wt.% iron glycerophosphate exhibited the optimum operating characteristics.« less

Transient Numerical Modeling of Catalytic Channels

NASA Technical Reports Server (NTRS)

Struk, Peter M.; Dietrich, Daniel L.; Miller, Fletcher J.; T'ien, James S.

2007-01-01

This paper presents a transient model of catalytic combustion suitable for isolated channels and monolith reactors. The model is a lumped two-phase (gas and solid) model where the gas phase is quasi-steady relative to the transient solid. Axial diffusion is neglected in the gas phase; lateral diffusion, however, is accounted for using transfer coefficients. The solid phase includes axial heat conduction and external heat loss due to convection and radiation. The combustion process utilizes detailed gas and surface reaction models. The gas-phase model becomes a system of stiff ordinary differential equations while the solid phase reduces, after discretization, into a system of stiff ordinary differential-algebraic equations. The time evolution of the system came from alternating integrations of the quasi-steady gas and transient solid. This work outlines the numerical model and presents some sensitivity studies on important parameters including internal transfer coefficients, catalytic surface site density, and external heat-loss (if applicable). The model is compared to two experiments using CO fuel: (1) steady-state conversion through an isothermal platinum (Pt) tube and (2) transient propagation of a catalytic reaction inside a small Pt tube. The model requires internal mass-transfer resistance to match the experiments at lower residence times. Under mass-transport limited conditions, the model reasonably predicted exit conversion using global mass-transfer coefficients. Near light-off, the model results did not match the experiment precisely even after adjustment of mass-transfer coefficients. Agreement improved for the first case after adjusting the surface kinetics such that the net rate of CO adsorption increased compared to O2. The CO / O2 surface mechanism came from a sub-set of reactions in a popular CH4 / O2 mechanism. For the second case, predictions improved for lean conditions with increased external heat loss or adjustment of the kinetics as in the first case. Finally, the results show that different initial surface-species distribution leads to different steady-states under certain conditions. These results demonstrate the utility of a lumped two-phase model of a transient catalytic combustor with detailed chemistry.

Carbon dioxide diffuse emission and thermal energy release from hydrothermal systems at Copahue-Caviahue Volcanic Complex (Argentina)

NASA Astrophysics Data System (ADS)

Chiodini, Giovanni; Cardellini, Carlo; Lamberti, María Clara; Agusto, Mariano; Caselli, Alberto; Liccioli, Caterina; Tamburello, Giancarlo; Tassi, Franco; Vaselli, Orlando; Caliro, Stefano

2015-10-01

The north-western sector of Caviahue caldera (Argentina), close to the active volcanic system of Copahue, is characterized by the presence of several hydrothermal sites that host numerous fumarolic emissions, anomalous soil diffuse degassing of CO2 and hot soils. In March 2014, measurements of soil CO2 fluxes in 5 of these sites (namely, Las Máquinas, Las Maquinitas I, Las Maquinitas II, Anfiteatro, and Termas de Copahue) allowed an estimation that 165 t of deeply derived CO2 is daily released. The gas source is likely related to a relatively shallow geothermal reservoir containing a single vapor phase as also suggested by both the geochemical data from the 3 deep wells drilled in the 1980s and gas geoindicators applied to the fumarolic discharges. Gas equilibria within the H-C-O gas system indicate the presence of a large, probably unique, single phase vapor zone at 200-210 °C feeding the hydrothermal manifestations of Las Máquinas, Las Maquinitas I and II and Termas de Copahue. A natural thermal release of 107 MW was computed by using CO2 as a tracer of the original vapor phase. The magmatic signature of the incondensable fumarolic gases, the wide expanse of the hydrothermal areas and the remarkable high amount of gas and heat released by fluid expulsion seem to be compatible with an active magmatic intrusion beneath this portion of the Caviahue caldera.

On the development and benchmarking of an approach to model gas transport in fractured media with immobile water storage

NASA Astrophysics Data System (ADS)

Harp, D. R.; Ortiz, J. P.; Pandey, S.; Karra, S.; Viswanathan, H. S.; Stauffer, P. H.; Anderson, D. N.; Bradley, C. R.

2017-12-01

In unsaturated fractured media, the rate of gas transport is much greater than liquid transport in many applications (e.g., soil vapor extraction operations, methane leaks from hydraulic fracking, shallow CO2 transport from geologic sequestration operations, and later-time radionuclide gas transport from underground nuclear explosions). However, the relatively immobile pore water can inhibit or promote gas transport for soluble constituents by providing storage. In scenarios with constant pressure gradients, the gas transport will be retarded. In scenarios with reversing pressure gradients (i.e. barometric pressure variations) pore water storage can enhance gas transport by providing a ratcheting mechanism. Recognizing the computational efficiency that can be gained using a single-phase model and the necessity of considering pore water storage, we develop a Richard's solution approach that includes kinetic dissolution/volatilization of constituents. Henry's Law governs the equilibrium gaseous/aqueous phase partitioning in the approach. The approach is implemented in a development branch of the PFLOTRAN simulator. We verify the approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) sinusoidal barometric pumping of a fracture, and (4) gas transport along a fracture with uniform flow and diffusive walls. We demonstrate the retardation of gas transport in cases with constant pressure gradients and the enhancement of gas transport with reversing pressure gradients. The figure presents the verification of our approach to the analytical solution of barometric pumping of a fracture from Nilson et al (1991) where the x-axis "Horizontal axis" is the distance into the matrix block from the fracture.

On the development and benchmarking of an approach to model gas transport in fractured media with immobile water storage

NASA Astrophysics Data System (ADS)

Harp, D. R.; Ortiz, J. P.; Pandey, S.; Karra, S.; Viswanathan, H. S.; Stauffer, P. H.; Anderson, D. N.; Bradley, C. R.

2016-12-01

In unsaturated fractured media, the rate of gas transport is much greater than liquid transport in many applications (e.g., soil vapor extraction operations, methane leaks from hydraulic fracking, shallow CO2 transport from geologic sequestration operations, and later-time radionuclide gas transport from underground nuclear explosions). However, the relatively immobile pore water can inhibit or promote gas transport for soluble constituents by providing storage. In scenarios with constant pressure gradients, the gas transport will be retarded. In scenarios with reversing pressure gradients (i.e. barometric pressure variations) pore water storage can enhance gas transport by providing a ratcheting mechanism. Recognizing the computational efficiency that can be gained using a single-phase model and the necessity of considering pore water storage, we develop a Richard's solution approach that includes kinetic dissolution/volatilization of constituents. Henry's Law governs the equilibrium gaseous/aqueous phase partitioning in the approach. The approach is implemented in a development branch of the PFLOTRAN simulator. We verify the approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) sinusoidal barometric pumping of a fracture, and (4) gas transport along a fracture with uniform flow and diffusive walls. We demonstrate the retardation of gas transport in cases with constant pressure gradients and the enhancement of gas transport with reversing pressure gradients. The figure presents the verification of our approach to the analytical solution of barometric pumping of a fracture from Nilson et al (1991) where the x-axis "Horizontal axis" is the distance into the matrix block from the fracture.

The diffusivity and solubility of deuterium in a high chromium martensitic steel

NASA Astrophysics Data System (ADS)

Forcey, K. S.; Iordanova, I.; Yaneva, M.

1997-01-01

The permeability, diffusivity and solubility of deuterium in the martensitic stainless steel MANET II have been studied in the temperature range 194-465°C by applying a time dependent gas-phase permeation technique. It was found that the temperature dependence of diffusivity and solubility could not be described by a simple Arrhenius expression over the entire temperature range investigated. At lower temperatures (below about 330°C) the diffusivity was found to be greatly reduced by the effects of trapping. Oriani's model has been applied to obtain the trapping energy and number density of the traps as well as the relative amounts of deuterium dissolved at lattice and trap sites. It is suggested that the most likely sites for trapping are at interfaces between the martensitic laths and between second phase particles and the surrounding metal matrix.

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.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Atmospheric-pressure diffuse dielectric barrier discharges in Ar/O2 gas mixture using 200 kHz/13.56 MHz dual frequency excitation

NASA Astrophysics Data System (ADS)

Liu, Y.; Starostin, S. A.; Peeters, F. J. J.; van de Sanden, M. C. M.; de Vries, H. W.

2018-03-01

Atmospheric-pressure diffuse dielectric barrier discharges (DBDs) were obtained in Ar/O2 gas mixture using dual-frequency (DF) excitation at 200 kHz low frequency (LF) and 13.56 MHz radio frequency (RF). The excitation dynamics and the plasma generation mechanism were studied by means of electrical characterization and phase resolved optical emission spectroscopy (PROES). The DF excitation results in a time-varying electric field which is determined by the total LF and RF gas voltage and the spatial ion distribution which only responds to the LF component. By tuning the amplitude ratio of the superimposed LF and RF signals, the effect of each frequency component on the DF discharge mechanism was analysed. The LF excitation results in a transient plasma with the formation of an electrode sheath and therefore a pronounced excitation near the substrate. The RF oscillation allows the electron trapping in the gas gap and helps to improve the plasma uniformity by contributing to the pre-ionization and by controlling the discharge development. The possibility of temporally modifying the electric field and thus the plasma generation mechanism in the DF discharge exhibits potential applications in plasma-assisted surface processing and plasma-assisted gas phase chemical conversion.

Two-phase thermodynamic model for computing entropies of liquids reanalyzed

NASA Astrophysics Data System (ADS)

Sun, Tao; Xian, Jiawei; Zhang, Huai; Zhang, Zhigang; Zhang, Yigang

2017-11-01

The two-phase thermodynamic (2PT) model [S.-T. Lin et al., J. Chem. Phys. 119, 11792-11805 (2003)] provides a promising paradigm to efficiently determine the ionic entropies of liquids from molecular dynamics. In this model, the vibrational density of states (VDoS) of a liquid is decomposed into a diffusive gas-like component and a vibrational solid-like component. By treating the diffusive component as hard sphere (HS) gas and the vibrational component as harmonic oscillators, the ionic entropy of the liquid is determined. Here we examine three issues crucial for practical implementations of the 2PT model: (i) the mismatch between the VDoS of the liquid system and that of the HS gas; (ii) the excess entropy of the HS gas; (iii) the partition of the gas-like and solid-like components. Some of these issues have not been addressed before, yet they profoundly change the entropy predicted from the model. Based on these findings, a revised 2PT formalism is proposed and successfully tested in systems with Lennard-Jones potentials as well as many-atom potentials of liquid metals. Aside from being capable of performing quick entropy estimations for a wide range of systems, the formalism also supports fine-tuning to accurately determine entropies at specific thermal states.

Nuclear magnetic resonance diffusion pore imaging: Experimental phase detection by double diffusion encoding

NASA Astrophysics Data System (ADS)

Demberg, Kerstin; Laun, Frederik Bernd; Windschuh, Johannes; Umathum, Reiner; Bachert, Peter; Kuder, Tristan Anselm

2017-02-01

Diffusion pore imaging is an extension of diffusion-weighted nuclear magnetic resonance imaging enabling the direct measurement of the shape of arbitrarily formed, closed pores by probing diffusion restrictions using the motion of spin-bearing particles. Examples of such pores comprise cells in biological tissue or oil containing cavities in porous rocks. All pores contained in the measurement volume contribute to one reconstructed image, which reduces the problem of vanishing signal at increasing resolution present in conventional magnetic resonance imaging. It has been previously experimentally demonstrated that pore imaging using a combination of a long and a narrow magnetic field gradient pulse is feasible. In this work, an experimental verification is presented showing that pores can be imaged using short gradient pulses only. Experiments were carried out using hyperpolarized xenon gas in well-defined pores. The phase required for pore image reconstruction was retrieved from double diffusion encoded (DDE) measurements, while the magnitude could either be obtained from DDE signals or classical diffusion measurements with single encoding. The occurring image artifacts caused by restrictions of the gradient system, insufficient diffusion time, and by the phase reconstruction approach were investigated. Employing short gradient pulses only is advantageous compared to the initial long-narrow approach due to a more flexible sequence design when omitting the long gradient and due to faster convergence to the diffusion long-time limit, which may enable application to larger pores.

Diffusive counter dispersion of mass in bubbly media.

PubMed

Goldobin, Denis S; Brilliantov, Nikolai V

2011-11-01

We consider a liquid bearing gas bubbles in a porous medium. When gas bubbles are immovably trapped in a porous matrix by surface-tension forces, the dominant mechanism of transfer of gas mass becomes the diffusion of gas molecules through the liquid. Essentially, the gas solution is in local thermodynamic equilibrium with vapor phase all over the system, i.e., the solute concentration equals the solubility. When temperature and/or pressure gradients are applied, diffusion fluxes appear and these fluxes are faithfully determined by the temperature and pressure fields, not by the local solute concentration, which is enslaved by the former. We derive the equations governing such systems, accounting for thermodiffusion and gravitational segregation effects, which are shown not to be neglected for geological systems-marine sediments, terrestrial aquifers, etc. The results are applied for the treatment of non-high-pressure systems and real geological systems bearing methane or carbon dioxide, where we find a potential possibility of the formation of gaseous horizons deep below a porous medium surface. The reported effects are of particular importance for natural methane hydrate deposits and the problem of burial of industrial production of carbon dioxide in deep aquifers.

Formulation, Implementation and Validation of a Two-Fluid model in a Fuel Cell CFD Code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, Kunal; Cole, J. Vernon; Kumar, Sanjiv

2008-12-01

Water management is one of the main challenges in PEM Fuel Cells. While water is essential for membrane electrical conductivity, excess liquid water leads to flooding of catalyst layers. Despite the fact that accurate prediction of two-phase transport is key for optimal water management, understanding of the two-phase transport in fuel cells is relatively poor. Wang et. al. have studied the two-phase transport in the channel and diffusion layer separately using a multiphase mixture model. The model fails to accurately predict saturation values for high humidity inlet streams. Nguyen et. al. developed a two-dimensional, two-phase, isothermal, isobaric, steady state modelmore » of the catalyst and gas diffusion layers. The model neglects any liquid in the channel. Djilali et. al. developed a three-dimensional two-phase multicomponent model. The model is an improvement over previous models, but neglects drag between the liquid and the gas phases in the channel. In this work, we present a comprehensive two-fluid model relevant to fuel cells. Models for two-phase transport through Channel, Gas Diffusion Layer (GDL) and Channel-GDL interface, are discussed. In the channel, the gas and liquid pressures are assumed to be same. The surface tension effects in the channel are incorporated using the continuum surface force (CSF) model. The force at the surface is expressed as a volumetric body force and added as a source to the momentum equation. In the GDL, the gas and liquid are assumed to be at different pressures. The difference in the pressures (capillary pressure) is calculated using an empirical correlations. At the Channel-GDL interface, the wall adhesion affects need to be taken into account. SIMPLE-type methods recast the continuity equation into a pressure-correction equation, the solution of which then provides corrections for velocities and pressures. However, in the two-fluid model, the presence of two phasic continuity equations gives more freedom and more complications. A general approach would be to form a mixture continuity equation by linearly combining the phasic continuity equations using appropriate weighting factors. Analogous to mixture equation for pressure correction, a difference equation is used for the volume/phase fraction by taking the difference between the phasic continuity equations. The relative advantages of the above mentioned algorithmic variants for computing pressure correction and volume fractions are discussed and quantitatively assessed. Preliminary model validation is done for each component of the fuel cell. The two-phase transport in the channel is validated using empirical correlations. Transport in the GDL is validated against results obtained from LBM and VOF simulation techniques. The Channel-GDL interface transport will be validated against experiment and empirical correlation of droplet detachment at the interface.« less

Chemical and isotopic fractionations by evaporation and their cosmochemical implications

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Nagahara, Hiroko

2001-07-01

A kinetic model for evaporation of a multi-component condensed phase with a fixed rate constant of the reaction is developed. A binary system with two isotopes for one of the components undergoing simple thermal histories (e.g., isothermal heating) is investigated in order to evaluate the extent of isotopic and chemical fractionations during evaporation. Diffusion in the condensed phase and the effect of back reaction from ambient gas are taken into consideration. Chemical and isotopic fractionation factors and the Péclet number for evaporation are the three main parameters that control the fractionation. Dust enrichment factor (η), the ratio of the initial dust quantity to that required for attainment of gas-dust equilibrium, is critical when back reactions become significant. Dust does not reach equilibrium with gas at η < 1. Notable chemical and isotopic fractionations usually take place under these conditions. There are two circumstances in which isotopic fractionation of a very volatile element does not accompany chemical fractionation during isothermal heating. One is free evaporation when diffusion in the condensed phase is very slow (η = 0), and the other is evaporation in the presence of ambient gas (η > 0). In the former case, a quasi-steady state in the diffusion boundary layer is maintained for isotopic fractionation but not for chemical fractionation. In the latter case, the back reaction brings the strong isotopic fractionation generated in the earlier stage of evaporation back to a negligibly small value in the later stage before complete evaporation. The model results are applied to cosmochemical fractionation of volatile elements during evaporation from a condensed phase that can be regarded as a binary solution phase. The wide range of potassium depletion without isotopic fractionation in various types of chondrules (Alexander et al., 2000) is explained by instantaneous heating followed by cooling in a closed system with various degrees of dust enrichment (η = 0.001-10) and cooling rates of less than ˜5°C/min. The extent of decoupling between isotopic and chemical fractionations of various elements in chondrules and matrix minerals may constrain the time scale and the conditions of heating and cooling processes in the early solar nebula.

Probing the impact of axial diffusion on nitric oxide exchange dynamics with heliox.

PubMed

Shin, Hye-Won; Condorelli, Peter; Rose-Gottron, Christine M; Cooper, Dan M; George, Steven C

2004-09-01

Exhaled nitric oxide (NO) is a potential noninvasive index of lung inflammation and is thought to arise from the alveolar and airway regions of the lungs. A two-compartment model has been used to describe NO exchange; however, the model neglects axial diffusion of NO in the gas phase, and recent theoretical studies suggest that this may introduce significant error. We used heliox (80% helium, 20% oxygen) as the insufflating gas to probe the impact of axial diffusion (molecular diffusivity of NO is increased 2.3-fold relative to air) in healthy adults (21-38 yr old, n = 9). Heliox decreased the plateau concentration of exhaled NO by 45% (exhalation flow rate of 50 ml/s). In addition, the total mass of NO exhaled in phase I and II after a 20-s breath hold was reduced by 36%. A single-path trumpet model that considers axial diffusion predicts a 50% increase in the maximum airway flux of NO and a near-zero alveolar concentration (Ca(NO)) and source. Furthermore, when NO elimination is plotted vs. constant exhalation flow rate (range 50-500 ml/s), the slope has been previously interpreted as a nonzero Ca(NO) (range 1-5 ppb); however, the trumpet model predicts a positive slope of 0.4-2.1 ppb despite a zero Ca(NO) because of a diminishing impact of axial diffusion as flow rate increases. We conclude that axial diffusion leads to a significant backdiffusion of NO from the airways to the alveolar region that significantly impacts the partitioning of airway and alveolar contributions to exhaled NO.

Application of gas diffusion electrodes in bioelectrochemical syntheses and energy conversion.

PubMed

Horst, Angelika E W; Mangold, Klaus-Michael; Holtmann, Dirk

2016-02-01

Combining the advantages of biological components (e.g., reaction specificity, self-replication) and electrochemical techniques in bioelectrochemical systems offers the opportunity to develop novel efficient and sustainable processes for the production of a number of valuable products. The choice of electrode material has a great impact on the performance of bioelectrochemical systems. In addition to the redox process at the electrodes, interactions of biocatalysts with electrodes (e.g., enzyme denaturation or biofouling) need to be considered. In recent years, gas diffusion electrodes (GDEs) have proved to be very attractive electrodes for bioelectrochemical purposes. GDEs are porous electrodes, that posses a large three-phase boundary surface. At this interface, a solid catalyst supports the electrochemical reaction between gaseous and liquid phase. This mini-review discusses the application of GDEs in microbial and enzymatic fuel cells, for microbial electrolysis, in biosensors and for electroenzymatic synthesis reactions. © 2015 Wiley Periodicals, Inc.

Validation of pore network simulations of ex-situ water distributions in a gas diffusion layer of proton exchange membrane fuel cells with X-ray tomographic images

NASA Astrophysics Data System (ADS)

Agaesse, Tristan; Lamibrac, Adrien; Büchi, Felix N.; Pauchet, Joel; Prat, Marc

2016-11-01

Understanding and modeling two-phase flows in the gas diffusion layer (GDL) of proton exchange membrane fuel cells are important in order to improve fuel cells performance. They are scientifically challenging because of the peculiarities of GDLs microstructures. In the present work, simulations on a pore network model are compared to X-ray tomographic images of water distributions during an ex-situ water invasion experiment. A method based on watershed segmentation was developed to extract a pore network from the 3D segmented image of the dry GDL. Pore network modeling and a full morphology model were then used to perform two-phase simulations and compared to the experimental data. The results show good agreement between experimental and simulated microscopic water distributions. Pore network extraction parameters were also benchmarked using the experimental data and results from full morphology simulations.

A Rate-Theory-Phase-Field Model of Irradiation-Induced Recrystallization in UMo Nuclear Fuels

NASA Astrophysics Data System (ADS)

Hu, Shenyang; Joshi, Vineet; Lavender, Curt A.

2017-12-01

In this work, we developed a recrystallization model to study the effect of microstructures and radiation conditions on recrystallization kinetics in UMo fuels. The model integrates the rate theory of intragranular gas bubble and interstitial loop evolutions and a phase-field model of recrystallization zone evolution. A first passage method is employed to describe one-dimensional diffusion of interstitials with a diffusivity value several orders of magnitude larger than that of fission gas xenons. With the model, the effect of grain sizes on recrystallization kinetics is simulated. The results show that (1) recrystallization in large grains starts earlier than that in small grains, (2) the recrystallization kinetics (recrystallization volume fraction) decrease as the grain size increases, (3) the predicted recrystallization kinetics are consistent with the experimental results, and (4) the recrystallization kinetics can be described by the modified Avrami equation, but the parameters of the Avrami equation strongly depend on the grain size.

Formation of amorphous materials

DOEpatents

Johnson, William L.; Schwarz, Ricardo B.

1986-01-01

Metastable amorphous or fine crystalline materials are formed by solid state reactions by diffusion of a metallic component into a solid compound or by diffusion of a gas into an intermetallic compound. The invention can be practiced on layers of metals deposited on an amorphous substrate or by intermixing powders with nucleating seed granules. All that is required is that the diffusion of the first component into the second component be much faster than the self-diffusion of the first component. The method is practiced at a temperature below the temperature at which the amorphous phase transforms into one or more crystalline phases and near or below the temperature at which the ratio of the rate of diffusion of the first component to the rate of self-diffusion is at least 10.sup.4. This anomalous diffusion criteria is found in many binary, tertiary and higher ordered systems of alloys and appears to be found in all alloy systems that form amorphous materials by rapid quenching. The method of the invention can totally convert much larger dimensional materials to amorphous materials in practical periods of several hours or less.

Biomass drying in a pulsed fluidized bed without inert bed particles

DOE PAGES

Jia, Dening; Bi, Xiaotao; Lim, C. Jim; ...

2016-08-29

Batch drying was performed in the pulsed fluidized bed with various species of biomass particles as an indicator of gas–solid contact efficiency and mass transfer rate under different operating conditions including pulsation duty cycle and particle size distribution. The fluidization of cohesive biomass particles benefited from the shorter opening time of pulsed gas flow and increased peak pressure drop. The presence of fines enhanced gas–solid contact of large and irregular biomass particles, as well as the mass transfer efficiency. A drying model based on two-phase theory was proposed, from which effective diffusivity was calculated for various gas flow rates, temperaturemore » and pulsation frequency. Intricate relationship was discovered between pulsation frequency and effective diffusivity, as mass transfer was deeply connected with the hydrodynamics. Effective diffusivity was also found to be proportional to gas flow rate and drying temperature. In conclusion, operating near the natural frequency of the system also favored drying and mass transfer.« less

CHEMKIN2. General Gas-Phase Chemical Kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rupley, F.M.

1992-01-24

CHEMKIN is a high-level tool for chemists to use to describe arbitrary gas-phase chemical reaction mechanisms and systems of governing equations. It remains, however, for the user to select and implement a solution method; this is not provided. It consists of two major components: the Interpreter and the Gas-phase Subroutine Library. The Interpreter reads a symbolic description of an arbitrary, user-specified chemical reaction mechanism. A data file is generated which forms a link to the Gas-phase Subroutine Library, a collection of about 200 modular subroutines which may be called to return thermodynamic properties, chemical production rates, derivatives of thermodynamic properties,more » derivatives of chemical production rates, or sensitivity parameters. Both single and double precision versions of CHEMKIN are included. Also provided is a set of FORTRAN subroutines for evaluating gas-phase transport properties such as thermal conductivities, viscosities, and diffusion coefficients. These properties are an important part of any computational simulation of a chemically reacting flow. The transport properties subroutines are designed to be used in conjunction with the CHEMKIN Subroutine Library. The transport properties depend on the state of the gas and on certain molecular parameters. The parameters considered are the Lennard-Jones potential well depth and collision diameter, the dipole moment, the polarizability, and the rotational relaxation collision number.« less

Functionalized low defect graphene nanoribbons and polyurethane composite film for improved gas barrier and mechanical performances.

PubMed

Xiang, Changsheng; Cox, Paris J; Kukovecz, Akos; Genorio, Bostjan; Hashim, Daniel P; Yan, Zheng; Peng, Zhiwei; Hwang, Chih-Chau; Ruan, Gedeng; Samuel, Errol L G; Sudeep, Parambath M; Konya, Zoltan; Vajtai, Robert; Ajayan, Pulickel M; Tour, James M

2013-11-26

A thermoplastic polyurethane (TPU) composite film containing hexadecyl-functionalized low-defect graphene nanoribbons (HD-GNRs) was produced by solution casting. The HD-GNRs were well distributed within the polyurethane matrix, leading to phase separation of the TPU. Nitrogen gas effective diffusivity of TPU was decreased by 3 orders of magnitude with only 0.5 wt % HD-GNRs. The incorporation of HD-GNRs also improved the mechanical properties of the composite films, as predicted by the phase separation and indicated by tensile tests and dynamic mechanical analyses. The improved properties of the composite film could lead to potential applications in food packaging and lightweight mobile gas storage containers.

Weighted Global Artificial Bee Colony Algorithm Makes Gas Sensor Deployment Efficient

PubMed Central

Jiang, Ye; He, Ziqing; Li, Yanhai; Xu, Zhengyi; Wei, Jianming

2016-01-01

This paper proposes an improved artificial bee colony algorithm named Weighted Global ABC (WGABC) algorithm, which is designed to improve the convergence speed in the search stage of solution search equation. The new method not only considers the effect of global factors on the convergence speed in the search phase, but also provides the expression of global factor weights. Experiment on benchmark functions proved that the algorithm can improve the convergence speed greatly. We arrive at the gas diffusion concentration based on the theory of CFD and then simulate the gas diffusion model with the influence of buildings based on the algorithm. Simulation verified the effectiveness of the WGABC algorithm in improving the convergence speed in optimal deployment scheme of gas sensors. Finally, it is verified that the optimal deployment method based on WGABC algorithm can improve the monitoring efficiency of sensors greatly as compared with the conventional deployment methods. PMID:27322262

Three-dimensional numerical simulation of water droplet emerging from a gas diffusion layer surface in micro-channels

NASA Astrophysics Data System (ADS)

Ding, Y.; Bi, H. T.; Wilkinson, D. P.

The dynamic formation of water droplets emerging from a gas diffusion layer (GDL) surface in micro-channels was simulated using the volume of fluid (VOF) method. The influence of GDL surface microstructure was investigated by changing the pore diameter and the number of pore openings on the GDL surface. Simulation results show that the microstructure of the GDL surface has a significant impact on the two-phase flow patterns in gas flow channels. For a non-uniform GDL surface, three stages were identified, namely emergence and merging on the GDL surface, accumulation on the channel sidewalls and detachment from the top wall. It was also found that if the pore size is small enough, the flow pattern in the channel does not change with further reduction in the pore diameter. However, the two-phase flow patterns change significantly with the wettability of the GDL surface and sidewalls, but remain the same when the liquid flow rate is reduced by two orders of magnitude from the reference case.

Carbon Chemistry in Transitional Clouds from the GOT C+ Survey of CII 158 micron Emission in the Galactic Plane

NASA Astrophysics Data System (ADS)

Langer, W. D.; Velusamy, T.; Pineda, J.; Willacy, K.; Goldsmith, P. F.

2011-05-01

In understanding the lifecycle and chemistry of the interstellar gas, the transition from diffuse atomic to molecular gas clouds is a very important stage. The evolution of carbon from C+ to C0 and CO is a fundamental part of this transition, and C+ along with its carbon chemistry is a key diagnostic. Until now our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the dense molecular H2 phase traced by CO. However, we have generally been missing an important layer in diffuse and transition clouds, which is denoted by the warm "dark gas'', that is mostly H2 and little HI and CO, and is best traced with C+. Here, we discuss the chemistry in the transition from C+ to C0 and CO in these clouds as understood by a survey of the CII 1.9 THz (158 micron) line from a sparse survey of the inner galaxy over about 40 degrees in longitude as part of the Galactic Observations of Terahertz C+ (GOT C+) program, a Herschel Space Observatory Open Time Key Program to study interstellar clouds by sampling ionized carbon. Using the first results from GOT C+ along 11 LOSs, in a sample of 53 transition clouds, Velusamy, Langer et al. (A&A 521, L18, 2010) detected an excess of CII intensities indicative of a thick H2 layer (a significant warm H2, "dark gas'' component) around the 12CO core. Here we present a much larger, statistically significant sample of a few hundred diffuse and transition clouds traced by CII, along with auxiliary HI and CO data in the inner Galaxy between l=-30° and +30°. Our new and more extensive sample of transition clouds is used to elucidate the time dependent physical and carbon chemical evolution of diffuse to transition clouds, and transition layers. We consider the C+ to CO conversion pathways such as H++ O and C+ + H2 chemistry for CO production to constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse transition clouds.

Portable vapor diffusion coefficient meter

DOEpatents

Ho, Clifford K [Albuquerque, NM

2007-06-12

An apparatus for measuring the effective vapor diffusion coefficient of a test vapor diffusing through a sample of porous media contained within a test chamber. A chemical sensor measures the time-varying concentration of vapor that has diffused a known distance through the porous media. A data processor contained within the apparatus compares the measured sensor data with analytical predictions of the response curve based on the transient diffusion equation using Fick's Law, iterating on the choice of an effective vapor diffusion coefficient until the difference between the predicted and measured curves is minimized. Optionally, a purge fluid can forced through the porous media, permitting the apparatus to also measure a gas-phase permeability. The apparatus can be made lightweight, self-powered, and portable for use in the field.

Cosmic-rays, gas, and dust in nearby anticentre clouds. II. Interstellar phase transitions and the dark neutral medium

NASA Astrophysics Data System (ADS)

Remy, Q.; Grenier, I. A.; Marshall, D. J.; Casandjian, J. M.

2018-03-01

Aim. H I 21-cm and 12CO 2.6-mm line emissions trace the atomic and molecular gas phases, respectively, but they miss most of the opaque H I and diffuse H2 present in the dark neutral medium (DNM) at the transition between the H I-bright and CO-bright regions. Jointly probing H I, CO, and DNM gas, we aim to constrain the threshold of the H I-H2 transition in visual extinction, AV, and in total hydrogen column densities, NHtot. We also aim to measure gas mass fractions in the different phases and to test their relation to cloud properties. Methods: We have used dust optical depth measurements at 353 GHz, γ-ray maps at GeV energies, and H I and CO line data to trace the gas column densities and map the DNM in nearby clouds toward the Galactic anticentre and Chamaeleon regions. We have selected a subset of 15 individual clouds, from diffuse to star-forming structures, in order to study the different phases across each cloud and to probe changes from cloud to cloud. Results: The atomic fraction of the total hydrogen column density is observed to decrease in the (0.6-1) × 1021 cm-2 range in NHtot (AV ≈ 0.4 mag) because of the formation of H2 molecules. The onset of detectable CO intensities varies by only a factor of 4 from cloud to cloud, between 0.6 × 1021 cm-2 and 2.5 × 1021 cm-2 in total gas column density. We observe larger H2 column densities than linearly inferred from the CO intensities at AV > 3 mag because of the large CO optical thickness; the additional H2 mass in this regime represents on average 20% of the CO-inferred molecular mass. In the DNM envelopes, we find that the fraction of diffuse CO-dark H2 in the molecular column densities decreases with increasing AV in a cloud. For a half molecular DNM, the fraction decreases from more than 80% at 0.4 mag to less than 20% beyond 2 mag. In mass, the DNM fraction varies with the cloud properties. Clouds with low peak CO intensities exhibit large CO-dark H2 fractions in molecular mass, in particular the diffuse clouds lying at high altitude above the Galactic plane. The mass present in the DNM envelopes appears to scale with the molecular mass seen in CO as MHDNM = 62 ± 7 MH2CO0.51 ± 0.02 across two decades in mass. Conclusions: The phase transitions in these clouds show both common trends and environmental differences. These findings will help support the theoretical modelling of H2 formation and the precise tracing of H2 in the interstellar medium.

Overview of zirconia with respect to gas turbine applications

NASA Technical Reports Server (NTRS)

Cawley, J. D.

1984-01-01

Phase relationships and the mechanical properties of zirconia are examined as well as the thermal conductivity, deformation, diffusion, and chemical reactivity of this refractory material. Observations from the literature particular to plasma-sprayed material and implications for gas turbine engine applications are discussed. The literature review indicates that Mg-PSZ (partially stabilized zirconia) and Ca-PSZ are unsuitable for advanced gas turbine applications; a thorough characterization of the microstructure of plasma-sprayed zirconia is needed. Transformation-toughened zirconia may be suitable for use in monolithic components.

Low cost fuel cell diffusion layer configured for optimized anode water management

DOEpatents

Owejan, Jon P; Nicotera, Paul D; Mench, Matthew M; Evans, Robert E

2013-08-27

A fuel cell comprises a cathode gas diffusion layer, a cathode catalyst layer, an anode gas diffusion layer, an anode catalyst layer and an electrolyte. The diffusion resistance of the anode gas diffusion layer when operated with anode fuel is higher than the diffusion resistance of the cathode gas diffusion layer. The anode gas diffusion layer may comprise filler particles having in-plane platelet geometries and be made of lower cost materials and manufacturing processes than currently available commercial carbon fiber substrates. The diffusion resistance difference between the anode gas diffusion layer and the cathode gas diffusion layer may allow for passive water balance control.

The effects of inlet temperature and turbulence characteristics on the flow development inside a gas turbine exhaust diffuser

NASA Astrophysics Data System (ADS)

Bomela, Christian Loangola

The overall industrial gas turbine efficiency is known to be influenced by the pressure recovery in the exhaust system. The design and, subsequently, the performance of an industrial gas turbine exhaust diffuser largely depend on its inflow conditions dictated by the turbine last stage exit flow state and the restraints of the diffuser internal geometry. Recent advances in Computational Fluid Dynamics (CFD) tools and the availability of computer hardware at an affordable cost made the virtual tool a very attractive one for the analysis of fluid flow through devices like a diffuser. In this backdrop, CFD analyses of a typical industrial gas turbine hybrid exhaust diffuser, consisting of an annular diffuser followed by a conical portion, have been carried out with the purpose of improving the performance of these thermal devices using an open-source CFD code "OpenFOAM". The first phase in the research involved the validation of the CFD approach using OpenFOAM by comparing CFD results against published benchmark experimental data. The numerical results closely captured the flow reversal and the separated boundary layer at the shroud wall where a steep velocity gradient has been observed. The standard k --epsilon turbulence model slightly over-predicted the mean velocity profile in the casing boundary layer while slightly under-predicted it in the reversed flow region. A reliable prediction of flow characteristics in this region is very important as the presence of the annular diffuser inclined wall has the most dominant effect on the downstream flow development. The core flow region and the presence of the hub wall have only a minor influence as reported by earlier experimental studies. Additional simulations were carried out in the second phase to test the veracity of other turbulence models; these include RNG k--epsilon, the SST k--o, and the Spalart-Allmaras turbulence models. It was found that a high resolution case with 47.5 million cells using the SST k--o turbulence model produced a mean flow velocity profile at the middle of the annular diffuser portion that had the best overall match with the experiment. The RNG k --epsilon, however, better predicted the diffuser performance along the exhaust diffuser length by means of the pressure recovery coefficient. These results were obtained using uniform inflow conditions and steady-state simulations. As such, the last phase of our investigations involved varying the inflow parameters like the turbulence intensity, the inlet flow temperature, and the flow angularity, which constitute important characteristics of the turbine blade wake, to investigate their impact on the diffuser design and performance. These isothermal CFD simulations revealed that by changing the flow temperature from 15 to 427°C, the pressure recovery coefficient significantly increased. However, it has been shown that the increase of temperature had no effects on the size of the reversed flow region and the thickness of the separated casing boundary layer, although the flow appears to be more turbulent. Furthermore, it has been established that an optimum turbulence intensity of about 4% produced comparable diffuser performance as the experiment. We also found that a velocity angle of about 2.5° at the last turbine stage will ensure a better exhaust diffuser performance.

Modeling of the anode of a liquid-feed DMFC: Inhomogeneous compression effects and two-phase transport phenomena

NASA Astrophysics Data System (ADS)

García-Salaberri, Pablo A.; Vera, Marcos; Iglesias, Immaculada

2014-01-01

An isothermal two-phase 2D/1D across-the-channel model for the anode of a liquid-feed Direct Methanol Fuel Cell (DMFC) is presented. The model takes into account the effects of the inhomogeneous assembly compression of the Gas Diffusion Layer (GDL), including the spatial variations of porosity, diffusivity, permeability, capillary pressure, and electrical conductivity. The effective anisotropic properties of the GDL are evaluated from empirical data reported in the literature corresponding to Toray carbon paper TGP-H series. Multiphase transport is modeled according to the classical theory of porous media (two-fluid model), considering the effect of non-equilibrium evaporation and condensation of methanol and water. The numerical results evidence that the hydrophobic Leverett J-function approach is physically inconsistent to describe capillary transport in the anode of a DMFC when assembly compression effects are considered. In contrast, more realistic results are obtained when GDL-specific capillary pressure curves reflecting the mixed-wettability characteristics of GDLs are taken into account. The gas coverage factor at the GDL/channel interface also exhibits a strong influence on the gas-void fraction distribution in the GDL, which in turn depends on the relative importance between the capillary resistance induced by the inhomogeneous compression, Rc(∝ ∂pc / ∂ ε) , and the capillary diffusivity, Dbarc(∝ ∂pc / ∂ s) .

Twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+x studied by neutron powder diffraction and gas volumetry

NASA Astrophysics Data System (ADS)

Poulsen, H. F.; Andersen, N. H.; Lebech, B.

1991-02-01

We report experimental results of twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+ x, which supplement a previous and simultaneous study of the structural phase diagram and oxygen equilibrium partial pressure. Analysis of neutron powder diffraction peak broadening show features which are identified to result from temperature independent twin-domain formation in to different orthorhombic phases with domain sizes and 250 and 350Å, respectively. The oxygen in-diffusion flow shows simple relaxation type behaviour J=J 0 exp( {-t}/{τ}) despite a rather broad particle size distribution. At higher temperatures, τ is activated with activation energies 0.55 and 0.25 eV in the tetragonal and orthorhombic phases, respectively. Comparison between twin-domain sizes and bulk oxygen in-diffusion time constants indicates that the twin-domain boundaries may contribute to the effective bulk oxygen in-diffusion. All our results may be interpreted in terms of the 2D ASYNNNI model description of the oxygen basal plane ordering, and they suggest that recent first principles interaction parameters should be modified.

Validation of a numerical method for interface-resolving simulation of multicomponent gas-liquid mass transfer and evaluation of multicomponent diffusion models

NASA Astrophysics Data System (ADS)

Woo, Mino; Wörner, Martin; Tischer, Steffen; Deutschmann, Olaf

2018-03-01

The multicomponent model and the effective diffusivity model are well established diffusion models for numerical simulation of single-phase flows consisting of several components but are seldom used for two-phase flows so far. In this paper, a specific numerical model for interfacial mass transfer by means of a continuous single-field concentration formulation is combined with the multicomponent model and effective diffusivity model and is validated for multicomponent mass transfer. For this purpose, several test cases for one-dimensional physical or reactive mass transfer of ternary mixtures are considered. The numerical results are compared with analytical or numerical solutions of the Maxell-Stefan equations and/or experimental data. The composition-dependent elements of the diffusivity matrix of the multicomponent and effective diffusivity model are found to substantially differ for non-dilute conditions. The species mole fraction or concentration profiles computed with both diffusion models are, however, for all test cases very similar and in good agreement with the analytical/numerical solutions or measurements. For practical computations, the effective diffusivity model is recommended due to its simplicity and lower computational costs.

Long-term behaviour of solid oxide fuel cell interconnect materials in contact with Ni-mesh during exposure in simulated anode gas at 700 and 800 °C

NASA Astrophysics Data System (ADS)

Garcia-Fresnillo, L.; Shemet, V.; Chyrkin, A.; de Haart, L. G. J.; Quadakkers, W. J.

2014-12-01

In the present study the long-term behaviour of two ferritic steels, Crofer 22 APU and Crofer 22H, in contact with a Ni-mesh during exposure in simulated anode gas, Ar-4%H2-2%H2O, at 700 and 800 °C for exposure times up to 3000 h was investigated. Ni diffusion from the Ni-mesh into the steel resulted in the formation of an austenitic zone whereas diffusion of iron and chromium from the steel into the Ni-mesh resulted in the formation of chromia base oxides in the Ni-mesh. Depending on the chemical composition of the steel, the temperature and the exposure time, interdiffusion processes between ferritic steel and Ni-mesh also resulted in σ-phase formation at the austenite-ferrite interface and in Laves-phase dissolution in the austenitic zone. The extent and morphology of the σ-phase formation are discussed on the basis of thermodynamic considerations, including reaction paths in the ternary alloy system Fe-Ni-Cr.

The hydrology of northern peatlands as affected by biogenic gas: Current developments and research needs

USGS Publications Warehouse

Rosenberry, D.O.; Glaser, P.H.; Siegel, D.I.

2006-01-01

Recent research indicates that accumulation and release of biogenic gas from northern peatlands may substantially affect future climate. Sudden release of free-phase gas bubbles into the atmosphere may preclude the conversion of methane to carbon dioxide in the uppermost oxic layer of the peat, resulting in greater contribution of methane to the atmosphere than is currently estimated. The hydrology of these peatlands also affects and is affected by this process, especially when gas is released suddenly and episodically. Indirect hydrological evidence indicates that ebullitive gas releases are relatively frequent in some peatlands and time-averaged rates may be significantly greater than diffusive releases. Estimates of free-phase gas contained in peat have ranged from 0 to nearly 20% of the peat volume. Abrupt changes in the volume of gas may alter hydraulic gradients and movement of water and solutes in peat, which in turn could alter composition and fluxes of the gas. Peat surfaces also move vertically and horizontally in response to accumulation and release of free-phase gas. Future research should address the distribution, temporal variability, and relative significance of ebullition in peatlands and the consequent hydrological responses to these gas-emission events. Copyright ?? 2006 John Wiley & Sons, Ltd.

Modeling of confined turbulent fluid-particle flows using Eulerian and Lagrangian schemes

NASA Technical Reports Server (NTRS)

Adeniji-Fashola, A.; Chen, C. P.

1990-01-01

Two important aspects of fluid-particulate interaction in dilute gas-particle turbulent flows (the turbulent particle dispersion and the turbulence modulation effects) are addressed, using the Eulerian and Lagrangian modeling approaches to describe the particulate phase. Gradient-diffusion approximations are employed in the Eulerian formulation, while a stochastic procedure is utilized to simulate turbulent dispersion in the Lagrangina formulation. The k-epsilon turbulence model is used to characterize the time and length scales of the continuous phase turbulence. Models proposed for both schemes are used to predict turbulent fully-developed gas-solid vertical pipe flow with reasonable accuracy.

Description of gas/particle sorption kinetics with an intraparticle diffusion model: Desorption experiments

USGS Publications Warehouse

Rounds, S.A.; Tiffany, B.A.; Pankow, J.F.

1993-01-01

Aerosol particles from a highway tunnel were collected on a Teflon membrane filter (TMF) using standard techniques. Sorbed organic compounds were then desorbed for 28 days by passing clean nitrogen through the filter. Volatile n-alkanes and polycyclic aromatic hydrocarbons (PAHs) were liberated from the filter quickly; only a small fraction of the less volatile ra-alkanes and PAHs were desorbed. A nonlinear least-squares method was used to fit an intraparticle diffusion model to the experimental data. Two fitting parameters were used: the gas/particle partition coefficient (Kp and an effective intraparticle diffusion coefficient (Oeff). Optimized values of Kp are in agreement with previously reported values. The slope of a correlation between the fitted values of Deff and Kp agrees well with theory, but the absolute values of Deff are a factor of ???106 smaller than predicted for sorption-retarded, gaseous diffusion. Slow transport through an organic or solid phase within the particles or preferential flow through the bed of particulate matter on the filter might be the cause of these very small effective diffusion coefficients. ?? 1993 American Chemical Society.

The effect of hydrate promoters on gas uptake.

PubMed

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

2017-08-16

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

Mixing of secondary organic aerosols versus relative humidity

PubMed Central

Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin

2016-01-01

Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions. PMID:27791066

Mixing of secondary organic aerosols versus relative humidity.

PubMed

Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin; Sullivan, Ryan C; Donahue, Neil M

2016-10-24

Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions.

Time-dependent gas-liquid interaction in molecular-sized nanopores.

PubMed

Sun, Yueting; Li, Penghui; Qiao, Yu; Li, Yibing

2014-10-08

Different from a bulk phase, a gas nanophase can have a significant effect on liquid motion. Herein we report a series of experimental results on molecular behaviors of water in a zeolite β of molecular-sized nanopores. If sufficient time is provided, the confined water molecules can be "locked" inside a nanopore; otherwise, gas nanophase provides a driving force for water "outflow". This is due to the difficult molecular site exchanges and the relatively slow gas-liquid diffusion in the nanoenvironment. Depending on the loading rate, the zeolite β/water system may exhibit either liquid-spring or energy-absorber characteristics.

Diffusion of Charged Species in Liquids

NASA Astrophysics Data System (ADS)

Del Río, J. A.; Whitaker, S.

2016-11-01

In this study the laws of mechanics for multi-component systems are used to develop a theory for the diffusion of ions in the presence of an electrostatic field. The analysis begins with the governing equation for the species velocity and it leads to the governing equation for the species diffusion velocity. Simplification of this latter result provides a momentum equation containing three dominant forces: (a) the gradient of the partial pressure, (b) the electrostatic force, and (c) the diffusive drag force that is a central feature of the Maxwell-Stefan equations. For ideal gas mixtures we derive the classic Nernst-Planck equation. For liquid-phase diffusion we encounter a situation in which the Nernst-Planck contribution to diffusion differs by several orders of magnitude from that obtained for ideal gases.

Diffusion of Charged Species in Liquids.

PubMed

Del Río, J A; Whitaker, S

2016-11-04

In this study the laws of mechanics for multi-component systems are used to develop a theory for the diffusion of ions in the presence of an electrostatic field. The analysis begins with the governing equation for the species velocity and it leads to the governing equation for the species diffusion velocity. Simplification of this latter result provides a momentum equation containing three dominant forces: (a) the gradient of the partial pressure, (b) the electrostatic force, and (c) the diffusive drag force that is a central feature of the Maxwell-Stefan equations. For ideal gas mixtures we derive the classic Nernst-Planck equation. For liquid-phase diffusion we encounter a situation in which the Nernst-Planck contribution to diffusion differs by several orders of magnitude from that obtained for ideal gases.

Diffusion of Charged Species in Liquids

PubMed Central

del Río, J. A.; Whitaker, S.

2016-01-01

In this study the laws of mechanics for multi-component systems are used to develop a theory for the diffusion of ions in the presence of an electrostatic field. The analysis begins with the governing equation for the species velocity and it leads to the governing equation for the species diffusion velocity. Simplification of this latter result provides a momentum equation containing three dominant forces: (a) the gradient of the partial pressure, (b) the electrostatic force, and (c) the diffusive drag force that is a central feature of the Maxwell-Stefan equations. For ideal gas mixtures we derive the classic Nernst-Planck equation. For liquid-phase diffusion we encounter a situation in which the Nernst-Planck contribution to diffusion differs by several orders of magnitude from that obtained for ideal gases. PMID:27811959

Modeling 3H-3He Gas-Liquid Phase Transport for Interpretation of Groundwater Age

NASA Astrophysics Data System (ADS)

Carle, S. F.; Esser, B.; Moran, J. E.

2009-12-01

California’s Groundwater Ambient Monitoring and Assessment (GAMA) Program has measured many hundreds of tritium (3H) and helium-3 (3He) concentrations in well water samples to derive estimates of groundwater age at production and monitoring wells in California basins. However, a 3H-3He age differs from an ideal groundwater age tracer in several respects: (1) the radioactive decay of 3H results in the accumulation of 3He being first-order with respect to 3H activity (versus a zero-order age-mass accumulation process for an ideal tracer), (2) surface concentrations of 3H as measured in precipitation over the last several decades have not been uniform, and (3) the 3H-3He “clock” begins at the water table and not at the ground surface where 3H source measurements are made. To better understand how these non-idealities affect interpretation of 3H-3He apparent groundwater age, we are modeling coupled gas-liquid phase flow and 3H-3He transport including processes of radiogenic decay, phase equilibrium, and molecular diffusion for water, air, 3H, and 3He components continuously through the vadose zone and saturated zone. Assessment of coupled liquid-gas phase processes enables consideration of 3H-3He residence time and dispersion within the vadose zone, including partitioning of tritiogenic 3He to the gas phase and subsequent diffusion into the atmosphere. The coupled gas-liquid phase modeling framework provides direct means to compare apparent 3H-3He age to ideal mean or advective groundwater ages for the same groundwater flow conditions. Examples are given for common groundwater flow systems involving areal recharge, discharge to streams or long-screened wells, and aquifer system heterogeneity. The Groundwater Ambient Monitoring and Assessment program is sponsored by the California State Water Resources Control Board and carried out in cooperation with the U.S. Geological Survey. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Spectral separation of gaseous fluorocarbon mixtures and measurement of diffusion constants by 19F gas phase DOSY NMR.

PubMed

Marchione, Alexander A; McCord, Elizabeth F

2009-11-01

Diffusion-ordered (DOSY) NMR techniques have for the first time been applied to the spectral separation of mixtures of fluorinated gases by diffusion rates. A mixture of linear perfluoroalkanes from methane to hexane was readily separated at 25 degrees C in an ordinary experimental setup with standard DOSY pulse sequences. Partial separation of variously fluorinated ethanes was also achieved. The constants of self-diffusion of a set of pure perfluoroalkanes were obtained at pressures from 0.25 to 1.34 atm and temperatures from 20 to 122 degrees C. Under all conditions there was agreement within 20% of experimental self-diffusion constant D and values calculated by the semiempirical Fuller method.

Gas transport processes in sea ice: How convection and diffusion processes might affect biological imprints, a challenge for modellers

NASA Astrophysics Data System (ADS)

Tison, J.-L.; Zhou, J.; Thomas, D. N.; Rysgaard, S.; Eicken, H.; Crabeck, O.; Deleu, F.; Delille, B.

2012-04-01

Recent data from a year-round survey of landfast sea ice growth in Barrow (Alaska) have shown how O2/N2 and O2/Ar ratios could be used to pinpoint primary production in sea ice and derive net productivity rates from the temporal evolution of the oxygen concentration at a given depth within the sea ice cover. These rates were however obtained surmising that neither convection, nor diffusion had affected the gas concentration profiles in the ice between discrete ice core collections. This paper discusses examples from three different field surveys (the above-mentioned Barrow experiment, the INTERICE IV tank experiment in Hamburg and a short field survey close to the Kapisilit locality in the South-East Greenland fjords) where convection or diffusion processes have clearly affected the temporal evolution of the gas profiles in the ice, therefore potentially affecting biological signatures. The INTERICE IV and Barrow experiment show that the initial equilibrium dissolved gas entrapment within the skeletal layer basically governs most of the profiles higher up in the sea ice cover during the active sea ice growth. However, as the ice layers age and cool down under the temperature gradient, bubble nucleation occurs while the concentration in the ice goes well above the theoretical one, calculated from brine equilibrium under temperature and salinity changes and observed brine volumes. This phase change locks the gases within the sea ice structure, preventing "degassing" of the ice, as is observed for salts under the mushy layer brine convection process. In some cases, mainly in the early stages of the freezing process (first 10-20 cm) where temperature gradients are strong and the ice still permeable on its whole thickness, repeated convection and bubble nucleation can actually increase the gas concentration in the ice above the one initially acquired within the skeletal layer. Convective processes will also occur on ice decay, when ice permeability is restored and the Rayleigh number reaches a critical value. The Barrow data set shows that these events, can be strong enough to redistribute the gases within the sea ice cover, including in the gaseous form. Diffusive processes will become dominant once internal melting is strong enough to stratify the brine network within the ice. In the Kapisilit case, the regular decrease of an internal gas peak intensity due to external forcing during ice growth (change of water type) has allowed us to deduce gas diffusivities from the temporal evolution of the peak. The values fit to the few previous estimates from experimental work, and lie close to diffusivity values in water. Finally, at the end of the decay phase, when the temperature profile is isothermal, the whole ice cover returns to ice concentrations equivalent to those calculated using gas solubility in water and observed brine volumes, to the exception of the very surface layer, generally for textural reasons.

Energy Dissipation and Nonthermal Diffusion on Interstellar Ice Grains

NASA Astrophysics Data System (ADS)

Fredon, A.; Lamberts, T.; Cuppen, H. M.

2017-11-01

Interstellar dust grains are known to facilitate chemical reactions by acting as a meeting place and adsorbing energy. This process strongly depends on the ability of the reactive species to effectively diffuse over the surface. The cold temperatures around 10 K strongly hamper this for species other than H and H2. However, complex organic molecules have been observed in the gas phase at these cold conditions, indicating that their formation, as well as their return to the gas phase, should be effective. Here, we show how the energy released following surface reactions can be employed to solve both problems by inducing desorption or diffusion. To this purpose, we have performed thousands of Molecular Dynamics simulations to quantify the outcome of an energy dissipation process. Admolecules on top of a crystalline water surface have been given translational energy between 0.5 and 5 eV. Three different surface species are considered (CO2, H2O, and CH4), spanning a range in binding energies, number of internal degrees of freedom, and molecular weights. The admolecules are found to be able to travel up to several hundreds of angstroms before coming to a stand still, allowing for follow-up reactions en route. The probability of travel beyond any particular radius, as determined by our simulations, shows the same r dependence for all three admolecule species. Furthermore, we have been able to quantify the desorption probability, which depends on the binding energy of the species and the translational excitation. We provide expressions that can be incorporated in astrochemical models to predict grain surface formation and return into the gas phase of these products.

Herschel HIFI GOT C+ Survey: CII, HI, and CO Emissions in a Sample of Transition Clouds and Star-Forming regions in the Inner Galaxy

NASA Astrophysics Data System (ADS)

Pineda, Jorge; Velusamy, Thangasamy; Langer, William D.; Goldsmith, Paul; Li, Di; Yorke, Harold

The GOT C+ a HIFI Herschel Key Project, studies the diffuse ISM throughout the Galactic Plane, using C+ as cloud tracer. The C+ line at 1.9 THz traces a so-far poorly studied stage in ISM cloud evolution -the transitional clouds going from atomic HI to molecular H2. This transition cloud phase, which is difficult to observe in HI and CO alone, may be best characterized via CII emission or absorption. The C+ line is also an excellent tracer of the warm diffuse gas and the warm, dense gas in the Photon Dominated Regions (PDRs). We can, therefore, use the CII emission as a probe to understand the effects of star formation on their interstellar environment. We present our first results on the transition between dense and hot gas (traced by CII) and dense and cold gas (traced by 12CO and 13CO) along a few representative lines of sight in the inner Galaxy from longitude 325 degrees to 25 degrees, taken during the HIFI Priority Science Phase. Comparisons of the high spectral resolution ( 1 km/s) HIFI data on C+ with HI, 12CO, and 13CO spectra allow us to separate out the different ISM components along each line of sight. Our results provide detailed information about the transition of diffuse atomic to molecular gas clouds needed to understand star formation and the lifecycle of the interstellar gas. These observations are being carried out with the Herschel Space Observatory, which is an ESA cornerstone mission, with contributions from NASA. This research was conducted at the Jet Propulsion Laboratory, California Institute of Technology under contract with the National Aeronautics and Space Administration. JLP was supported under the NASA Postdoctoral Program at JPL, Caltech, administered by Oak Ridge Associated Universities through a contract with NASA, and is currently supported as a Caltech-JPL Postdoctoral associate.

Single-layer model to predict the source/sink behavior of diffusion-controlled building materials.

PubMed

Kumar, Deept; Little, John C

2003-09-01

Building materials may act as both sources of and sinks forvolatile organic compounds (VOCs) in indoor air. A strategy to characterize the rate of absorption and desorption of VOCs by diffusion-controlled building materials is validated. A previously developed model that predicts mass transfer between a flat slab of material and the well-mixed air within a chamber or room is extended. The generalized model allows a nonuniform initial material-phase concentration and a transient influent gas-phase concentration to be simultaneously considered. An analytical solution to the more general model is developed. Experimental data are obtained by placing samples of vinyl flooring inside a small stainless steel chamber and exposing them to absorption/desorption cycles of n-dodecane and phenol. Measured values for the material-air partition coefficient and the material-phase diffusion coefficient were obtained previously in a series of completely independent experiments. The a priori model predictions are in close agreement with the observed experimental data.

Development of Novel PEM Membrane and Multiphase CD Modeling of PEM Fuel Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. J. Berry; Susanta Das

2009-12-30

To understand heat and water management phenomena better within an operational proton exchange membrane fuel cell's (PEMFC) conditions, a three-dimensional, two-phase computational fluid dynamic (CFD) flow model has been developed and simulated for a complete PEMFC. Both liquid and gas phases are considered in the model by taking into account the gas flow, diffusion, charge transfer, change of phase, electro-osmosis, and electrochemical reactions to understand the overall dynamic behaviors of species within an operating PEMFC. The CFD model is solved numerically under different parametric conditions in terms of water management issues in order to improve cell performance. The results obtainedmore » from the CFD two-phase flow model simulations show improvement in cell performance as well as water management under PEMFCs operational conditions as compared to the results of a single phase flow model available in the literature. The quantitative information obtained from the two-phase model simulation results helped to develop a CFD control algorithm for low temperature PEM fuel cell stacks which opens up a route in designing improvement of PEMFC for better operational efficiency and performance. To understand heat and water management phenomena better within an operational proton exchange membrane fuel cell's (PEMFC) conditions, a three-dimensional, two-phase computational fluid dynamic (CFD) flow model has been developed and simulated for a complete PEMFC. Both liquid and gas phases are considered in the model by taking into account the gas flow, diffusion, charge transfer, change of phase, electro-osmosis, and electrochemical reactions to understand the overall dynamic behaviors of species within an operating PEMFC. The CFD model is solved numerically under different parametric conditions in terms of water management issues in order to improve cell performance. The results obtained from the CFD two-phase flow model simulations show improvement in cell performance as well as water management under PEMFCs operational conditions as compared to the results of a single phase flow model available in the literature. The quantitative information obtained from the two-phase model simulation results helped to develop a CFD control algorithm for low temperature PEM fuel cell stacks which opens up a route in designing improvement of PEMFC for better operational efficiency and performance.« less

A fabrication and characterictics of microbolometer detectors using VOx/ZnO/VOx multilayer thin film processing

NASA Astrophysics Data System (ADS)

Han, Myung-Soo; Kim, Dae Hyeon; Ko, Hang Ju; Shin, Jae Chul; Kim, Hyo Jin; Kim, Do Gun

2014-06-01

In this work, a novel fabrication method for VOx-ZnO multilayers with mixed phase of the VO2 and V2O3 through the diffusion of oxygen by annealing at low temperature is presented. A stable sandwich structure of a VOx/ZnO/VOx multilayer was deposited at room temperature, through the oxygen gas flow rate, by RF sputtering system, and the mixed phase was formed through oxygen diffusion by annealing at O2 atmosphere. The results show that the single phase like multilayer formed by this process has a high TCR of more than -2.5%/K and low resistance of about 100 kohm at room temperature. XRD results for the as-deposited VOx/ZnO/VOx multilayer.

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1988-01-01

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Transport of dissolved gases through unsaturated porous media

NASA Astrophysics Data System (ADS)

Maryshev, B. S.

2017-06-01

The natural porous media (e.g. soil, sand, peat etc.) usually are partially saturated by groundwater. The saturation of soil depends on hydrostatic pressure which is linearly increased with depth. Often some gases (e.g. nitrogen, oxygen, carbon dioxide, methane etc.) are dissolved into the groundwater. The solubility of gases is very small because of that two assumptions is applied: I. The concentration of gas is equal to solubility, II. Solubility depends only on pressure (for isothermal systems). In this way some part of dissolved gas transfers from the solution to the bubble phase. The gas bubbles are immovably trapped in a porous matrix by surface-tension forces and the dominant mechanism of transport of gas mass becomes the diffusion of gas molecules through the liquid. If the value of water content is small then the transport of gas becomes slow and gas accumulates into bubble phase. The presence of bubble phase additionally decreases the water content and slows down the transport. As result the significant mass of gas should be accumulated into the massif of porous media. We derive the transport equations and find the solution which is demonstrated the accumulation of gases. The influence of saturation, porosity and filtration velocity to accumulation process is investigated and discussed.

Thermophysical properties of gas phase uranium tetrafluoride

NASA Technical Reports Server (NTRS)

Watanabe, Yoichi; Anghaie, Samim

1993-01-01

Thermophysical data of gaseous uranium tetrafluoride (UF4) are theoretically obtained by taking into account dissociation of molecules at high temperatures (2000-6000 K). Determined quantities include specific heat, optical opacity, diffusion coefficient, viscosity, and thermal conductivity. A computer program is developed for the calculation.

Barrier Coatings for Refractory Metals and Superalloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

SM Sabol; BT Randall; JD Edington

2006-02-23

In the closed working fluid loop of the proposed Prometheus space nuclear power plant (SNPP), there is the potential for reaction of core and plant structural materials with gas phase impurities and gas phase transport of interstitial elements between superalloy and refractory metal alloy components during service. Primary concerns are surface oxidation, interstitial embrittlement of refractory metals and decarburization of superalloys. In parallel with kinetic investigations, this letter evaluates the ability of potential coatings to prevent or impede communication between reactor and plant components. Key coating requirements are identified and current technology coating materials are reviewed relative to these requirements.more » Candidate coatings are identified for future evaluation based on current knowledge of design parameters and anticipated environment. Coatings were identified for superalloys and refractory metals to provide diffusion barriers to interstitial transport and act as reactive barriers to potential oxidation. Due to their high stability at low oxygen potential, alumina formers are most promising for oxidation protection given the anticipated coolant gas chemistry. A sublayer of iridium is recommended to provide inherent diffusion resistance to interstitials. Based on specific base metal selection, a thin film substrate--coating interdiffusion barrier layer may be necessary to meet mission life.« less

Gas sorption in poly-(2,6-dimethyl-1,4-phenylene)oxide containing nanoporous crystalline phases

NASA Astrophysics Data System (ADS)

Galizia, M.; Daniel, C.; Fasano, G.; Guerra, G.; Mensitieri, G.

2012-07-01

In this contribution is presented an analysis of mass transport properties of low molecular weight compounds in amorphous PPO and in semi-crystalline PPO obtained by treating with benzene and carbon tetrachloride the amorphous sample. It is found that semi-crystalline samples are endowed with larger gas sorption capacity and diffusivity as compared to the amorphous ones: this behaviour has been attributed to the nanoporous nature of the crystalline phases induced by treatment with solvents. In particular, sorption experiments, carried out at 30°C with methane, carbon dioxide, propane and propylene, have shown that both semi-crystalline PPOs display rather interesting features which make them suitable for use as membrane materials in gas separation processes, in view of the relatively high values of solubility and diffusivity. Moreover, these peculiar sorption and mass transport properties have been found to be virtually unaffected by thermal ageing: in fact, sorption experiments conducted on amorphous and semi-crystalline PPO after treatment at 65°C for three months showed that sorption properties of aged samples are the same as for the untreated samples. This is an important feature to assure the stability of performances in membrane applications.

Ion-plasma protective coatings for gas-turbine engine blades

NASA Astrophysics Data System (ADS)

Kablov, E. N.; Muboyadzhyan, S. A.; Budinovskii, S. A.; Lutsenko, A. N.

2007-10-01

Evaporated, diffusion, and evaporation—diffusion protective and hardening multicomponent ionplasma coatings for turbine and compressor blades and other gas-turbine engine parts are considered. The processes of ion surface treatment (ion etching and ion saturation of a surface in the metallic plasma of a vacuum arc) and commercial equipment for the deposition of coatings and ion surface treatment are analyzed. The specific features of the ion-plasma coatings deposited from the metallic plasma of a vacuum arc are described, and the effect of the ion energy on the phase composition of the coatings and the processes occurring in the surface layer of an article to be treated are discussed. Some properties of ion-plasma coatings designed for various purposes are presented. The ion surface saturation of articles made from structural materials is shown to change the structural and phase states of their surfaces and, correspondingly, the related properties of these materials (i.e., their heat resistance, corrosion resistance, fatigue strength, and so on).

Probing the regional distribution of pulmonary gas exchange through single-breath gas- and dissolved-phase 129Xe MR imaging.

PubMed

Kaushik, S Sivaram; Freeman, Matthew S; Cleveland, Zackary I; Davies, John; Stiles, Jane; Virgincar, Rohan S; Robertson, Scott H; He, Mu; Kelly, Kevin T; Foster, W Michael; McAdams, H Page; Driehuys, Bastiaan

2013-09-01

Although some central aspects of pulmonary function (ventilation and perfusion) are known to be heterogeneous, the distribution of diffusive gas exchange remains poorly characterized. A solution is offered by hyperpolarized 129Xe magnetic resonance (MR) imaging, because this gas can be separately detected in the lung's air spaces and dissolved in its tissues. Early dissolved-phase 129Xe images exhibited intensity gradients that favored the dependent lung. To quantitatively corroborate this finding, we developed an interleaved, three-dimensional radial sequence to image the gaseous and dissolved 129Xe distributions in the same breath. These images were normalized and divided to calculate "129Xe gas-transfer" maps. We hypothesized that, for healthy volunteers, 129Xe gas-transfer maps would retain the previously observed posture-dependent gradients. This was tested in nine subjects: when the subjects were supine, 129Xe gas transfer exhibited a posterior-anterior gradient of -2.00 ± 0.74%/cm; when the subjects were prone, the gradient reversed to 1.94 ± 1.14%/cm (P < 0.001). The 129Xe gas-transfer maps also exhibited significant heterogeneity, as measured by the coefficient of variation, that correlated with subject total lung capacity (r = 0.77, P = 0.015). Gas-transfer intensity varied nonmonotonically with slice position and increased in slices proximal to the main pulmonary arteries. Despite substantial heterogeneity, the mean gas transfer for all subjects was 1.00 ± 0.01 while supine and 1.01 ± 0.01 while prone (P = 0.25), indicating good "matching" between gas- and dissolved-phase distributions. This study demonstrates that single-breath gas- and dissolved-phase 129Xe MR imaging yields 129Xe gas-transfer maps that are sensitive to altered gas exchange caused by differences in lung inflation and posture.

Computation of three-dimensional three-phase flow of carbon dioxide using a high-order WENO scheme

NASA Astrophysics Data System (ADS)

Gjennestad, Magnus Aa.; Gruber, Andrea; Lervåg, Karl Yngve; Johansen, Øyvind; Ervik, Åsmund; Hammer, Morten; Munkejord, Svend Tollak

2017-11-01

We have developed a high-order numerical method for the 3D simulation of viscous and inviscid multiphase flow described by a homogeneous equilibrium model and a general equation of state. Here we focus on single-phase, two-phase (gas-liquid or gas-solid) and three-phase (gas-liquid-solid) flow of CO2 whose thermodynamic properties are calculated using the Span-Wagner reference equation of state. The governing equations are spatially discretized on a uniform Cartesian grid using the finite-volume method with a fifth-order weighted essentially non-oscillatory (WENO) scheme and the robust first-order centered (FORCE) flux. The solution is integrated in time using a third-order strong-stability-preserving Runge-Kutta method. We demonstrate close to fifth-order convergence for advection-diffusion and for smooth single- and two-phase flows. Quantitative agreement with experimental data is obtained for a direct numerical simulation of an air jet flowing from a rectangular nozzle. Quantitative agreement is also obtained for the shape and dimensions of the barrel shock in two highly underexpanded CO2 jets.

Evaporation Kinetics of Polyol Droplets: Determination of Evaporation Coefficients and Diffusion Constants

NASA Astrophysics Data System (ADS)

Su, Yong-Yang; Marsh, Aleksandra; Haddrell, Allen E.; Li, Zhi-Ming; Reid, Jonathan P.

2017-11-01

In order to quantify the kinetics of mass transfer between the gas and condensed phases in aerosol, physicochemical properties of the gas and condensed phases and kinetic parameters (mass/thermal accommodation coefficients) are crucial for estimating mass fluxes over a wide size range from the free molecule to continuum regimes. In this study, we report measurements of the evaporation kinetics of droplets of 1-butanol, ethylene glycol (EG), diethylene glycol (DEG), and glycerol under well-controlled conditions (gas flow rates and temperature) using the previously developed cylindrical electrode electrodynamic balance technique. Measurements are compared with a model that captures the heat and mass transfer occurring at the evaporating droplet surface. The aim of these measurements is to clarify the discrepancy in the reported values of mass accommodation coefficient (αM, equals to evaporation coefficient based on microscopic reversibility) for 1-butanol, EG, and DEG and improve the accuracy of the value of the diffusion coefficient for glycerol in gaseous nitrogen. The uncertainties in the thermophysical and experimental parameters are carefully assessed, the literature values of the vapor pressures of these components are evaluated, and the plausible ranges of the evaporation coefficients for 1-butanol, EG, and DEG as well as uncertainty in diffusion coefficient for glycerol are reported. Results show that αM should be greater than 0.4, 0.2, and 0.4 for EG, DEG, and 1-butanol, respectively. The refined values are helpful for accurate prediction of the evaporation/condensation rates.

Application of gas diffusion biocathode in microbial electrosynthesis from carbon dioxide.

PubMed

Bajracharya, Suman; Vanbroekhoven, Karolien; Buisman, Cees J N; Pant, Deepak; Strik, David P B T B

2016-11-01

Microbial catalysis of carbon dioxide (CO 2 ) reduction to multi-carbon compounds at the cathode is a highly attractive application of microbial electrosynthesis (MES). The microbes reduce CO 2 by either taking the electrons or reducing the equivalents produced at the cathode. While using gaseous CO 2 as the carbon source, the biological reduction process depends on the dissolution and mass transfer of CO 2 in the electrolyte. In order to deal with this issue, a gas diffusion electrode (GDE) was investigated by feeding CO 2 through the GDE into the MES reactor for its reduction at the biocathode. A combination of the catalyst layer (porous activated carbon and Teflon binder) and the hydrophobic gas diffusion layer (GDL) creates a three-phase interface at the electrode. So, CO 2 and reducing equivalents will be available to the biocatalyst on the cathode surface. An enriched inoculum consisting of acetogenic bacteria, prepared from an anaerobic sludge, was used as a biocatalyst. The cathode potential was maintained at -1.1 V vs Ag/AgCl to facilitate direct and/or hydrogen-mediated CO 2 reduction. Bioelectrochemical CO 2 reduction mainly produced acetate but also extended the products to ethanol and butyrate. Average acetate production rates of 32 and 61 mg/L/day, respectively, with 20 and 80 % CO 2 gas mixture feed were achieved with 10 cm 2 of GDE. The maximum acetate production rate remained 238 mg/L/day for 20 % CO 2 gas mixture. In conclusion, a gas diffusion biocathode supported bioelectrochemical CO 2 reduction with enhanced mass transfer rate at continuous supply of gaseous CO 2 . Graphical abstract ᅟ.

Morphological bubble evolution induced by air diffusion on submerged hydrophobic structures

NASA Astrophysics Data System (ADS)

Lv, Pengyu; Xiang, Yaolei; Xue, Yahui; Lin, Hao; Duan, Huiling

2017-03-01

Bubbles trapped in the cavities always play important roles in the underwater applications of structured hydrophobic surfaces. Air exchange between bubbles and surrounding water has a significant influence on the morphological bubble evolution, which in turn frequently affects the functionalities of the surfaces, such as superhydrophobicity and drag reduction. In this paper, air diffusion induced bubble evolution on submerged hydrophobic micropores under reduced pressures is investigated experimentally and theoretically. The morphological behaviors of collective and single bubbles are observed using confocal microscopy. Four representative evolution phases of bubbles are captured in situ. After depressurization, bubbles will not only grow and coalesce but also shrink and split although the applied pressure remains negative. A diffusion-based model is used to analyze the evolution behavior and the results are consistent with the experimental data. A criterion for bubble growth and shrinkage is also derived along with a phase diagram, revealing that the competition of effective gas partial pressures across the two sides of the diffusion layer dominates the bubble evolution process. Strategies for controlling the bubble evolution behavior are also proposed based on the phase diagram. The current work provides a further understanding of the general behavior of bubble evolution induced by air diffusion and can be employed to better designs of functional microstructured hydrophobic surfaces.

The effects of stimulated star formation on the evolution of the galaxy. III - The chemical evolution of nonlinear systems

NASA Technical Reports Server (NTRS)

Shore, Steven N.; Ferrini, Federico; Palla, Francesco

1987-01-01

The evolution of models for star formation in galaxies with disk and halo components is discussed. Two phases for the halo (gas and stars) and three for the disk (including clouds) are used in these calculations. The star-formation history is followed using nonlinear phase-coupling models which completely determine the populations of the phases as a function of time. It is shown that for a wide range of parameters, including the effects of both spontaneous and stimulated star formation and mass exchange between the spatial components of the system, the observed chemical history of the galaxy can easily be obtained. The most sensitive parameter in the detailed metallicity and star-formation history for the system is the rate of return of gas to the diffuse phase upon stellar death.

Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion.

PubMed

Arangio, Andrea M; Slade, Jonathan H; Berkemeier, Thomas; Pöschl, Ulrich; Knopf, Daniel A; Shiraiwa, Manabu

2015-05-14

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pauly, Tyler; Garrod, Robin T., E-mail: tap74@cornell.edu

Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry of dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual grain-size population. We find that the temperature difference plays amore » significant role in determining the total bulk ice composition across the grain-size distribution, while the effects of geometrical differences between size populations appear marginal. We also consider collapse from a diffuse to a dark cloud, allowing dust temperatures to fall. Under the initial diffuse conditions, small grains are too warm to promote grain-mantle build-up, with most ices forming on the mid-sized grains. As collapse proceeds, the more abundant, smallest grains cool and become the dominant ice carriers; the large population of small grains means that this ice is distributed across many grains, with perhaps no more than 40 monolayers of ice each (versus several hundred assuming a single grain size). This effect may be important for the subsequent processing and desorption of the ice during the hot-core phase of star formation, exposing a significant proportion of the ice to the gas phase, increasing the importance of ice-surface chemistry and surface–gas interactions.« less

Monitoring of hemodynamic changes induced in the healthy breast through inspired gas stimuli with MR-guided diffuse optical imaging

PubMed Central

Carpenter, C. M.; Rakow-Penner, R.; Jiang, S.; Pogue, B. W.; Glover, G. H.; Paulsen, K. D.

2010-01-01

Purpose: The modulation of tissue hemodynamics has important clinical value in medicine for both tumor diagnosis and therapy. As an oncological tool, increasing tissue oxygenation via modulation of inspired gas has been proposed as a method to improve cancer therapy and determine radiation sensitivity. As a radiological tool, inducing changes in tissue total hemoglobin may provide a means to detect and characterize malignant tumors by providing information about tissue vascular function. The ability to change and measure tissue hemoglobin and oxygenation concentrations in the healthy breast during administration of three different types of modulated gas stimuli (oxygen∕carbogen, air∕carbogen, and air∕oxygen) was investigated. Methods: Subjects breathed combinations of gases which were modulated in time. MR-guided diffuse optical tomography measured total hemoglobin and oxygen saturation in the breast every 30 s during the 16 min breathing stimulus. Metrics of maximum correlation and phase lag were calculated by cross correlating the measured hemodynamics with the stimulus. These results were compared to an air∕air control to determine the hemodynamic changes compared to the baseline physiology. Results: This study demonstrated that a gas stimulus consisting of alternating oxygen∕carbogen induced the largest and most robust hemodynamic response in healthy breast parenchyma relative to the changes that occurred during the breathing of room air. This stimulus caused increases in total hemoglobin and oxygen saturation during the carbogen phase of gas inhalation, and decreases during the oxygen phase. These findings are consistent with the theory that oxygen acts as a vasoconstrictor, while carbogen acts as a vasodilator. However, difficulties in inducing a consistent change in tissue hemoglobin and oxygenation were observed because of variability in intersubject physiology, especially during the air∕oxygen or air∕carbogen modulated breathing protocols. Conclusions: MR-guided diffuse optical imaging is a unique tool that can measure tissue hemodynamics in the breast during modulated breathing. This technique may have utility in determining the therapeutic potential of pretreatment tissue oxygenation or in investigating vascular function. Future gas modulation studies in the breast should use a combination of oxygen and carbogen as the functional stimulus. Additionally, control measures of subject physiology during air breathing are critical for robust measurements. PMID:20443485

Report on simulation of fission gas and fission product diffusion in UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders David; Perriot, Romain Thibault; Pastore, Giovanni

2016-07-22

In UO 2 nuclear fuel, the retention and release of fission gas atoms such as xenon (Xe) are important for nuclear fuel performance by, for example, reducing the fuel thermal conductivity, causing fuel swelling that leads to mechanical interaction with the clad, increasing the plenum pressure and reducing the fuel–clad gap thermal conductivity. We use multi-­scale simulations to determine fission gas diffusion mechanisms as well as the corresponding rates in UO 2 under both intrinsic and irradiation conditions. In addition to Xe and Kr, the fission products Zr, Ru, Ce, Y, La, Sr and Ba have been investigated. Density functionalmore » theory (DFT) calculations are used to study formation, binding and migration energies of small clusters of Xe atoms and vacancies. Empirical potential calculations enable us to determine the corresponding entropies and attempt frequencies for migration as well as investigate the properties of large clusters or small fission gas bubbles. A continuum reaction-­diffusion model is developed for Xe and point defects based on the mechanisms and rates obtained from atomistic simulations. Effective fission gas diffusivities are then obtained by solving this set of equations for different chemical and irradiation conditions using the MARMOT phase field code. The predictions are compared to available experimental data. The importance of the large Xe U3O cluster (a Xe atom in a uranium + oxygen vacancy trap site with two bound uranium vacancies) is emphasized, which is a consequence of its high mobility and high binding energy. We find that the Xe U3O cluster gives Xe diffusion coefficients that are higher for intrinsic conditions than under irradiation over a wide range of temperatures. Under irradiation the fast-­moving Xe U3O cluster recombines quickly with irradiation-induced interstitial U ions, while this mechanism is less important for intrinsic conditions. The net result is higher concentration of the Xe U3O cluster for intrinsic conditions than under irradiation. We speculate that differences in the irradiation conditions and their impact on the Xe U3O cluster can explain the wide range of diffusivities reported in experimental studies. However, all vacancy-­mediated mechanisms underestimate the Xe diffusivity compared to the empirical radiation-­enhanced rate used in most fission gas release models. We investigate the possibility that diffusion of small fission gas bubbles or extended Xe-­vacancy clusters may give rise to the observed radiation-­enhanced diffusion coefficient. These studies highlight the importance of U divacancies and an octahedron coordination of uranium vacancies encompassing a Xe fission gas atom. The latter cluster can migrate via a multistep mechanism with a rather low effective barrier, which together with irradiation-induced clusters of uranium vacancies, gives rise to the irradiation-enhanced diffusion coefficient observed in experiments.« less

Release and Gas-Particle Partitioning Behaviors of Short-Chain Chlorinated Paraffins (SCCPs) During the Thermal Treatment of Polyvinyl Chloride Flooring.

PubMed

Zhan, Faqiang; Zhang, Haijun; Wang, Jing; Xu, Jiazhi; Yuan, Heping; Gao, Yuan; Su, Fan; Chen, Jiping

2017-08-15

Chlorinated paraffin (CP) mixture is a common additive in polyvinyl chloride (PVC) products as a plasticizer and flame retardant. During the PVC plastic life cycle, intentional or incidental thermal processes inevitably cause an abrupt release of short-chain CPs (SCCPs). In this study, the thermal processing of PVC plastics was simulated by heating PVC flooring at 100-200 °C in a chamber. The 1 h thermal treatment caused the release of 1.9-10.7% of the embedded SCCPs. A developed emission model indicated that SCCP release was mainly controlled by material-gas partitioning at 100 °C. However, release control tended to be subjected to material-phase diffusion above 150 °C, especially for SCCP congeners with shorter carbon-chain lengths. A cascade impactor (NanoMoudi) was used to collect particles of different sizes and gas-phase SCCPs. The elevated temperature resulted in a higher partition of SCCPs from the gas-phase to particle-phase. SCCPs were not strongly inclined to form aerosol particles by nucleation, and less present in the Aitken mode particles. Junge-Pankow adsorption model well fitted the partitioning of SCCPs between the gas-phase and accumulation mode particles. Inhalation exposure estimation indicated that PVC processing and recycling workers could face a considerably high risk for exposure to SCCPs.

Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions.

PubMed

Zhang, Jun-Jun; Lv, Li-Bing; Zhao, Tian-Jian; Lin, Yun-Xiao; Yu, Qiu-Ying; Su, Juan; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2018-05-30

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-dependent Gas-liquid Interaction in Molecular-sized Nanopores

PubMed Central

Sun, Yueting; Li, Penghui; Qiao, Yu; Li, Yibing

2014-01-01

Different from a bulk phase, a gas nanophase can have a significant effect on liquid motion. Herein we report a series of experimental results on molecular behaviors of water in a zeolite β of molecular-sized nanopores. If sufficient time is provided, the confined water molecules can be “locked” inside a nanopore; otherwise, gas nanophase provides a driving force for water “outflow”. This is due to the difficult molecular site exchanges and the relatively slow gas-liquid diffusion in the nanoenvironment. Depending on the loading rate, the zeolite β/water system may exhibit either liquid-spring or energy-absorber characteristics. PMID:25293525

Ammonia Gas Transport and Reactions in Unsaturated Sediments: Implications for Use as an Amendment to Immobilize Inorganic Contaminants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Lirong; Szecsody, James E.; Truex, Michael J.

Use of gas-phase amendments for in situ remediation of inorganic contaminants in unsaturated sediments of the vadose zone may be advantageous, but there has been limited development and testing of gas remediation technologies. Treatment with ammonia gas has been studied and has a potential for use in treating inorganic contaminants such as uranium because it induces a high pore-water pH causing mineral dissolution and subsequent formation of stable precipitates that decrease the mobility of some contaminants. For field application, knowledge of ammonia transport and the geochemical reactions induced by ammonia is needed. Laboratory studies were conducted to support calculations neededmore » for field treatment design, to quantify advective and diffusive ammonia transport in unsaturated sediments, to evaluate reactions among gas, sediment, and water, and to study reaction-induced pore-water chemistry changes as a function of ammonia delivery conditions. Ammonia gas quickly partitions into sediment pore water and increases pH up to 13.2. Injected ammonia gas front movement can be reasonably predicted by gas flow rate and equilibrium partitioning. The ammonia gas diffusion rate is a function of the water content in the sediment. Measured diffusion front movement was 0.05, 0.03, and 0.02 cm/hr. in sediments with 2.0%, 8.7%, and 13.0% water content, respectively. Sodium, aluminum, and silica pore-water concentrations increase on exposure to ammonia and then decline as aluminosilicates precipitate with declining pH. When uranium is present in the sediment and pore water, up to 85% of the water-leachable uranium was immobilized by ammonia treatment.« less

Application of ToFSIMS to Studying Surface Diffusion: Do cocaine and heroin form a two-dimensional gas on surfaces?

NASA Astrophysics Data System (ADS)

Avci, Recep; Maccagnano, Sara; Bohannan, Gary; Gresham, Gary; Groenewold, Gary

2001-03-01

Imaging time-of-flight secondary ion mass spectroscopy ( ToFSIMS) is a practical tool for studying the movement of molecules on material surfaces as a function of time. The high detection sensitivity, rapid data acquisition and reasonable spatial resolution present ideal conditions for such studies. An application of ToFSIMS is presented characterizing the diffusion of large molecules on gold-coated Si wafers. Polydimethylsiloxane (PDMS) was selected for study because it contaminates material surfaces and can be detected easily. Also, the temperature dependent diffusion properties of hydrochlorinated heroin and cocaine are presented as part of a forensic application. While the PDMS diffusion could be explained by a two-dimensional ( 2-D) Brownian motion with a Gaussian probability distribution function (pdf) with a diffusion coefficient of 1.6 μ m^2/sec, the cocaine and to a lesser extent heroin were observed to move nearly freely on the surfaces as though they were part of a 2-D gas evaporating in 2-D from a condensed phase. The results could be described reasonably well using an extreme Lévi pdf with an index of stability α<= 0.01.

Additive manufacturing of liquid/gas diffusion layers for low-cost and high-efficiency hydrogen production

DOE PAGES

Mo, Jingke; Zhang, Feng -Yuan; Dehoff, Ryan R.; ...

2016-01-14

The electron beam melting (EBM) additive manufacturing technology was used to fabricate titanium liquid/gas diffusion media with high-corrosion resistances and well-controllable multifunctional parameters, including two-phase transport and excellent electric/thermal conductivities, has been first demonstrated. Their applications in proton exchange membrane eletrolyzer cells have been explored in-situ in a cell and characterized ex-situ with SEM and XRD. Compared with the conventional woven liquid/gas diffusion layers (LGDLs), much better performance with EBM fabricated LGDLs is obtained due to their significant reduction of ohmic loss. The EBM technology components exhibited several distinguished advantages in fabricating gas diffusion layer: well-controllable pore morphology and structure,more » rapid prototyping, fast manufacturing, highly customizing and economic. In addition, by taking advantage of additive manufacturing, it possible to fabricate complicated three-dimensional designs of virtually any shape from a digital model into one single solid object faster, cheaper and easier, especially for titanium. More importantly, this development will provide LGDLs with control of pore size, pore shape, pore distribution, and therefore porosity and permeability, which will be very valuable to develop modeling and to validate simulations of electrolyzers with optimal and repeatable performance. Further, it will lead to a manufacturing solution to greatly simplify the PEMEC/fuel cell components and to couple the LGDLs with other parts, since they can be easily integrated together with this advanced manufacturing process« less

Analysis of factors affecting gas exchange in intravascular blood gas exchanger.

PubMed

Niranjan, S C; Clark, J W; San, K Y; Zwischenberger, J B; Bidani, A

1994-10-01

A mathematical model of an intravascular hollow-fiber gas-exchange device, called IVOX, has been developed using a Krogh cylinder-like approach with a repeating unit structure comprised of a single fiber with gas flowing through its lumen surrounded by a coaxial cylinder of blood flowing in the opposite direction. Species mass balances on O2 and CO2 result in a nonlinear coupled set of convective-diffusion parabolic partial differential equations that are solved numerically using an alternating-direction implicit finite-difference method. Computed results indicated the presence of a large resistance to gas transport on the external (blood) side of the hollow-fiber exchanger. Increasing gas flow through the device favored CO2 removal from but not O2 addition to blood. Increasing blood flow over the device favored both CO2 removal as well as O2 addition. The rate of CO2 removal increased linearly with the transmural PCO2 gradient imposed across the device. The effect of fiber crimping on blood phase mass transfer resistance was evaluated indirectly by varying species blood diffusivity. Computed results indicated that CO2 excretion by IVOX can be significantly enhanced with improved bulk mixing of vena caval blood around the IVOX fibers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Linyun; Mei, Zhi-Gang; Yacout, Abdellatif M.

We have developed a mesoscale phase-field model for studying the effect of recrystallization on the gas-bubble-driven swelling in irradiated U-Mo alloy fuel. The model can simulate the microstructural evolution of the intergranular gas bubbles on the grain boundaries as well as the recrystallization process. Our simulation results show that the intergranular gas-bubble-induced fuel swelling exhibits two stages: slow swelling kinetics before recrystallization and rapid swelling kinetics with recrystallization. We observe that the recrystallization can significantly expedite the formation and growth of gas bubbles at high fission densities. The reason is that the recrystallization process increases the nucleation probability of gasmore » bubbles and reduces the diffusion time of fission gases from grain interior to grain boundaries by increasing the grain boundary area and decreasing the diffusion distance. The simulated gas bubble shape, size distribution, and density on the grain boundaries are consistent with experimental measurements. We investigate the effect of the recrystallization on the gas-bubble-driven fuel swelling in UMo through varying the initial grain size and grain aspect ratio. We conclude that the initial microstructure of fuel, such as grain size and grain aspect ratio, can be used to effectively control the recrystallization and therefore reduce the swelling in U-Mo fuel.« less

Possibility of increasing the fire-suppression efficiency of the foam in automatic extinguishing installations

NASA Astrophysics Data System (ADS)

Kachanov, I. V.; Veremenyuk, V. V.; Karpenchuk, I. V.; Pavlyukov, S. Yu.

2013-05-01

The mechanics of movement of a liquid in the diffuser of the injector of an automatic extinguishing installation with preaeration of the fire-fighting substance was theoretically investigated. An integral solution of the equation for movement of the preaerated fire-fighting gas-liquid mixture in the indicated diffuser has been obtained. A mathematical model of two-phase liquid flow in this diffuser, which allows one to calculate the distribution of the average pressure in the diffuser along its length and to determine the loss in this pressure, has been developed. This model can be used for designing the output region of a hydraulic system with a hydrodynamic drag providing the operation of its injector in a definite regime.

Experimental determination of pore shapes using phase retrieval from q -space NMR diffraction

NASA Astrophysics Data System (ADS)

Demberg, Kerstin; Laun, Frederik Bernd; Bertleff, Marco; Bachert, Peter; Kuder, Tristan Anselm

2018-05-01

This paper presents an approach to solving the phase problem in nuclear magnetic resonance (NMR) diffusion pore imaging, a method that allows imaging the shape of arbitrary closed pores filled with an NMR-detectable medium for investigation of the microstructure of biological tissue and porous materials. Classical q -space imaging composed of two short diffusion-encoding gradient pulses yields, analogously to diffraction experiments, the modulus squared of the Fourier transform of the pore image which entails an inversion problem: An unambiguous reconstruction of the pore image requires both magnitude and phase. Here the phase information is recovered from the Fourier modulus by applying a phase retrieval algorithm. This allows omitting experimentally challenging phase measurements using specialized temporal gradient profiles. A combination of the hybrid input-output algorithm and the error reduction algorithm was used with dynamically adapting support (shrinkwrap extension). No a priori knowledge on the pore shape was fed to the algorithm except for a finite pore extent. The phase retrieval approach proved successful for simulated data with and without noise and was validated in phantom experiments with well-defined pores using hyperpolarized xenon gas.

Experimental determination of pore shapes using phase retrieval from q-space NMR diffraction.

PubMed

Demberg, Kerstin; Laun, Frederik Bernd; Bertleff, Marco; Bachert, Peter; Kuder, Tristan Anselm

2018-05-01

This paper presents an approach to solving the phase problem in nuclear magnetic resonance (NMR) diffusion pore imaging, a method that allows imaging the shape of arbitrary closed pores filled with an NMR-detectable medium for investigation of the microstructure of biological tissue and porous materials. Classical q-space imaging composed of two short diffusion-encoding gradient pulses yields, analogously to diffraction experiments, the modulus squared of the Fourier transform of the pore image which entails an inversion problem: An unambiguous reconstruction of the pore image requires both magnitude and phase. Here the phase information is recovered from the Fourier modulus by applying a phase retrieval algorithm. This allows omitting experimentally challenging phase measurements using specialized temporal gradient profiles. A combination of the hybrid input-output algorithm and the error reduction algorithm was used with dynamically adapting support (shrinkwrap extension). No a priori knowledge on the pore shape was fed to the algorithm except for a finite pore extent. The phase retrieval approach proved successful for simulated data with and without noise and was validated in phantom experiments with well-defined pores using hyperpolarized xenon gas.

Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

2016-06-01

Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

Photoacoustic, Photothermal, and Diffusion-Wave Sciences in the Twenty-First Century: Triumphs of the Past Set the Trends for the Future

NASA Astrophysics Data System (ADS)

Mandelis, Andreas

2012-11-01

A handful of early breakthroughs in photoacoustic science and engineering since its modern-day (scientific) renaissance in the 1970s has defined directions in the development of the photoacoustic, photothermal, and diffusion-wave fields in the past 40 years that have shaped modern day developments and have led to an impressive range of vibrant and unique technologies in the third millennium (technological renaissance). A power-point presentation on the ICPPP-16 opening plenary talk focuses on the historical roots of what I perceive to be some of today's most successful and unique technologies, while readily acknowledging the impossibility to be all inclusive. It can be found under the url: http://cadift.mie.utoronto.ca/History_of_Photoacoustics-Photothermics.ppt. The thematic areas in question include historical reviews selected among the following topics: Piezoelectric photoacoustic microscopy (PAM) which, along with early gas-phase PA spectroscopic studies of biomaterials such as blood haemoglobin and progress in the physics of photon diffusion waves, has led to the modern-day explosion in biomedical photoacoustic imaging technologies with future trends for photoacoustic and ultrasound co-registered imagers; Thermoreflectance, piezoelectric, and gas-phase PA imaging of semiconductors which, along with developments in photocarrier diffusion wave physics, led to photocarrier radiometry, nanolayer diagnostics, carrierographic imaging of optoelectronic materials, and devices with industrial trends in solar cell inspection and control; Photoacoustic gas-phase and infrared radiometric probing and scanning imaging NDE which led to lock-in thermography and have spawned industrial and biomedical technologies; Thermal-wave interferometry and the quest for thermal coherence which led to thermal-wave cavities, the thermal-wave radar, and derivative depth profiling technologies, and, very recently, thermal coherence tomography. This review is meant to be a growing public record of work in progress, with new materials in the given thematic areas and other thematic areas being added as more information on the rich history of the field becomes available. Direct inputs to the author by the broader photoacoustic, photothermal, and diffusion-wave community are solicited and strongly encouraged to ensure that all landmark and seminal work that shaped the state of the science and art in the field receives fair and deserving exposure and the historical review becomes truly representative and comprehensive.

Magnetic Fields Recorded by Chondrules Formed in Nebular Shocks

NASA Astrophysics Data System (ADS)

Mai, Chuhong; Desch, Steven J.; Boley, Aaron C.; Weiss, Benjamin P.

2018-04-01

Recent laboratory efforts have constrained the remanent magnetizations of chondrules and the magnetic field strengths to which the chondrules were exposed as they cooled below their Curie points. An outstanding question is whether the inferred paleofields represent the background magnetic field of the solar nebula or were unique to the chondrule-forming environment. We investigate the amplification of the magnetic field above background values for two proposed chondrule formation mechanisms, large-scale nebular shocks and planetary bow shocks. Behind large-scale shocks, the magnetic field parallel to the shock front is amplified by factors of ∼10–30, regardless of the magnetic diffusivity. Therefore, chondrules melted in these shocks probably recorded an amplified magnetic field. Behind planetary bow shocks, the field amplification is sensitive to the magnetic diffusivity. We compute the gas properties behind a bow shock around a 3000 km radius planetary embryo, with and without atmospheres, using hydrodynamics models. We calculate the ionization state of the hot, shocked gas, including thermionic emission from dust, thermal ionization of gas-phase potassium atoms, and the magnetic diffusivity due to Ohmic dissipation and ambipolar diffusion. We find that the diffusivity is sufficiently large that magnetic fields have already relaxed to background values in the shock downstream where chondrules acquire magnetizations, and that these locations are sufficiently far from the planetary embryos that chondrules should not have recorded a significant putative dynamo field generated on these bodies. We conclude that, if melted in planetary bow shocks, chondrules probably recorded the background nebular field.

Carbon-Based Honeycomb Monoliths for Environmental Gas-Phase Applications

PubMed Central

Moreno-Castilla, Carlos; Pérez-Cadenas, Agustín F.

2010-01-01

Honeycomb monoliths consist of a large number of parallel channels that provide high contact efficiencies between the monolith and gas flow streams. These structures are used as adsorbents or supports for catalysts when large gas volumes are treated, because they offer very low pressure drop, short diffusion lengths and no obstruction by particulate matter. Carbon-based honeycomb monoliths can be integral or carbon-coated ceramic monoliths, and they take advantage of the versatility of the surface area, pore texture and surface chemistry of carbon materials. Here, we review the preparation methods of these monoliths, their characteristics and environmental applications.

On the Relative "Transparency" of Gas-phase Coronene Molecules to Low-energy Electrons: Effects on the Interstellar Medium

NASA Astrophysics Data System (ADS)

Carelli, F.; Gianturco, F. A.

2011-12-01

Free, gas-phase polycyclic aromatic hydrocarbons (PAHs) are understood to play an important role in the interstellar medium (ISM), as they are thought to significantly contribute to both diffused and unidentified infrared interstellar bands. They are also considered fundamental blocks of the interstellar dust, whose nature has important implications for a plethora of physical and chemical nanoscopic processes within the ISM. Since free electrons represent a versatile alternative way to transport energy in the interstellar space, in this paper we compute from quantum scattering methods the angular redistributions of free electrons by gas-phase coronene molecules, the latter of which are believed to be one of the most representative PAHs, in order to assess their role in describing the efficiency of electron deflection by this molecule. The associated rates can provide useful information about the coupling mechanism between external radio-frequency fields and complex molecular plasmas containing neutral and ionized PAHs. They can also yield information on the possible presence of such species in the dust phase of the medium.

Ignition and Combustion of Bulk Metals in a Microgravity Environment

NASA Technical Reports Server (NTRS)

Branch, Melvyn C.; Daily, John W.; Abbud-Madrid, Angel

1999-01-01

Results of a study of heterogeneous and homogeneous combustion of metals in reduced gravity are presented. Cylindrical titanium and magnesium samples are radiatively ignited in pure-oxygen at 1 atm. Qualitative observations, propagation rates, and burning times are extracted from high-speed cinematography. Time-resolved emission spectra of gas-phase reactions are acquired with an imaging spectrograph. Lower propagation rates of the reacting mass on titanium and of ignition waves on magnesium are obtained at reduced gravity. These rates are compared to theoretical results from fire-spread analyses with a diffusion/convection controlled reaction. The close agreement found between experimental and theoretical propagation rates indicates the strong influence of natural-convection-enhanced oxygen transp6rt on burning rates. Lower oxygen flux and lack of condensed product removal appear to be responsible for longer burning times of magnesium gas-phase diffusion flames in reduced gravity. Spherically symmetric explosions in magnesium flames at reduced gravity (termed radiation-induced metal explosions, or RIME) may be driven by increased radiation heat transfer from accumulated condensed products to an evaporating metal core covered by a porous, flexible oxide coating. In titanium specimens, predominantly heterogeneous burning characterizes the initial steady propagation of the molten mass, while homogeneous gas-phase reactions are detected around particles ejected from the molten mixture. In magnesium specimens, band and line reversal of all the UV spectral systems of Mg and MgO are attributed to the interaction between small oxide particles and the principal gaseous emitters.

Development of an Advanced Computational Model for OMCVD of Indium Nitride

NASA Technical Reports Server (NTRS)

Cardelino, Carlos A.; Moore, Craig E.; Cardelino, Beatriz H.; Zhou, Ning; Lowry, Sam; Krishnan, Anantha; Frazier, Donald O.; Bachmann, Klaus J.

1999-01-01

An advanced computational model is being developed to predict the formation of indium nitride (InN) film from the reaction of trimethylindium (In(CH3)3) with ammonia (NH3). The components are introduced into the reactor in the gas phase within a background of molecular nitrogen (N2). Organometallic chemical vapor deposition occurs on a heated sapphire surface. The model simulates heat and mass transport with gas and surface chemistry under steady state and pulsed conditions. The development and validation of an accurate model for the interactions between the diffusion of gas phase species and surface kinetics is essential to enable the regulation of the process in order to produce a low defect material. The validation of the model will be performed in concert with a NASA-North Carolina State University project.

Nonisothermal Brownian motion: Thermophoresis as the macroscopic manifestation of thermally biased molecular motion.

PubMed

Brenner, Howard

2005-12-01

A quiescent single-component gravity-free gas subject to a small steady uniform temperature gradient T, despite being at rest, is shown to experience a drift velocity UD=-D* gradient ln T, where D* is the gas's nonisothermal self-diffusion coefficient. D* is identified as being the gas's thermometric diffusivity alpha. The latter differs from the gas's isothermal isotopic self-diffusion coefficient D, albeit only slightly. Two independent derivations are given of this drift velocity formula, one kinematical and the other dynamical, both derivations being strictly macroscopic in nature. Within modest experimental and theoretical uncertainties, this virtual drift velocity UD=-alpha gradient ln T is shown to be constitutively and phenomenologically indistinguishable from the well-known experimental and theoretical formulas for the thermophoretic velocity U of a macroscopic (i.e., non-Brownian) non-heat-conducting particle moving under the influence of a uniform temperature gradient through an otherwise quiescent single-component rarefied gas continuum at small Knudsen numbers. Coupled with the size independence of the particle's thermophoretic velocity, the empirically observed equality, U=UD, leads naturally to the hypothesis that these two velocities, the former real and the latter virtual, are, in fact, simply manifestations of the same underlying molecular phenomenon, namely the gas's Brownian movement, albeit biased by the temperature gradient. This purely hydrodynamic continuum-mechanical equality is confirmed by theoretical calculations effected at the kinetic-molecular level on the basis of an existing solution of the Boltzmann equation for a quasi-Lorentzian gas, modulo small uncertainties pertaining to the choice of collision model. Explicitly, this asymptotically valid molecular model allows the virtual drift velocity UD of the light gas and the thermophoretic velocity U of the massive, effectively non-Brownian, particle, now regarded as the tracer particle of the light gas's drift velocity, to each be identified with the Chapman-Enskog "thermal diffusion velocity" of the quasi-Lorentzian gas, here designated by the symbol UM/M, as calculated by de la Mora and Mercer. It is further pointed out that, modulo the collective uncertainties cited above, the common velocities UD,U, and UM/M are identical to the single-component gas's diffuse volume current jv, the latter representing yet another, independent, strictly continuum-mechanical concept. Finally, comments are offered on the extension of the single-component drift velocity notion to liquids, and its application towards rationalizing Soret thermal-diffusion separation phenomena in quasi-Lorentzian liquid-phase binary mixtures composed of disparately sized solute and solvent molecules, with the massive Brownian solute molecules (e.g., colloidal particles) present in disproportionately small amounts relative to that of the solvent.

The study of the Boltzmann equation of solid-gas two-phase flow with three-dimensional BGK model

NASA Astrophysics Data System (ADS)

Liu, Chang-jiang; Pang, Song; Xu, Qiang; He, Ling; Yang, Shao-peng; Qing, Yun-jie

2018-06-01

The motion of many solid-gas two-phase flows can be described by the Boltzmann equation. In order to simplify the Boltzmann equation, the convective-diffusion term is reserved and the collision term is replaced by the three-dimensional Bharnagar-Gross-Krook (BGK) model. Then the simplified Boltzmann equation is solved by homotopy perturbation method (HPM), and its approximate analytical solution is obtained. Through the analyzing, it is proved that the analytical solution satisfies all the constraint conditions, and its formation is in accord with the formation of the solution that is obtained by traditional Chapman-Enskog method, and the solving process of HPM is much more simple and convenient. This preliminarily shows the effectiveness and rapidness of HPM to solve the Boltzmann equation. The results obtained herein provide some theoretical basis for the further study of dynamic model of solid-gas two-phase flows, such as the sturzstrom of high-speed distant landslide caused by microseism and the sand storm caused by strong breeze.

Optical Absorptions of Oxygenated Carbon Chain Cations in the Gas Phase

NASA Astrophysics Data System (ADS)

Hardy, F.-X.; Rice, C. A.; Chakraborty, A.; Fulara, J.; Maier, J. P.

2016-06-01

The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the 1{}2{{{\\Pi }}}u ≤ftarrow X{}2{{{\\Pi }}}g transition of OC4O+ and the 1{}2A{}2 ≤ftarrow X{}2B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.

Gas-phase Absorptions of {{\\rm{C}}}_{42}{{\\rm{H}}}_{18}^{+} near 8300 Å below 10 K: Astronomical Implications

NASA Astrophysics Data System (ADS)

Campbell, E. K.; Maier, J. P.

2017-11-01

The gas-phase electronic spectrum of {{{C}}}42{{{H}}}18+ ({{HBC}}+) with an origin band at 8281 \\mathringA has been measured below 10 {{K}} by photofragmentation of helium complexes ({{{C}}}42{{{H}}}18+{--}{{He}}n) in a radiofrequency trap. {{HBC}}+ is a medium-sized polycyclic aromatic hydrocarbon (PAH) cation, and using an ion trapping technique it has been possible to record a high-quality gas-phase spectrum to directly compare with astronomical observations. No diffuse interstellar bands (DIBs) have been reported at the wavelengths of the strongest absorption bands in the {{{C}}}42{{{H}}}18+ spectrum. Measurement of absolute absorption cross sections in the ion trap allows upper limits to the column density of this ion to be {10}12 {{cm}}-2, indicating that even PAH cations of this size, which are believed to be stable in the interstellar medium, should be excluded as candidates for at least the strong DIBs.

Rhenium/Oxygen Interactions at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan; Myers, Dwight; Zhu, Dong-Ming; Humphrey, Donald

2000-01-01

The oxidation of pure rhenium is examined from 600-1400 C in oxygen/argon mixtures. Linear weight loss kinetics are observed. Gas pressures, flow rates, and temperatures are methodically varied to determine the rate controlling steps. The reaction at 600 and 800 C appears to be controlled by a chemical reaction step at the surface; whereas the higher temperature reactions appear to be controlled by gas phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appears to be along grain boundaries and crystallographic planes.

Modeling and Optimization for Epitaxial Growth: Transport and Growth Studies

DTIC Science & Technology

1999-01-01

effect . It is expressed as the sum of these two components j i jC i jT i where jC i and jT i denote the concentration driven and thermally driven...improve manufacturing effectiveness for epitaxial growth of silicon and silicon-germanium (Si-Ge) thin films on a silicon wafer. Growth takes place in the...non-uniformity to compensate for the effects of other phenomena such as reactant depletion, gas heating and gas phase reactions, thermal diffusion of

Galactic neutral hydrogen and the magnetic ISM foreground

NASA Astrophysics Data System (ADS)

Clark, S. E.

2018-05-01

The interstellar medium is suffused with magnetic fields, which inform the shape of structures in the diffuse gas. Recent high-dynamic range observations of Galactic neutral hydrogen, combined with novel data analysis techniques, have revealed a deep link between the morphology of neutral gas and the ambient magnetic field. At the same time, an observational revolution is underway in low-frequency radio polarimetry, driven in part by the need to characterize foregrounds to the cosmological 21-cm signal. A new generation of experiments, capable of high angular and Faraday depth resolution, are revealing complex filamentary structures in diffuse polarization. The relationship between filamentary structures observed in radio-polarimetric data and those observed in atomic hydrogen is not yet well understood. Multiwavelength observations will enable new insights into the magnetic interstellar medium across phases.

Predicting the weathering of fuel and oil spills: A diffusion-limited evaporation model.

PubMed

Kotzakoulakis, Konstantinos; George, Simon C

2018-01-01

The majority of the evaporation models currently available in the literature for the prediction of oil spill weathering do not take into account diffusion-limited mass transport and the formation of a concentration gradient in the oil phase. The altered surface concentration of the spill caused by diffusion-limited transport leads to a slower evaporation rate compared to the predictions of diffusion-agnostic evaporation models. The model presented in this study incorporates a diffusive layer in the oil phase and predicts the diffusion-limited evaporation rate. The information required is the composition of the fluid from gas chromatography or alternatively the distillation data. If the density or a single viscosity measurement is available the accuracy of the predictions is higher. Environmental conditions such as water temperature, air pressure and wind velocity are taken into account. The model was tested with synthetic mixtures, petroleum fuels and crude oils with initial viscosities ranging from 2 to 13,000 cSt. The tested temperatures varied from 0 °C to 23.4 °C and wind velocities from 0.3 to 3.8 m/s. The average absolute deviation (AAD) of the diffusion-limited model ranged between 1.62% and 24.87%. In comparison, the AAD of a diffusion-agnostic model ranged between 2.34% and 136.62% against the same tested fluids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Liquid phase diffusion bonding of A1070 by using metal formate coated Zn sheet

NASA Astrophysics Data System (ADS)

Ozawa, K.; Koyama, S.; shohji, I.

2017-05-01

Aluminium alloy have high strength and easily recycle due to its low melting point. Therefore, aluminium is widely used in the manufacturing of cars and electronic devices. In recent years, the most common way for bonding aluminium alloy is brazing and friction stir welding. However, brazing requires positional accuracy and results in the formation of voids by the flax residue. Moreover, aluminium is an excellent heat radiating and electricity conducting material; therefore, it is difficult to bond together using other bonding methods. Because of these limitations, liquid phase diffusion bonding is considered to the suitable method for bonding aluminium at low temperature and low bonding pressure. In this study, the effect of metal formate coating processing of zinc surface on the bond strength of the liquid phase diffusion bonded interface of A1070 has been investigated by SEM observation of the interfacial microstructures and fractured surfaces after tensile test. Liquid phase diffusion bonding was carried out under a nitrogen gas atmosphere at a bonding temperature of 673 K and 713 K and a bonding load of 6 MPa (bonding time: 15 min). As a result of the metal formate coating processing, a joint having the ultimate tensile strength of the base aluminium was provided. It is hypothesized that this is because metallic zinc is generated as a result of thermal decomposition of formate in the bonded interface at lower bonding temperatures.

Gas production and migration in landfills and geological materials.

PubMed

Nastev, M; Therrien, R; Lefebvre, R; Gélinas, P

2001-11-01

Landfill gas, originating from the anaerobic biodegradation of the organic content of waste, consists mainly of methane and carbon dioxide, with traces of volatile organic compounds. Pressure, concentration and temperature gradients that develop within the landfill result in gas emissions to the atmosphere and in lateral migration through the surrounding soils. Environmental and safety issues associated with the landfill gas require control of off-site gas migration. The numerical model TOUGH2-LGM (Transport of Unsaturated Groundwater and Heat-Landfill Gas Migration) has been developed to simulate landfill gas production and migration processes within and beyond landfill boundaries. The model is derived from the general non-isothermal multiphase flow simulator TOUGH2, to which a new equation of state module is added. It simulates the migration of five components in partially saturated media: four fluid components (water, atmospheric air, methane and carbon dioxide) and one energy component (heat). The four fluid components are present in both the gas and liquid phases. The model incorporates gas-liquid partitioning of all fluid components by means of dissolution and volatilization. In addition to advection in the gas and liquid phase, multi-component diffusion is simulated in the gas phase. The landfill gas production rate is proportional to the organic substrate and is modeled as an exponentially decreasing function of time. The model is applied to the Montreal's CESM landfill site, which is located in a former limestone rock quarry. Existing data were used to characterize hydraulic properties of the waste and the limestone. Gas recovery data at the site were used to define the gas production model. Simulations in one and two dimensions are presented to investigate gas production and migration in the landfill, and in the surrounding limestone. The effects of a gas recovery well and landfill cover on gas migration are also discussed.

Calibration of mass spectrometric measurements of gas phase reactions on steel surfaces

NASA Astrophysics Data System (ADS)

Falk, H.; Falk, M.; Wuttke, T.

2015-03-01

The sampling of the surface-near gas composition using a mass spectrometer (MS-Probe) is a valuable tool within a hot dip process simulator. Since reference samples with well characterized surface coverage are usually not available, steel samples can deliver quantifiable amounts of the process relevant species H2O, CO and H2 using the decarburization reaction with water vapor. Such "artificial calibration samples" (ACS) can be used for the calibration of the MS-Probe measurements. The carbon release rate, which is governed by the diffusion law, was determined by GDOES, since the diffusion coefficients of carbon in steel samples are usually not known. The measured carbon concentration profiles in the ACS after the thermal treatment confirmed the validity of the diffusion model described in this paper. The carbon bulk concentration > 100 ppm is sufficient for the use of a steel material as ACS. The experimental results reported in this paper reveal, that with the MS-Probe the LOQ of less than one monolayer of iron oxide can be achieved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lienhard, D. M.; Huisman, A. J.; Krieger, U. K.

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4HSO 4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous icemore » nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.« less

The Effects of Grain Size and Temperature Distributions on the Formation of Interstellar Ice Mantles

NASA Astrophysics Data System (ADS)

Pauly, Tyler; Garrod, Robin T.

2016-02-01

Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry of dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual grain-size population. We find that the temperature difference plays a significant role in determining the total bulk ice composition across the grain-size distribution, while the effects of geometrical differences between size populations appear marginal. We also consider collapse from a diffuse to a dark cloud, allowing dust temperatures to fall. Under the initial diffuse conditions, small grains are too warm to promote grain-mantle build-up, with most ices forming on the mid-sized grains. As collapse proceeds, the more abundant, smallest grains cool and become the dominant ice carriers; the large population of small grains means that this ice is distributed across many grains, with perhaps no more than 40 monolayers of ice each (versus several hundred assuming a single grain size). This effect may be important for the subsequent processing and desorption of the ice during the hot-core phase of star formation, exposing a significant proportion of the ice to the gas phase, increasing the importance of ice-surface chemistry and surface-gas interactions.

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 liquid injection is developed that quantifies the conditions under which classical sprays transition to dense-fluid jets. It is shown that the chamber pressure required to support diffusion-dominated mixing dynamics depends on the composition and temperature of the injected liquid and ambient gas. To illustrate the method and analysis, we use conditions typical of diesel engine injection. We also present a companion set of high-speed images to provide experimental validation of the presented theory. The basic theory is quite general and applies to a wide range of modern propulsion and power systems such as liquid rockets, gas turbines, and reciprocating engines. Interestingly, the regime diagram associated with diesel engine injection suggests that classical spray phenomena at typical injection conditions do not occur.

Phase behavior of casein micelles/exocellular polysaccharide mixtures: Experiment and theory

NASA Astrophysics Data System (ADS)

Tuinier, R.; de Kruif, C. G.

1999-05-01

Dispersions of casein micelles and an exocellular polysaccharide (EPS), obtained from Lactococcus lactis subsp. cremoris NIZO B40 EPS, show a phase separation. The phase separation is of the colloidal gas-liquid type. We have determined a phase diagram that describes the separation of skim milk with EPS into a casein-micelle rich phase and an EPS rich phase. We compare the phase diagram with those calculated from theories developed by Vrij, and by Lekkerkerker and co-workers, showing that the experimental phase boundary can be predicted quite well. From dynamic light scattering measurements of the self-diffusion of the casein micelles in the presence of EPS the spinodal could be located and it corresponds with the experimental phase boundary.

Chemical vapour deposition growth of carbon nanotube forests: kinetics, morphology, composition, and their mechanisms

NASA Astrophysics Data System (ADS)

Vinten, Phillip

This thesis analyzes the chemical vapour deposition (CVD) growth of vertically aligned carbon nanotube (CNT) forests in order to understand how CNT forests grow, why they stop growing, and how to control the properties of the synthesized CNTs. in situ kinetics data of the growth of CNT forests are gathered by in situ optical microscopy. The overall morphology of the forests and the characteristics of the individual CNTs in the forests are investigated using scanning electron microscopy and Raman spectroscopy. The in situ data show that forest growth and termination are activated processes (with activation energies on the order of 1 eV), suggesting a possible chemical origin. The activation energy changes at a critical temperature for ethanol CVD (approximately 870°C). These activation energies and critical temperature are also seen in the temperature dependence of several important characteristics of the CNTs, including the defect density as determined by Raman spectroscopy. This observation is seen across several CVD processes and suggests a mechanism of defect healing. The CNT diameter also depends on the growth temperature. In this thesis, a thermodynamic model is proposed. This model predicts a temperature and pressure dependence of the CNT diameter from the thermodynamics of the synthesis reaction and the effect of strain on the enthalpy of formation of CNTs. The forest morphology suggests significant interaction between the constituent CNTs. These interactions may play a role in termination. The morphology, in particular a microscale rippling feature that is capable of diffracting light, suggest a non-uniform growth rate across the forest. A gas phase diffusion model predicts a non-uniform distribution of the source gas. This gas phase diffusion is suggested as a possible explanation for the non-uniform growth rate. The gas phase diffusion is important because growth by acetylene CVD is found to be very efficient (approximately 30% of the acetylene is converted to CNTs). It is seen that multiple mechanisms are active during CNT growth. The results of this thesis provide insight into both the basic understanding of the microscopic processes involved in CVD growth and how to control the properties of the synthesized CNTs.

Investigating the Effectiveness of Computer Simulations for Chemistry Learning

ERIC Educational Resources Information Center

Plass, Jan L.; Milne, Catherine; Homer, Bruce D.; Schwartz, Ruth N.; Hayward, Elizabeth O.; Jordan, Trace; Verkuilen, Jay; Ng, Florrie; Wang, Yan; Barrientos, Juan

2012-01-01

Are well-designed computer simulations an effective tool to support student understanding of complex concepts in chemistry when integrated into high school science classrooms? We investigated scaling up the use of a sequence of simulations of kinetic molecular theory and associated topics of diffusion, gas laws, and phase change, which we designed…

High temperature gas nitriding and tempering in 17Cr-1Ni-0.5C-0.4V steel

NASA Astrophysics Data System (ADS)

Kong, J. H.; Lee, D. J.; On, H. Y.; Park, S. J.; Kim, S. K.; Kang, C. Y.; Sung, J. H.; Lee, H. W.

2010-12-01

High temperature gas nitriding (HTGN) at 1050 °C and tempering of a 17Cr-1Ni-0.5C-0.4V (CNV) steel were experimentally investigated. The phases appearing in the surface layer of the HTGN-treated steel were martensite and austenite with mostly Cr2N precipitates that were formed by permeated nitrogen, and a small amount of Cr23C6 and VN precipitates. The reverse migration of carbon hindered the diffusion of nitrogen when nitrogen permeated from the surface to the interior, which resulted in the accumulation of nitrogen on the outermost surface. The strong affinity between nitrogen and chromium atoms induced the diffusion of chromium from the interior to the surface, leading to the substitution of Cr23C6 for Cr2N. After tempering the HTGN-treated steel at 500 °C, the dense precipitates of Cr2N and the increased martensite phase in the surface layer led to secondary hardening, which increased the hardness value up to 901 Hv.

Reduction Kinetics of Wüstite Scale on Pure Iron and Steel Sheets in Ar and H2 Gas Mixture

NASA Astrophysics Data System (ADS)

Mao, Weichen; Sloof, Willem G.

2017-10-01

A dense and closed Wüstite scale is formed on pure iron and Mn alloyed steel after oxidation in Ar + 33 vol pct CO2 + 17 vol pct CO gas mixture. Reducing the Wüstite scale in Ar + H2 gas mixture forms a dense and uniform iron layer on top of the remaining Wüstite scale, which separates the unreduced scale from the gas mixture. The reduction of Wüstite is controlled by the bulk diffusion of dissolved oxygen in the formed iron layer and follows parabolic growth rate law. The reduction kinetics of Wüstite formed on pure iron and on Mn alloyed steel are the same. The parabolic rate constant of Wüstite reduction obeys an Arrhenius relation with an activation energy of 104 kJ/mol if the formed iron layer is in the ferrite phase. However, at 1223 K (950 °C) the parabolic rate constant of Wüstite reduction drops due to the phase transformation of the iron layer from ferrite to austenite. The effect of oxygen partial pressure on the parabolic rate constant of Wüstite reduction is negligible when reducing in a gas mixture with a dew point below 283 K (10 °C). During oxidation of the Mn alloyed steel, Mn is dissolved in the Wüstite scale. Subsequently, during reduction of the Wüstite layer, Mn diffuses into the unreduced Wüstite. Ultimately, an oxide-free iron layer is obtained at the surface of the Mn alloyed steel, which is beneficial for coating application.

Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

DOE PAGES

Lienhard, D. M.; Huisman, A. J.; Krieger, U. K.; ...

2015-01-01

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4HSO 4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous icemore » nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.« less

Hydrodynamic effects on phase separation morphologies in evaporating thin films of polymer solutions

NASA Astrophysics Data System (ADS)

Zoumpouli, Garyfalia A.; Yiantsios, Stergios G.

2016-08-01

We examine effects of hydrodynamics on phase separation morphologies developed during drying of thin films containing a volatile solvent and two dissolved polymers. Cahn-Hilliard and Flory-Huggins theories are used to describe the free energy of the phase separating systems. The thin films, considered as Newtonian fluids, flow in response to Korteweg stresses arising due to concentration non-uniformities that develop during solvent evaporation. Numerical simulations are employed to investigate the effects of a Peclet number, defined in terms of system physical properties, as well as the effects of parameters characterizing the speed of evaporation and preferential wetting of the solutes at the gas interface. For systems exhibiting preferential wetting, diffusion alone is known to favor lamellar configurations for the separated phases in the dried film. However, a mechanism of hydrodynamic instability of a short length scale is revealed, which beyond a threshold Peclet number may deform and break the lamellae. The critical Peclet number tends to decrease as the evaporation rate increases and to increase with the tendency of the polymers to selectively wet the gas interface. As the Peclet number increases, the instability moves closer to the gas interface and induces the formation of a lateral segregation template that guides the subsequent evolution of the phase separation process. On the other hand, for systems with no preferential wetting or any other property asymmetries between the two polymers, diffusion alone favors the formation of laterally separated configurations. In this case, concentration perturbation modes that lead to enhanced Korteweg stresses may be favored for sufficiently large Peclet numbers. For such modes, a second mechanism is revealed, which is similar to the solutocapillary Marangoni instability observed in evaporating solutions when interfacial tension increases with the concentration of the non-volatile component. This mechanism may lead to multiple length scales in the laterally phase separated configurations.

The Impact of Diffuse Ionized Gas on Emission-line Ratios and Gas Metallicity Measurements

NASA Astrophysics Data System (ADS)

Zhang, Kai; Yan, Renbin; MaNGA Team

2016-01-01

Diffuse Ionized Gas (DIG) is prevalent in star-forming galaxies. Using a sample of galaxies observed by MaNGA, we demonstrate how DIG in star-forming galaxies impact the measurements of emission line ratios, hence the gas-phase metallicity measurements and the interpretation of diagnostic diagrams. We demonstrate that emission line surface brightness (SB) is a reasonably good proxy to separate HII regions from regions dominated by diffuse ionized gas. For spatially-adjacent regions or regions at the same radius, many line ratios change systematically with emission line surface brightness, reflecting a gradual increase of dominance by DIG towards low SB. DIG could significantly bias the measurement of gas metallicity and metallicity gradient. Because DIG tend to have a higher temperature than HII regions, at fixed metallicity DIG displays lower [NII]/[OII] ratios. DIG also show lower [OIII]/[OII] ratios than HII regions, due to extended partially-ionized regions that enhance all low-ionization lines ([NII], [SII], [OII], [OI]). The contamination by DIG is responsible for a substantial portion of the scatter in metallicity measurements. At different surface brightness, line ratios and line ratio gradients can differ systematically. As DIG fraction could change with radius, it can affect the metallicity gradient measurements in systematic ways. The three commonly used strong-line metallicity indicators, R23, [NII]/[OII], O3N2, are all affected in different ways. To make robust metallicity gradient measurements, one has to properly isolate HII regions and correct for DIG contamination. In line ratio diagnostic diagrams, contamination by DIG moves HII regions towards composite or LINER-like regions.

Infrared gas phase study on plasma-polymer interactions in high-current diffuse dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Liu, Y.; Welzel, S.; Starostin, S. A.; van de Sanden, M. C. M.; Engeln, R.; de Vries, H. W.

2017-06-01

A roll-to-roll high-current diffuse dielectric barrier discharge at atmospheric pressure was operated in air and Ar/N2/O2 gas mixtures. The exhaust gas from the discharge was studied using a high-resolution Fourier-transform infrared spectrometer in the range from 3000 to 750 cm-1 to unravel the plasma-polymer interactions. The absorption features of HxNyOz, COx, and HCOOH (formic acid) were identified, and the relative densities were deduced by fitting the absorption bands of the detected molecules. Strong interactions between plasma and polymer (Polyethylene-2,6-naphthalate, or PEN) in precursor-free oxygen-containing gas mixtures were observed as evidenced by a high COx production. The presence of HCOOH in the gas effluent, formed through plasma-chemical synthesis of COx, turns out to be a sensitive indicator for etching. By adding tetraethylorthosilicate precursor in the plasma, dramatic changes in the COx production were measured, and two distinct deposition regimes were identified. At high precursor flows, a good agreement with the precursor combustion and the COx production was observed, whereas at low precursor flows an etching-deposition regime transpires, and the COx production is dominated by polymer etching.

Observation of the Leggett-Rice Effect in a Unitary Fermi Gas

NASA Astrophysics Data System (ADS)

Trotzky, S.; Beattie, S.; Luciuk, C.; Smale, S.; Bardon, A. B.; Enss, T.; Taylor, E.; Zhang, S.; Thywissen, J. H.

2015-01-01

We observe that the diffusive spin current in a strongly interacting degenerate Fermi gas of 40K precesses about the local magnetization. As predicted by Leggett and Rice, precession is observed both in the Ramsey phase of a spin-echo sequence, and in the nonlinearity of the magnetization decay. At unitarity, we measure a Leggett-Rice parameter γ =1.08 (9 ) and a bare transverse spin diffusivity D0⊥=2.3 (4 )ℏ/m for a normal-state gas initialized with full polarization and at one-fifth of the Fermi temperature, where m is the atomic mass. One might expect γ =0 at unitarity, where two-body scattering is purely dissipative. We observe γ →0 as temperature is increased towards the Fermi temperature, consistent with calculations that show the degenerate Fermi sea restores a nonzero γ . Tuning the scattering length a , we find that a sign change in γ occurs in the range 0 <(kFa )-1≲1.3 , where kF is the Fermi momentum. We discuss how γ reveals the effective interaction strength of the gas, such that the sign change in γ indicates a switching of branch between a repulsive and an attractive Fermi gas.

Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F-, Cl-, and Br-.

PubMed

Trumm, Michael; Martínez, Yansel Omar Guerrero; Réal, Florent; Masella, Michel; Vallet, Valérie; Schimmelpfennig, Bernd

2012-01-28

In this work, we investigate the hydration of the halide ions fluoride, chloride, and bromide using classical molecular dynamics simulations at the 10 ns scale and based on a polarizable force-field approach, which treats explicitly the cooperative bond character of strong hydrogen bond networks. We have carried out a thorough analysis of the ab initio data at the MP2 or CCSD(T) level concerning anion/water clusters in gas phase to adjust the force-field parameters. In particular, we consider the anion static polarizabilities computed in gas phase using large atomic basis sets including additional diffuse functions. The information extracted from trajectories in solution shows well structured first hydration shells formed of 6.7, 7.0, and 7.6 water molecules at about 2.78 Å, 3.15 Å, and 3.36 Å for fluoride, chloride, and bromide, respectively. These results are in excellent agreement with the latest neutron- and x-ray diffraction studies. In addition, our model reproduces several other properties of halide ions in solution, such as diffusion coefficients, description of hydration processes, and exchange reactions. Moreover, it is also able to reproduce the electrostatic properties of the anions in solution (in terms of anion dipole moment) as reported by recent ab initio quantum simulations. All the results show the ability of the proposed model in predicting data, as well as the need of accounting explicitly for the cooperative character of strong hydrogen bonds to reproduce ab initio potential energy surfaces in a mean square sense and to build up a reliable force field. © 2012 American Institute of Physics

Atmospheric pressure flow reactor: Gas phase chemical kinetics under tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L. (Inventor); Davis, Dennis D. (Inventor)

1991-01-01

A flow reactor for simulating the interaction in the troposphere is set forth. A first reactant mixed with a carrier gas is delivered from a pump and flows through a duct having louvers therein. The louvers straighten out the flow, reduce turbulence and provide laminar flow discharge from the duct. A second reactant delivered from a source through a pump is input into the flowing stream, the second reactant being diffused through a plurality of small diffusion tubes to avoid disturbing the laminar flow. The commingled first and second reactants in the carrier gas are then directed along an elongated duct where the walls are spaced away from the flow of reactants to avoid wall interference, disturbance or turbulence arising from the walls. A probe connected with a measuring device can be inserted through various sampling ports in the second duct to complete measurements of the first and second reactants and the product of their reaction at selected XYZ locations relative to the flowing system.

Water Transport in the Micro Porous Layer and Gas Diffusion Layer of a Polymer Electrolyte Fuel Cell

NASA Astrophysics Data System (ADS)

Qin, C.; Hassanizadeh, S. M.

2015-12-01

In this work, a recently developed dynamic pore-network model is presented [1]. The model explicitly solves for both water pressure and capillary pressure. A semi-implicit scheme is used in updating water saturation in each pore body, which considerably increases the numerical stability at low capillary number values. Furthermore, a multiple-time-step algorithm is introduced to reduce the computational effort. A number of case studies of water transport in the micro porous layer (MPL) and gas diffusion layer (GDL) are conducted. We illustrate the role of MPL in reducing water flooding in the GDL. Also, the dynamic water transport through the MPL-GDL interface is explored in detail. This information is essential to the reduced continua model (RCM), which was developed for multiphase flow through thin porous layers [2, 3]. C.Z. Qin, Water transport in the gas diffusion layer of a polymer electrolyte fuel cell: dynamic pore-network modeling, J Electrochimical. Soci., 162, F1036-F1046, 2015. C.Z. Qin and S.M. Hassanizadeh, Multiphase flow through multilayers of thin porous media: general balance equations and constitutive relationships for a solid-gas-liquid three-phase system, Int. J. Heat Mass Transfer, 70, 693-708, 2014. C.Z. Qin and S.M. Hassanizadeh, A new approach to modeling water flooding in a polymer electrolyte fuel cell, Int. J. Hydrogen Energy, 40, 3348-3358, 2015.

Experimental advances and preliminary mathematical modeling of the Swiss-roll mixed-reactant direct borohydride fuel cell

NASA Astrophysics Data System (ADS)

Aziznia, Amin; Oloman, Colin W.; Gyenge, Előd L.

2014-11-01

The Swiss-roll single-cell mixed reactant (SR-MRFC) borohydride - oxygen fuel cell equipped with Pt/carbon cloth 3D anode and either MnO2 or Ag gas-diffusion cathodes is investigated by a combination of experimental studies and preliminary mathematical modeling of the polarization curve. We investigate the effects of four variables: cathode side metallic mesh fluid distributor, separator type (Nafion 112® vs. Viledon®), cathode catalyst (MnO2 vs. Ag), and the hydrophilic pore volume fraction of the gas-diffusion cathode. Using a two-phase feed of alkaline borohydride solution (1 M NaBH4 - 2 M NaOH) and O2 gas in an SR-MRFC equipped with Pt/C 3D anode, MnO2 gas diffusion cathode, Viledon® porous diaphragm, expanded mesh cathode-side fluid distributor, the maximum superficial power density is 2230 W m-2 at 323 K and 105 kPa(abs). The latter superficial power density is almost 3.5 times higher than our previously reported superficial power density for the same catalyst combinations. Furthermore, with a Pt anode and Ag cathode catalyst combination, a superficial power density of 2500 W m-2 is achieved with superior performance durability compared to the MnO2 cathode. The fuel cell results are substantiated by impedance spectroscopy analysis and preliminary mathematical model predictions based on mixed potential theory.

Density PDFs of diffuse gas in the Milky Way

NASA Astrophysics Data System (ADS)

Berkhuijsen, E. M.; Fletcher, A.

2012-09-01

The probability distribution functions (PDFs) of the average densities of the diffuse ionized gas (DIG) and the diffuse atomic gas are close to lognormal, especially when lines of sight at |b| < 5∘ and |b|≥ 5∘ are considered separately. Our results provide strong support for the existence of a lognormal density PDF in the diffuse ISM, consistent with a turbulent origin of density structure in the diffuse gas.

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions.

PubMed

Tillman, Fred D; Smith, James A

2004-11-01

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.

Effects of Lewis Number on Temperatures of Spherical Diffusion Flames

NASA Technical Reports Server (NTRS)

Santa, K. J.; Sun, Z.; Chao, B. H.; Sunderland, P. B.; Axelbaum, R. I.; Urban, D. L.; Stocker, D. P.

2007-01-01

Spherical diffusion flames supported on a porous sphere were studied numerically and experimentally. Experiments were performed in 2.2 s and 5.2 s microgravity facilities. Numerical results were obtained from a Chemkin-based program. The program simulates flow from a porous sphere into a quiescent environment, yields both steady-state and transient results, and accounts for optically thick gas-phase radiation. The low flow velocities and long residence times in these diffusion flames lead to enhanced radiative and diffusive effects. Despite similar adiabatic flame temperatures, the measured and predicted temperatures varied by as much as 700 K. The temperature reduction correlates with flame size but characteristic flow times and, importantly, Lewis number also influence temperature. The numerical results show that the ambient gas Lewis number would have a strong effect on flame temperature if the flames were steady and nonradiating. For example, a 10% decrease in Lewis number would increase the steady-state flame temperature by 200 K. However, for these transient, radiating flames the effect of Lewis number is small. Transient predictions of flame sizes are larger than those observed in microgravity experiments. Close agreement could not be obtained without either increasing the model s thermal and mass diffusion properties by 30% or reducing mass flow rate by 25%.

Stochastic algorithm for simulating gas transport coefficients

NASA Astrophysics Data System (ADS)

Rudyak, V. Ya.; Lezhnev, E. V.

2018-02-01

The aim of this paper is to create a molecular algorithm for modeling the transport processes in gases that will be more efficient than molecular dynamics method. To this end, the dynamics of molecules are modeled stochastically. In a rarefied gas, it is sufficient to consider the evolution of molecules only in the velocity space, whereas for a dense gas it is necessary to model the dynamics of molecules also in the physical space. Adequate integral characteristics of the studied system are obtained by averaging over a sufficiently large number of independent phase trajectories. The efficiency of the proposed algorithm was demonstrated by modeling the coefficients of self-diffusion and the viscosity of several gases. It was shown that the accuracy comparable to the experimental one can be obtained on a relatively small number of molecules. The modeling accuracy increases with the growth of used number of molecules and phase trajectories.

Spin-Hall effect and emergent antiferromagnetic phase transition in n-Si

NASA Astrophysics Data System (ADS)

Lou, Paul C.; Kumar, Sandeep

2018-04-01

Spin current experiences minimal dephasing and scattering in Si due to small spin-orbit coupling and spin-lattice interactions is the primary source of spin relaxation. We hypothesize that if the specimen dimension is of the same order as the spin diffusion length then spin polarization will lead to non-equilibrium spin accumulation and emergent phase transition. In n-Si, spin diffusion length has been reported up to 6 μm. The spin accumulation in Si will modify the thermal transport behavior of Si, which can be detected with thermal characterization. In this study, we report observation of spin-Hall effect and emergent antiferromagnetic phase transition behavior using magneto-electro-thermal transport characterization. The freestanding Pd (1 nm)/Ni80Fe20 (75 nm)/MgO (1 nm)/n-Si (2 μm) thin film specimen exhibits a magnetic field dependent thermal transport and spin-Hall magnetoresistance behavior attributed to Rashba effect. An emergent phase transition is discovered using self-heating 3ω method, which shows a diverging behavior at 270 K as a function of temperature similar to a second order phase transition. We propose that spin-Hall effect leads to the spin accumulation and resulting emergent antiferromagnetic phase transition. We propose that the length scale for Rashba effect can be equal to the spin diffusion length and two-dimensional electron gas is not essential for it. The emergent antiferromagnetic phase transition is attributed to the site inversion asymmetry in diamond cubic Si lattice.

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations

DOE PAGES

Ji, Ho-Il; Davenport, Timothy C.; Gopal, Chirranjeevi Balaji; ...

2016-07-18

The redox kinetics of undoped ceria (CeO 2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO 2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant k chem is found to obey the correlation log(k chem/cm s -1) = (0.84 ± 0.02) × log(pO 2/atm) - (0.99 ± 0.05) and increases withmore » oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.« less

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations.

PubMed

Ji, Ho-Il; Davenport, Timothy C; Gopal, Chirranjeevi Balaji; Haile, Sossina M

2016-08-03

The redox kinetics of undoped ceria (CeO2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant kchem is found to obey the correlation log(kchem/cm s(-1)) = (0.84 ± 0.02) × log(pO2/atm) - (0.99 ± 0.05) and increases with oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.

Diffusion of CO2 in Large Crystals of Cu-BTC MOF.

PubMed

Tovar, Trenton M; Zhao, Junjie; Nunn, William T; Barton, Heather F; Peterson, Gregory W; Parsons, Gregory N; LeVan, M Douglas

2016-09-14

Carbon dioxide adsorption in metal-organic frameworks has been widely studied for applications in carbon capture and sequestration. A critical component that has been largely overlooked is the measurement of diffusion rates. This paper describes a new reproducible procedure to synthesize millimeter-scale Cu-BTC single crystals using concentrated reactants and an acetic acid modulator. Microscopic images, X-ray diffraction patterns, Brunauer-Emmett-Teller surface areas, and thermogravimetric analysis results all confirm the high quality of these Cu-BTC single crystals. The large crystal size aids in the accurate measurement of micropore diffusion coefficients. Concentration-swing frequency response performed at varying gas-phase concentrations gives diffusion coefficients that show very little dependence on the loading up to pressures of 0.1 bar. The measured micropore diffusion coefficient for CO2 in Cu-BTC is 1.7 × 10(-9) m(2)/s.

An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard; Liu, Yun

2013-01-01

Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

Diffusion Driven Combustion Waves in Porous Media

NASA Technical Reports Server (NTRS)

Aldushin, A. P.; Matkowsky, B. J.

2000-01-01

Filtration of gas containing oxidizer, to the reaction zone in a porous medium, due, e.g., to a buoyancy force or to an external pressure gradient, leads to the propagation of Filtration combustion (FC) waves. The exothermic reaction occurs between the fuel component of the solid matrix and the oxidizer. In this paper, we analyze the ability of a reaction wave to propagate in a porous medium without the aid of filtration. We find that one possible mechanism of propagation is that the wave is driven by diffusion of oxidizer from the environment. The solution of the combustion problem describing diffusion driven waves is similar to the solution of the Stefan problem describing the propagation of phase transition waves, in that the temperature on the interface between the burned and unburned regions is constant, the combustion wave is described by a similarity solution which is a function of the similarity variable x/square root of(t) and the wave velocity decays as 1/square root of(t). The difference between the two problems is that in the combustion problem the temperature is not prescribed, but rather, is determined as part of the solution. We will show that the length of samples in which such self-sustained combustion waves can occur, must exceed a critical value which strongly depends on the combustion temperature T(sub b). Smaller values of T(sub b) require longer sample lengths for diffusion driven combustion waves to exist. Because of their relatively small velocity, diffusion driven waves are considered to be relevant for the case of low heat losses, which occur for large diameter samples or in microgravity conditions, Another possible mechanism of porous medium combustion describes waves which propagate by consuming the oxidizer initially stored in the pores of the sample. This occurs for abnormally high pressure and gas density. In this case, uniformly propagating planar waves, which are kinetically controlled, can propagate, Diffusion of oxidizer decreases the wave velocity. In addition to the reaction and diffusion layers, the uniformly propagating wave structure includes a layer with a pressure gradient, where the gas motion is induced by the production or consumption of the gas in the reaction as well as by thermal expansion of the gas. The width of this zone determines the scale of the combustion wave in the porous medium.

Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami’s law

NASA Astrophysics Data System (ADS)

Frank, Stefan; Rikvold, Per Arne

2006-06-01

The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov, Johnson and Mehl, and Avrami (KJMA), which we extend to an exponentially decaying nucleation rate. Such a decay may occur due to a suppression of nucleation around existing clusters in the presence of lateral adsorbate diffusion. Correlation functions prove the existence of such exclusion zones. By comparison with microscopic results for the nucleation rate I and the interface velocity of the growing clusters v, we can show that the KJMA theory yields the correct order of magnitude for Iv2. This is true even though the spatial correlations mediated by diffusion are neglected. The decaying nucleation rate causes a gradual crossover from continuous to instantaneous nucleation, which is complete when the decay of the nucleation rate is very fast on the time scale of the phase transformation. Hence, instantaneous nucleation can be homogeneous, producing negative minima in the two-point correlation functions. We also present in this paper an n-fold way Monte Carlo algorithm for a square lattice gas with adsorption/desorption and lateral diffusion.

Pattern formation for NO+N H3 on Pt(100): Two-dimensional numerical results

NASA Astrophysics Data System (ADS)

Uecker, Hannes

2005-01-01

The Lombardo-Fink-Imbihl model of the NO+NH3 reaction on a Pt(100) surface consists of seven coupled ordinary differential equations (ODE) and shows stable relaxation oscillations with sharp transitions in the relevant temperature range. Here we study numerically the effect of coupling of these oscillators by surface diffusion in two dimensions. We find different types of patterns, in particular phase clusters and standing waves. In models of related surface reactions such clustered solutions are known to exist only under a global coupling through the gas phase. This global coupling is replaced here by relatively fast diffusion of two variables which are kinetically slaved in the ODE. We also compare our simulations with experimental results and discuss some shortcomings of the model.

Ge auto-doping and out-diffusion in InGaP grown on Ge substrate and their effects on the ordering of InGaP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hong-Ming; Ho, Hao-I; Tsai, Shi-Jane

2016-03-21

We report on the Ge auto-doping and out-diffusion in InGaP epilayer with Cu-Pt ordering grown on 4-in. Ge substrate. Ge profiles determined from secondary ion mass spectrometry indicate that the Ge out-diffusion depth is within 100 nm. However, the edge of the wafer suffers from stronger Ge gas-phase auto-doping than the center, leading to ordering deterioration in the InGaP epilayer. In the edge, we observed a residual Cu-Pt ordering layer left beneath the surface, suggesting that the ordering deterioration takes place after the deposition rather than during the deposition and In/Ga inter-diffusion enhanced by Ge vapor-phase auto-doping is responsible for themore » deterioration. We thus propose a di-vacancy diffusion model, in which the amphoteric Ge increases the di-vacancy density, resulting in a Ge density dependent diffusion. In the model, the In/Ga inter-diffusion and Ge out-diffusion are realized by the random hopping of In/Ga host atoms and Ge atoms to di-vacancies, respectively. Simulation based on this model well fits the Ge out-diffusion profiles, suggesting its validity. By comparing the Ge diffusion coefficient obtained from the fitting and the characteristic time constant of ordering deterioration estimated from the residual ordering layer, we found that the hopping rates of Ge and the host atoms are in the same order of magnitude, indicating that di-vacancies are bound in the vicinity of Ge atoms.« less

Identifying Methane Sources in Groundwater; Quantifying Changes in Compositional and Stable Isotope Values during Multiphase Transport

NASA Astrophysics Data System (ADS)

Larson, T.; Sathaye, K.

2014-12-01

A dramatic expansion of hydraulic fracturing and horizontal drilling for natural gas in unconventional reserves is underway. This expansion is fueling considerable public concern, however, that extracted natural gas, reservoir brines and associated fracking fluids may infiltrate to and contaminate shallower (< 500m depth) groundwater reservoirs, thereby posing a health threat. Attributing methane found in shallow groundwater to either deep thermogenic 'fracking' operations or locally-derived shallow microbial sources utilizes geochemical methods including alkane wetness and stable carbon and hydrogen isotope ratios of short chain (C1-C5) hydrocarbons. Compared to shallow microbial gas, thermogenic gas is wetter and falls within a different range of δ13C and δD values. What is not clear, however, is how the transport of natural gas through water saturated geological media may affect its compositional and stable isotope values. What is needed is a means to differentiate potential flow paths of natural gas including 'fast paths' along preexisting fractures and drill casings vs. 'slow paths' through low permeability rocks. In this study we attempt quantify transport-related effects using experimental 1-dimensional two-phase column experiments and analytical solutions to multi-phase gas injection equations. Two-phase experimental results for an injection of natural gas into a water saturated column packed with crushed illite show that the natural gas becomes enriched in methane compared to ethane and propane during transport. Carbon isotope measurements are ongoing. Results from the multi-phase gas injection equations that include methane isotopologue solubility and diffusion effects predict the development of a 'bank' of methane depleted in 13C relative to 12C at the front of a plume of fugitive natural gas. These results, therefore, suggest that transport of natural gas through water saturated geological media may complicate attribution methods needed to distinguish thermogenic and microbial methane.

Narrow groove welding gas diffuser assembly and welding torch

DOEpatents

Rooney, Stephen J.

2001-01-01

A diffuser assembly is provided for narrow groove welding using an automatic gas tungsten arc welding torch. The diffuser assembly includes a manifold adapted for adjustable mounting on the welding torch which is received in a central opening in the manifold. Laterally extending manifold sections communicate with a shield gas inlet such that shield gas supplied to the inlet passes to gas passages of the manifold sections. First and second tapered diffusers are respectively connected to the manifold sections in fluid communication with the gas passages thereof. The diffusers extend downwardly along the torch electrode on opposite sides thereof so as to release shield gas along the length of the electrode and at the distal tip of the electrode. The diffusers are of a transverse width which is on the order of the thickness of the electrode so that the diffusers can, in use, be inserted into a narrow welding groove before and after the electrode in the direction of the weld operation.

Effect of Soret diffusion on lean hydrogen/air flames at normal and elevated pressure and temperature

NASA Astrophysics Data System (ADS)

Zhou, Zhen; Hernández-Pérez, Francisco E.; Shoshin, Yuriy; van Oijen, Jeroen A.; de Goey, Laurentius P. H.

2017-09-01

The influence of Soret diffusion on lean premixed flames propagating in hydrogen/air mixtures is numerically investigated with a detailed chemical and transport models at normal and elevated pressure and temperature. The Soret diffusion influence on the one-dimensional (1D) flame mass burning rate and two-dimensional (2D) flame propagating characteristics is analysed, revealing a strong dependency on flame stretch rate, pressure and temperature. For 1D flames, at normal pressure and temperature, with an increase of Karlovitz number from 0 to 0.4, the mass burning rate is first reduced and then enhanced by Soret diffusion of H2 while it is reduced by Soret diffusion of H. The influence of Soret diffusion of H2 is enhanced by pressure and reduced by temperature. On the contrary, the influence of Soret diffusion of H is reduced by pressure and enhanced by temperature. For 2D flames, at normal pressure and temperature, during the early phase of flame evolution, flames with Soret diffusion display more curved flame cells. Pressure enhances this effect, while temperature reduces it. The influence of Soret diffusion of H2 on the global consumption speed is enhanced at elevated pressure. The influence of Soret diffusion of H on the global consumption speed is enhanced at elevated temperature. The flame evolution is more affected by Soret diffusion in the early phase of propagation than in the long run due to the local enrichment of H2 caused by flame curvature effects. The present study provides new insights into the Soret diffusion effect on the characteristics of lean hydrogen/air flames at conditions that are relevant to practical applications, e.g. gas engines and turbines.

Fractal Model of Fission Product Release in Nuclear Fuel

NASA Astrophysics Data System (ADS)

Stankunas, Gediminas

2012-09-01

A model of fission gas migration in nuclear fuel pellet is proposed. Diffusion process of fission gas in granular structure of nuclear fuel with presence of inter-granular bubbles in the fuel matrix is simulated by fractional diffusion model. The Grunwald-Letnikov derivative parameter characterizes the influence of porous fuel matrix on the diffusion process of fission gas. A finite-difference method for solving fractional diffusion equations is considered. Numerical solution of diffusion equation shows correlation of fission gas release and Grunwald-Letnikov derivative parameter. Calculated profile of fission gas concentration distribution is similar to that obtained in the experimental studies. Diffusion of fission gas is modeled for real RBMK-1500 fuel operation conditions. A functional dependence of Grunwald-Letnikov derivative parameter with fuel burn-up is established.

Assessment of water droplet evaporation mechanisms on hydrophobic and superhydrophobic substrates.

PubMed

Pan, Zhenhai; Dash, Susmita; Weibel, Justin A; Garimella, Suresh V

2013-12-23

Evaporation rates are predicted and important transport mechanisms identified for evaporation of water droplets on hydrophobic (contact angle ~110°) and superhydrophobic (contact angle ~160°) substrates. Analytical models for droplet evaporation in the literature are usually simplified to include only vapor diffusion in the gas domain, and the system is assumed to be isothermal. In the comprehensive model developed in this study, evaporative cooling of the interface is accounted for, and vapor concentration is coupled to local temperature at the interface. Conjugate heat and mass transfer are solved in the solid substrate, liquid droplet, and surrounding gas. Buoyancy-driven convective flows in the droplet and vapor domains are also simulated. The influences of evaporative cooling and convection on the evaporation characteristics are determined quantitatively. The liquid-vapor interface temperature drop induced by evaporative cooling suppresses evaporation, while gas-phase natural convection acts to enhance evaporation. While the effects of these competing transport mechanisms are observed to counterbalance for evaporation on a hydrophobic surface, the stronger influence of evaporative cooling on a superhydrophobic surface accounts for an overprediction of experimental evaporation rates by ~20% with vapor diffusion-based models. The local evaporation fluxes along the liquid-vapor interface for both hydrophobic and superhydrophobic substrates are investigated. The highest local evaporation flux occurs at the three-phase contact line region due to proximity to the higher temperature substrate, rather than at the relatively colder droplet top; vapor diffusion-based models predict the opposite. The numerically calculated evaporation rates agree with experimental results to within 2% for superhydrophobic substrates and 3% for hydrophobic substrates. The large deviations between past analytical models and the experimental data are therefore reconciled with the comprehensive model developed here.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

PubMed

Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

2018-02-21

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Measurement of gas diffusion coefficient in liquid-saturated porous media using magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Song, Yongchen; Hao, Min; Zhao, Yuechao; Zhang, Liang

2014-12-01

In this study, the dual-chamber pressure decay method and magnetic resonance imaging (MRI) were used to dynamically visualize the gas diffusion process in liquid-saturated porous media, and the relationship of concentration-distance for gas diffusing into liquid-saturated porous media at different times were obtained by MR images quantitative analysis. A non-iterative finite volume method was successfully applied to calculate the local gas diffusion coefficient in liquid-saturated porous media. The results agreed very well with the conventional pressure decay method, thus it demonstrates that the method was feasible of determining the local diffusion coefficient of gas in liquid-saturated porous media at different times during diffusion process.

Dual-channel microreactor for gas-liquid syntheses.

PubMed

Park, Chan Pil; Kim, Dong-Pyo

2010-07-28

A microreactor consisting of two microfluidic channels that are separated by a thin membrane is devised for intimate contact between gas and liquid phases. Gas flowing in one microchannel can diffuse into the liquid flowing in the other microchannel through the thin membrane. An oxidative Heck reaction carried out in the dual-channel (DC) microreactor, in which gaseous oxygen plays a key role in the catalytic reaction, shows the significant improvement that can be made over the traditional batch reactor and the conventional segmental microreactor in terms of yield, selectivity, and reaction time. It also allows independent control of the flow of the gaseous reagent. The proposed DC microreactor should prove to be a powerful tool for fully exploring gas-liquid microchemistry.

The speed of sound in a gas-vapour bubbly liquid.

PubMed

Prosperetti, Andrea

2015-10-06

In addition to the vapour of the liquid, bubbles in cavitating flows usually contain also a certain amount of permanent gas that diffuses out of the liquid as they grow. This paper presents a simplified linear model for the propagation of monochromatic pressure waves in a bubbly liquid with these characteristics. Phase change effects are included in detail, while the gas is assumed to follow a polytropic law. It is shown that even a small amount of permanent gas can have a major effect on the behaviour of the system. Particular attention is paid to the low-frequency range, which is of special concern in flow cavitation. Numerical results for water and liquid oxygen illustrate the implications of the model.

SDSS-IV MaNGA: A SERENDIPITOUS OBSERVATION OF A POTENTIAL GAS ACCRETION EVENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheung, Edmond; Stark, David V.; Huang, Song

The nature of warm, ionized gas outside of galaxies may illuminate several key galaxy evolutionary processes. A serendipitous observation by the MaNGA survey has revealed a large, asymmetric H α complex with no optical counterpart that extends ≈8″ (≈6.3 kpc) beyond the effective radius of a dusty, starbursting galaxy. This H α extension is approximately three times the effective radius of the host galaxy and displays a tail-like morphology. We analyze its gas-phase metallicities, gaseous kinematics, and emission-line ratios and discuss whether this H α extension could be diffuse ionized gas, a gas accretion event, or something else. We findmore » that this warm, ionized gas structure is most consistent with gas accretion through recycled wind material, which could be an important process that regulates the low-mass end of the galaxy stellar mass function.« less

SDSS-IV MaNGA: A Serendipitous Observation of a Potential Gas Accretion Event

NASA Astrophysics Data System (ADS)

Cheung, Edmond; Stark, David V.; Huang, Song; Rubin, Kate H. R.; Lin, Lihwai; Tremonti, Christy; Zhang, Kai; Yan, Renbin; Bizyaev, Dmitry; Boquien, Médéric; Brownstein, Joel R.; Drory, Niv; Gelfand, Joseph D.; Knapen, Johan H.; Maiolino, Roberto; Malanushenko, Olena; Masters, Karen L.; Merrifield, Michael R.; Pace, Zach; Pan, Kaike; Riffel, Rogemar A.; Roman-Lopes, Alexandre; Rujopakarn, Wiphu; Schneider, Donald P.; Stott, John P.; Thomas, Daniel; Weijmans, Anne-Marie

2016-12-01

The nature of warm, ionized gas outside of galaxies may illuminate several key galaxy evolutionary processes. A serendipitous observation by the MaNGA survey has revealed a large, asymmetric Hα complex with no optical counterpart that extends ≈8″ (≈6.3 kpc) beyond the effective radius of a dusty, starbursting galaxy. This Hα extension is approximately three times the effective radius of the host galaxy and displays a tail-like morphology. We analyze its gas-phase metallicities, gaseous kinematics, and emission-line ratios and discuss whether this Hα extension could be diffuse ionized gas, a gas accretion event, or something else. We find that this warm, ionized gas structure is most consistent with gas accretion through recycled wind material, which could be an important process that regulates the low-mass end of the galaxy stellar mass function.

Three mechanisms model of shale gas in real state transport through a single nanopore

NASA Astrophysics Data System (ADS)

Li, Dongdong; Zhang, Yanyu; Sun, Xiaofei; Li, Peng; Zhao, Fengkai

2018-02-01

At present, the apparent permeability models of shale gas consider only the viscous flow and Knudsen diffusion of free gas, but do not take into account the influence of surface diffusion. Moreover, it is assumed that shale gas is in ideal state. In this paper, shale gas is assumed in real state, a new apparent permeability model for shale gas transport through a single nanopore is developed that captures many important migration mechanisms, such as viscous flow and Knudsen diffusion of free gas, surface diffusion of adsorbed gas. According to experimental data, the accuracy of apparent permeability model was verified. What’s more, the effects of pressure and pore radius on apparent permeability, and the effects on the permeability fraction of viscous flow, Knudsen diffusion and surface diffusion were analysed, separately. Finally, the results indicate that the error of the developed model in this paper was 3.02%, which is less than the existing models. Pressure and pore radius seriously affect the apparent permeability of shale gas. When the pore radius is small or pressure is low, the surface diffusion cannot be ignored. When the pressure and the pore radius is big, the viscous flow occupies the main position.

TOGA: A TOUGH code for modeling three-phase, multi-component, and non-isothermal processes involved in CO 2-based Enhanced Oil Recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Lehua; Oldenburg, Curtis M.

TOGA is a numerical reservoir simulator for modeling non-isothermal flow and transport of water, CO 2, multicomponent oil, and related gas components for applications including CO 2-enhanced oil recovery (CO 2-EOR) and geologic carbon sequestration in depleted oil and gas reservoirs. TOGA uses an approach based on the Peng-Robinson equation of state (PR-EOS) to calculate the thermophysical properties of the gas and oil phases including the gas/oil components dissolved in the aqueous phase, and uses a mixing model to estimate the thermophysical properties of the aqueous phase. The phase behavior (e.g., occurrence and disappearance of the three phases, gas +more » oil + aqueous) and the partitioning of non-aqueous components (e.g., CO 2, CH 4, and n-oil components) between coexisting phases are modeled using K-values derived from assumptions of equal-fugacity that have been demonstrated to be very accurate as shown by comparison to measured data. Models for saturated (water) vapor pressure and water solubility (in the oil phase) are used to calculate the partitioning of the water (H 2O) component between the gas and oil phases. All components (e.g., CO 2, H 2O, and n hydrocarbon components) are allowed to be present in all phases (aqueous, gaseous, and oil). TOGA uses a multiphase version of Darcy’s Law to model flow and transport through porous media of mixtures with up to three phases over a range of pressures and temperatures appropriate to hydrocarbon recovery and geologic carbon sequestration systems. Transport of the gaseous and dissolved components is by advection and Fickian molecular diffusion. New methods for phase partitioning and thermophysical property modeling in TOGA have been validated against experimental data published in the literature for describing phase partitioning and phase behavior. Flow and transport has been verified by testing against related TOUGH2 EOS modules and CMG. The code has also been validated against a CO 2-EOR experimental core flood involving flow of three phases and 12 components. Results of simulations of a hypothetical 3D CO 2-EOR problem involving three phases and multiple components are presented to demonstrate the field-scale capabilities of the new code. This user guide provides instructions for use and sample problems for verification and demonstration.« less

Amplitude death and synchronized states in nonlinear time-delay systems coupled through mean-field diffusion

NASA Astrophysics Data System (ADS)

Banerjee, Tanmoy; Biswas, Debabrata

2013-12-01

We explore and experimentally demonstrate the phenomena of amplitude death (AD) and the corresponding transitions through synchronized states that lead to AD in coupled intrinsic time-delayed hyperchaotic oscillators interacting through mean-field diffusion. We identify a novel synchronization transition scenario leading to AD, namely transitions among AD, generalized anticipatory synchronization (GAS), complete synchronization (CS), and generalized lag synchronization (GLS). This transition is mediated by variation of the difference of intrinsic time-delays associated with the individual systems and has no analogue in non-delayed systems or coupled oscillators with coupling time-delay. We further show that, for equal intrinsic time-delays, increasing coupling strength results in a transition from the unsynchronized state to AD state via in-phase (complete) synchronized states. Using Krasovskii-Lyapunov theory, we derive the stability conditions that predict the parametric region of occurrence of GAS, GLS, and CS; also, using a linear stability analysis, we derive the condition of occurrence of AD. We use the error function of proper synchronization manifold and a modified form of the similarity function to provide the quantitative support to GLS and GAS. We demonstrate all the scenarios in an electronic circuit experiment; the experimental time-series, phase-plane plots, and generalized autocorrelation function computed from the experimental time series data are used to confirm the occurrence of all the phenomena in the coupled oscillators.

Bubble-facilitated VOC transport: Laboratory experiments and numerical modelling

NASA Astrophysics Data System (ADS)

Mumford, K. G.; Soucy, N. C.

2017-12-01

Most conceptual and numerical models of vapor intrusion assume that the transport of volatile organic compounds (VOCs) from the source to near the building foundation is a diffusion-limited processes. However, the transport of VOCs by mobilized gas bubbles through the saturated zone could lead to increased rates of transport and advection through the unsaturated zone, thereby increasing mass flux and risks associated with vapor intrusion. This mobilized gas could be biogenic (methanogenic) but could also result from the partitioning of VOC to trapped atmospheric gases in light non-aqueous phase liquid (LNAPL) smear zones. The potential for bubble-facilitated VOC transport to increase mass flux was investigated in a series of 1D and 2D laboratory experiments. Pentane source zones were emplaced in sand using sequential drainage and imbibition steps to mimic a water table fluctuation and trap air alongside LNAPL residual. This source was placed below an uncontaminated, water saturated sand (occlusion zone) and a gravel-sized (glass beads) unsaturated zone. Water was pumped laterally through the source zone and occlusion zone to deliver the dissolved gases (air) that are required for the expansion of trapped gas bubbles. Images from 2D flow cell experiments were used to demonstrate fluid rearrangement in the source zone and gas expansion to the occlusion zone, and 1D column experiments were used to measure gas-phase pentane mass flux. This flux was found to be 1-2 orders of magnitude greater than that measured in diffusion-dominated control columns, and showed intermittent behavior consistent with bubble transport by repeated expansion, mobilization, coalescence and trapping. Numerical simulation results under a variety of conditions using an approach that couples macroscopic invasion percolation with mass transfer (MIP-MT) between the aqueous and gas phases will also be presented. The results of this study demonstrate the potential for bubble-facilitated transport to increase transport rates linked to vapor intrusion, and will serve as a basis for further development of conceptual and numerical models to investigate the conditions under which this mechanism may play an important role.

Radial inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy (Invited)

NASA Astrophysics Data System (ADS)

Krieger, U. K.; Steimer, S.; Lienhard, D.; Bastelberger, S.

2013-12-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous MBTCA (3-methyl-1,2,3-Butanetricarboxylic acid) and shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a 'white light ' LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. Potential implications for gas to particle partitioning and heterogeneous chemistry are discussed. [1] A. Virtanen et al. (2010): An amorphous solid state of biogenic secondary organic aerosol particles, Nature 467, 824-827. [2] B. Zobrist et al. (2011): Ultra-slow water diffusion in aqueous sucrose glasses, Phys. Chem. Chem. Phys. 13, 3514-3526. [3] D. L. Bones, J. P. Reid, D. M. Lienhard, and U. K. Krieger (2012): Comparing the mechanism of water condensation and evaporation in glassy aerosol, PNAS 109, 11613-11618. [4] O. Peña and U. Pal (2009): Scattering of electromagnetic radiation by a multilayered sphere, Comput. Phys. Commun. 180, 2348-2354.

Quenching star formation with quasar outflows launched by trapped IR radiation

NASA Astrophysics Data System (ADS)

Costa, Tiago; Rosdahl, Joakim; Sijacki, Debora; Haehnelt, Martin G.

2018-06-01

We present cosmological radiation-hydrodynamic simulations, performed with the code RAMSES-RT, of radiatively-driven outflows in a massive quasar host halo at z = 6. Our simulations include both single- and multi-scattered radiation pressure on dust from a quasar and are compared against simulations performed with thermal feedback. For radiation pressure-driving, we show that there is a critical quasar luminosity above which a galactic outflow is launched, set by the equilibrium of gravitational and radiation forces. While this critical luminosity is unrealistically high in the single-scattering limit for plausible black hole masses, it is in line with a ≈ 3 × 10^9 M_⊙ black hole accreting at its Eddington limit, if infrared (IR) multi-scattering radiation pressure is included. The outflows are fast (v ≳ 1000 km s^{-1}) and strongly mass-loaded with peak mass outflow rates ≈ 10^3 - 10^4 M_⊙ yr^{-1}, but short-lived (< 10 Myr). Outflowing material is multi-phase, though predominantly composed of cool gas, forming via a thermal instability in the shocked swept-up component. Radiation pressure- and thermally-driven outflows both affect their host galaxies significantly, but in different, complementary ways. Thermally-driven outflows couple more efficiently to diffuse halo gas, generating more powerful, hotter and more volume-filling outflows. IR radiation, through its ability to penetrate dense gas via diffusion, is more efficient at ejecting gas from the bulge. The combination of gas ejection through outflows with internal pressurisation by trapped IR radiation leads to a complete shut down of star formation in the bulge. We hence argue that radiation pressure-driven feedback may be an important ingredient in regulating star formation in compact starbursts, especially during the quasar's `obscured' phase.

Modeling of turbulence effects on the heat and mass transfer of evaporating sprays

NASA Astrophysics Data System (ADS)

Madhanabharatam, Balasubramanyam

A large diversity of two-phase gas-liquid flows of both scientific and practical interest involves the evaporation of near spherical liquid droplets in high temperature turbulent environments. Current numerical modeling approaches are predominantly focused towards the effects of continuous phase (gas phase) turbulence on the evaporation rates of liquid fuel sprays during the evaporation process, failing to account for the inherent turbulence present in the dispersed phase (liquid phase), due to the injection of sprays at high velocities. Existing models accounting for internal turbulence effects use Direct Numerical Simulations and Large Eddy Simulations that are computationally intensive. This research provides an alternative phenomenological approach of modeling droplet internal turbulence effects through the mass and heat transfer between the droplet surface and the external gas phase within a thin film inside the droplet. This finite conductivity (F-C) model was based on the two-temperature film theory, where the turbulence characteristics of the droplet are used to estimate the effective thermal diffusivity (alphaeff) within the droplet phase. The alphaeff is estimated from the physical properties of the flow within the droplet rather than from a 'curve-fit' as done conventionally. The results of the one-way coupled study indicated that the equilibrium drop temperature predictions were higher than calculations by the infinite conductivity (I-C) model. The liquid internal turbulence has a considerable effect on the diffusivity in the primary atomization regime. The thermal boundary layer was found to be substantially thick initially, decreasing quickly to a small value, exhibiting a reasonable physical trend. The two-way coupled studies (CFD) indicated that the F-C model, slowed down the evaporation process, produced larger droplets and longer tip penetration lengths during the initial stages of injection. For a jet in a supersonic cross-flow, results indicated that jet penetration increased rapidly in the vicinity of the injector exit and then gradually increased due to increase in the drag of the air stream. A modified drag coefficient was incorporated to improve model accuracy in predictions. Overall the results obtained from the numerical calculations during this study were reasonably comparable to measured data and showed more accurate comparisons to that of the I-C model.

Modeling gas displacement kinetics in coal with Maxwell-Stefan diffusion theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, X.R.; Wang, G.X.; Massarotto, P.

2007-12-15

The kinetics of binary gas counter-diffusion and Darcy flow in a large coal sample were modeled, and the results compared with data from experimental laboratory investigations. The study aimed for a better understanding of the CO{sub 2}-sequestration enhanced coalbed methane (ECBM) recovery process. The transport model used was based on the bidisperse diffusion mechanism and Maxwell-Stefan (MS) diffusion theory. This provides an alternative approach to simulate multicomponent gas diffusion and flow in bulk coals. A series of high-stress core flush tests were performed on a large coal sample sourced from a Bowen Basin coal mine in Queensland, Australia to investigatemore » the kinetics of one gas displacing another. These experimental results were used to derive gas diffusivities, and to examine the predictive capability of the diffusion model. The simulations show good agreements with the displacement experiments revealing that MS diffusion theory is superior for describing diffusion of mixed gases in coals compared with the constant Fick diffusivity model. The optimized effective micropore and macropore diffusivities are comparable with experimental measurements achieved by other researchers.« less

Sorption-induced effects of humic substances on mass transfer of organic pollutants through aqueous diffusion boundary layers: the example of water/air exchange.

PubMed

Ramus, Ksenia; Kopinke, Frank-Dieter; Georgi, Anett

2012-02-21

This study examines the effect of dissolved humic substances (DHS) on the rate of water-gas exchange of organic compounds under conditions where diffusion through the aqueous boundary layer is rate-determining. A synthetic surfactant was applied for comparison. Mass-transfer coefficients were determined from the rate of depletion of the model compounds by means of an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution. In addition, experiments with continuous passive dosing of analytes into the water phase were conducted to simulate a system where thermodynamic activity of the chemical in the aqueous phase is identical in the presence and absence of DHS. The experimental results show that DHS and surfactants can affect water-gas exchange rates by the superposition of two mechanisms: (1) hydrodynamic effects due to surface film formation ("surface smoothing"), and (2) sorption-induced effects. Whether sorption accelerates or retards mass transfer depends on its effect on the thermodynamic activity of the pollutant in the aqueous phase. Mass transfer will be retarded if the activity (or freely dissolved concentration) of the pollutant is decreased due to sorption. If it remains unchanged (e.g., due to fast equilibration with a sediment acting as a large source phase), then DHS and surfactant micelles can act as an additional shuttle for the pollutants, enhancing the flux through the boundary layer.

Surface diffusion of CO on silica-supported Ru particles: 13C nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Duncan, T. M.; Thayer, A. M.; Root, T. W.

1990-02-01

Portions of CO adsorbed on Ru particles, selected by the orientation of the C-O bond relative to an external magnetic field, are labeled by inversion of the 13C nuclear magnetic dipole. Changes in the orientation of the CO bond of these labeled molecules are then observed with 13C NMR spectroscopy. The temperature dependence and rate of reorientation are consistent with surface diffusion on Ru particles with small numbers of flat faces. The insensitivity to CO pressure in the range 0.5-100 Torr discounts stimulated desorption by gas-phase CO.

Nanocrystalline Al7075 + 1 wt % Zr Alloy Prepared Using Mechanical Milling and Spark Plasma Sintering

PubMed Central

Málek, Přemysl; Minárik, Peter; Chráska, Tomáš; Novák, Pavel; Průša, Filip

2017-01-01

The microstructure, phase composition, and microhardness of both gas-atomized and mechanically milled powders of the Al7075 + 1 wt % Zr alloy were investigated. The gas-atomized powder exhibited a cellular microstructure (grain size of a few µm) with layers of intermetallic phases along the cell boundaries. Mechanical milling (400 revolutions per minute (RPM)/8 h) resulted in a grain size reduction to the nanocrystalline range (20 to 100 nm) along with the dissolution of the intermetallic phases. Milling led to an increase in the powder’s microhardness from 97 to 343 HV. Compacts prepared by spark plasma sintering (SPS) exhibited negligible porosity. The grain size of the originally gas-atomized material was retained, but the continuous layers of intermetallic phases were replaced by individual particles. Recrystallization led to a grain size increase to 365 nm in the SPS compact prepared from the originally milled powder. Small precipitates of the Al3Zr phase were observed in the SPS compacts, and they are believed to be responsible for the retainment of the sub-microcrystalline microstructure during SPS. A more intensive precipitation in this SPS compact can be attributed to a faster diffusion due to a high density of dislocations and grain boundaries in the milled powder. PMID:28930192

Effect of freeze-thaw cycles on greenhouse gas fluxes from peat soils

NASA Astrophysics Data System (ADS)

Oh, H. D.; Rezanezhad, F.; Markelov, I.; McCarter, C. P. R.; Van Cappellen, P.

2017-12-01

The ongoing displacement of climate zones by global warming is increasing the frequency and intensity of freeze-thaw cycles in middle and high latitude regions, many of which are dominated by organic soils such as peat. Repeated freezing and thawing of soils changes their physical properties, geochemistry, and microbial community structure, which together govern the biogeochemical cycling of carbon and nutrients. In this presentation, we focus on how freeze-thaw cycles influence greenhouse gas fluxes from peat using a newly developed experimental soil column system that simulates realistic soil temperature profiles during freeze-thaw cycles. We measured the surface and subsurface changes to gas and aqueous phase chemistry to delineate the diffusion pathways and quantify soil greenhouse gas fluxes during freeze-thaw cycles using sulfur hexafluoride (SF6) as a conservative tracer. Three peat columns were assembled inside a temperature controlled chamber with different soil structures. All three columns were packed with 40 cm of undisturbed, slightly decomposed peat, where the soil of two columns had an additional 10 cm layer on top (one with loose Sphagnum moss and one with an impermeable plug). The results indicate that the release of SF6 and CO2 gas from the soil surface was influenced by the recurrent development of a physical ice barrier, which prevented gas exchange between the soil and atmosphere during freezing conditions. With the onset of thawing a pulse of SF6 and CO2 occurred, resulting in a flux of 3.24 and 2095.52 µmol/m2h, respectively, due to the build-up of gases in the liquid-phase pore space during freezing. Additionally, we developed a model to determine the specific diffusion coefficients for each peat column. These data allow us to better predict how increased frequency and intensity of freeze-thaw cycles will affect greenhouse gas emissions in northern peat soils.

Constraining Gas Diffusivity-Soil Water Content Relationships in Forest Soils Using Surface Chamber Fluxes and Depth Profiles of Multiple Trace Gases

NASA Astrophysics Data System (ADS)

Dore, J. E.; Kaiser, K.; Seybold, E. C.; McGlynn, B. L.

2012-12-01

Forest soils are sources of carbon dioxide (CO2) to the atmosphere and can act as either sources or sinks of methane (CH4) and nitrous oxide (N2O), depending on redox conditions and other factors. Soil moisture is an important control on microbial activity, redox conditions and gas diffusivity. Direct chamber measurements of soil-air CO2 fluxes are facilitated by the availability of sensitive, portable infrared sensors; however, corresponding CH4 and N2O fluxes typically require the collection of time-course physical samples from the chamber with subsequent analyses by gas chromatography (GC). Vertical profiles of soil gas concentrations may also be used to derive CH4 and N2O fluxes by the gradient method; this method requires much less time and many fewer GC samples than the direct chamber method, but requires that effective soil gas diffusivities are known. In practice, soil gas diffusivity is often difficult to accurately estimate using a modeling approach. In our study, we apply both the chamber and gradient methods to estimate soil trace gas fluxes across a complex Rocky Mountain forested watershed in central Montana. We combine chamber flux measurements of CO2 (by infrared sensor) and CH4 and N2O (by GC) with co-located soil gas profiles to determine effective diffusivity in soil for each gas simultaneously, over-determining the diffusion equations and providing constraints on both the chamber and gradient methodologies. We then relate these soil gas diffusivities to soil type and volumetric water content in an effort to arrive at empirical parameterizations that may be used to estimate gas diffusivities across the watershed, thereby facilitating more accurate, frequent and widespread gradient-based measurements of trace gas fluxes across our study system. Our empirical approach to constraining soil gas diffusivity is well suited for trace gas flux studies over complex landscapes in general.

Relevance of anisotropy and spatial variability of gas diffusivity for soil-gas transport

NASA Astrophysics Data System (ADS)

Schack-Kirchner, Helmer; Kühne, Anke; Lang, Friederike

2017-04-01

Models of soil gas transport generally do not consider neither direction dependence of gas diffusivity, nor its small-scale variability. However, in a recent study, we could provide evidence for anisotropy favouring vertical gas diffusion in natural soils. We hypothesize that gas transport models based on gas diffusion data measured with soil rings are strongly influenced by both, anisotropy and spatial variability and the use of averaged diffusivities could be misleading. To test this we used a 2-dimensional model of soil gas transport to under compacted wheel tracks to model the soil-air oxygen distribution in the soil. The model was parametrized with data obtained from soil-ring measurements with its central tendency and variability. The model includes vertical parameter variability as well as variation perpendicular to the elongated wheel track. Different parametrization types have been tested: [i)]Averaged values for wheel track and undisturbed. em [ii)]Random distribution of soil cells with normally distributed variability within the strata. em [iii)]Random distributed soil cells with uniformly distributed variability within the strata. All three types of small-scale variability has been tested for [j)] isotropic gas diffusivity and em [jj)]reduced horizontal gas diffusivity (constant factor), yielding in total six models. As expected the different parametrizations had an important influence to the aeration state under wheel tracks with the strongest oxygen depletion in case of uniformly distributed variability and anisotropy towards higher vertical diffusivity. The simple simulation approach clearly showed the relevance of anisotropy and spatial variability in case of identical central tendency measures of gas diffusivity. However, until now it did not consider spatial dependency of variability, that could even aggravate effects. To consider anisotropy and spatial variability in gas transport models we recommend a) to measure soil-gas transport parameters spatially explicit including different directions and b) to use random-field stochastic models to assess the possible effects for gas-exchange models.

Gradient Augmented Level Set Method for Two Phase Flow Simulations with Phase Change

NASA Astrophysics Data System (ADS)

Anumolu, C. R. Lakshman; Trujillo, Mario F.

2016-11-01

A sharp interface capturing approach is presented for two-phase flow simulations with phase change. The Gradient Augmented Levelset method is coupled with the two-phase momentum and energy equations to advect the liquid-gas interface and predict heat transfer with phase change. The Ghost Fluid Method (GFM) is adopted for velocity to discretize the advection and diffusion terms in the interfacial region. Furthermore, the GFM is employed to treat the discontinuity in the stress tensor, velocity, and temperature gradient yielding an accurate treatment in handling jump conditions. Thermal convection and diffusion terms are approximated by explicitly identifying the interface location, resulting in a sharp treatment for the energy solution. This sharp treatment is extended to estimate the interfacial mass transfer rate. At the computational cell, a d-cubic Hermite interpolating polynomial is employed to describe the interface location, which is locally fourth-order accurate. This extent of subgrid level description provides an accurate methodology for treating various interfacial processes with a high degree of sharpness. The ability to predict the interface and temperature evolutions accurately is illustrated by comparing numerical results with existing 1D to 3D analytical solutions.

The effect of heat treatment on structural and electronic properties of niobium nitride prepared by a thermal diffusion method

DOE PAGES

Farha, Ashraf Hassan; Ozkendir, Osman Murat; Elsayed-Ali, Hani E.; ...

2016-11-15

NbN coatings are prepared onto Nb substrate by thermal diffusion at high temperatures. The formation of NbN coating by thermal diffusion was studied in the range of 1250-1500 °C at constant nitrogen background gas pressure (1.3x10 -3 Pa) and processing time (180 min). The electronic and crystal structures of the NbN coatings were investigated. It was found that nitrogen diffuses into Nb forming the Nb-N solid solution (bcc) a-NbN phase that starts to appear above 1250 °C. Increasing the processing temperature gives richer a-phase concentration. Besides, X-ray absorption spectroscopy (XAS) was performed to study the electronic structure of the NbNmore » layer. The results of the electronic structural study corroborate the crystal structural analysis. The Nb M 3,2 edge X-ray absorption spectroscopy (XAS) spectrum shows strong temperature dependence. At the highest processing temperature (1500 °C), the number of d holes increased. Nitrogen diffusion into Nb is resulting to increase electrostatic interaction between d electron and core hole. Lastly, for the studied conditions, only the α-NbN was observed in the X-ray diffraction patterns.« less

The effect of heat treatment on structural and electronic properties of niobium nitride prepared by a thermal diffusion method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farha, Ashraf Hassan; Ozkendir, Osman Murat; Elsayed-Ali, Hani E.

NbN coatings are prepared onto Nb substrate by thermal diffusion at high temperatures. The formation of NbN coating by thermal diffusion was studied in the range of 1250-1500 °C at constant nitrogen background gas pressure (1.3x10 -3 Pa) and processing time (180 min). The electronic and crystal structures of the NbN coatings were investigated. It was found that nitrogen diffuses into Nb forming the Nb-N solid solution (bcc) a-NbN phase that starts to appear above 1250 °C. Increasing the processing temperature gives richer a-phase concentration. Besides, X-ray absorption spectroscopy (XAS) was performed to study the electronic structure of the NbNmore » layer. The results of the electronic structural study corroborate the crystal structural analysis. The Nb M 3,2 edge X-ray absorption spectroscopy (XAS) spectrum shows strong temperature dependence. At the highest processing temperature (1500 °C), the number of d holes increased. Nitrogen diffusion into Nb is resulting to increase electrostatic interaction between d electron and core hole. Lastly, for the studied conditions, only the α-NbN was observed in the X-ray diffraction patterns.« less

Core-shell fuel cell electrodes

DOEpatents

Adzic, Radoslav; Bliznakov, Stoyan; Vukmirovic, Miomir

2017-07-25

Embodiments of the disclosure relate to electrocatalysts. The electrocatalyst may include at least one gas-diffusion layer having a first side and a second side, and particle cores adhered to at least one of the first and second sides of the at least one gas-diffusion layer. The particle cores includes surfaces adhered to the at least one of the first and second sides of the at least one gas-diffusion layer and surfaces not in contact with the at least one gas-diffusion layer. Furthermore, a thin layer of catalytically atoms may be adhered to the surfaces of the particle cores not in contact with the at least one gas-diffusion layer.

Multiparameter Analysis of Gas Transport Phenomena in Shale Gas Reservoirs: Apparent Permeability Characterization.

PubMed

Shen, Yinghao; Pang, Yu; Shen, Ziqi; Tian, Yuanyuan; Ge, Hongkui

2018-02-08

The large amount of nanoscale pores in shale results in the inability to apply Darcy's law. Moreover, the gas adsorption of shale increases the complexity of pore size characterization and thus decreases the accuracy of flow regime estimation. In this study, an apparent permeability model, which describes the adsorptive gas flow behavior in shale by considering the effects of gas adsorption, stress dependence, and non-Darcy flow, is proposed. The pore size distribution, methane adsorption capacity, pore compressibility, and matrix permeability of the Barnett and Eagle Ford shales are measured in the laboratory to determine the critical parameters of gas transport phenomena. The slip coefficients, tortuosity, and surface diffusivity are predicted via the regression analysis of the permeability data. The results indicate that the apparent permeability model, which considers second-order gas slippage, Knudsen diffusion, and surface diffusion, could describe the gas flow behavior in the transition flow regime for nanoporous shale. Second-order gas slippage and surface diffusion play key roles in the gas flow in nanopores for Knudsen numbers ranging from 0.18 to 0.5. Therefore, the gas adsorption and non-Darcy flow effects, which involve gas slippage, Knudsen diffusion, and surface diffusion, are indispensable parameters of the permeability model for shale.

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2013-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2017-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

Dynamic least-squares kernel density modeling of Fokker-Planck equations with application to neural population.

PubMed

Shotorban, Babak

2010-04-01

The dynamic least-squares kernel density (LSQKD) model [C. Pantano and B. Shotorban, Phys. Rev. E 76, 066705 (2007)] is used to solve the Fokker-Planck equations. In this model the probability density function (PDF) is approximated by a linear combination of basis functions with unknown parameters whose governing equations are determined by a global least-squares approximation of the PDF in the phase space. In this work basis functions are set to be Gaussian for which the mean, variance, and covariances are governed by a set of partial differential equations (PDEs) or ordinary differential equations (ODEs) depending on what phase-space variables are approximated by Gaussian functions. Three sample problems of univariate double-well potential, bivariate bistable neurodynamical system [G. Deco and D. Martí, Phys. Rev. E 75, 031913 (2007)], and bivariate Brownian particles in a nonuniform gas are studied. The LSQKD is verified for these problems as its results are compared against the results of the method of characteristics in nondiffusive cases and the stochastic particle method in diffusive cases. For the double-well potential problem it is observed that for low to moderate diffusivity the dynamic LSQKD well predicts the stationary PDF for which there is an exact solution. A similar observation is made for the bistable neurodynamical system. In both these problems least-squares approximation is made on all phase-space variables resulting in a set of ODEs with time as the independent variable for the Gaussian function parameters. In the problem of Brownian particles in a nonuniform gas, this approximation is made only for the particle velocity variable leading to a set of PDEs with time and particle position as independent variables. Solving these PDEs, a very good performance by LSQKD is observed for a wide range of diffusivities.

Density probability distribution functions of diffuse gas in the Milky Way

NASA Astrophysics Data System (ADS)

Berkhuijsen, E. M.; Fletcher, A.

2008-10-01

In a search for the signature of turbulence in the diffuse interstellar medium (ISM) in gas density distributions, we determined the probability distribution functions (PDFs) of the average volume densities of the diffuse gas. The densities were derived from dispersion measures and HI column densities towards pulsars and stars at known distances. The PDFs of the average densities of the diffuse ionized gas (DIG) and the diffuse atomic gas are close to lognormal, especially when lines of sight at |b| < 5° and |b| >= 5° are considered separately. The PDF of at high |b| is twice as wide as that at low |b|. The width of the PDF of the DIG is about 30 per cent smaller than that of the warm HI at the same latitudes. The results reported here provide strong support for the existence of a lognormal density PDF in the diffuse ISM, consistent with a turbulent origin of density structure in the diffuse gas.

The Thermal Pressure in Low Metallicity Galaxies

NASA Astrophysics Data System (ADS)

Wolfire, Mark; McKee, Christopher; Ostriker, Eve C.; Bolatto, Alberto; Jenkins, Edward

2015-08-01

The thermal pressure in the diffuse interstellar medium (ISM) is a relatively small fraction of the total ISM pressure yet it is extremely important for the evolution of the ISM phases. A multi-phase medium can exist between a range of thermal pressures Pmin < Pth < Pmax. The phase separation is driven by thermal instability and produces a cold (T ˜ 100 K) neutral atomic gas and a warm (T ˜ 8000 K) neutral atomic gas separated by thermally unstable gas. At thermal pressures greater than Pmax only the cold phase can exist and at thermal pressures less than Pmin only the warm phase can exist. The ISM is also highly turbulent and turbulence can both initiate the thermal phase transition and be produced in a rapid phase transition. Hydrodynamic modeling also points to a strong two-phase distribution (.e.g., Kim et al. 2011; Audit & Hennebelle 2010) with a median thermal pressure in the cold gas very near the expected two-phase pressure. Global, theoretical models including star-formation feedback have been developed for the molecular fraction in galactic disks using, at their core, the paradigm that thermal pressure determines the phase transitions to warm, cold, or multiphase medium (e.g., Krumholz et al. 2009; Ostriker et al. 2010).Here we present a phase diagram for a low metallicity galaxy using the Small Magellanic Clouds as an example. We find that although the heating rates and metallicities can differ by factors of 5 to 10 from the Milky Way, the resulting two-phase pressure and physical conditions of the phases are not very different from Galactic. We also confirm that a widely used fitting function for Pmin presented in Wolfire et al. 2003 provides an accurate prediction for the new results. We demonstrate how the variation in input parameters determine the final pressures and physical conditions.

Chemical desorption and diffusive dust chemistry

NASA Astrophysics Data System (ADS)

Dulieu, Francois; Pirronello, Valerio; Minissale, Marco; Congiu, Emanuele; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Accolla, Mario; Cazaux, Stephanie; Manicò, Giulio

In molecular clouds, gaseous species can accrete efficiently on the cold surfaces of dust grains. As for radical-radical reactions, the surface of the grains acts as a third body, and changes dramatically the efficiency of the reactions (i.e., H2 formation), or lowers considerably the barrier to formation (i.e., H2O synthesis) in comparison with gas phase reaction processes. These properties make dust grains efficient catalytic templates. However, the chemical role of dust grains depends on the diffusive properties of the reactive partners. Over the last years, we have developed experimental tools and methods to explore the chemistry occurring on cold (6-50K) surfaces. We have obtained some hints about the diffusivity of H on amorphous ice, and studied in detail the diffusion of O atoms. The latter species appears to have a hopping rate in the range 0.01-100 hops/sec. The diffusion rate of O atoms is dependent on the surface morphology and on the surface temperature. The diffusion law is compatible with a diffusion dominated by quantum tunnelling rather than classical thermal hopping. Using H, O, N atoms and, indirectly, OH and HCO radicals, we have begun to explore many chemical reactive networks. In this presentation, I will focus on the formation of H2O and CO2, and will propose many possible formation routes to obtain these chemical traps. The molecules formed on surfaces have a certain probability of desorbing upon their formation. This non-thermal desorption mechanism, or chemical desorption, has been proposed to explain why some molecules can be detected in the gas phase of those region where they were believed to be part of the icy mantles covering dust grains. We have shown that this process can be very efficient, but is very sensitive to the substrate and the surroundings of the reaction site, is dependent on the kind of molecule formed and its chemical pathway. In my presentation I will present how the surface coverage and the type of reaction can play a major role in the chemical desorption process. I will discuss of possible key parameters that rule this process.

Quantifying phosphoric acid in high-temperature polymer electrolyte fuel cell components by X-ray tomographic microscopy.

PubMed

Eberhardt, S H; Marone, F; Stampanoni, M; Büchi, F N; Schmidt, T J

2014-11-01

Synchrotron-based X-ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high-temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro- and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40-100 wt% H3PO4). This renders the quantification and concentration determination challenging. The problem is solved by using propagation-based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non-operating fuel cell. The non-destructive imaging methodology was verified by comparing image-based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.

Polycyclic Aromatic Hydrocarbons and the Diffuse Interstellar Bands: a Survey

NASA Technical Reports Server (NTRS)

Salama, F.; Galazutdinov, G. A.; Krelowski, J.; Allamandola, L. J.; Musaev, F. A.; DeVincenzi, Donald L. (Technical Monitor)

1999-01-01

We discuss the proposal relating the origin of some of the diffuse interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons (PAHs) present in interstellar clouds. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices, are compared with an extensive set of astronomical spectra of reddened, early type stars. From this comparison, it is concluded that PAN ions are good candidates to explain some of the DIBs. Unambiguous assignments are difficult, however, due to the shift in wavelengths and the band broadening induced in the laboratory spectra by the solid matrix. Definitive band assignments and, ultimately, the test of the of the proposal that PAH ions carry some of the DIB must await the availability of gas-phase measurements in the laboratory. The present assessment offers a guideline for future laboratory experiments by allowing the preselection of promising PAH molecules to be studied in jet expansions.

Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM

NASA Astrophysics Data System (ADS)

Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

2011-06-01

The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1 × 1 km2) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm, while the moving-center method is preferable when only a few size bins are selected. The particle number size distribution in the center of the urban plume from Malmö was mainly affected by dry deposition, coagulation and vertical dilution. The modeled PM2.5 mass was dominated by organic material, nitrate, sulfate and ammonium. If the condensation of HNO3 and NH3 was treated as a coupled process (pH independent) the model gave lower nitrate PM2.5 mass than if considering uncoupled condensation. Although the time of ageing from that SOA precursors are emitted until condensable products are formed is substantially different with the 2D-VBS and two product model, the models gave similar total organic mass concentrations.

Spectroscopy of Cosmic Carbon Analogs in Inert-Gas Matrices and in the Gas-Phase: Comparative Results and Perspectives for Astrophysics

NASA Technical Reports Server (NTRS)

Salama, Farid; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

Recent studies of the spectroscopy of large (up to approx. 50 carbon atoms) neutral and Ionized polycyclic aromatic hydrocarbons (PAHs) and Fullerenes isolated in inert gas matrices will be presented. The advantages and the limitations of matrix isolation spectroscopy for the study of the molecular spectroscopy of interstellar dust analogs will be discussed. The laboratory data will be compared to the astronomical spectra (the interstellar extinction, the diffuse interstellar bands). Finally, the spectra of PAH ions isolated in neon/argon matrices will be compared to the spectra obtained for PAH ion seeded in a supersonic expansion. The astrophysical implications and future perspectives will be discussed.

Characterization of Biogenic Gas and Mineral Formation Process by Denitrification in Porous Media

NASA Astrophysics Data System (ADS)

Hall, C. A.; Kim, D.; Mahabadi, N.; van Paassen, L. A.

2017-12-01

Biologically mediated processes have been regarded and developed as an alternative approach to traditional ground improvement techniques. Denitrification has been investigated as a potential ground improvement process towards liquefaction hazard mitigation. During denitrification, microorganisms reduce nitrate to dinitrogen gas and facilitate calcium carbonate precipitation as a by-product under adequate environmental conditions. The formation of dinitrogen gas desaturates soils and allows for potential pore pressure dampening during earthquake events. While, precipitation of calcium carbonate can improve the mechanical properties by filling the voids and cementing soil particles. As a result of small changes in gas and mineral phases, the mechanical properties of soils can be significantly affected. Prior research has primarily focused on quantitative analysis of overall residual calcium carbonate mineral and biogenic gas products in lab-scale porous media. However, the distribution of these products at the pore-scale has not been well-investigated. In this research, denitrification is activated in a microfluidic chip simulating a homogenous pore structure. The denitrification process is monitored by sequential image capture, where gas and mineral phase changes are evaluated by image processing. Analysis of these images correspond with previous findings, which demonstrate that biogenic gas behaviour at the pore scale is affected by the balance between reaction, diffusion, and convection rates.

Formation of methane nano-bubbles during hydrate decomposition and their effect on hydrate growth.

PubMed

Bagherzadeh, S Alireza; Alavi, Saman; Ripmeester, John; Englezos, Peter

2015-06-07

Molecular dynamic simulations are performed to study the conditions for methane nano-bubble formation during methane hydrate dissociation in the presence of water and a methane gas reservoir. Hydrate dissociation leads to the quick release of methane into the liquid phase which can cause methane supersaturation. If the diffusion of methane molecules out of the liquid phase is not fast enough, the methane molecules agglomerate and form bubbles. Under the conditions of our simulations, the methane-rich quasi-spherical bubbles grow to become cylindrical with a radius of ∼11 Å. The nano-bubbles remain stable for about 35 ns until they are gradually and homogeneously dispersed in the liquid phase and finally enter the gas phase reservoirs initially set up in the simulation box. We determined that the minimum mole fraction for the dissolved methane in water to form nano-bubbles is 0.044, corresponding to about 30% of hydrate phase composition (0.148). The importance of nano-bubble formation to the mechanism of methane hydrate formation, growth, and dissociation is discussed.

Shallow Methane Hydrates: Rates, Mechanisms of Formation and Environmental Significance.

NASA Astrophysics Data System (ADS)

Torres, M. E.; Trehu, A. M.

2005-05-01

Shallow gas hydrates have been identified at more than 20 locations worldwide, and are commonly associated with observations of bubble discharge at the seafloor. These deposits are host to active chemosynthetic communities and are likely to play a predominant role in energy, climate and carbon cycle issues associated with hydrate processes. Because seafloor gas hydrates are not in equilibrium with seawater, these deposits require a constant supply of methane to replace loss by continuous diffusion to bottom water. We will summarize evidence documenting that at the shallow deposits on Hydrate Ridge (OR) methane must be delivered in the free gas phase and present simple models used to infer formation rates, which are orders of magnitude higher than those for hydrates formed deeper in the sediment column (Torres et al., 2004). At Hydrate Ridge, methane gas is channeled from deep accretionary margin sequences to the gas hydrate stability zone (GHSZ) through a permeable layer that has been mapped seismically (Horizon A). High gas pressure in this horizon can drive gas through the GHSZ to the seafloor (Trehu et al., 2004). We will review current ideas that address mechanisms whereby gas migrates from Horizon A to the seafloor, including inhibition by capillary effects and the development of a high salinity front that can shift the hydrate stability field enough to allow for methane transport as a gas phase.

Evolution and development of gas exchange structures in Mammalia: the placenta and the lung.

PubMed

Mess, Andrea M; Ferner, Kirsten J

2010-08-31

Appropriate oxygen supply is crucial for organisms. Here we examine the evolution of structures associated with the delivery of oxygen in the pre- and postnatal phases in mammals. There is an enormous structural and functional variability in the placenta that has facilitated the evolution of specialized reproductive strategies, such as precociality. In particular the cell layers separating fetal and maternal blood differ markedly: a non-invasive epitheliochorial placenta, which increases the diffusion distance, represents a derived state in ungulates. Rodents and their relatives have an invasive haemochorial placental type as optimum for the diffusion distance. In contrast, lung development is highly conserved and differences in the lungs of neonates can be explained by different developmental rates. Monotremes and marsupials have altricial stages with lungs at the early saccular phase, whereas newborn eutherians have lungs at the late saccular or alveolar phase. In conclusion, the evolution of exchange structures in the pre- and postnatal periods does not follow similar principles. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Random Walk Particle Tracking For Multiphase Heat Transfer

NASA Astrophysics Data System (ADS)

Lattanzi, Aaron; Yin, Xiaolong; Hrenya, Christine

2017-11-01

As computing capabilities have advanced, direct numerical simulation (DNS) has become a highly effective tool for quantitatively predicting the heat transfer within multiphase flows. Here we utilize a hybrid DNS framework that couples the lattice Boltzmann method (LBM) to the random walk particle tracking (RWPT) algorithm. The main challenge of such a hybrid is that discontinuous fields pose a significant challenge to the RWPT framework and special attention must be given to the handling of interfaces. We derive a method for addressing discontinuities in the diffusivity field, arising at the interface between two phases. Analytical means are utilized to develop an interfacial tracer balance and modify the RWPT algorithm. By expanding the modulus of the stochastic (diffusive) step and only allowing a subset of the tracers within the high diffusivity medium to undergo a diffusive step, the correct equilibrium state can be restored (globally homogeneous tracer distribution). The new RWPT algorithm is implemented within the SUSP3D code and verified against a variety of systems: effective diffusivity of a static gas-solids mixture, hot sphere in unbounded diffusion, cooling sphere in unbounded diffusion, and uniform flow past a hot sphere.

Bulk diffusion in a kinetically constrained lattice gas

NASA Astrophysics Data System (ADS)

Arita, Chikashi; Krapivsky, P. L.; Mallick, Kirone

2018-03-01

In the hydrodynamic regime, the evolution of a stochastic lattice gas with symmetric hopping rules is described by a diffusion equation with density-dependent diffusion coefficient encapsulating all microscopic details of the dynamics. This diffusion coefficient is, in principle, determined by a Green-Kubo formula. In practice, even when the equilibrium properties of a lattice gas are analytically known, the diffusion coefficient cannot be computed except when a lattice gas additionally satisfies the gradient condition. We develop a procedure to systematically obtain analytical approximations for the diffusion coefficient for non-gradient lattice gases with known equilibrium. The method relies on a variational formula found by Varadhan and Spohn which is a version of the Green-Kubo formula particularly suitable for diffusive lattice gases. Restricting the variational formula to finite-dimensional sub-spaces allows one to perform the minimization and gives upper bounds for the diffusion coefficient. We apply this approach to a kinetically constrained non-gradient lattice gas in two dimensions, viz. to the Kob-Andersen model on the square lattice.

Core-shell fuel cell electrodes

DOEpatents

Adzic, Radoslav; Bliznakov, Stoyan; Vukmirovic, Miomir

2017-12-26

Embodiments of the disclosure relate to membrane electrode assemblies. The membrane electrode assembly may include at least one gas-diffusion layer having a first side and a second side, and particle cores adhered to at least one of the first and second sides of the at least one gas-diffusion layer. The particle cores includes surfaces adhered to the at least one of the first and second sides of the at least one gas-diffusion layer and surfaces not in contact with the at least one gas-diffusion layer. Furthermore, a thin layer of catalytically atoms may be adhered to the surfaces of the particle cores not in contact with the at least one gas-diffusion layer.

Thickness limitations in carbon nanotube reinforced silicon nitride coatings synthesized by vapor infiltration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eres, Gyula

Chemical vapor infiltration is a convenient method for synthesizing carbon nanotube (CNT)-reinforced ceramic coatings. The thickness over which infiltration is relatively uniform is limited by gas phase diffusion in the pore structure. These effects were investigated in two types of silicon nitride matrix composites. With CNTs that were distributed uniformly on the substrate surface dense coatings were limited to thicknesses of several microns. With dual structured CNT arrays produced by photolithography coatings up to 400 gm thick were obtained with minimal residual porosity. Gas transport into these dual structured materials was facilitated by creating micron sized channels between "CNT pillars"more » (i.e. each pillar consisted of a large number of individual CNTs). The experimental results are consistent with basic comparisons between the rates of gas diffusion and silicon nitride growth in porous structures. This analysis also provides a general insight into optimizing infiltration conditions during the fabrication of thick CNT-reinforced composite coatings. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.« less

Phase-Contrast MRI and CFD Modeling of Apparent 3He Gas Flow in Rat Pulmonary Airways

PubMed Central

Minard, Kevin R.; Kuprat, Andrew P.; Kabilan, Senthil; Jacob, Richard E.; Einstein, Daniel R.; Carson, James P.; Corley, Richard A.

2012-01-01

Phase-contrast (PC) magnetic resonance imaging (MRI) with hyperpolarized 3He is potentially useful for developing and testing patient-specific models of pulmonary airflow. One challenge, however, is that PC-MRI provides apparent values of local 3He velocity that not only depend on actual airflow but also on gas diffusion. This not only blurs laminar flow patterns in narrow airways but also introduces anomalous airflow structure that reflects gas-wall interactions. Here, both effects are predicted in a live rat using computational fluid dynamics (CFD), and for the first time, simulated patterns of apparent 3He gas velocity are compared with in-vivo PC-MRI. Results show 1) that correlations (R2) between measured and simulated airflow patterns increase from 0.23 to 0.79 simply by accounting for apparent 3He transport, and 2) that remaining differences are mainly due to uncertain airway segmentation and partial volume effects stemming from relatively coarse MRI resolution. Higher-fidelity testing of pulmonary airflow predictions should therefore be possible with future imaging improvements. PMID:22771528

Phase-contrast MRI and CFD modeling of apparent 3He gas flow in rat pulmonary airways

NASA Astrophysics Data System (ADS)

Minard, Kevin R.; Kuprat, Andrew P.; Kabilan, Senthil; Jacob, Richard E.; Einstein, Daniel R.; Carson, James P.; Corley, Richard A.

2012-08-01

Phase-contrast (PC) magnetic resonance imaging (MRI) with hyperpolarized 3He is potentially useful for developing and testing patient-specific models of pulmonary airflow. One challenge, however, is that PC-MRI provides apparent values of local 3He velocity that not only depend on actual airflow but also on gas diffusion. This not only blurs laminar flow patterns in narrow airways but also introduces anomalous airflow structure that reflects gas-wall interactions. Here, both effects are predicted in a live rat using computational fluid dynamics (CFD), and for the first time, simulated patterns of apparent 3He gas velocity are compared with in vivo PC-MRI. Results show (1) that correlations (R2) between measured and simulated airflow patterns increase from 0.23 to 0.79 simply by accounting for apparent 3He transport, and (2) that remaining differences are mainly due to uncertain airway segmentation and partial volume effects stemming from relatively coarse MRI resolution. Higher-fidelity testing of pulmonary airflow predictions should therefore be possible with future imaging improvements.

Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters

NASA Astrophysics Data System (ADS)

Curotto, E.; Mella, M.

2018-03-01

We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D2(H2)n and HD(H2)n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D2 from the adsorbed clusters is always much higher than that of H2 from both pure and doped aggregates. Radial distributions of D2 and H2 are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H2, and at the periphery of the aggregate, H2 molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D2-(H2)n clusters with n ≥12 , such preference leads to the desorption of D2 from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H2)12. The same happens for (H2)13, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.

Simulation of xenon, uranium vacancy and interstitial diffusion and grain boundary segregation in UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Tonks, Michael R.; Casillas, Luis

2014-10-31

In light water reactor fuel, gaseous fission products segregate to grain boundaries, resulting in the nucleation and growth of large intergranular fission gas bubbles. Based on the mechanisms established from density functional theory (DFT) and empirical potential calculations 1, continuum models for diffusion of xenon (Xe), uranium (U) vacancies and U interstitials in UO 2 have been derived for both intrinsic conditions and under irradiation. Segregation of Xe to grain boundaries is described by combining the bulk diffusion model with a model for the interaction between Xe atoms and three different grain boundaries in UO 2 ( Σ5 tilt, Σ5more » twist and a high angle random boundary),as derived from atomistic calculations. All models are implemented in the MARMOT phase field code, which is used to calculate effective Xe and U diffusivities as well as redistribution for a few simple microstructures.« less

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2014-01-01

The Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model is designed to be modular with different user options depending on the computing time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption on the aqueous phase of particles, activity coefficients, phase separation). Each surrogate can be hydrophilic (condenses only on the aqueous phase of particles), hydrophobic (condenses only on the organic phase of particles) or both (condenses on both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC thermodynamic model for short-range interactions and with the AIOMFAC parameterization for medium and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium and a dynamic representation of the organic aerosol. In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol (OA) is not at equilibrium with the gas phase because the organic phase could be semi-solid (very viscous liquid phase). The condensation or evaporation of organic compounds could then be limited by the diffusion in the organic phase due to the high viscosity. A dynamic representation of secondary organic aerosols (SOA) is used with OA divided into layers, the first layer at the center of the particle (slowly reaches equilibrium) and the final layer near the interface with the gas phase (quickly reaches equilibrium).

Effect of stress on the diffusion kinetics of methane during gas desorption in coal matrix under different equilibrium pressures

NASA Astrophysics Data System (ADS)

Li, Chengwu; Xue, Honglai; Hu, Po; Guan, Cheng; Liu, Wenbiao

2018-06-01

Stress has a significant influence on gas diffusion, which is a key factor for methane recovery in coal mines. In this study, a series of experiments were performed to investigate effect of stress on the gas diffusivity during desorption in tectonic coal. Additionally, the desorbed data were modeled using the unipore and bidisperse models. The results show that the bidisperse model better describes the diffusion kinetics than the unipore model in this study. Additionally, the modeling results using the bidisperse approach suggest that the stress impact on the macropore diffusivity is greater than the stress on the micropore diffusivity. Under the same equilibrium pressure, the diffusivity varies with stress according to a four-stage function, which shows an ‘M-shape’. As the equilibrium gas pressure increased from 0.6 to 1.7 MPa, the critical point between stage 2 and stage 3 and between stage 3 and stage 4 transferred to a low stress. This difference is attributed to the gas pressure effects on the physical and mechanical properties of coal. These observations indicate that both the stress and gas pressure can significantly impact gas diffusion and may have significant implications on methane recovery in coal mines.

Unsteady flowfield in an integrated rocket ramjet engine and combustion dynamics of a gas turbine swirl-stabilized injector

NASA Astrophysics Data System (ADS)

Sung, Hong-Gye

This research focuses on the time-accurate simulation and analysis of the unsteady flowfield in an integrated rocket-ramjet engine (IRR) and combustion dynamics of a swirl-stabilized gas turbine engine. The primary objectives are: (1) to establish a unified computational framework for studying unsteady flow and flame dynamics in ramjet propulsion systems and gas turbine combustion chambers, and (2) to investigate the parameters and mechanisms responsible for driving flow oscillations. The first part of the thesis deals with a complete axi-symmetric IRR engine. The domain of concern includes a supersonic inlet diffuser, a combustion chamber, and an exhaust nozzle. This study focused on the physical mechanism of the interaction between the oscillatory terminal shock in the inlet diffuser and the flame in the combustion chamber. In addition, the flow and ignition transitions from the booster to the sustainer phase were analyzed comprehensively. Even though the coupling between the inlet dynamics and the unsteady motions of flame shows that they are closely correlated, fortunately, those couplings are out of phase with a phase lag of 90 degrees, which compensates for the amplification of the pressure fluctuation in the inlet. The second part of the thesis treats the combustion dynamics of a lean-premixed gas turbine swirl injector. A three-dimensional computation method utilizing the message passing interface (MPI) Parallel architecture and large-eddy-simulation technique was applied. Vortex breakdown in the swirling flow is clearly visualized and explained on theoretical bases. The unsteady turbulent flame dynamics are carefully simulated so that the flow motion can be characterized in detail. It was observed that some fuel lumps escape from the primary combustion zone, and move downstream and consequently produce hot spots and large vortical structures in the azimuthal direction. The correlation between pressure oscillation and unsteady heat release is examined by both the spatial and temporal Rayleigh parameters. In addition, basis modes of the unsteady turbulent flame are characterized using proper orthogonal decomposition (POD) analysis.

Gas flows in the circumgalactic medium around simulated high-redshift galaxies

NASA Astrophysics Data System (ADS)

Mitchell, Peter D.; Blaizot, Jérémy; Devriendt, Julien; Kimm, Taysun; Michel-Dansac, Léo; Rosdahl, Joakim; Slyz, Adrianne

2018-03-01

We analyse the properties of circumgalactic gas around simulated galaxies in the redshift range z ≥ 3, utilizing a new sample of cosmological zoom simulations. These simulations are intended to be representative of the observed samples of Lyman α (Ly α) emitters recently obtained with the multi unit spectroscopic explorer (MUSE) instrument (halo masses ˜1010-1011 M⊙). We show that supernova feedback has a significant impact on both the inflowing and outflowing circumgalactic medium (CGM) by driving outflows, reducing diffuse inflow rates, and by increasing the neutral fraction of inflowing gas. By temporally stacking simulation outputs, we find that significant net mass exchange occurs between inflowing and outflowing phases: none of the phases are mass-conserving. In particular, we find that the mass in neutral outflowing hydrogen declines exponentially with radius as gas flows outwards from the halo centre. This is likely caused by a combination of both fountain-like cycling processes and gradual photoionization/collisional ionization of outflowing gas. Our simulations do not predict the presence of fast-moving neutral outflows in the CGM. Neutral outflows instead move with modest radial velocities (˜50 km s-1), and the majority of the kinetic energy is associated with tangential rather than radial motion.

Dissolution without disappearing: multicomponent gas exchange for CO2 bubbles in a microfluidic channel.

PubMed

Shim, Suin; Wan, Jiandi; Hilgenfeldt, Sascha; Panchal, Prathamesh D; Stone, Howard A

2014-07-21

We studied the dissolution dynamics of CO2 gas bubbles in a microfluidic channel, both experimentally and theoretically. In the experiments, spherical CO2 bubbles in a flow of a solution of sodium dodecyl sulfate (SDS) first shrink rapidly before attaining an equilibrium size. In the rapid dissolution regime, the time to obtain a new equilibrium is 30 ms regardless of SDS concentration, and the equilibrium radius achieved varies with the SDS concentration. To explain the lack of complete dissolution, we interpret the results by considering the effects of other gases (O2, N2) that are already dissolved in the aqueous phase, and we develop a multicomponent dissolution model that includes the effect of surface tension and the liquid pressure drop along the channel. Solutions of the model for a stationary gas bubble show good agreement with the experimental results, which lead to our conclusion that the equilibrium regime is obtained by gas exchange between the bubbles and liquid phase. Also, our observations from experiments and model calculations suggest that SDS molecules on the gas-liquid interface form a diffusion barrier, which controls the dissolution behaviour and the eventual equilibrium radius of the bubble.

Numerical Simulation of Combustion and Extinction of a Solid Cylinder in Low-Speed Cross Flow

NASA Technical Reports Server (NTRS)

Tien, J. S.; Yang, Chin Tien

1998-01-01

The combustion and extinction behavior of a diffusion flame around a solid fuel cylinder (PMMA) in low-speed forced flow in zero gravity was studied numerically using a quasi-steady gas phase model. This model includes two-dimensional continuity, full Navier Stokes' momentum, energy, and species equations with a one-step overall chemical reaction and second-order finite-rate Arrhenius kinetics. Surface radiation and Arrhenius pyrolysis kinetics are included on the solid fuel surface description and a parameter Phi, representing the percentage of gas-phase conductive heat flux going into the solid, is introduced into the interfacial energy balance boundary condition to complete the description for the quasi-steady gas-phase system. The model was solved numerically using a body-fitted coordinate transformation and the SIMPLE algorithm. The effects of varying freestream velocity and Phi were studied. These parameters have a significant effect on the flame structure and extinction limits. Two flame modes were identified: envelope flame and wake flame. Two kinds of flammability limits were found: quenching at low-flow speeds due to radiative loss and blow-off at high flow speeds due to insufficient gas residence time. A flammability map was constructed showing the existence of maximum Phi above which the solid is not flammable at any freestream velocity.

The structure of premixed particle-cloud flames

NASA Technical Reports Server (NTRS)

Seshadri, K.; Berlad, A. L.; Tangirala, V.

1992-01-01

The structure of premixed flames propagating in combustible systems, containing uniformly distributed volatile fuel particles, in an oxidizing gas mixture, is analyzed. It is presumed that the fuel particles vaporize first to yield a gaseous fuel of known chemical structure, which is subsequently oxidized in the gas phase. The analysis is performed in the asymptotic limit, where the value of the characteristic Zeldovich number, based on the gas-phase oxidation of the gaseous fuel is large, and for values of phi(u) greater than or equal to 1.0, where phi(u) is the equivalence ratio based on the fuel available in the fuel particles. The structure of the flame is presumed to consist of a preheat vaporization zone where the rate of the gas-phase chemical reaction is small, a reaction zone where convection and the rate of vaporization of the fuel particles are small and a convection zone where diffusive terms in the conservation equations are small. For given values phi(u) the analysis yields results for the burning velocity and phi(g) where phi(g) is the effective equivalence ratio in the reaction zone. The analysis shows that even though phi(u) greater than or equal to 1.0, for certain cases the calculated value of phi(g) is less than unity. This prediction is in agreement with experimental observations.

Pulsed-field-gradient measurements of time-dependent gas diffusion

NASA Technical Reports Server (NTRS)

Mair, R. W.; Cory, D. G.; Peled, S.; Tseng, C. H.; Patz, S.; Walsworth, R. L.

1998-01-01

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O2, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 x 10(-6) m2 s-1 for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times. Copyright 1998 Academic Press.

Apparatus for diffusion separation

DOEpatents

Nierenberg, William A.; Pontius, Rex B.

1976-08-10

1. The method of testing the separation efficiency of porous permeable membranes which comprises causing a stream of a gaseous mixture to flow into contact with one face of a finely porous permeable membrane under such conditions that a major fraction of the mixture diffuses through the membrane, maintaining a rectangular cross section of the gaseous stream so flowing past said membrane, continuously recirculating the gas that diffuses through said membrane and continuously withdrawing the gas that does not diffuse through said membrane and maintaining the volume of said recirculating gas constant by continuously introducing into said continuously recirculating gas stream a mass of gas equivalent to that which is continuously withdrawn from said gas stream and comparing the concentrations of the light component in the entering gas, the withdrawn gas and the recirculated gas in order to determine the efficiency of said membrane.

Investigation of fluorocarbon blowing agents in insulating polymer foams by 19F NMR imaging.

PubMed

Fyfe, C A; Mei, Z; Grondey, H

1996-01-01

Currently, there is no reliable and readily accessible technique with which the distribution and diffusion of blowing agents in rigid insulating foams can be detected and monitored. In this paper, we demonstrate that 19F NMR microscopic imaging together with 19F solid-state MAS NMR spectroscopy is ideally suited for such measurements and yield quantitatively reliable information that will be critical to the development and fabrication of optimized insulating materials with alternative blowing agents. Polystyrene (PS) and polyurethane (PU) foam samples were investigated with the objective of determining quantitatively the amount of blowing agents in the gaseous phase and dissolved in the polymer phase, and to determine and monitor the distribution of the blowing agents in aged foams as a function of time and temperature. The concentrations of the gaseous blowing agents in the cells and dissolved in the solid were simultaneously and quantitatively measured by 19F MAS NMR spectroscopy. An unfaced 1-yr-old PS foam filled with CH3CF2Cl has about 13% of total HCFCs dissolved in the solid; while there is about 24% of HCFCs in the solid of a faced 3-mos-old PU foam filled with CH3CCl2F. The data from 19F NMR imaging demonstrate that the distributions of the blowing agents in an aged foam are quite uniform around the center part (2 cm away from any edge) of a foam board; however, a gradient in blowing agent concentration was found as a function of distance from the initial factory cut edge. The effective diffusion coefficients of the blowing agents can be directly calculated from the imaging data. Quantitative diffusion constants and activation barriers were determined. Additionally, a foam treated with a second blowing agent was monitored with chemical shift selective imaging and the diffusion of the second gas into the foam and the out-diffusion of the original gas were determined.

Biomimetic air sampling for detection of low concentrations of molecules and bioagents : LDRD 52744 final report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hughes, Robert Clark

2003-12-01

Present methods of air sampling for low concentrations of chemicals like explosives and bioagents involve noisy and power hungry collectors with mechanical parts for moving large volumes of air. However there are biological systems that are capable of detecting very low concentrations of molecules with no mechanical moving parts. An example is the silkworm moth antenna which is a highly branched structure where each of 100 branches contains about 200 sensory 'hairs' which have dimensions of 2 microns wide by 100 microns long. The hairs contain about 3000 pores which is where the gas phase molecules enter the aqueous (lymph)more » phase for detection. Simulations of diffusion of molecules indicate that this 'forest' of hairs is 'designed' to maximize the extraction of the vapor phase molecules. Since typical molecules lose about 4 decades in diffusion constant upon entering the liquid phase, it is important to allow air diffusion to bring the molecule as close to the 'sensor' as possible. The moth acts on concentrations as low as 1000 molecules per cubic cm. (one part in 1e16). A 3-D collection system of these dimensions could be fabricated by micromachining techniques available at Sandia. This LDRD addresses the issues involved with extracting molecules from air onto micromachined structures and then delivering those molecules to microsensors for detection.« less

Analysis of opposed jet hydrogen-air counter flow diffusion flame

NASA Technical Reports Server (NTRS)

Ho, Y. H.; Isaac, K. M.

1989-01-01

A computational simulation of the opposed-jet diffusion flame is performed to study its structure and extinction limits. The present analysis concentrates on the nitrogen-diluted hydrogen-air diffusion flame, which provides the basic information for many vehicle designs such as the aerospace plane for which hydrogen is a candidate as the fuel. The computer program uses the time-marching technique to solve the energy and species equations coupled with the momentum equation solved by the collocation method. The procedure is implemented in two stages. In the first stage, a one-step forward overal chemical reaction is chosen with the gas phase chemical reaction rate determined by comparison with experimental data. In the second stage, a complete chemical reaction mechanism is introduced with detailed thermodynamic and transport property calculations. Comparison between experimental extinction data and theoretical predictions is discussed. The effects of thermal diffusion as well as Lewis number and Prandtl number variations on the diffusion flame are also presented.

Modeling diffusion and reaction in soils: 9. The Buckingham-Burdine-Campbell equation for gas diffusivity in undisturbed soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moldrup, P.; Olesen, T.; Yamaguchi, T.

1999-08-01

Accurate description of gas diffusivity (ratio of gas diffusion coefficients in soil and free air, D{sub s}/D{sub 0}) in undisturbed soils is a prerequisite for predicting in situ transport and fate of volatile organic chemicals and greenhouse gases. Reference point gas diffusivities (R{sub p}) in completely dry soil were estimated for 20 undisturbed soils by assuming a power function relation between gas diffusivity and air-filled porosity ({epsilon}). Among the classical gas diffusivity models, the Buckingham (1904) expression, equal to the soil total porosity squared, best described R{sub p}. Inasmuch, as their previous works implied a soil-type dependency of D{sub s}/D{submore » 0}({epsilon}) in undisturbed soils, the Buckingham R{sub p} expression was inserted in two soil-type-dependent D{sub s}/D{sub 0}({epsilon}) models. One D{sub s}/D{sub 0}({epsilon}) model is a function of pore-size distribution (the Campbell water retention parameter used in a modified Burdine capillary tube model), and the other is a calibrated, empirical function of soil texture (silt + sand fraction). Both the Buckingham-Burdine-Campbell (BBC) and the Buckingham/soil texture-based D{sub s}/D{sub 0}({epsilon}) models described well the observed soil type effects on gas diffusivity and gave improved predictions compared with soil type independent models when tested against an independent data set for six undisturbed surface soils. This study emphasizes that simple but soil-type-dependent power function D{sub s}/D{sub 0}({epsilon}) models can adequately describe and predict gas diffusivity in undisturbed soil. The authors recommend the new BBC model as basis for modeling gas transport and reactions in undisturbed soil systems.« less

Assessment of Remote Sensing Technologies for Location of Hydrogen and Helium Leaks

NASA Technical Reports Server (NTRS)

Sellar, R. Glenn; Wang, Danli

2000-01-01

The objective of this initial phase of this research effort is to: 1) Evaluate remote sensing technologies for location of leaks of gaseous molecular hydrogen (H2) and gaseous helium (He) in air, for space transportation applications; and 2) Develop a diffusion model that predicts concentration of H2 or He gas as a function of leak rate and distance from the leak.

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

NASA Technical Reports Server (NTRS)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

The diffuse interstellar medium

NASA Technical Reports Server (NTRS)

Cox, Donald P.

1990-01-01

The last 20 years of the efforts to understand the diffuse ISM are reviewed, with recent changes of fundamental aspects being highlighted. Attention is given to the interstellar pressure and its components, the weight of the ISM, the midplane pressure contributions, and pressure contributions at 1 kpc. What velocity dispersions, cosmic ray pressure, and magnetic field pressure that can be expected for a gas in a high magnetic field environment is addressed. The intercloud medium is described, with reference to the work of Cox and Slavin (1989). Various caveats are discussed and a number of areas for future investigation are identified. Steps that could be taken toward a successful phase segregation model are discussed.

Dynamics and mass transport of solutal convection in a closed porous media system

NASA Astrophysics Data System (ADS)

Wen, Baole; Akhbari, Daria; Hesse, Marc

2016-11-01

Most of the recent studies of CO2 sequestration are performed in open systems where the constant partial pressure of CO2 in the vapor phase results in a time-invariant saturated concentration of CO2 in the brine (Cs). However, in some closed natural CO2 reservoirs, e.g., Bravo Dome in New Mexico, the continuous dissolution of CO2 leads to a pressure drop in the gas that is accompanied by a reduction of Cs and thereby affects the dynamics and mass transport of convection in the brine. In this talk, I discuss the characteristics of convective CO2 dissolution in a closed system. The gas is assumed to be ideal and its solubility given by Henry's law. An analytical solution shows that the diffusive base state is no longer self-similar and that diffusive mass transfer declines rapidly. Scaling analysis reveals that the volume ratio of brine and gas η determines the behavior of the system. DNS show that no constant flux regime exists for η > 0 nevertheless, the quantity F /Cs2 remains constant, where F is the dissolution flux. The onset time is only affected by η when the Rayleigh number Ra is small. In this case, the drop in Cs during the initial diffusive regime significantly reduces the effective Ra and therefore delays the onset.

Biophysical mechanisms of trichloroethene uptake and loss in baldcypress growing in shallow contaminated groundwater

USGS Publications Warehouse

Nietch, C.T.; Morris, J.T.; Vroblesky, D.A.

1999-01-01

Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass- carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass-carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.

Detailed analysis of particle launch velocities, size distributions and gas densities during normal explosions at Stromboli

NASA Astrophysics Data System (ADS)

Harris, Andrew J. L.; Ripepe, Maurizio; Hughes, Elizabeth A.

2012-06-01

Using high frame rate (33 Hz) thermal video data we describe and parameterize the emission and ascent dynamics of a mixed plume of gas and particles emitted during a normal explosion at Stromboli (Aeolian Islands, Italy). Analysis of 34 events showed that 31 of them were characterized by a first phase characterized by an initial diffuse spray of relatively small (lapilli-sized) particles moving at high velocities (up to 213 m s- 1; average 66-82 m s- 1). This was followed, typically within 0.1 s, by a burst comprising a mixture of ash and lapilli, but dominated by larger bomb-sized particles, moving at lower exit velocities of up to 129 m s- 1, but typically 46 m s- 1. We interpret these results as revealing initial emission of a previously unrecorded high velocity gas-jet phase, to which the lapilli are coupled. This is followed by emission of slower moving larger particles that are decoupled from the faster moving gas-phase. Diameters for particles carried by the gas phase are typically around 4 cm, but can be up to 9 cm, with the diameter of the particles carried by the gas jet (D) decreasing with increased density and velocity of the erupted gas cloud (ρgas and Ugas). Data for 101 particles identified as moving with the gas jet during 32 eruptions allow us to define a new relation, whereby Ugas = Uparticle + a [ρgas√{D}]b. Here, Uparticle is the velocity of bombs whose motion is decoupled from that of the gas cloud, and a and b are two empirically-derived coefficients. This replaces the old relation, whereby Ugas = Uparticle + k √{D}; a relation that requires a constant gas density for each eruption. This is an assumption that we show to be invalid, with gas density potentially varying between 0.04 kg m- 3 and 9 kg m- 3 for the 32 cases considered, so that k varies between 54 m1/2 s- 1 and 828 m1/2 s- 1, compared with the traditionally used constant of 150 m1/2 s- 1.

Mixed Matrix Membranes for O2/N2 Separation: The Influence of Temperature

PubMed Central

Fernández-Barquín, Ana; Casado-Coterillo, Clara; Valencia, Susana; Irabien, Angel

2016-01-01

In this work, mixed matrix membranes (MMMs) composed of small-pore zeolites with various topologies (CHA (Si/Al = 5), LTA (Si/Al = 1 and 5), and Rho (Si/Al = 5)) as dispersed phase, and the hugely permeable poly(1-trimethylsilyl-1-propyne) (PTMSP) as continuous phase, have been synthesized via solution casting, in order to obtain membranes that could be attractive for oxygen-enriched air production. The O2/N2 gas separation performance of the MMMs has been analyzed in terms of permeability, diffusivity, and solubility in the temperature range of 298–333 K. The higher the temperature of the oxygen-enriched stream, the lower the energy required for the combustion process. The effect of temperature on the gas permeability, diffusivity, and solubility of these MMMs is described in terms of the Arrhenius and Van’t Hoff relationships with acceptable accuracy. Moreover, the O2/N2 permselectivity of the MMMs increases with temperature, the O2/N2 selectivities being considerably higher than those of the pure PTMSP. In consequence, most of the MMMs prepared in this work exceeded the Robeson’s upper bound for the O2/N2 gas pair in the temperature range under study, with not much decrease in the O2 permeabilities, reaching O2/N2 selectivities of up to 8.43 and O2 permeabilities up to 4,800 Barrer at 333 K. PMID:27196937

A new in-situ method to determine the apparent gas diffusion coefficient of soils

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Paulus, Sinikka; Schack-Kirchner, Helmer; Maier, Martin

2015-04-01

Soil aeration is an important factor for the biological activity in the soil and soil respiration. Generally, gas exchange between soil and atmosphere is assumed to be governed by diffusion and Fick's Law is used to describe the fluxes in the soil. The "apparent soil gas diffusion coefficient" represents the proportional factor between the flux and the gas concentration gradient in the soil and reflects the ability of the soil to "transport passively" gases through the soil. One common way to determine this coefficient is to take core samples in the field and determine it in the lab. Unfortunately this method is destructive and needs laborious field work and can only reflect a small fraction of the whole soil. As a consequence insecurity about the resulting effective diffusivity on the profile scale must remain. We developed a new in-situ method using new gas sampling device, tracer gas and inverse soil gas modelling. The gas sampling device contains several sampling depths and can be easily installed into vertical holes of an auger, which allows for fast installation of the system. At the lower end of the device inert tracer gas is injected continuously. The tracer gas diffuses into the surrounding soil. The resulting distribution of the tracer gas concentrations is used to deduce the diffusivity profile of the soil. For Finite Element Modeling of the gas sampling device/soil system the program COMSOL is used. We will present the results of a field campaign comparing the new in-situ method with lab measurements on soil cores. The new sampling pole has several interesting advantages: it can be used in-situ and over a long time; so it allows following modifications of diffusion coefficients in interaction with rain but also vegetation cycle and wind.

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

Use of ion beams to simulate reaction of reactor fuels with their cladding

NASA Astrophysics Data System (ADS)

Birtcher, R. C.; Baldo, P.

2006-01-01

Processes occurring within reactor cores are not amenable to direct experimental observation. Among major concerns are damage, fission gas accumulation and reaction between the fuel and its cladding all of which lead to swelling. These questions can be investigated through simulation with ion beams. As an example, we discuss the irradiation driven interaction of uranium-molybdenum alloys, intended for use as low-enrichment reactor fuels, with aluminum, which is used as fuel cladding. Uranium-molybdenum coated with a 100 nm thin film of aluminum was irradiated with 3 MeV Kr ions to simulate fission fragment damage. Mixing and diffusion of aluminum was followed as a function of irradiation with RBS and nuclear reaction analysis using the 27Al(p,γ)28Si reaction which occurs at a proton energy of 991.9 keV. During irradiation at 150 °C, aluminum diffused into the uranium alloy at a irradiation driven diffusion rate of 30 nm2/dpa. At a dose of 90 dpa, uranium diffusion into the aluminum layer resulted in formation of an aluminide phase at the initial interface. The thickness of this phase grew until it consumed the aluminum layer. The rapid diffusion of Al into these reactor fuels may offer explanation of the observation that porosity is not observed in the fuel particles but on their periphery.

Effect of Gas Pressure on Polarization of SOFC Cathode Prepared by Plasma Spray

NASA Astrophysics Data System (ADS)

Li, Cheng-Xin; Wang, Zhun-Zhun; Liu, Shuai; Li, Chang-Jiu

2013-06-01

A cermet-supported tubular SOFC was fabricated using thermal spray. The cell performance was investigated at temperatures from 750 to 900 °C and pressures from 0.1 to 0.5 MPa to examine the effect of operating gas pressure on the cell performance. The influence of gas pressure on the cathodic polarization was studied through the electrochemical impedance approach to examine the controlling electrochemical processes during cell operation. Results show that increasing the operating gas pressure improves the power output performance significantly. When the gas pressure is increased from 0.1 to 0.3 MPa, the maximum power density is increased by a factor of 32% at a temperature of 800 °C. The cathode polarization decreases significantly with the increase of the gas pressure. The electrochemical analysis shows that the main control processes of the cathode reaction are the oxygen species transfer at the three-phase boundary and oxygen diffusion on the surface or in the bulk of the cathode, which are enhanced with increasing gas pressure.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium.

PubMed

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10 -13 to 10 -11  m 2 . The results showed that the Knudsen diffusion coefficient of N 2 (D N2 ) (cm 2 /s) was related to the effective permeability coefficient k e (m 2 ) as D N2  = 7.39 × 10 7 k e 0.767 . Thus, the Knudsen diffusion coefficients of N 2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium

NASA Astrophysics Data System (ADS)

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10-13 to 10-11 m2. The results showed that the Knudsen diffusion coefficient of N2 (DN2) (cm2/s) was related to the effective permeability coefficient ke (m2) as DN2 = 7.39 × 107ke0.767. Thus, the Knudsen diffusion coefficients of N2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium.

Electrochemical Device Comprising an Electrically-Conductive, Selectively-Permeable Membrane

NASA Technical Reports Server (NTRS)

Laicer, Castro S. T. (Inventor); Mittelsteadt, Cortney K. (Inventor); Harrison, Katherine E. (Inventor); McPheeters, Bryn M. (Inventor)

2017-01-01

An electrochemical device, such as a fuel cell or an electrolyzer. In one embodiment, the electrochemical device includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, the membrane including a solid polymer electrolyte and a non-particulate, electrically-conductive material, such as carbon nanotubes, carbon nanofibers, and/or metal nanowires. In addition, each bipolar plate also includes an electrically-conductive fluid chamber in contact with the electrically-conductive, selectively-permeable membrane and further includes a non-porous and electrically-conductive plate in contact with the fluid chamber.

The speed of sound in a gas–vapour bubbly liquid

PubMed Central

Prosperetti, Andrea

2015-01-01

In addition to the vapour of the liquid, bubbles in cavitating flows usually contain also a certain amount of permanent gas that diffuses out of the liquid as they grow. This paper presents a simplified linear model for the propagation of monochromatic pressure waves in a bubbly liquid with these characteristics. Phase change effects are included in detail, while the gas is assumed to follow a polytropic law. It is shown that even a small amount of permanent gas can have a major effect on the behaviour of the system. Particular attention is paid to the low-frequency range, which is of special concern in flow cavitation. Numerical results for water and liquid oxygen illustrate the implications of the model. PMID:26442146

Predicting the fate of methane emanating from the seafloor using a marine two-phase gas model in one dimension (M2PG1) - Example from a known Arctic methane seep site offshore Svalbard

NASA Astrophysics Data System (ADS)

Jansson, Pär; Ferré, Benedicte

2017-04-01

Transport of methane in seawater occurs by diffusion and advection in the dissolved phase, and/or as free gas in form of bubbles. The fate of methane in bubbles emitted from the seafloor depends on both bubble size and ambient conditions. Larger bubbles can transport methane higher into the water column, potentially reaching the atmosphere and contributing to greenhouse gas concentrations and impacts. Single bubble or plume models have been used to predict the fate of bubble mediated methane gas emissions. Here, we present a new process based two-phase (free and dissolved) gas model in one dimension, which has the capability to dynamically couple water column properties such as temperature, salinity and dissolved gases with the free gas species contained in bubbles. The marine two-phase gas model in one dimension (M2PG1) uses a spectrum of bubbles and an Eulerian formulation, discretized on a finite-volume grid. It employs the most up-to-date equations for solubility and compressibility of the included gases, nitrogen, oxygen, carbon dioxide and methane. M2PG1 is an extension of PROBE (Omstedt, 2011), which facilitates atmospheric coupling and turbulence closures to realistically predict vertical mixing of all properties, including dissolved methane. This work presents the model's first application in an Arctic Ocean environment at the landward limit of the methane-hydrate stability zone west of Svalbard, where we observe substantial methane bubble release over longer time periods. The research is part of the Centre for Arctic Gas Hydrate, Environment and Climate (CAGE) and is supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259 and UiT. Omstedt, A. (2011). Guide to process based modeling of lakes and coastal seas: Springer.

Intricate but tight coupling of spiracular activity and abdominal ventilation during locust discontinuous gas exchange cycles.

PubMed

Talal, Stav; Gefen, Eran; Ayali, Amir

2018-03-15

Discontinuous gas exchange (DGE) is the best studied among insect gas exchange patterns. DGE cycles comprise three phases, which are defined by their spiracular state: closed, flutter and open. However, spiracle status has rarely been monitored directly; rather, it is often assumed based on CO 2 emission traces. In this study, we directly recorded electromyogram (EMG) signals from the closer muscle of the second thoracic spiracle and from abdominal ventilation muscles in a fully intact locust during DGE. Muscular activity was monitored simultaneously with CO 2 emission, under normoxia and under various experimental oxic conditions. Our findings indicate that locust DGE does not correspond well with the commonly described three-phase cycle. We describe unique DGE-related ventilation motor patterns, coupled to spiracular activity. During the open phase, when CO 2 emission rate is highest, the thoracic spiracles do not remain open; rather, they open and close rapidly. This fast spiracle activity coincides with in-phase abdominal ventilation, while alternating with the abdominal spiracle and thus facilitating a unidirectional air flow along the main trachea. A change in the frequency of rhythmic ventilation during the open phase suggests modulation by intra-tracheal CO 2 levels. A second, slow ventilatory movement pattern probably serves to facilitate gas diffusion during spiracle closure. Two flutter-like patterns are described in association with the different types of ventilatory activity. We offer a modified mechanistic model for DGE in actively ventilating insects, incorporating ventilatory behavior and changes in spiracle state. © 2018. Published by The Company of Biologists Ltd.

Physical Chemical Controls of Methane and other Hydrocarbon gases in Outer Solar System Water-Ice Systems

NASA Astrophysics Data System (ADS)

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

2012-12-01

Saturn's moon Enceladus appear to have liquid water under its thin icy surface that has venting water and complex hydrocarbons. Jupiter's moon Europa is locked under a very thick layer of surface ice. Because Saturn's moon Titan contains abundant hydrocarbon gasses and liquids and both Saturn and Jupiter contain abundant hydrocarbon gases, it is likely that Europa also may have significant quantities of hydrocarbon gases in their water-ice systems. Both of these moons have the potential for life. We have begun to explore the impact that gas hydrate, which is a crystalline material composed of water and gas molecules, has on the availability of liquid water on a planet's surface: what conditions need to be present to initiate hydrate formation from a primordial selection of gases, salts, and water, how isolated hydrate systems evolve under the condition of mass transfer from ex-hydrate stability conditions to pro-hydrate stability conditions, the timespan of conditions that hydrate formation can host liquid solutions in an otherwise cooling regime; and the impact that additional chemistry, such as primitive chemosynthesis, may have on the sequestered hydrocarbon gases in hydrate. The analog for gas hydrate on these moons is the Permafrost hydrate system of Earth. Gas hydrate and water ice are stable in a compound cryosphere with ice extending downward from cold surface conditions to about the 273 K isotherm. Hydrate, depending on the mixture of gases in it, is stable from some depth below the surface to some isotherm that could be considerably in excess of 273 K. Salinity may strongly affect stability conditions. In order to estimate the thickness of the gas hydrate stability zone and its effect on 'planetary' heat flow, we model heat production as a function of mass flow. Variables are gravity, ice thickness, temperature of the surrounding medium (space, ice, and water), the thickness of the "ocean", the and the thermophysical properties of the gas being transferred. The model is constrained by the molecular diffusion rate of gas approaching the hydrate phase boundary. The heat produced or consumed by the hydrate system will affect the ice system and phase boundary. Fick's law can be used to model steady state diffusion. Flux is related to the diffusivity of the component and as a function of concentration and the distance over which the reactions take place. Initial model calculations indicate that in some cases, methane (ΔH = -56 kJ/mol for small molecules (CH4, N2, CO2, H2S) may affect the water-ice energy balance sufficiently to contribute to the maintenance of a deep ocean below ice. The effect of the presence of higher density hydrocarbons (ΔH = -72 kJ/mol for ethane and -126 kJ/mol for propane) accentuate the thermal transfer effect but may diffuse too slowly to be a thermal forcing agent in the hydrate system.

Modeling Secondary Organic Aerosols over Europe: Impact of Activity Coefficients and Viscosity

NASA Astrophysics Data System (ADS)

Kim, Y.; Sartelet, K.; Couvidat, F.

2014-12-01

Semi-volatile organic species (SVOC) can condense on suspended particulate materials (PM) in the atmosphere. The modeling of condensation/evaporation of SVOC often assumes that gas-phase and particle-phase concentrations are at equilibrium. However, recent studies show that secondary organic aerosols (SOA) may not be accurately represented by an equilibrium approach between the gas and particle phases, because organic aerosols in the particle phase may be very viscous. The condensation in the viscous liquid phase is limited by the diffusion from the surface of PM to its core. Using a surrogate approach to represent SVOC, depending on the user's choice, the secondary organic aerosol processor (SOAP) may assume equilibrium or model dynamically the condensation/evaporation between the gas and particle phases to take into account the viscosity of organic aerosols. The model is implemented in the three-dimensional chemistry-transport model of POLYPHEMUS. In SOAP, activity coefficients for organic mixtures can be computed using UNIFAC for short-range interactions between molecules and AIOMFAC to also take into account the effect of inorganic species on activity coefficients. Simulations over Europe are performed and POLYPHEMUS/SOAP is compared to POLYPHEMUS/H2O, which was previously used to model SOA using the equilibrium approach with activity coefficients from UNIFAC. Impacts of the dynamic approach on modeling SOA over Europe are evaluated. The concentrations of SOA using the dynamic approach are compared with those using the equilibrium approach. The increase of computational cost is also evaluated.

Development of a trickle bed reactor of electro-Fenton process for wastewater treatment.

PubMed

Lei, Yangming; Liu, Hong; Shen, Zhemin; Wang, Wenhua

2013-10-15

To avoid electrolyte leakage and gas bubbles in the electro-Fenton (E-Fenton) reactors using a gas diffusion cathode, we developed a trickle bed cathode by coating a layer composed of carbon black and polytetrafluoroethylene (C-PTFE) onto graphite chips instead of carbon cloth. The trickle bed cathode was optimized by single-factor and orthogonal experiments, in which carbon black, PTFE, and a surfactant were considered as the determinant of the performance of graphite chips. In the reactor assembled by the trickle bed cathode, H2O2 was generated with a current of 0.3A and a current efficiency of 60%. This performance was attributed to the fine distribution of electrolyte and air, as well as the effective oxygen transfer from the gas phase to the electrolyte-cathode interface. In terms of H2O2 generation and current efficiency, the developed trickle bed reactor had a performance comparable to that of the conventional E-Fenton reactor using a gas diffusion cathode. Further, 123 mg L(-1) of reactive brilliant red X-3B in aqueous solution was decomposed in the optimized trickle bed reactor as E-Fenton reactor. The decolorization ratio reached 97% within 20 min, and the mineralization reached 87% within 3h. Copyright © 2013 Elsevier B.V. All rights reserved.

SH Observations In and Toward Sgr B2(N): Linking the Missing Sulfur

NASA Astrophysics Data System (ADS)

McCarthy, Michael

Where is the missing sulfur in the molecular reservoir of the interstellar medium (ISM)? In the warm gas phase ISM, the abundance of sulfur is nearly equivalent to its solar value, but in the cold, diffuse clouds which span the space between stars, sulfur is depleted by several orders of magnitude. Our inability to account for this depletion represents a significant gap in our understanding of the fundamental chemical and physical processes occurring in the primordial reservoirs of gas and dust in the ISM. Central to this chemistry is SH, a radical for which few observations presently exist, and for which SOFIA is uniquely capable of accessing in its ground rotational state. We propose observations of SH in the cold, shocked molecular shell surrounding Sgr B2(N), and, simultaneously, in diffuse and translucent clouds along the line of sight to Sgr B2(N). We will constrain the abundance of SH, and compare it to previous measurements of SO, CS, C_2S, HCS(+) , H_2CS, and H_2S in these sources which span the evolutionary timescale from diffuse clouds to dense, cold shocked regions.

Pore-scale lattice Boltzmann simulation of micro-gaseous flow considering surface diffusion effect

DOE PAGES

Wang, Junjian; Kang, Qinjun; Chen, Li; ...

2016-11-21

Some recent studies have shown that adsorbed gas and its surface diffusion have profound influence on micro-gaseous flow through organic pores in shale gas reservoirs. Here, a multiple-relaxation-time (MRT) LB model is adopted to estimate the apparent permeability of organic shale and a new boundary condition, which combines Langmuir adsorption theory with Maxwellian diffusive reflection boundary condition, is proposed to capture gas slip and surface diffusion of adsorbed gas. The simulation results match well with previous studies carried out using Molecular Dynamics (MD) and show that Maxwell slip boundary condition fails to characterize gas transport in the near wall regionmore » under the influence of the adsorbed gas. The total molar flux can be either enhanced or reduced depending on variations in adsorbed gas coverage and surface diffusion velocity. The effects of pore width, pressure as well as Langmuir properties on apparent permeability of methane transport in organic pores are further studied. It is found that the surface transport plays a significant role in determining the apparent permeability, and the variation of apparent permeability with pore size and pressure is affected by the adsorption and surface diffusion.« less

Transport of Gas Phase Radionuclides in a Fractured, Low-Permeability Reservoir

NASA Astrophysics Data System (ADS)

Cooper, C. A.; Chapman, J.

2001-12-01

The U.S. Atomic Energy Commission (predecessor to the Department of Energy, DOE) oversaw a joint program between industry and government in the 1960s and 1970s to develop technology to enhance production from low-permeability gas reservoirs using nuclear stimulation rather than conventional means (e.g., hydraulic and/or acid fracturing). Project Rio Blanco, located in the Piceance Basin, Colorado, was the third experiment under the program. Three 30-kiloton nuclear explosives were placed in a 2134 m deep well at 1780, 1899, and 2039 m below the land surface and detonated in May 1973. Although the reservoir was extensively fractured, complications such as radionuclide contamination of the gas prevented production and subsequent development of the technology. Two-dimensional numerical simulations were conducted to identify the main transport processes that have occurred and are currently occurring in relation to the detonations, and to estimate the extent of contamination in the reservoir. Minor modifications were made to TOUGH2, the multiphase, multicomponent reservoir simulator developed at Lawrence Berkeley National Laboratories. The simulator allows the explicit incorporation of fractures, as well as heat transport, phase change, and first order radionuclide decay. For a fractured two-phase (liquid and gas) reservoir, the largest velocities are of gases through the fractures. In the gas phase, tritium and one isotope of krypton are the principle radionuclides of concern. However, in addition to existing as a fast pathway, fractures also permit matrix diffusion as a retardation mechanism. Another retardation mechanism is radionuclide decay. Simulations show that incorporation of fractures can significantly alter transport rates, and that radionuclides in the gas phase can preferentially migrate upward due to the downward gravity drainage of liquid water in the pores. This project was funded by the National Nuclear Security Administration, Nevada Operations Office, under DOE Contract no. DE-AC08-00NV13609.

Probing the oxidation kinetics of small permalloy particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xiaolei; Song, Xiao; Yin, Shiliu

2017-02-15

The oxidation of permalloys is important to apply in a wide range. The oxidation and diffusion mechanisms of small permalloy particles with different Fe content are studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. Fe{sub 2}O{sub 3}/(Ni, Fe){sub 3}O{sub 4} plays a key role in the morphology evolution and diffusion mechanisms of small NiFe particles upon oxidation. The activation energies of grain boundary diffusion for the NiFe alloys increase from 141 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to ~50 wt%. We have developed a diffusion process resolved temperature programed oxidation (PR-TPO) analysis method.more » Three diffusion mechanisms have been recognized by using this method: In addition to the grain boundary diffusion and lattice diffusion, our TGA analysis suggests that the phase conversion from Fe{sub 2}O{sub 3} to (Ni, Fe){sub 3}O{sub 4} induces diffusion change and affects the diffusion process at the intermediate temperature. Relevant oxidation kinetics and diffusion mechanisms are discussed. - Graphical abstract: The oxidation mechanisms of small Permalloy particles with different Fe content is studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. The activation energies of grain boundary diffusion for the NiFe alloys increases from 140 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to 50 wt% as determined by TGA. We have developed a diffusion process resolved temperature programed oxidation (DPR-TPO) analysis method, and three diffusion mechanisms have been recognized by using this method: In addition to the well-known grain boundary diffusion and lattice diffusion, we found that the phase conversion from Fe{sub 2}O{sub 3} to (Ni, Fe){sub 3}O{sub 4} will induce diffusion changes and affect the diffusion process at the intermediate temperature. The diffusion processes can be characterized by the corresponding characteristic peak temperatures in temperature programmed oxidation (TPO) analysis. This work not only give insight knowledge about the oxidation and diffusion processes of small permalloy particles, but also, provides a useful tool for analyzing solid-gas reactions of other materials. - Highlights: • The oxidation kinetics of small NiFe particles were studied by using thermoanalysis. • Grain boundary, lattice, and phase conversion induced diffusions were recognized. • The activation energy of oxidation increases with the Fe content in the alloy. • Each diffusion process corresponds to a characteristic temperature in TPO analysis. • NiFe alloys with ~5–10 wt% Fe content have the lowest oxidation rates.« less

ASSIGNMENT OF 5069 A DIFFUSE INTERSTELLAR BAND TO HC{sub 4}H{sup +}: DISAGREEMENT WITH LABORATORY ABSORPTION BAND

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maier, J. P.; Chakrabarty, S.; Mazzotti, F. J.

2011-03-10

Krelowski et al. have reported a weak, diffuse interstellar band (DIB) at 5069 A which appears to match in both mid-wavelength and width the A {sup 2}{Pi}{sub u}-X {sup 2}{Pi}{sub g} gas-phase origin absorption band of HC{sub 4}H{sup +}. Here, we present laboratory rotational profiles at low temperatures which are then compared with the 5069 A DIB using {approx}0.1 and 0.3 A line widths based on a realistic line-of-sight interstellar velocity dispersion. Neither the band shape nor the wavelength of the maximum absorption match, which makes the association of the 5069 A DIB with HC{sub 4}H{sup +} unlikely. The magneticmore » dipole transition X {sup 2}{Pi}{sub g} {Omega} = 1/2{yields}X {sup 2}{Pi}{sub g} {Omega} = 3/2 within the ground electronic state which competes with collisional excitation is also considered. In addition, we present the laboratory gas-phase spectrum of the A {sup 2}{Pi}{sub u}-X {sup 2}{Pi}{sub g} transition of HC{sub 4}H{sup +} measured at 25 K in an ion trap and identify further absorption bands at shorter wavelengths for comparison with future DIB data.« less

Hundred Thousand Degree Gas in the Virgo Cluster of Galaxies

NASA Astrophysics Data System (ADS)

Sparks, W. B.; Pringle, J. E.; Carswell, R. F.; Donahue, M.; Martin, R.; Voit, M.; Cracraft, M.; Manset, N.; Hough, J. H.

2012-05-01

The physical relationship between low-excitation gas filaments at ~104 K, seen in optical line emission, and diffuse X-ray emitting coronal gas at ~107 K in the centers of many galaxy clusters is not understood. It is unclear whether the ~104 K filaments have cooled and condensed from the ambient hot (~107 K) medium or have some other origin such as the infall of cold gas in a merger, or the disturbance of an internal cool reservoir of gas by nuclear activity. Observations of gas at intermediate temperatures (~105-106 K) can potentially reveal whether the central massive galaxies are gaining cool gas through condensation or losing it through conductive evaporation and hence identify plausible scenarios for transport processes in galaxy cluster gas. Here we present spectroscopic detection of ~105 K gas spatially associated with the Hα filaments in a central cluster galaxy, M87, in the Virgo Cluster. The measured emission-line fluxes from triply ionized carbon (C IV 1549 Å) and singly ionized helium (He II 1640 Å) are consistent with a model in which thermal conduction determines the interaction between hot and cold phases.

Fuel cell membrane humidification

DOEpatents

Wilson, Mahlon S.

1999-01-01

A polymer electrolyte membrane fuel cell assembly has an anode side and a cathode side separated by the membrane and generating electrical current by electrochemical reactions between a fuel gas and an oxidant. The anode side comprises a hydrophobic gas diffusion backing contacting one side of the membrane and having hydrophilic areas therein for providing liquid water directly to the one side of the membrane through the hydrophilic areas of the gas diffusion backing. In a preferred embodiment, the hydrophilic areas of the gas diffusion backing are formed by sewing a hydrophilic thread through the backing. Liquid water is distributed over the gas diffusion backing in distribution channels that are separate from the fuel distribution channels.

Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.

2014-12-01

Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.

METAL DIFFUSION IN SMOOTHED PARTICLE HYDRODYNAMICS SIMULATIONS OF DWARF GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williamson, David; Martel, Hugo; Kawata, Daisuke, E-mail: david-john.williamson.1@ulaval.ca

2016-05-10

We perform a series of smoothed particle hydrodynamics simulations of isolated dwarf galaxies to compare different metal mixing models. In particular, we examine the role of diffusion in the production of enriched outflows and in determining the metallicity distributions of gas and stars. We investigate different diffusion strengths by changing the pre-factor of the diffusion coefficient, by varying how the diffusion coefficient is calculated from the local velocity distribution, and by varying whether the speed of sound is included as a velocity term. Stronger diffusion produces a tighter [O/Fe]–[Fe/H] distribution in the gas and cuts off the gas metallicity distributionmore » function at lower metallicities. Diffusion suppresses the formation of low-metallicity stars, even with weak diffusion, and also strips metals from enriched outflows. This produces a remarkably tight correlation between “metal mass-loading” (mean metal outflow rate divided by mean metal production rate) and the strength of diffusion, even when the diffusion coefficient is calculated in different ways. The effectiveness of outflows at removing metals from dwarf galaxies and the metal distribution of the gas is thus dependent on the strength of diffusion. By contrast, we show that the metallicities of stars are not strongly dependent on the strength of diffusion, provided that some diffusion is present.« less

Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

NASA Astrophysics Data System (ADS)

Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

2018-06-01

Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

Unifying diffusion and seepage for nonlinear gas transport in multiscale porous media

NASA Astrophysics Data System (ADS)

Song, Hongqing; Wang, Yuhe; Wang, Jiulong; Li, Zhengyi

2016-09-01

We unify the diffusion and seepage process for nonlinear gas transport in multiscale porous media via a proposed new general transport equation. A coherent theoretical derivation indicates the wall-molecule and molecule-molecule collisions drive the Knudsen and collective diffusive fluxes, and constitute the system pressure across the porous media. A new terminology, nominal diffusion coefficient can summarize Knudsen and collective diffusion coefficients. Physical and numerical experiments show the support of the new formulation and provide approaches to obtain the diffusion coefficient and permeability simultaneously. This work has important implication for natural gas extraction and greenhouse gases sequestration in geological formations.

Direct monitoring of wind-induced pressure-pumping on gas transport in soil

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Mohr, Manuel; Schindler, Dirk; Schack-Kirchner, Helmer; Maier, Martin

2017-04-01

Gas exchange between soil and atmosphere is important for the biogeochemistry of soils and is commonly assumed to be governed by molecular diffusion. Yet a few previous field studies identified other gas transport processes such as wind-induced pressure-pumping to enhance soil-atmosphere fluxes significantly. However, since these wind-induced non-diffusive gas transport processes in soil often occur intermittently, the quantification of their contribution to soil gas emissions is challenging. To quantify the effects of wind-induced pressure-pumping on soil gas transport, we developed a method for in situ monitoring of soil gas transport. The method includes the use of Helium (He) as a tracer gas which was continuously injected into the soil. The resulting He steady-state concentration profile was monitored. Gas transport parameters of the soil were inversely modelled. We used our method during a field campaign in a well-aerated forest soil over three months. During periods of low wind speed, soil gas transport was modelled assuming diffusion as transport process. During periods of high wind speed, the previously steady diffusive He concentration profile showed temporary concentration decreases in the topsoil, indicating an increase of the effective gas transport rate in the topsoil up to 30%. The enhancement of effective topsoil soil gas diffusivity resulted from wind-induced air pressure fluctuations which are referred to as pressure-pumping. These air pressure fluctuations had frequencies between 0.1 and 0.01 Hz and amplitudes up to 10 Pa and occurred at above-canopy wind speeds greater than 5 m s-1. We could show the importance of the enhancement of the gas transport rate in relation with the wind intensity and corresponding air pressure fluctuations characteristics. We directly detected and quantified the pressure-pumping effect on gas transport in soil in a field study for the first time, and could thus validate and underpin the importance of this non-diffusive gas transport process. Our method can also be used to study other non-diffusive gas transport processes occurring in soil and snow, and their possible feedbacks or interactions with biogeochemical processes.

Biodegradation of vapor-phase toluene in unsaturated porous media: Column experiments.

PubMed

Khan, Ali M; Wick, Lukas Y; Harms, Hauke; Thullner, Martin

2016-04-01

Biodegradation of organic chemicals in the vapor phase of soils and vertical flow filters has gained attention as promising approach to clean up volatile organic compounds (VOC). The drivers of VOC biodegradation in unsaturated systems however still remain poorly understood. Here, we analyzed the processes controlling aerobic VOC biodegradation in a laboratory setup mimicking the unsaturated zone above a shallow aquifer. The setup allowed for diffusive vapor-phase transport and biodegradation of three VOC: non-deuterated and deuterated toluene as two compounds of highly differing biodegradability but (nearly) identical physical and chemical properties, and MTBE as (at the applied experimental conditions) non-biodegradable tracer and internal control. Our results showed for toluene an effective microbial degradation within centimeter VOC transport distances despite high gas-phase diffusivity. Degradation rates were controlled by the reactivity of the compounds while oxic conditions were found everywhere in the system. This confirms hypotheses that vadose zone biodegradation rates can be extremely high and are able to prevent the outgassing of VOC to the atmosphere within a centimeter range if compound properties and site conditions allow for sufficiently high degradation rates. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Fast Vector Radiative Transfer Model for Atmospheric and Oceanic Remote Sensing

NASA Astrophysics Data System (ADS)

Ding, J.; Yang, P.; King, M. D.; Platnick, S. E.; Meyer, K.

2017-12-01

A fast vector radiative transfer model is developed in support of atmospheric and oceanic remote sensing. This model is capable of simulating the Stokes vector observed at the top of the atmosphere (TOA) and the terrestrial surface by considering absorption, scattering, and emission. The gas absorption is parameterized in terms of atmospheric gas concentrations, temperature, and pressure. The parameterization scheme combines a regression method and the correlated-K distribution method, and can easily integrate with multiple scattering computations. The approach is more than four orders of magnitude faster than a line-by-line radiative transfer model with errors less than 0.5% in terms of transmissivity. A two-component approach is utilized to solve the vector radiative transfer equation (VRTE). The VRTE solver separates the phase matrices of aerosol and cloud into forward and diffuse parts and thus the solution is also separated. The forward solution can be expressed by a semi-analytical equation based on the small-angle approximation, and serves as the source of the diffuse part. The diffuse part is solved by the adding-doubling method. The adding-doubling implementation is computationally efficient because the diffuse component needs much fewer spherical function expansion terms. The simulated Stokes vector at both the TOA and the surface have comparable accuracy compared with the counterparts based on numerically rigorous methods.

HYDROGEN CHLORIDE IN DIFFUSE INTERSTELLAR CLOUDS ALONG THE LINE OF SIGHT TO W31C (G10.6-0.4)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monje, R. R.; Lis, D. C.; Phillips, T. G.

2013-04-10

We report the detection of hydrogen chloride, HCl, in diffuse molecular clouds on the line of sight toward the star-forming region W31C (G10.6-0.4). The J = 1-0 lines of the two stable HCl isotopologues, H{sup 35}Cl and H{sup 37}Cl, are observed using the 1b receiver of the Heterodyne Instrument for the Far-Infrared (HIFI) on board the Herschel Space Observatory. The HCl line is detected in absorption, over a wide range of velocities associated with diffuse clouds along the line of sight to W31C. The analysis of the absorption strength yields a total HCl column density of a few 10{sup 13}more » cm{sup -2}, implying that HCl accounts for {approx}0.6% of the total gas-phase chlorine, which exceeds the theoretical model predictions by a factor of {approx}6. This result is comparable to those obtained from the chemically related species H{sub 2}Cl{sup +} and HCl{sup +}, for which large column densities have also been reported on the same line of sight. The source of discrepancy between models and observations is still unknown; however, the detection of these Cl-bearing molecules provides key constraints for the chlorine chemistry in the diffuse gas.« less

Measuring surface-area-to-volume ratios in soft porous materials using laser-polarized xenon interphase exchange nuclear magnetic resonance

NASA Technical Reports Server (NTRS)

Butler, J. P.; Mair, R. W.; Hoffmann, D.; Hrovat, M. I.; Rogers, R. A.; Topulos, G. P.; Walsworth, R. L.; Patz, S.

2002-01-01

We demonstrate a minimally invasive nuclear magnetic resonance (NMR) technique that enables determination of the surface-area-to-volume ratio (S/V) of soft porous materials from measurements of the diffusive exchange of laser-polarized 129Xe between gas in the pore space and 129Xe dissolved in the solid phase. We apply this NMR technique to porous polymer samples and find approximate agreement with destructive stereological measurements of S/V obtained with optical confocal microscopy. Potential applications of laser-polarized xenon interphase exchange NMR include measurements of in vivo lung function in humans and characterization of gas chromatography columns.

Thermostable ferroelectric capacitors based on graded films of barium strontium titanate

NASA Astrophysics Data System (ADS)

Tumarkin, A. V.; Razumov, S. V.; Volpyas, V. A.; Gagarin, A. G.; Odinets, A. A.; Zlygostov, M. V.; Sapego, E. N.

2017-10-01

The influence of the pressure of working gas during the ion-plasma sputtering on properties of deposited ferroelectric barium strontium titanate coatings has been experimentally studied. Variations in the of pressure of the working gas during deposition allows the component composition of the deposited layer to be changed, which leads to the diffusion of the phase transition and the improvement of temperature stability of properties of ferroelectric film. The gradation of layers has an impact on the temperature of the dielectric permittivity maximum, the shape of the dependence of the capacity on temperature, and the capacitance-voltage characteristics of the capacitor structures.

An Approach Using Gas Monitoring to Find the Residual TCE Location in the Unsaturated Zone of Woosan Industrial Complex (WIC), Korea

NASA Astrophysics Data System (ADS)

Koh, Y.; Lee, S.; Yang, J.; Lee, K.

2012-12-01

An area accommodating various industrial facilities has fairly high probability of groundwater contamination with multiple chlorinated solvents such as trichloroethene (TCE), carbon tetrachloride (CT), and chloroform (CF). Source tracing of chlorinated solvents in the unsaturated zone is an essential procedure for the management and remediation of contaminated area. From the previous study on seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume, the existence of residual DNAPLs at or above the water table has proved. Since TCE is one of the frequently detected VOCs (Volatile Organic Compounds) in groundwater, residual TCE can be detected by gas monitoring. Therefore, monitoring of temporal and spatial variations in the gas phase TCE contaminant at an industrial complex in Wonju, Korea, were used to find the residual TCE locations. As pilot tests, TCE gas samples collected in the unsaturated zone at 4 different wells were analyzed using SPME (Solid Phase MicroExtraction) fiber and Gas Chromatography (GC). The results indicated that detecting TCE in gas phase was successful from these wells and TCE analysis on gas samples, collected from the unsaturated zone, will be useful for source area characterization. However, some values were too high to doubt the accuracy of the current method, which needs a preliminary lab test with known concentrations. The modified experiment setups using packer at different depths are in process to find residual TCE locations in the unsaturated zone. Meanwhile, several PVD (polyethylene-membrane Passive Vapor Diffusion) samplers were placed under water table to detect VOCs by equilibrium between air in the vial and VOCs in pore water.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shum, Andrew D.; Parkinson, Dilworth Y.; Xiao, Xianghui

The performance of polymer-electrolyte fuel cells is heavily dependent on proper management of liquid water. One particular reason is that liquid water can collect in the gas diffusion layers (GDLs) blocking the reactant flow to the catalyst layer. This results in increased mass-transport losses. At higher temperatures, evaporation of water becomes a dominant water-removal mechanism and specifically phase-change-induced (PCI) flow is present due to thermal gradients. This study used synchrotron based micro X-ray computed tomography (CT) to visualize and quantify the water distribution within gas diffusion layers subject to a thermal gradient. Plotting saturation as a function of through-plane distancemore » quantitatively shows water redistribution, where water evaporates at hotter locations and condenses in colder locations. The morphology of the 2 GDLs on the micro-scale, as well as evaporating water clusters, are resolved, indicating that the GDL voids are slightly prolate, whereas water clusters are oblate. From the mean radii of water distributions and visual inspection, it is observed that larger water clusters evaporate faster than smaller ones.« less

Factors controlling the concentration of methane and other volatiles in groundwater and soil-gas around a waste site

NASA Astrophysics Data System (ADS)

Barber, C.; Davis, G. B.; Briegel, D.; Ward, J. K.

1990-01-01

The concentration of methane in groundwater and soil-gas in the vicinity of a waste landfill on an unconfined sand aquifer has been investigated in detail. These data have been used to evaluate techniques which use volatile organic compounds in soil-gas as indicators of groundwater contamination. Simple one-dimensional models of gas advection and diffusion have been adapted for use in the study. Lateral advection of gas in the unsaturated sand was found to be seasonal and was most noticeable in winter when the profile was wet; a mean velocity of 1 m d - was measured from breakthrough of a helium tracer in an injection test. The effects of advection on trace concentrations of methane in soil-gas were limited to within 150-200m from the waste site and resulted from pressure gradients brought about by positive gas pressures in the landfill, and also as a result of ebullition (gas bubbling) from contaminated groundwater. The distribution of methane in soil-gas at shallow (2m) depth gave a general indication of the direction of movement of contaminants with groundwater in close proximity to the landfill. Outside this zone, diffusional transport of methane from groundwater to soil-gas occurred and methane in soil-gas sampled close to the water table was found to be a useful indicator of contaminated groundwater. Modelling the exchange of volatiles between aqueous and gas phases indicates that a wide range of organic compounds, particularly those with Henry's Law constants greater than 2.5 × 10 t-2 kPam 3mol -1, would have potential for use as indicators of pollution, if these were present in groundwater and they behaved relatively conservatively. In general, the principal factors controlling the concentration of these volatiles in soil-gas were the concentration gradient at the water table and capillary fringe and the ratio of diffusion coefficients in the saturated and unsaturated zones.

First-principles study of fission gas incorporation and migration in zirconium nitride

DOE PAGES

Mei, Zhi-Gang; Liang, Linyun; Yacout, Abdellatif M.

2017-03-24

To evaluate the effectiveness of ZrN as a diffusion barrier against fission gases, we investigate in this paper the incorporation and migration of fission gas atoms, with a focus on Xe, in ZrN by first-principles calculations. The formations of point defects in ZrN, including vacancies, interstitials, divacancies, Frenkel pairs, and Schottky defects, are first studied. Among all the defects, the Schottky defect with two vacancies as first nearest neighbor is predicted to be the most favorable incorporation site for fission gas Xe in ZrN. The migration of Xe gas atom in ZrN is investigated through two diffusion mechanisms, i.e., interstitialmore » and vacancy-assisted diffusions. The migration barrier of Xe gas atom through the intrinsic interstitials in ZrN is considerably lower than that through vacancies. Finally, therefore, at low temperatures fission gas Xe atoms diffuse mainly through interstitials in single crystal ZrN, whereas at high temperatures Xe may diffuse in ZrN assisted by vacancies.« less

X-ray fluorescence measurements of dissolved gas and cavitation

DOE PAGES

Duke, Daniel J.; Kastengren, Alan L.; Swantek, Andrew B.; ...

2016-09-28

The dynamics of dissolved gas and cavitation are strongly coupled, yet these phenomena are difficult to measure in-situ. Both create voids in the fluid that can be difficult to distinguish. In this paper, we present an application of X-ray fluorescence in which liquid density and total noncondensible gas concentration (both dissolved and nucleated) are simultaneously measured. The liquid phase is doped with 400 ppm of a bromine tracer, and dissolved air is removed and substituted with krypton. Fluorescent emission at X-ray wavelengths is simultaneously excited from the Br and Kr with a focused monochromatic X-ray beam from a synchrotron source.more » We measure the flow in a cavitating nozzle 0.5 mm in diameter. From Br fluorescence, total displacement of the liquid is measured. From Kr fluorescence, the mass fraction of both dissolved and nucleated gas is measured. Volumetric displacement of liquid due to both cavitation and gas precipitation can be separated through estimation of the local equilibrium dissolved mass fraction. The uncertainty in the line of sight projected densities of the liquid and gas phases is 4–6 %. The high fluorescence yields and energies of Br and Kr allow small mass fractions of gas to be measured, down to 10 -5, with an uncertainty of 8 %. Finally, these quantitative measurements complement existing optical diagnostic techniques and provide new insight into the diffusion of gas into cavitation bubbles, which can increase their internal density, pressure and lifetimes by orders of magnitude.« less

An in situ method for real-time monitoring of soil gas diffusivity

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Maier, Martin; Schack-Kirchner, Helmer; Lang, Friederike

2016-04-01

Soil aeration is an important factor for the biogeochemistry of soils. Generally, gas exchange between soil and atmosphere is assumed to be governed by molecular diffusion and by this way fluxes can be calculated using by Fick's Law. The soil gas diffusion coefficient DS represents the proportional factor between the gas flux and the gas concentration gradient in the soil and reflects the ability of the soil to "transport passively" gas through the soil. One common way to determine DS is taking core samples in the field and measuring DS in the lab. Unfortunately this method is destructive and laborious and it can only reflect a small fraction of the whole soil. As a consequence, uncertainty about the resulting effective diffusivity on the profile scale, i.e. the real aeration status remains. We developed a method to measure and monitor DS in situ. The set-up consists of a custom made gas sampling device, the continuous injection of an inert tracer gas and inverse gas transport modelling in the soil. The gas sampling device has seven sampling depths (from 0 to -43 cm of depth) and can be easily installed into vertical holes drilled by an auger, which allows for fast installation of the system. Helium (He) as inert tracer gas was injected continuously at the lower end of the device. The resulting steady state distribution of He was used to deduce the DS depth distribution of the soil. For Finite Element Modeling of the gas-sampling-device/soil system the program COMSOL was used. We tested our new method both in the lab and in a field study and compared the results with a reference lab method using soil cores. DS profiles obtained by our in-situ method were consistent with DS profiles determined based on soil core analyses. Soil gas profiles could be measured with a temporal resolution of 30 minutes. During the field study, there was an important rain event and we could monitor the decrease in soil gas diffusivity in the top soil due to water infiltration. The effect of soil water infiltration deeper into the soil on soil gas diffusivity could be observed during the following hours. Our new DS determination device can be quickly and easily installed and allows for monitoring continuously soil gas transport over a long time. It allows following modifications of soil gas diffusivity due to rain events. In addition it enables the analysis of non-diffusive soil gas transport processes.

Nondestructive natural gas hydrate recovery driven by air and carbon dioxide.

PubMed

Kang, Hyery; Koh, Dong-Yeun; Lee, Huen

2014-10-14

Current technologies for production of natural gas hydrates (NGH), which include thermal stimulation, depressurization and inhibitor injection, have raised concerns over unintended consequences. The possibility of catastrophic slope failure and marine ecosystem damage remain serious challenges to safe NGH production. As a potential approach, this paper presents air-driven NGH recovery from permeable marine sediments induced by simultaneous mechanisms for methane liberation (NGH decomposition) and CH₄-air or CH₄-CO₂/air replacement. Air is diffused into and penetrates NGH and, on its surface, forms a boundary between the gas and solid phases. Then spontaneous melting proceeds until the chemical potentials become equal in both phases as NGH depletion continues and self-regulated CH4-air replacement occurs over an arbitrary point. We observed the existence of critical methane concentration forming the boundary between decomposition and replacement mechanisms in the NGH reservoirs. Furthermore, when CO₂ was added, we observed a very strong, stable, self-regulating process of exchange (CH₄ replaced by CO₂/air; hereafter CH₄-CO₂/air) occurring in the NGH. The proposed process will work well for most global gas hydrate reservoirs, regardless of the injection conditions or geothermal gradient.

Nondestructive natural gas hydrate recovery driven by air and carbon dioxide

PubMed Central

Kang, Hyery; Koh, Dong-Yeun; Lee, Huen

2014-01-01

Current technologies for production of natural gas hydrates (NGH), which include thermal stimulation, depressurization and inhibitor injection, have raised concerns over unintended consequences. The possibility of catastrophic slope failure and marine ecosystem damage remain serious challenges to safe NGH production. As a potential approach, this paper presents air-driven NGH recovery from permeable marine sediments induced by simultaneous mechanisms for methane liberation (NGH decomposition) and CH4-air or CH4-CO2/air replacement. Air is diffused into and penetrates NGH and, on its surface, forms a boundary between the gas and solid phases. Then spontaneous melting proceeds until the chemical potentials become equal in both phases as NGH depletion continues and self-regulated CH4-air replacement occurs over an arbitrary point. We observed the existence of critical methane concentration forming the boundary between decomposition and replacement mechanisms in the NGH reservoirs. Furthermore, when CO2 was added, we observed a very strong, stable, self-regulating process of exchange (CH4 replaced by CO2/air; hereafter CH4-CO2/air) occurring in the NGH. The proposed process will work well for most global gas hydrate reservoirs, regardless of the injection conditions or geothermal gradient. PMID:25311102

Mechanism of Methane Transport from the Rhizosphere to the Atmosphere through Rice Plants 1

PubMed Central

Nouchi, Isamu; Mariko, Shigeru; Aoki, Kazuyuki

1990-01-01

To clarify the mechanisms of methane transport from the rhizosphere into the atmosphere through rice plants (Oryza sativa L.), the methane emission rate was measured from a shoot whose roots had been kept in a culture solution with a high methane concentration or exposed to methane gas in the gas phase by using a cylindrical chamber. No clear correlation was observed between change in the transpiration rate and that in the methane emission rate. Methane was mostly released from the culm, which is an aggregation of leaf sheaths, but not from the leaf blade. Micropores which are different from stomata were newly found at the abaxial epidermis of the leaf sheath by scanning electron microscopy. The measured methane emission rate was much higher than the calculated methane emission rate that would result from transpiration and the methane concentration in the culture solution. Rice roots could absorb methane gas in the gas phase without water uptake. These results suggest that methane dissolved in the soil water surrounding the roots diffuses into the cell-wall water of the root cells, gasifies in the root cortex, and then is mostly released through the micropores in the leaf sheaths. Images Figure 7 PMID:16667719

Methods for Solving Gas Damping Problems in Perforated Microstructures Using a 2D Finite-Element Solver

PubMed Central

Veijola, Timo; Råback, Peter

2007-01-01

We present a straightforward method to solve gas damping problems for perforated structures in two dimensions (2D) utilising a Perforation Profile Reynolds (PPR) solver. The PPR equation is an extended Reynolds equation that includes additional terms modelling the leakage flow through the perforations, and variable diffusivity and compressibility profiles. The solution method consists of two phases: 1) determination of the specific admittance profile and relative diffusivity (and relative compressibility) profiles due to the perforation, and 2) solution of the PPR equation with a FEM solver in 2D. Rarefied gas corrections in the slip-flow region are also included. Analytic profiles for circular and square holes with slip conditions are presented in the paper. To verify the method, square perforated dampers with 16–64 holes were simulated with a three-dimensional (3D) Navier-Stokes solver, a homogenised extended Reynolds solver, and a 2D PPR solver. Cases for both translational (in normal to the surfaces) and torsional motion were simulated. The presented method extends the region of accurate simulation of perforated structures to cases where the homogenisation method is inaccurate and the full 3D Navier-Stokes simulation is too time-consuming.

An integrated simulator of structure and anisotropic flow in gas diffusion layers with hydrophobic additives

NASA Astrophysics Data System (ADS)

Burganos, Vasilis N.; Skouras, Eugene D.; Kalarakis, Alexandros N.

2017-10-01

The lattice-Boltzmann (LB) method is used in this work to reproduce the controlled addition of binder and hydrophobicity-promoting agents, like polytetrafluoroethylene (PTFE), into gas diffusion layers (GDLs) and to predict flow permeabilities in the through- and in-plane directions. The present simulator manages to reproduce spreading of binder and hydrophobic additives, sequentially, into the neat fibrous layer using a two-phase flow model. Gas flow simulation is achieved by the same code, sidestepping the need for a post-processing flow code and avoiding the usual input/output and data interface problems that arise in other techniques. Compression effects on flow anisotropy of the impregnated GDL are also studied. The permeability predictions for different compression levels and for different binder or PTFE loadings are found to compare well with experimental data for commercial GDL products and with computational fluid dynamics (CFD) predictions. Alternatively, the PTFE-impregnated structure is reproduced from Scanning Electron Microscopy (SEM) images using an independent, purely geometrical approach. A comparison of the two approaches is made regarding their adequacy to reproduce correctly the main structural features of the GDL and to predict anisotropic flow permeabilities at different volume fractions of binder and hydrophobic additives.

Isentropic phase changes in dissociating gases and the method of sound dispersion for the investigation of homogeneous gas reactions with very high speed : Conclusion

NASA Technical Reports Server (NTRS)

Damkohler, Gerhard

1950-01-01

The analytical results of Part I are also applied to sound dispersion by friction and heat conduction, An irreversible change of momentum, energy, and type of particle corresponding to friction, heat conduction, and diffusion effects can appear both in the direction of the sound field and traverse to it. Longitudinal damping, the coupling of longitudinal damping and that due to chemical and physical changes, and coupling of diffusion and compositional changes are treated for a plane sound wave of infinite extent. The same principles are also applied to sound effects in cylindrical tubes. The limitations of the method are discussed in some detail.

Conductive polymer layers to limit transfer of fuel reactants to catalysts of fuel cells to reduce reactant crossover

DOEpatents

Stanis, Ronald J.; Lambert, Timothy N.

2016-12-06

An apparatus of an aspect includes a fuel cell catalyst layer. The fuel cell catalyst layer is operable to catalyze a reaction involving a fuel reactant. A fuel cell gas diffusion layer is coupled with the fuel cell catalyst layer. The fuel cell gas diffusion layer includes a porous electrically conductive material. The porous electrically conductive material is operable to allow the fuel reactant to transfer through the fuel cell gas diffusion layer to reach the fuel cell catalyst layer. The porous electrically conductive material is also operable to conduct electrons associated with the reaction through the fuel cell gas diffusion layer. An electrically conductive polymer material is coupled with the fuel cell gas diffusion layer. The electrically conductive polymer material is operable to limit transfer of the fuel reactant to the fuel cell catalyst layer.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

The influence of temperature induced phase transition on the energy storage density of anti-ferroelectric ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Jinqiao; Zhang, Ling; Xie, Bing

2015-09-28

Anti-ferroelectric (AFE) composite ceramics of (Pb{sub 0.858}Ba{sub 0.1}La{sub 0.02}Y{sub 0.008})(Zr{sub 0.65}Sn{sub 0.3}Ti{sub 0.05})O{sub 3}-(Pb{sub 0.97}La{sub 0.02})(Zr{sub 0.9}Sn{sub 0.05} Ti{sub 0.05})O{sub 3} (PBLYZST-PLZST) were fabricated by the conventional solid-state sintering process (CS), the glass-aided sintering (GAS), and the spark plasma sintering (SPS), respectively. The influence of the temperature induced phase transition on the phase structure, hysteresis loops, and energy storage properties of the composite ceramics were investigated in detail. The measured results of X-ray diffraction demonstrate that the composite ceramics exhibit the perovskite phases and small amounts of non-functional pyrochlore phases. Compared with the CS process, the GAS and SPS processesmore » are proven more helpful to suppress the diffusion behaviors between the PBLYZST and PLZST phases according to the field emission scanning electron microscopy, thereby being able to improve the contribution of PBLYZST phase to the temperature stability of the orthogonal AFE phase. When the ambient temperature rises from 25 °C to 125 °C, CS and GAS samples have undergone a phase transition from orthorhombic AFE phase to tetragonal AFE phase, which results in a sharp decline in the energy storage density. However, the phase transition temperature of SPS samples is higher than 125 °C, and the energy storage density only slightly decreases due to the disorder of material microstructure caused by the high temperature. As a result, the SPS composite ceramics obtain a recoverable high energy storage density of 6.46 J/cm{sup 3} and the excellent temperature stability of the energy storage density of 1.16 × 10{sup −2} J/°C·cm{sup 3}, which is 1.29 × 10{sup −2} J/°C·cm{sup 3} lower than that of CS samples and about 0.43 times as that of GAS samples.« less

A Study on the Characteristics of Design Variables for IRSS Diffuser

NASA Astrophysics Data System (ADS)

Cho, Yong-Jin; Ko, Dae-Eun

2017-11-01

In modern naval ships, infrared signature suppression systems (IRSS) are installed to decrease the temperature of waste gas generated in propulsion engine and the metallic surface temperature of heated exhaust pipes. Generally, IRSS is composed of eductor, mixing tube, and diffuser. Diffuser serves to reduce the temperature by creating an air film using the pressure difference between internal gas and external air. In this study, design variables were selected by analyzing the diffuser and the characteristics of design variables that affect the performance of diffuser were examined using Taguchi experiment method. For the diffuser performance analysis, a heat flow analysis technique established in previous research was used. The IRSS performance evaluation was carried out based on the average area value of the metal surface temperature and the temperature of the exhaust gas at the outlet of the diffuser, which are variables directly related to the intensity of infrared signature in naval ships. It was verified that the exhaust gas temperature is greatly affected by changes in the diameter of the diffuser outlet, and the metal surface temperature of diffuser is greatly affected by changes in the number of diffuser rings.

Bacterial chemotaxis along vapor-phase gradients of naphthalene.

PubMed

Hanzel, Joanna; Harms, Hauke; Wick, Lukas Y

2010-12-15

The role of bacterial growth and translocation for the bioremediation of organic contaminants in the vadose zone is poorly understood. Whereas air-filled pores restrict the mobility of bacteria, diffusion of volatile organic compounds in air is more efficient than in water. Past research, however, has focused on chemotactic swimming of bacteria along gradients of water-dissolved chemicals. In this study we tested if and to what extent Pseudomonas putida PpG7 (NAH7) chemotactically reacts to vapor-phase gradients forming above their swimming medium by the volatilization from a spot source of solid naphthalene. The development of an aqueous naphthalene gradient by air-water partitioning was largely suppressed by means of activated carbon in the agar. Surprisingly, strain PpG7 was repelled by vapor-phase naphthalene although the steady state gaseous concentrations were 50-100 times lower than the aqueous concentrations that result in positive chemotaxis of the same strain. It is thus assumed that the efficient gas-phase diffusion resulting in a steady, and possibly toxic, naphthalene flux to the cells controlled the chemotactic reaction rather than the concentration to which the cells were exposed. To our knowledge this is the first demonstration of apparent chemotactic behavior of bacteria in response to vapor-phase effector gradients.

The gas phase origin of complex organic molecules precursors in prestellar cores

NASA Astrophysics Data System (ADS)

Bacmann, A.; Faure, A.

2015-05-01

Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

Detecting gas hydrate behavior in crude oil using NMR.

PubMed

Gao, Shuqiang; House, Waylon; Chapman, Walter G

2006-04-06

Because of the associated experimental difficulties, natural gas hydrate behavior in black oil is poorly understood despite its grave importance in deep-water flow assurance. Since the hydrate cannot be visually observed in black oil, traditional methods often rely on gas pressure changes to monitor hydrate formation and dissociation. Because gases have to diffuse through the liquid phase for hydrate behavior to create pressure responses, the complication of gas mass transfer is involved and hydrate behavior is only indirectly observed. This pressure monitoring technique encounters difficulties when the oil phase is too viscous, the amount of water is too small, or the gas phase is absent. In this work we employ proton nuclear magnetic resonance (NMR) spectroscopy to observe directly the liquid-to-solid conversion of the water component in black oil emulsions. The technique relies on two facts. The first, well-known, is that water becomes essentially invisible to liquid state NMR as it becomes immobile, as in hydrate or ice formation. The second, our recent finding, is that in high magnetic fields of sufficient homogeneity, it is possible to distinguish water from black oil spectrally by their chemical shifts. By following changes in the area of the water peak, the process of hydrate conversion can be measured, and, at lower temperatures, the formation of ice. Taking only seconds to accomplish, this measurement is nearly direct in contrast to conventional techniques that measure the pressure changes of the whole system and assume these changes represent formation or dissociation of hydrates - rather than simply changes in solubility. This new technique clearly can provide accurate hydrate thermodynamic data in black oils. Because the technique measures the total mobile water with rapidity, extensions should prove valuable in studying the dynamics of phase transitions in emulsions.

Experimental Study of the Exciton Gas-Liquid Transition in Coupled Quantum Wells.

PubMed

Misra, Subhradeep; Stern, Michael; Joshua, Arjun; Umansky, Vladimir; Bar-Joseph, Israel

2018-01-26

We study the exciton gas-liquid transition in GaAs/AlGaAs coupled quantum wells. Below a critical temperature, T_{C}=4.8  K, and above a threshold laser power density the system undergoes a phase transition into a liquid state. We determine the density-temperature phase diagram over the temperature range 0.1-4.8 K. We find that the latent heat increases linearly with temperature at T≲1.1  K, similarly to a Bose-Einstein condensate transition, and becomes constant at 1.1≲T<4.8  K. Resonant Rayleigh scattering measurements reveal that the disorder in the sample is strongly suppressed and the diffusion coefficient sharply increases with decreasing temperature at T

Experimental Study of the Exciton Gas-Liquid Transition in Coupled Quantum Wells

NASA Astrophysics Data System (ADS)

Misra, Subhradeep; Stern, Michael; Joshua, Arjun; Umansky, Vladimir; Bar-Joseph, Israel

2018-01-01

We study the exciton gas-liquid transition in GaAs /AlGaAs coupled quantum wells. Below a critical temperature, TC=4.8 K , and above a threshold laser power density the system undergoes a phase transition into a liquid state. We determine the density-temperature phase diagram over the temperature range 0.1-4.8 K. We find that the latent heat increases linearly with temperature at T ≲1.1 K , similarly to a Bose-Einstein condensate transition, and becomes constant at 1.1 ≲T <4.8 K . Resonant Rayleigh scattering measurements reveal that the disorder in the sample is strongly suppressed and the diffusion coefficient sharply increases with decreasing temperature at T

Microbial use of gas phase organic compounds in the surface ocean

NASA Astrophysics Data System (ADS)

Arrieta, Jesus M.; Duarte, Carlos M.; Monserrat Sala, M.; Dachs, Jordi

2016-04-01

Large diffusive air-sea fluxes of gas-phase organic carbon (GOC) have been identified, indicating that the ocean may be a major sink for these compounds. However, little is known about the fate of these GOC compounds entering the surface ocean. We report efficient use of atmospheric GOC by marine prokaryotes at different locations in the NE Subtropical Atlantic Ocean, the Arctic Ocean and the Mediterranean Sea. Our results indicate that between 2 to 27% of the prokaryotic carbon demand was supported by GOC. Between 1 and 94% of the GOC entering the ocean was consumed by prokaryotes depending on locations, thus sustaining a disequilibrium, which drives the transfer of GOC from the atmosphere into the ocean. The magnitude of this, previously unnoticed, microbial GOC utilization stresses the need for incorporating the oceanic uptake of gaseous organic carbon into the global carbon budget.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.

Modeling condensation with a noncondensable gas for mixed convection flow

NASA Astrophysics Data System (ADS)

Liao, Yehong

2007-05-01

This research theoretically developed a novel mixed convection model for condensation with a noncondensable gas. The model developed herein is comprised of three components: a convection regime map; a mixed convection correlation; and a generalized diffusion layer model. These components were developed in a way to be consistent with the three-level methodology in MELCOR. The overall mixed convection model was implemented into MELCOR and satisfactorily validated with data covering a wide variety of test conditions. In the development of the convection regime map, two analyses with approximations of the local similarity method were performed to solve the multi-component two-phase boundary layer equations. The first analysis studied effects of the bulk velocity on a basic natural convection condensation process and setup conditions to distinguish natural convection from mixed convection. It was found that the superimposed velocity increases condensation heat transfer by sweeping away the noncondensable gas accumulated at the condensation boundary. The second analysis studied effects of the buoyancy force on a basic forced convection condensation process and setup conditions to distinguish forced convection from mixed convection. It was found that the superimposed buoyancy force increases condensation heat transfer by thinning the liquid film thickness and creating a steeper noncondensable gas concentration profile near the condensation interface. In the development of the mixed convection correlation accounting for suction effects, numerical data were obtained from boundary layer analysis for the three convection regimes and used to fit a curve for the Nusselt number of the mixed convection regime as a function of the Nusselt numbers of the natural and forced convection regimes. In the development of the generalized diffusion layer model, the driving potential for mass transfer was expressed as the temperature difference between the bulk and the liquid-gas interface using the Clausius-Clapeyron equation. The model was developed on a mass basis instead of a molar basis to be consistent with general conservation equations. It was found that vapor diffusion is not only driven by a gradient of the molar fraction but also a gradient of the mixture molecular weight at the diffusion layer.

Evaluating BTEX concentration in soil using a simple one-dimensional vado zone model: application to a new fuel station in Valencia (Spain)

NASA Astrophysics Data System (ADS)

Rodrigo-Ilarri, Javier; Rodrigo-Clavero, María-Elena

2017-04-01

Specific studies of the impact of fuel spills on the vadose zone are currently required when trying to obtain the environmental permits for new fuel stations. The development of One-Dimensional mathematical models of fate and transport of BTEX on the vadose zone can therefore be used to understand the behavior of the pollutants under different scenarios. VLEACH - a simple One-Dimensional Finite Different Vadose Zone Leaching Model - uses an numerical approximation of the Millington Equation, a theoretical based model for gaseous diffusion in porous media. This equation has been widely used in the fields of soil physics and hydrology to calculate the gaseous or vapor diffusion in porous media. The model describes the movement of organic contaminants within and between three different phases: (1) as a solute dissolved in water, (2) as a gas in the vapor phase, and (3) as an absorbed compound in the soil phase. Initially, the equilibrium distribution of contaminant mass between liquid, gas and sorbed phases is calculated. Transport processes are then simulated. Liquid advective transport is calculated based on values defined by the user for infiltration and soil water content. The contaminant in the vapor phase migrates into or out of adjacent cells based on the calculated concentration gradients that exist between adjacent cells. After the mass is exchanged between the cells, the total mass in each cell is recalculated and re-equilibrated between the different phases. At the end of the simulation, (1) an overall area-weighted groundwater impact for the entire modeled area and (2) the concentration profile of BTEX on the vadose zone are calculated. This work shows the results obtained when applying VLEACH to analyze the contamination scenario caused by a BTEX spill coming from a set of future underground storage tanks located on a new fuel station in Aldaia (Valencia region - Spain).

Ternary gas mixture for diffuse discharge switch

DOEpatents

Christophorou, Loucas G.; Hunter, Scott R.

1988-01-01

A new diffuse discharge gas switch wherein a mixture of gases is used to take advantage of desirable properties of the respective gases. There is a conducting gas, an insulating gas, and a third gas that has low ionization energy resulting in a net increase in the number of electrons available to produce a current.

Enhanced Carbon Diffusion in Austenitic Stainless Steel Carburized at Low Temperature

NASA Astrophysics Data System (ADS)

Ernst, F.; Avishai, A.; Kahn, H.; Gu, X.; Michal, G. M.; Heuer, A. H.

2009-08-01

Austenitic stainless steel AISI 316L was carburized by a novel, low-temperature gas-phase process. Using a calibrated scanning Auger microprobe (SAM) analysis of cross-sectional specimens under dynamic sputtering, we determined the fraction-depth profile of carbon. The profile is concave—very different from the shape expected for concentration-independent diffusion—and indicates a carbide-free solid solution with carbon levels up to 15 at. pct and a case depth of ≈30 μm. A Boltzmann-Matano analysis with a careful evaluation of the stochastic and potential systematic errors indicates that increasing levels of carbon significantly enhance carbon diffusion. For the highest carbon level observed (15 at. pct), the carbon diffusion coefficient is more than two orders of magnitude larger than in dilute solution. The most likely explanation for this strong increase is that carbon-induced local expansion of metal-metal atom distances, observed as an expansion of the lattice parameter, reduces the activation energy for carbon diffusion.

Composition, structure and chemistry of interstellar dust

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.; Allamandola, Louis J.

1986-01-01

The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.

Experimental Methodology for Estimation of Local Heat Fluxes and Burning Rates in Steady Laminar Boundary Layer Diffusion Flames.

PubMed

Singh, Ajay V; Gollner, Michael J

2016-06-01

Modeling the realistic burning behavior of condensed-phase fuels has remained out of reach, in part because of an inability to resolve the complex interactions occurring at the interface between gas-phase flames and condensed-phase fuels. The current research provides a technique to explore the dynamic relationship between a combustible condensed fuel surface and gas-phase flames in laminar boundary layers. Experiments have previously been conducted in both forced and free convective environments over both solid and liquid fuels. A unique methodology, based on the Reynolds Analogy, was used to estimate local mass burning rates and flame heat fluxes for these laminar boundary layer diffusion flames utilizing local temperature gradients at the fuel surface. Local mass burning rates and convective and radiative heat feedback from the flames were measured in both the pyrolysis and plume regions by using temperature gradients mapped near the wall by a two-axis traverse system. These experiments are time-consuming and can be challenging to design as the condensed fuel surface burns steadily for only a limited period of time following ignition. The temperature profiles near the fuel surface need to be mapped during steady burning of a condensed fuel surface at a very high spatial resolution in order to capture reasonable estimates of local temperature gradients. Careful corrections for radiative heat losses from the thermocouples are also essential for accurate measurements. For these reasons, the whole experimental setup needs to be automated with a computer-controlled traverse mechanism, eliminating most errors due to positioning of a micro-thermocouple. An outline of steps to reproducibly capture near-wall temperature gradients and use them to assess local burning rates and heat fluxes is provided.

Experimental Methodology for Estimation of Local Heat Fluxes and Burning Rates in Steady Laminar Boundary Layer Diffusion Flames

PubMed Central

Singh, Ajay V.; Gollner, Michael J.

2016-01-01

Modeling the realistic burning behavior of condensed-phase fuels has remained out of reach, in part because of an inability to resolve the complex interactions occurring at the interface between gas-phase flames and condensed-phase fuels. The current research provides a technique to explore the dynamic relationship between a combustible condensed fuel surface and gas-phase flames in laminar boundary layers. Experiments have previously been conducted in both forced and free convective environments over both solid and liquid fuels. A unique methodology, based on the Reynolds Analogy, was used to estimate local mass burning rates and flame heat fluxes for these laminar boundary layer diffusion flames utilizing local temperature gradients at the fuel surface. Local mass burning rates and convective and radiative heat feedback from the flames were measured in both the pyrolysis and plume regions by using temperature gradients mapped near the wall by a two-axis traverse system. These experiments are time-consuming and can be challenging to design as the condensed fuel surface burns steadily for only a limited period of time following ignition. The temperature profiles near the fuel surface need to be mapped during steady burning of a condensed fuel surface at a very high spatial resolution in order to capture reasonable estimates of local temperature gradients. Careful corrections for radiative heat losses from the thermocouples are also essential for accurate measurements. For these reasons, the whole experimental setup needs to be automated with a computer-controlled traverse mechanism, eliminating most errors due to positioning of a micro-thermocouple. An outline of steps to reproducibly capture near-wall temperature gradients and use them to assess local burning rates and heat fluxes is provided. PMID:27285827

Diffusion of Zr, Ru, Ce, Y, La, Sr and Ba fission products in UO 2

DOE PAGES

Perriot, R.; Liu, X. -Y.; Stanek, C. R.; ...

2015-01-08

The diffusivity of the solid fission products (FP) Zr (Zr 4+), Ru (Ru 4+, Ru 3+), Ce (Ce 4+), Y (Y 3+), La (La 3+), Sr (Sr 2+) and Ba (Ba 2+) by a vacancy mechanism has been calculated, using a combination of density functional theory (DFT) and empirical potential (EP) calculations. The activation energies for the solid fission products are compared to the activation energy for Xe fission gas atoms calculated previously. Apart from Ru, the solid fission products all exhibit higher activation energy than Xe. Furthermore, for all solid FPs except Y 3+, the migration of the FPmore » has lower barrier than the migration of a neighboring U atom, making the latter the rate limiting step for direct migration. An indirect mechanism, consisting of two successive migrations around the FP, is also investigated. The calculated diffusivities show that most solid fission products diffuse with rates similar to U self-diffusion. But, Ru, Ba and Sr exhibit faster diffusion than the other solid FPs, with Ru 3+ and Ru 4+ diffusing even faster than Xe for T < 1200 K. The diffusivities correlate with the observed fission product solubility in UO 2, and the tendency to form metallic and oxide second phase inclusions.« less

Respiratory dynamics of discontinuous gas exchange in the tracheal system of the desert locust, Schistocerca gregaria.

PubMed

Groenewald, Berlizé; Hetz, Stefan K; Chown, Steven L; Terblanche, John S

2012-07-01

Gas exchange dynamics in insects is of fundamental importance to understanding evolved variation in breathing patterns, such as discontinuous gas exchange cycles (DGCs). Most insects do not rely solely on diffusion for the exchange of respiratory gases but may also make use of respiratory movements (active ventilation) to supplement gas exchange at rest. However, their temporal dynamics have not been widely investigated. Here, intratracheal pressure, V(CO2) and body movements of the desert locust Schistocerca gregaria were measured simultaneously during the DGC and revealed several important aspects of gas exchange dynamics. First, S. gregaria employs two different ventilatory strategies, one involving dorso-ventral contractions and the other longitudinal telescoping movements. Second, although a true spiracular closed (C)-phase of the DGC could be identified by means of subatmospheric intratracheal pressure recordings, some CO(2) continued to be released. Third, strong pumping actions do not necessarily lead to CO(2) release and could be used to ensure mixing of gases in the closed tracheal system, or enhance water vapour reabsorption into the haemolymph from fluid-filled tracheole tips by increasing the hydrostatic pressure or forcing fluid into the haemocoel. Finally, this work showed that the C-phase of the DGC can occur at any pressure. These results provide further insights into the mechanistic basis of insect gas exchange.

Structural Measurements from Images of Noble Gas Diffusion

NASA Astrophysics Data System (ADS)

Cadman, Robert V.; Kadlecek, Stephen J.; Emami, Kiarash; MacDuffie Woodburn, John; Vahdat, Vahid; Ishii, Masaru; Rizi, Rahim R.

2009-03-01

Magnetic resonance imaging of externally polarized noble gases such as ^3He has been used for pulmonary imaging for more than a decade. Because gas diffusion is impeded by the alveoli, the diffusion coefficient of gas in the lung, measured on a time scale of milliseconds, is reduced compared to that of the same gas mixture in the absence of restrictions. When the alveolar walls decay, as in emphysema, diffusivity in the lung increases. In this paper, the relationship between diffusion measurements and the size of the restricting structures will be discussed. The simple case of diffusion in an impermeable cylinder, a structure similar to the upper respiratory airways in mammals, has been studied. A procedure will be presented by which airways of order 2 mm in diameter may be accurately measured; demonstration experiments with plastic tubes will also be presented. The additional developments needed before this technique becomes practical will be briefly discussed.

Viscous and gravitational fingering in multiphase compositional and compressible flow

NASA Astrophysics Data System (ADS)

Moortgat, Joachim

2016-03-01

Viscous and gravitational fingering refer to flow instabilities in porous media that are triggered by adverse mobility or density ratios, respectively. These instabilities have been studied extensively in the past for (1) single-phase flow (e.g., contaminant transport in groundwater, first-contact-miscible displacement of oil by gas in hydrocarbon production), and (2) multi-phase immiscible and incompressible flow (e.g., water-alternating-gas (WAG) injection in oil reservoirs). Fingering in multiphase compositional and compressible flow has received much less attention, perhaps due to its high computational complexity. However, many important subsurface processes involve multiple phases that exchange species. Examples are carbon sequestration in saline aquifers and enhanced oil recovery (EOR) by gas or WAG injection below the minimum miscibility pressure. In multiphase flow, relative permeabilities affect the mobility contrast for a given viscosity ratio. Phase behavior can also change local fluid properties, which can either enhance or mitigate viscous and gravitational instabilities. This work presents a detailed study of fingering behavior in compositional multiphase flow in two and three dimensions and considers the effects of (1) Fickian diffusion, (2) mechanical dispersion, (3) flow rates, (4) domain size and geometry, (5) formation heterogeneities, (6) gravity, and (7) relative permeabilities. Results show that fingering in compositional multiphase flow is profoundly different from miscible conditions and upscaling techniques used for the latter case are unlikely to be generalizable to the former.

Oscillatory Extinction Of Spherical Diffusion Flames

NASA Technical Reports Server (NTRS)

Law, C. K.; Yoo, S. W.; Christianson, E. W.

2003-01-01

Since extinction has been observed in an oscillatory manner in Le greater than 1 premixed flames, it is not unreasonable to expect that extinction could occur in an unsteady manner for diffusion flames. Indeed, near-limit oscillations have been observed experimentally under microgravity conditions for both candle flames and droplet flames. Furthermore, the analysis of Cheatham and Matalon on the unsteady behavior of diffusion flames with heat loss, identified an oscillatory regime which could be triggered by either a sufficiently large Lewis number (even without heat loss) or an appreciable heat loss (even for Le=1). In light of these recent understanding, the present investigation aims to provide a well-controlled experiment that can unambiguously demonstrate the oscillation of diffusion flames near both the transport- and radiation-induced limits. That is, since candle and jet flames are stabilized through flame segments that are fundamentally premixed in nature, and since premixed flames are prone to oscillate, there is the possibility that the observed oscillation of these bulk diffusion flames could be triggered and sustained by the oscillation of the premixed flame segments. Concerning the observed oscillatory droplet extinction, it is well-known that gas-phase oscillation in heterogeneous burning can be induced by and is thereby coupled with condensed-phase unsteadiness. Consequently, a convincing experiment on diffusion flame oscillation must exclude any ingredients of premixed flames and other sources that may either oscillate themselves or promote the oscillation of the diffusion flame. The present experiment on burner-generated spherical flames with a constant reactant supply endeavored to accomplish this goal. The results are further compared with those from computational simulation for further understanding and quantification of the flame dynamics and extinction.

Membrane permeation process for dehydration of organic liquid mixtures using sulfonated ion-exchange polyalkene membranes

DOEpatents

Cabasso, Israel; Korngold, Emmanuel

1988-01-01

A membrane permeation process for dehydrating a mixture of organic liquids, such as alcohols or close boiling, heat sensitive mixtures. The process comprises causing a component of the mixture to selectively sorb into one side of sulfonated ion-exchange polyalkene (e.g., polyethylene) membranes and selectively diffuse or flow therethrough, and then desorbing the component into a gas or liquid phase on the other side of the membranes.

Rhenium-Oxygen Interactions at High Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Myers, Dwight L.; Zhu, Dongming; Humphrey, Donald

2000-01-01

The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

HST/COS detection of a Ne VIII absorber towards PG 1407+265: an unambiguous tracer of collisionally ionized hot gas?

NASA Astrophysics Data System (ADS)

Hussain, T.; Muzahid, S.; Narayanan, A.; Srianand, R.; Wakker, B. P.; Charlton, J. C.; Pathak, A.

2015-01-01

We report the detection of Ne VIII in a zabs = 0.599 61 absorber towards the QSO PG1407+265 (zem= 0.94). Besides Ne VIII, absorption from H I Lyman series lines (H I λ1025-λ915), several other low (C II, N II, O II and S II), intermediate (C III, N III, N IV, O III, S IV and S V) and high (S VI, O VI and Ne VIII) ionization metal lines are detected. Disparity in the absorption line kinematics between different ions implies that the absorbing gas comprises of multiple ionization phases. The low and the intermediate ions (except S V) trace a compact (˜410 pc), metal-rich (Z ˜ Z⊙) and overdense (log nH ˜ -2.6) photoionized region that sustained star formation for a prolonged period. The high ions, Ne VIII and O VI, can be explained as arising in a low density (-5.3 ≤ log nH ≤ -5.0), metal-rich (Z ≳ Z⊙) and diffuse (˜180 kpc) photoionized gas. The S V, S VI and C IV [detected in the Faint Object Spectrograph (FOS) spectrum] require an intermediate photoionization phase with -4.2 < log nH < -3.5. Alternatively, a pure collisional ionization model, as used to explain the previous known Ne VIII absorbers, with 5.65 < log T < 5.72, can reproduce the S VI, O VI and Ne VIII column densities simultaneously in a single phase. However, even such models require an intermediate phase to reproduce any observable S V and/or C IV. Therefore, we conclude that when multiple phases are present, the presence of Ne VIII is not necessarily an unambiguous indication of collisionally ionized hot gas.

Cu-Zn binary phase diagram and diffusion couples

NASA Technical Reports Server (NTRS)

Mccoy, Robert A.

1992-01-01

The objectives of this paper are to learn: (1) what information a binary phase diagram can yield; (2) how to construct and heat treat a simple diffusion couple; (3) how to prepare a metallographic sample; (4) how to operate a metallograph; (5) how to correlate phases found in the diffusion couple with phases predicted by the phase diagram; (6) how diffusion couples held at various temperatures could be used to construct a phase diagram; (7) the relation between the thickness of an intermetallic phase layer and the diffusion time; and (8) the effect of one species of atoms diffusing faster than another species in a diffusion couple.

Simulating the volatilization of solvents in unsaturated soils during laboratory and field infiltration experiments

USGS Publications Warehouse

Cho, H. Jean; Jaffe, Peter R.; Smith, James A.

1993-01-01

This paper describes laboratory and field experiments which were conducted to study the dynamics of trichloroethylene (TCE) as it volatilized from contaminated groundwater and diffused in the presence of infiltrating water through the unsaturated soil zone to the land surface. The field experiments were conducted at the Picatinny Arsenal, which is part of the United States Geological Survey Toxic Substances Hydrology Program. In both laboratory and field settings the gas and water phase concentrations of TCE were not in equilibrium during infiltration. Gas-water mass transfer rate constants were calibrated to the experimental data using a model in which the water phase was treated as two phases: a mobile water phase and an immobile water phase. The mass transfer limitations of a volatile organic compound between the gas and liquid phases were described explicitly in the model. In the laboratory experiment the porous medium was nonsorbing, and water infiltration rates ranged from 0.076 to 0.28 cm h−1. In the field experiment the water infiltration rate was 0.34 cm h−1, and sorption onto the soil matrix was significant. The laboratory-calibrated gas-water mass transfer rate constant is 3.3×10−4 h−1 for an infiltration rate of 0.076 cm h−1 and 1.4×10−3 h−1 for an infiltration rate of 0.28 cm h−1. The overall mass transfer rate coefficients, incorporating the contribution of mass transfer between mobile and immobile water phases and the variation of interfacial area with moisture content, range from 3×10−4 h−1 to 1×10−2 h−1. A power law model relates the gas-water mass transfer rate constant to the infiltration rate and the fraction of the water phase which is mobile. It was found that the results from the laboratory experiments could not be extrapolated to the field. In order to simulate the field experiment the very slow desorption of TCE from the soil matrix was incorporated into the mathematical model. When desorption from the soil matrix was added to the model, the calibrated gas-water mass transfer rate constant is 2 orders of magnitude lower than that predicted using the power law model developed for the nonsorbing laboratory soil.

Solute diffusion in liquid metals

NASA Technical Reports Server (NTRS)

Bhat, B. N.

1973-01-01

A gas model of diffusion in liquid metals is presented. In this model, ions of liquid metals are assumed to behave like the molecules in a dense gas. Diffusion coefficient of solute is discussed with reference to its mass, ionic size, and pair potential. The model is applied to the case of solute diffusion in liquid silver. An attempt was made to predict diffusion coefficients of solutes with reasonable accuracy.

Study on low intensity aeration oxygenation model and optimization for shallow water

NASA Astrophysics Data System (ADS)

Chen, Xiao; Ding, Zhibin; Ding, Jian; Wang, Yi

2018-02-01

Aeration/oxygenation is an effective measure to improve self-purification capacity in shallow water treatment while high energy consumption, high noise and expensive management refrain the development and the application of this process. Based on two-film theory, the theoretical model of the three-dimensional partial differential equation of aeration in shallow water is established. In order to simplify the equation, the basic assumptions of gas-liquid mass transfer in vertical direction and concentration diffusion in horizontal direction are proposed based on engineering practice and are tested by the simulation results of gas holdup which are obtained by simulating the gas-liquid two-phase flow in aeration tank under low-intensity condition. Based on the basic assumptions and the theory of shallow permeability, the model of three-dimensional partial differential equations is simplified and the calculation model of low-intensity aeration oxygenation is obtained. The model is verified through comparing the aeration experiment. Conclusions as follows: (1)The calculation model of gas-liquid mass transfer in vertical direction and concentration diffusion in horizontal direction can reflect the process of aeration well; (2) Under low-intensity conditions, the long-term aeration and oxygenation is theoretically feasible to enhance the self-purification capacity of water bodies; (3) In the case of the same total aeration intensity, the effect of multipoint distributed aeration on the diffusion of oxygen concentration in the horizontal direction is obvious; (4) In the shallow water treatment, reducing the volume of aeration equipment with the methods of miniaturization, array, low-intensity, mobilization to overcome the high energy consumption, large size, noise and other problems can provide a good reference.

Influence of wind-induced air pressure fluctuations on topsoil gas concentrations within a Scots pine forest

NASA Astrophysics Data System (ADS)

Mohr, Manuel; Laemmel, Thomas; Maier, Martin; Schindler, Dirk

2017-04-01

Commonly it is assumed that soil gas transport is dominated by molecular diffusion. Few recent studies indicate that the atmosphere above the soil triggers non-diffusive gas transport processes in the soil, which can enhance soil gas transport and therefore soil gas efflux significantly. During high wind speed conditions, the so called pressure pumping effect has been observed: the enhancement of soil gas transport through dynamic changes in the air pressure field above the soil. However, the amplitudes and frequencies of the air pressure fluctuations responsible for pressure pumping are still uncertain. Moreover, an in situ observation of the pressure pumping effect is still missing. To investigate the pressure pumping effect, airflow measurements above and below the canopy of a Scots pine forest and high-precision relative air pressure measurements were conducted in the below-canopy space and in the soil over a measurement period of 16 weeks. To monitor the soil gas transport, a newly developed gas measurement system was used. The gas measurement system continuously injects helium as a tracer gas into the soil until a diffusive steady state is reached. With the steady state concentration profile of the tracer gas, it is possible to inversely model the gas diffusion coefficient profile of the soil. If the gas diffusion coefficient profile differed from steady state, we deduced that the soil gas transport is not only diffusive, but also influenced by non-diffusive processes. Results show that the occurrence of small air pressure fluctuations is strongly dependent on the mean above-canopy wind speed. The wind-induced air pressure fluctuations have mean amplitudes up to 10 Pa and lie in the frequency range 0.01-0.1 Hz. To describe the pumping motion of the air pressure field, the pressure pumping coefficient (PPC) was defined as the mean change in pressure per second. The PPC shows a clear quadratic dependence on mean above-canopy wind speed. Empirical modelling of the measured topsoil helium concentration demonstrated that the PPC is the most important predictor for changes in the topsoil helium concentration. Comparison of time periods with high PPC and periods of low PPC showed that the soil gas diffusion coefficient in depths between 5-10 cm increased up to 30% during periods of high PPC compared to steady state. Thus, the air pressure fluctuations observed in the atmosphere and described by the PPC penetrate into the soil and influence the topsoil gas transport.

A time fractional convection-diffusion equation to model gas transport through heterogeneous soil and gas reservoirs

NASA Astrophysics Data System (ADS)

Chang, Ailian; Sun, HongGuang; Zheng, Chunmiao; Lu, Bingqing; Lu, Chengpeng; Ma, Rui; Zhang, Yong

2018-07-01

Fractional-derivative models have been developed recently to interpret various hydrologic dynamics, such as dissolved contaminant transport in groundwater. However, they have not been applied to quantify other fluid dynamics, such as gas transport through complex geological media. This study reviewed previous gas transport experiments conducted in laboratory columns and real-world oil-gas reservoirs and found that gas dynamics exhibit typical sub-diffusive behavior characterized by heavy late-time tailing in the gas breakthrough curves (BTCs), which cannot be effectively captured by classical transport models. Numerical tests and field applications of the time fractional convection-diffusion equation (fCDE) have shown that the fCDE model can capture the observed gas BTCs including their apparent positive skewness. Sensitivity analysis further revealed that the three parameters used in the fCDE model, including the time index, the convection velocity, and the diffusion coefficient, play different roles in interpreting the delayed gas transport dynamics. In addition, the model comparison and analysis showed that the time fCDE model is efficient in application. Therefore, the time fractional-derivative models can be conveniently extended to quantify gas transport through natural geological media such as complex oil-gas reservoirs.

Grain Surface Chemistry and the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.

2006-01-01

Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

DUST AND GAS IN THE MAGELLANIC CLOUDS FROM THE HERITAGE HERSCHEL KEY PROJECT. II. GAS-TO-DUST RATIO VARIATIONS ACROSS INTERSTELLAR MEDIUM PHASES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roman-Duval, Julia; Gordon, Karl D.; Meixner, Margaret

2014-12-20

The spatial variations of the gas-to-dust ratio (GDR) provide constraints on the chemical evolution and lifecycle of dust in galaxies. We examine the relation between dust and gas at 10-50 pc resolution in the Large and Small Magellanic Clouds (LMC and SMC) based on Herschel far-infrared (FIR), H I 21 cm, CO, and Hα observations. In the diffuse atomic interstellar medium (ISM), we derive the GDR as the slope of the dust-gas relation and find GDRs of 380{sub −130}{sup +250} ± 3 in the LMC, and 1200{sub −420}{sup +1600} ± 120 in the SMC, not including helium. The atomic-to-molecular transition is locatedmore » at dust surface densities of 0.05 M {sub ☉} pc{sup –2} in the LMC and 0.03 M {sub ☉} pc{sup –2} in the SMC, corresponding to A {sub V} ∼ 0.4 and 0.2, respectively. We investigate the range of CO-to-H{sub 2} conversion factor to best account for all the molecular gas in the beam of the observations, and find upper limits on X {sub CO} to be 6 × 10{sup 20} cm{sup –2} K{sup –1} km{sup –1} s in the LMC (Z = 0.5 Z {sub ☉}) at 15 pc resolution, and 4 × 10{sup 21} cm{sup –2} K{sup –1} km{sup –1} s in the SMC (Z = 0.2 Z {sub ☉}) at 45 pc resolution. In the LMC, the slope of the dust-gas relation in the dense ISM is lower than in the diffuse ISM by a factor ∼2, even after accounting for the effects of CO-dark H{sub 2} in the translucent envelopes of molecular clouds. Coagulation of dust grains and the subsequent dust emissivity increase in molecular clouds, and/or accretion of gas-phase metals onto dust grains, and the subsequent dust abundance (dust-to-gas ratio) increase in molecular clouds could explain the observations. In the SMC, variations in the dust-gas slope caused by coagulation or accretion are degenerate with the effects of CO-dark H{sub 2}. Within the expected 5-20 times Galactic X {sub CO} range, the dust-gas slope can be either constant or decrease by a factor of several across ISM phases. Further modeling and observations are required to break the degeneracy between dust grain coagulation, accretion, and CO-dark H{sub 2}. Our analysis demonstrates that obtaining robust ISM masses remains a non-trivial endeavor even in the local Universe using state-of-the-art maps of thermal dust emission.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duke, Daniel J.; Kastengren, Alan L.; Swantek, Andrew B.

The dynamics of dissolved gas and cavitation are strongly coupled, yet these phenomena are difficult to measure in-situ. Both create voids in the fluid that can be difficult to distinguish. In this paper, we present an application of X-ray fluorescence in which liquid density and total noncondensible gas concentration (both dissolved and nucleated) are simultaneously measured. The liquid phase is doped with 400 ppm of a bromine tracer, and dissolved air is removed and substituted with krypton. Fluorescent emission at X-ray wavelengths is simultaneously excited from the Br and Kr with a focused monochromatic X-ray beam from a synchrotron source.more » We measure the flow in a cavitating nozzle 0.5 mm in diameter. From Br fluorescence, total displacement of the liquid is measured. From Kr fluorescence, the mass fraction of both dissolved and nucleated gas is measured. Volumetric displacement of liquid due to both cavitation and gas precipitation can be separated through estimation of the local equilibrium dissolved mass fraction. The uncertainty in the line of sight projected densities of the liquid and gas phases is 4–6 %. The high fluorescence yields and energies of Br and Kr allow small mass fractions of gas to be measured, down to 10 -5, with an uncertainty of 8 %. Finally, these quantitative measurements complement existing optical diagnostic techniques and provide new insight into the diffusion of gas into cavitation bubbles, which can increase their internal density, pressure and lifetimes by orders of magnitude.« less

Generation mechanism of hydrogen peroxide in dc plasma with a liquid electrode

NASA Astrophysics Data System (ADS)

Takeuchi, Nozomi; Ishibashi, Naoto

2018-04-01

The production mechanism of liquid-phase H2O2 in dc driven plasma in O2 and Ar with a water electrode was investigated. When a water anode was used, the concentration of H2O2 increased linearly with the treatment time. The production rate was proportional to the discharge current, and there was no dependence on the gap distance. On the other hand, the production rate was much smaller with a water anode. We concluded that the production of gas-phase H2O2 in the cathode sheath just above a water cathode and diffusion of this H2O2 into the water constitute the key mechanism in the production of liquid-phase H2O2.

Numerical Study of Pressure Influence on Methane-Oxygen Laminar Counterflow Diffusion Flames

NASA Astrophysics Data System (ADS)

Iino, Kimio; Akamatsu, Fumiteru; Katsuki, Masashi

We carried out numerical studies on methane/oxygen diffusion flames of counter-flow configuration to elucidate the influence of pressure on flame structure, heat release rate and reaction mechanisms. The chemistry in gas-phase was based on GRI-Mech 3.0 database. The thickness of diffusion flame became thinner with increasing strain rate a , with its characteristic flame thickness varying inversely with √a, especially its relation became significant with increasing pressure. Flame temperature increased with increasing pressure. Enhanced H2O production reactions, especially chain terminal reactions for H2O production, were found to be important in determining the flame temperature at high pressures. The small reduction in the flame temperature with increasing strain rate at high pressures, compared to the atmospheric pressure, is caused by the capacitor effect of product dissociation. From QRPDs, the third body dependent reactions were enhanced in high pressure conditions, hence C2 pathway was enhanced.

Li diffusion in epitaxial (11 $bar 2$ 0) ZnO thin films

NASA Astrophysics Data System (ADS)

Wu, P.; Zhong, J.; Emanetoglu, N. W.; Chen, Y.; Muthukumar, S.; Lu, Y.

2004-06-01

Zinc oxide (ZnO) possesses many interesting properties, such as a wide energy bandgap, large photoconductivity, and high excitonic binding energy. Chemical-vapor-deposition-grown ZnO films generally show n-type conductivity. A compensation doping process is needed to achieve piezoelectric ZnO, which is needed for surface acoustic wave (SAW), bulk acoustic wave, and micro-electromechanical system devices. In this work, a gas-phase diffusion process is developed to achieve piezoelectric (11bar 20) ZnO films. Comparative x-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements confirmed that high crystal quality and good surface morphology were preserved after diffusion. Photoluminescence (PL) measurements show a broad band emission with a peak wavelength at ˜580 nm, which is associated with Li doping. The SAW, including both Rayleigh-wave and Love-wave modes, is achieved along different directions in piezoelectric (11bar 20) ZnO films grown on an r-plane sapphire substrate.

Dependence of growth of the phases of multiphase binary systems on the diffusion parameters

NASA Astrophysics Data System (ADS)

Molokhina, L. A.; Rogalin, V. E.; Filin, S. A.; Kaplunov, I. A.

2017-12-01

A mathematical model of the diffusion interaction of a binary system with several phases on the equilibrium phase diagram is presented. The theoretical and calculated dependences of the layer thickness of each phase in the multiphase diffusion zone on the isothermal annealing time and the ratio of the diffusion parameters in the neighboring phases with an unlimited supply of both components were constructed. The phase formation and growth in the diffusion zone during "reactive" diffusion corresponds to the equilibrium state diagram for two components, and the order of their appearance in the diffusion zone depends only on the ratio of the diffusion parameters in the phases themselves and on the duration of the incubation periods. The dependence of phase appearance on the incubation periods, annealing time, and difference in the movement rates of the components across the interface boundaries was obtained. An example of the application of the model for processing the experimental data on phase growth in a two-component three-phase system was given.

Modeling of corona discharge combined with Mn²⁺ catalysis for the removal of SO₂ from simulated flue gas.

PubMed

Jiwu, Li; Lei, Fan

2013-05-01

This study investigated a mass-transfer process of the removal of SO₂ from simulated flue gas by corona discharge combined with Mn(2+) catalysis in wet reactor, including gas migration, liquid phase diffusion, and chemical reaction. The novelty formula of desulphurization efficiency and the flow rate of flue gas, discharge voltage, reaction enhancement factor, and the flow rate of water were established. It is reported that desulphurization efficiency remarkably increased with the increasing of enhancement factor and discharge voltage at 4000 mg m(-3) of SO₂ and 0.05 m(3)s(-1) of gas flow rate. However, the desulphurization efficiency had a slightly increase with the increasing of water flow rate. It is realizable that the energy consumption could be reduced to be lower than 0.3 kJ m(-3), which was acceptable for industrial application. The experimental data were well in accord with the calculated results of theoretical model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

Cellular Automaton Study of Hydrogen Porosity Evolution Coupled with Dendrite Growth During Solidification in the Molten Pool of Al-Cu Alloys

NASA Astrophysics Data System (ADS)

Gu, Cheng; Wei, Yanhong; Yu, Fengyi; Liu, Xiangbo; She, Lvbo

2017-09-01

Welding porosity defects significantly reduce the mechanical properties of welded joints. In this paper, the hydrogen porosity evolution coupled with dendrite growth during solidification in the molten pool of Al-4.0 wt pct Cu alloy was modeled and simulated. Three phases, including a liquid phase, a solid phase, and a gas phase, were considered in this model. The growth of dendrites and hydrogen gas pores was reproduced using a cellular automaton (CA) approach. The diffusion of solute and hydrogen was calculated using the finite difference method (FDM). Columnar and equiaxed dendrite growth with porosity evolution were simulated. Competitive growth between different dendrites and porosities was observed. Dendrite morphology was influenced by porosity formation near dendrites. After solidification, when the porosities were surrounded by dendrites, they could not escape from the liquid, and they made pores that existed in the welded joints. With the increase in the cooling rate, the average diameter of porosities decreased, and the average number of porosities increased. The average diameter of porosities and the number of porosities in the simulation results had the same trend as the experimental results.

FIRST CONNECTION BETWEEN COLD GAS IN EMISSION AND ABSORPTION: CO EMISSION FROM A GALAXY–QUASAR PAIR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neeleman, Marcel; Prochaska, J. Xavier; Zwaan, Martin A.

2016-04-01

We present the first detection of molecular emission from a galaxy selected to be near a projected background quasar using the Atacama Large Millimeter/submillimeter Array (ALMA). The ALMA detection of CO(1−0) emission from the z = 0.101 galaxy toward quasar PKS 0439–433 is coincident with its stellar disk and yields a molecular gas mass of M{sub mol} ≈ 4.2 × 10{sup 9} M{sub ⊙} (for a Galactic CO-to-H{sub 2} conversion factor), larger than the upper limit on its atomic gas mass. We resolve the CO velocity field, obtaining a rotational velocity of 134 ± 11 km s{sup −1} and a resultant dynamical mass of ≥4 × 10{sup 10} M{sub ⊙}.more » Despite its high metallicity and large molecular mass, the z = 0.101 galaxy has a low star formation rate, implying a large gas consumption timescale, larger than that typical of late-type galaxies. Most of the molecular gas is hence likely to be in a diffuse extended phase, rather than in dense molecular clouds. By combining the results of emission and absorption studies, we find that the strongest molecular absorption component toward the quasar cannot arise from the molecular disk, but is likely to arise from diffuse gas in the galaxy’s circumgalactic medium. Our results emphasize the potential of combining molecular and stellar emission line studies with optical absorption line studies to achieve a more complete picture of the gas within and surrounding high-redshift galaxies.« less

Growth model for large branched three-dimensional hydraulic crack system in gas or oil shale

PubMed Central

Chau, Viet T.

2016-01-01

Recent analysis of gas outflow histories at wellheads shows that the hydraulic crack spacing must be of the order of 0.1 m (rather than 1 m or 10 m). Consequently, the existing models, limited to one or several cracks, are unrealistic. The reality is 105–106 almost vertical hydraulic cracks per fracking stage. Here, we study the growth of two intersecting near-orthogonal systems of parallel hydraulic cracks spaced at 0.1 m, preferably following pre-existing rock joints. One key idea is that, to model lateral cracks branching from a primary crack wall, crack pressurization, by viscous Poiseuille-type flow, of compressible (proppant-laden) frac water must be complemented with the pressurization of a sufficient volume of micropores and microcracks by Darcy-type water diffusion into the shale, to generate tension along existing crack walls, overcoming the strength limit of the cohesive-crack or crack-band model. A second key idea is that enforcing the equilibrium of stresses in cracks, pores and water, with the generation of tension in the solid phase, requires a new three-phase medium concept, which is transitional between Biot’s two-phase medium and Terzaghi’s effective stress and introduces the loading of the solid by pressure gradients of diffusing pore water. A computer program, combining finite elements for deformation and fracture with volume elements for water flow, is developed to validate the new model. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597791

Growth model for large branched three-dimensional hydraulic crack system in gas or oil shale.

PubMed

Chau, Viet T; Bažant, Zdeněk P; Su, Yewang

2016-10-13

Recent analysis of gas outflow histories at wellheads shows that the hydraulic crack spacing must be of the order of 0.1 m (rather than 1 m or 10 m). Consequently, the existing models, limited to one or several cracks, are unrealistic. The reality is 10(5)-10(6) almost vertical hydraulic cracks per fracking stage. Here, we study the growth of two intersecting near-orthogonal systems of parallel hydraulic cracks spaced at 0.1 m, preferably following pre-existing rock joints. One key idea is that, to model lateral cracks branching from a primary crack wall, crack pressurization, by viscous Poiseuille-type flow, of compressible (proppant-laden) frac water must be complemented with the pressurization of a sufficient volume of micropores and microcracks by Darcy-type water diffusion into the shale, to generate tension along existing crack walls, overcoming the strength limit of the cohesive-crack or crack-band model. A second key idea is that enforcing the equilibrium of stresses in cracks, pores and water, with the generation of tension in the solid phase, requires a new three-phase medium concept, which is transitional between Biot's two-phase medium and Terzaghi's effective stress and introduces the loading of the solid by pressure gradients of diffusing pore water. A computer program, combining finite elements for deformation and fracture with volume elements for water flow, is developed to validate the new model.This article is part of the themed issue 'Energy and the subsurface'. © 2016 The Author(s).

Global distribution of secondary organic aerosol particle phase state

NASA Astrophysics Data System (ADS)

Shiraiwa, M.; Li, Y., Sr.; Tsimpidi, A.; Karydis, V.; Berkemeier, T.; Pandis, S. N.; Lelieveld, J.; Koop, T.; Poeschl, U.

2016-12-01

Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere and play a key role in aerosol effects on climate, air quality and public health. The formation and aging of SOA proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of SOA evolution in atmospheric aerosol models. SOA particles can adopt liquid, semi-solid and amorphous solid (glassy) phase states depending on chemical composition, relative humidity and temperature. The particle phase state is crucial for various atmospheric gas-particle interactions, including SOA formation, heterogeneous and multiphase reactions and ice nucleation. We found that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. Based on the concept of molecular corridors, we develop a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, which is a key property for determination of particle phase state. We use the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the atmospheric SOA phase state. For the planetary boundary layer, global simulations indicate that SOA is mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes, and solid over dry lands. We find that in the middle and upper troposphere (>500 hPa) SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants, and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded within SOA.

A novel in-situ method for real-time monitoring of gas transport in soil

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Maier, Martin; Schack-Kirchner, Helmer; Lang, Friederike

2017-04-01

Gas exchange between soil and atmosphere is important for the biogeochemistry of soils. Gas transport in soil is commonly assumed to be governed by molecular diffusion and is usually described by the soil gas diffusion coefficient DS characterizing the ability of the soil to "transport passively" gas through the soil. One way to determine DS is sampling soil cores in the field and measuring DS in the lab. Unfortunately this method is destructive and laborious. Moreover, a few previous field studies identified other gas transport processes in soil to significantly enhance the diffusive gas transport. However, until now, no method is available to measure gas transport in situ in the soil. We developed a novel method to monitor gas transport in soil in situ. The method includes a custom made gas sampling device, the continuous injection of an inert tracer gas and inverse gas transport modelling in the soil. The gas sampling device has several sampling depths and can be easily installed into a vertical hole drilled by an auger, which allows for fast installation of the system. Helium (He) as inert tracer gas was injected continuously at the lower end of the device. The resulting steady state distribution of He was used to deduce the depth profile of DS. Gas transport in the soil surrounding the gas-sampling-device/soil system was modeled using the Finite Element Modeling program COMSOL . We tested our new method both in the lab and during two short field studies and compared the results with a reference method using soil cores. DS profiles obtained by our in-situ method were consistent with DS profiles determined based on soil core analyses. During a longer monitoring field campaign, typical soil-moisture effects upon gas diffusivity such as an increase during a drying period or a decrease after rain could be observed consistently. Under windy conditions we additionally measured for the first time the direct enhancement of gas transport in soil due to wind-induced pressure-pumping which could increase the effective DS up to 30% in the topsoil. Our novel monitoring method can be quickly and easily installed and allows for monitoring continuously soil gas transport over a long time. It allows monitoring physical modifications of soil gas diffusivity due to rain events or evaporation but it also allows studying non-diffusive gas transport processes in the soil.

Experimental and Computational Study of Trapped Vortex Combustor Sector Rig With Tri-Pass Diffuser

NASA Technical Reports Server (NTRS)

Hendricks, R. C.; Shouse, D. T.; Roquernore, W. M.; Burrus, D. L.; Duncan, B. S.; Ryder, R. C.; Brankovic, A.; Liu, N.-S.; Gallagher, J. R.; Hendricks, J. A.

2004-01-01

The Trapped Vortex Combustor (TVC) potentially offers numerous operational advantages over current production gas turbine engine combustors. These include lower weight, lower pollutant emissions, effective flame stabilization, high combustion efficiency, excellent high altitude relight capability, and operation in the lean burn or RQL modes of combustion. The present work describes the operational principles of the TVC, and extends diffuser velocities toward choked flow and provides system performance data. Performance data include EINOx results for various fuel-air ratios and combustor residence times, combustion efficiency as a function of combustor residence time, and combustor lean blow-out (LBO) performance. Computational fluid dynamics (CFD) simulations using liquid spray droplet evaporation and combustion modeling are performed and related to flow structures observed in photographs of the combustor. The CFD results are used to understand the aerodynamics and combustion features under different fueling conditions. Performance data acquired to date are favorable compared to conventional gas turbine combustors. Further testing over a wider range of fuel-air ratios, fuel flow splits, and pressure ratios is in progress to explore the TVC performance. In addition, alternate configurations for the upstream pressure feed, including bi-pass diffusion schemes, as well as variations on the fuel injection patterns, are currently in test and evaluation phases.

Bulk Growth of Wide Band Gap II-VI Compound Semiconductors by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua

1997-01-01

The mechanism of physical vapor transport of II-VI semiconducting compounds was studied both theoretically, using a one-dimensional diffusion model, as well as experimentally. It was found that the vapor phase stoichiometry is critical in determining the vapor transport rate. The experimental heat treatment methods to control the vapor composition over the starting materials were investigated and the effectiveness of the heat treatments was confirmed by partial pressure measurements using an optical absorption technique. The effect of residual (foreign) gas on the transport rate was also studies theoretically by the diffusion model and confirmed experimentally by the measurements of total pressure and compositions of the residual gas. An in-situ dynamic technique for the transport rate measurements and a further extension of the technique that simultaneously measured the partial pressures and transport rates were performed and, for the first time, the experimentally determined mass fluxes were compared with those calculated, without any adjustable parameters, from the diffusion model. Using the information obtained from the experimental transport rate measurements as guideline high quality bulk crystal of wide band gap II-VI semiconductor were grown from the source materials which undergone the same heat treatment methods. The grown crystals were then extensively characterized with emphasis on the analysis of the crystalline structural defects.

Negative Ion Drift Velocity and Longitudinal Diffusion in Mixtures of Carbon Disulfide and Methane

NASA Technical Reports Server (NTRS)

Dion, Michael P.; Son, S.; Hunter, S. D.; deNolfo, G. A.

2011-01-01

Negative ion drift velocity and longitudinal diffusion has been measured for gas mixtures of carbon disulfide (CS2) and methane (CH4)' Measurements were made as a function of total pressure, CS2 partial pressure and electric field. Constant mobility and thermal-limit longitudinal diffusion is observed for all gas mixtures tested. Gas gain for some of the mixtures is also included.

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas. The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.

Energy and mass balance in the three-phase interstellar medium

NASA Technical Reports Server (NTRS)

Wang, Zhong; Cowie, Lennox L.

1988-01-01

Details of the energy and mass balances are considered in the context of a three-phase interstellar medium. The rates of mass exchange between the different phases are derived based on the pressure variations created by supernova remnant expansions. It is shown that the pressure-confined warm and cold gases have stable temperatures under a variety of interstellar conditions. The three-phase quasi-static configuration is found to be a natural outcome, and both warm and cold phases generally contribute about half of the total mass density to the diffuse interstellar gas. The model is also likely to be self-regulatory in the sense that variations of the input parameters do not strongly alter the general result, which is consistent with most current observations. The consequences of extreme conditions on this model are considered, and the possible implications for interstellar medium in other galaxies are briefly discussed.

Numerical modelling of soot formation and oxidation in laminar coflow non-smoking and smoking ethylene diffusion flames

NASA Astrophysics Data System (ADS)

Liu, Fengshan; Guo, Hongsheng; Smallwood, Gregory J.; Gülder, Ömer L.

2003-06-01

A numerical study of soot formation and oxidation in axisymmetric laminar coflow non-smoking and smoking ethylene diffusion flames was conducted using detailed gas-phase chemistry and complex thermal and transport properties. A modified two-equation soot model was employed to describe soot nucleation, growth and oxidation. Interaction between the gas-phase chemistry and soot chemistry was taken into account. Radiation heat transfer by both soot and radiating gases was calculated using the discrete-ordinates method coupled with a statistical narrow-band correlated-k based band model, and was used to evaluate the simple optically thin approximation. The governing equations in fully elliptic form were solved. The current models in the literature describing soot oxidation by O2 and OH have to be modified in order to predict the smoking flame. The modified soot oxidation model has only moderate effects on the calculation of the non-smoking flame, but dramatically affects the soot oxidation near the flame tip in the smoking flame. Numerical results of temperature, soot volume fraction and primary soot particle size and number density were compared with experimental data in the literature. Relatively good agreement was found between the prediction and the experimental data. The optically thin approximation radiation model significantly underpredicts temperatures in the upper portion of both flames, seriously affecting the soot prediction.

Large scale simulation of liquid water transport in a gas diffusion layer of polymer electrolyte membrane fuel cells using the lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Sakaida, Satoshi; Tabe, Yutaka; Chikahisa, Takemi

2017-09-01

A method for the large-scale simulation with the lattice Boltzmann method (LBM) is proposed for liquid water movement in a gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells. The LBM is able to analyze two-phase flows in complex structures, however the simulation domain is limited due to heavy computational loads. This study investigates a variety means to reduce computational loads and increase the simulation areas. One is applying an LBM treating two-phases as having the same density, together with keeping numerical stability with large time steps. The applicability of this approach is confirmed by comparing the results with rigorous simulations using actual density. The second is establishing the maximum limit of the Capillary number that maintains flow patterns similar to the precise simulation; this is attempted as the computational load is inversely proportional to the Capillary number. The results show that the Capillary number can be increased to 3.0 × 10-3, where the actual operation corresponds to Ca = 10-5∼10-8. The limit is also investigated experimentally using an enlarged scale model satisfying similarity conditions for the flow. Finally, a demonstration is made of the effects of pore uniformity in GDL as an example of a large-scale simulation covering a channel.

Solid-state diffusion-controlled growth of the phases in the Au-Sn system

NASA Astrophysics Data System (ADS)

Baheti, Varun A.; Kashyap, Sanjay; Kumar, Praveen; Chattopadhyay, Kamanio; Paul, Aloke

2018-01-01

The solid state diffusion-controlled growth of the phases is studied for the Au-Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn4 phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn4 phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.

Excitable dynamics in high-Lewis number premixed gas combustion at normal and microgravity

NASA Technical Reports Server (NTRS)

Pearlman, Howard

1995-01-01

Freely-propagating, premixed gas flames in high-Lewis (Le) number, quiescent mixtures are studied experimentally in tubes of various diameter at normal (lg) and microgravity (mu g). A premixture of lean butane and oxygen diluted with helium, argon, neon, nitrogen or a mixture of multiple diluents is examined such that the thermal diffusivity of the mixture (and to a lesser extent, the mass diffusivity of the rate-limiting component) is systematically varied. In effect, different diluents allow variation of the Le without changing the chemistry. The flames are recorded with high speed cinematography and their stability is visually assessed. Different modes of propagation were observed depending on the diameter of the tubes (different conductive heat loss), the composition of the mixture and the g-level. At 1g, four modes of propagation were observed in small and intermediate diameter tubes (large conductive heat loss): (1) steadily propagating flames, (2) radial and longitudinal pulsating flames, (3) 'wavering' flames, and (4) rotating spiral flames. As the diameter of the tube increases, the radial modes become more pronounced while the longitudinal modes systematically disappear. Also, multiple, simultaneous, spatially-separated 'pacemaker' sites are observed in intermediate and large diameter tubes. Each site starts as a small region of high luminosity and develops into a flamelet which assumes the form of one of the fore mentioned modes. These flamelets eventually interact, annihilate each other in their regions of intersection and merge at their newly created free-ends. For very large tubes, radially-propagating wave-trains (believed to be 'trigger waves') are observed. These are analogous to the radial pulsations observed in the smaller diameter tubes. At mu g, three modes of propagation have been observed: (1) steadily propagating flames, (2) radial and longitudinal pulsating flames, and (3) multi-armed, rotating flames. Since the pulsating mode exists at mu g and 1g, buoyant flicker is not the mechanism which drives the pulsations. Moreover, all of the instabilities at 1g and mu g have characteristic frequencies on the O(100Hz). This value is lower than the fundamental, longitudinal acoustic frequencies of the tubes which suggests that the instabilities are not acoustically driven. The patterns formed by this reaction bear remarkable similarities with the patterns formed in most excitable media when the behavior of the system is driven by couplings between chemical reaction and diffusion (e.g., Belousov-Zhabotinsky reaction, Patterns in slime molds, spiral waves in the retina of a bird's eye). While it is recognized that the chemical mechanism associated with this premixed gas reaction is exponentially sensitive to temperature and undoubtedly different from those which govern previously observed excitable media (most are isothermal, or weakly exothermic, liquid phase reactions), similar spatial and temporal patterns should not come as a complete surprise considering heat and mass diffusion are self similar. It is concluded that this premixed gas system is a definitive example of a diffusive-thermal, gas-phase oscillator based on these experimental results and their favorable comparison with theory.

C+/CO Transitions in the Diffuse ISM: Transitional Cloud Sample from the GOT C+ Survey of [CII] in the inner Galaxy at l = -30deg to 30deg

NASA Astrophysics Data System (ADS)

Velusamy, T.; Pineda, J. L.; Langer, W. D.; Willacy, K.; Goldsmith, P. F.

2011-05-01

Our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the well-shielded molecular phase traced by CO. Recently, using the first results of the Herschel Key Project GOT C+, a HIFI C+ survey of the Galactic plane, Velusamy, Langer, Pineda et al. (A&A 521, L18, 2010) have shown that in the diffuse interstellar transition clouds a significant fraction of the carbon exists primarily as C^+ with little C^0 and CO in a warm 'dark gas' layer in which hydrogen is mostly H_2 with little atomic H, surrounding a modest 12CO-emitting core. The [CII] fine structure transition, at 1.9 THz (158 μm) is the best tracer of this component of the interstellar medium, which is critical to our understanding of the atomic to molecular cloud transitions. The Herschel Key Project GOT C+ is designed to study such clouds by observing with HIFI the [CII] line emission along 500 lines of sight (LOSs) throughout the Galactic disk. Here we present the identification and chemical status of a few hundred diffuse and transition clouds traced by [CII], along with auxiliary HI and CO data covering ~100 LOSs in the inner Galaxy between l= -30° and 30°. We identify transition clouds as [CII] components that are characterized by the presence of both HI and 12CO, but no 13CO emission. The intensities, I(CII) and I(HI), are used as measures of the visual extinction, AV, in the cloud up to the C^+/C^0/CO transition layer and a comparison with I(12CO) yields a more complete H_2 molecular inventory. Our results show that [CII] emission is an excellent tool to study transition clouds and their carbon chemistry in the ISM, in particular as a unique tracer of molecular H_2, which is not easily observed by other means. The large sample presented here will serve as a resource to study the chemical and physical status of diffuse transition clouds in a wide range of Galactic environments and constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse ISM.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2015-04-01

In this paper the Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model determines the partitioning of organic compounds between the gas and particle phases. It is designed to be modular with different user options depending on the computation time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption into the aqueous phase of particles, activity coefficients and phase separation). Each surrogate can be hydrophilic (condenses only into the aqueous phase of particles), hydrophobic (condenses only into the organic phases of particles) or both (condenses into both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC (UNIversal Functional group Activity Coefficient; Fredenslund et al., 1975) thermodynamic model for short-range interactions and with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) parameterization for medium- and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium representation and a dynamic representation of organic aerosols (OAs). In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol is not at equilibrium with the gas phase because the organic phases could be semi-solid (very viscous liquid phase). The condensation-evaporation of organic compounds could then be limited by the diffusion in the organic phases due to the high viscosity. An implicit dynamic representation of secondary organic aerosols (SOAs) is available in SOAP with OAs divided into layers, the first layer being at the center of the particle (slowly reaches equilibrium) and the final layer being near the interface with the gas phase (quickly reaches equilibrium). Although this dynamic implicit representation is a simplified approach to model condensation-evaporation with a low number of layers and short CPU (central processing unit) time, it shows good agreements with an explicit representation of condensation-evaporation (no significant differences after a few hours of condensation).

The Galactic interstellar medium: foregrounds and star formation

NASA Astrophysics Data System (ADS)

Miville-Deschênes, Marc-Antoine

2018-05-01

This review presents briefly two aspects of Galactic interstellar medium science that seem relevant for studying EoR. First, we give some statistical properties of the Galactic foreground emission in the diffuse regions of the sky. The properties of the emission observed in projection on the plane of the sky are then related to how matter is organised along the line of sight. The diffuse atomic gas is multi-phase, with dense filamentary structures occupying only about 1% of the volume but contributing to about 50% of the emission. The second part of the review presents aspect of structure formation in the Galactic interstellar medium that could be relevant for the subgrid physics used to model the formation of the first stars.

A semi-empirical model for the complete orientation dependence of the growth rate for vapor phase epitaxy - Chloride VPE of GaAs

NASA Technical Reports Server (NTRS)

Seidel-Salinas, L. K.; Jones, S. H.; Duva, J. M.

1992-01-01

A semi-empirical model has been developed to determine the complete crystallographic orientation dependence of the growth rate for vapor phase epitaxy (VPE). Previous researchers have been able to determine this dependence for a limited range of orientations; however, our model yields relative growth rate information for any orientation. This model for diamond and zincblende structure materials is based on experimental growth rate data, gas phase diffusion, and surface reactions. Data for GaAs chloride VPE is used to illustrate the model. The resulting growth rate polar diagrams are used in conjunction with Wulff constructions to simulate epitaxial layer shapes as grown on patterned substrates. In general, this model can be applied to a variety of materials and vapor phase epitaxy systems.

Single-shot diffusion measurement in laser-polarized Gas

NASA Technical Reports Server (NTRS)

Peled, S.; Tseng, C. H.; Sodickson, A. A.; Mair, R. W.; Walsworth, R. L.; Cory, D. G.

1999-01-01

A single-shot pulsed gradient stimulated echo sequence is introduced to address the challenges of diffusion measurements of laser polarized 3He and 129Xe gas. Laser polarization enhances the NMR sensitivity of these noble gases by >10(3), but creates an unstable, nonthermal polarization that is not readily renewable. A new method is presented which permits parallel acquisition of the several measurements required to determine a diffusive attenuation curve. The NMR characterization of a sample's diffusion behavior can be accomplished in a single measurement, using only a single polarization step. As a demonstration, the diffusion coefficient of a sample of laser-polarized 129Xe gas is measured via this method. Copyright 1999 Academic Press.

Methane and carbon dioxide concentrations in sediments and diffusive fluxes at the sediment-water interface from three tropical systems in Brazil during the pre-impoundment phase

NASA Astrophysics Data System (ADS)

Abe, D. S.; Sidagis-Galli, C.; Grimberg, D. E.; Blanco, F. D.; Rodrigues-Filho, J. L.; Tundisi, J. G.; Matsumura-Tundisi, T.; Tundisi, J. E.; Cimbleris, A. C.; Damázio, J. M.; Project Balcar

2013-05-01

The concentrations of methane and carbon dioxide in the sediments pore water were quantified by gas chromatography in three hydroelectric reservoirs under construction during the pre-impoundment phase. Sediment sampling was performed in ten to twelve stations in each river by a Kajak-Brinkhurst corer coupled to a 3 m long aluminum rod in four seasons. The theoretical diffusive fluxes of these gases at the sediment-water interface were also calculated using the Fick's first law of diffusion. The mean annual concentration and diffusive flux of methane were highest in the sediments of the Xingu River (12.71 ± 3.03 mmol CH4 m-2 and 3.84 ± 0.91 mmol CH4 m-2 d-1), located in the Amazon, influenced by the presence of organic matter originating from the surrounding forest. The mean annual concentration of carbon dioxide was highest in the São Marcos River (71.36 ± 10.36 mmol CO2 m-2), located in an area of cerrado savanna, while the highest diffusive flux of carbon dioxide was observed in the Madeira River (30.23 ± 2.41 mmol CO2 m-2 d-1), which rises in the Andes Cordillera and has a very high water flow. The mean concentration and diffusive flux of carbon dioxide in the three studied systems were much higher (64-98%) in comparison with the methane, influenced by the oxic condition in these lotic systems. Nevertheless, the present study shows that the sediments of these systems, especially in the Xingu River, have significant amount of methane dissolved in the pore water which is being diffused to the overlying water. The information obtained in this study during the pre-filling phase will be important for the calculation of net flows of greenhouse gases after the impoundment of these future reservoirs. This study is part of the Strategic Project "Monitoring Emissions of Greenhouse Gases in Hydroelectric Reservoirs" - Call 099/2008 of the Brazilian Agency of Electric Energy (ANEEL) and sponsored by ELETRONORTE, FURNAS and CHESF.

Local Dynamics of Chemical Kinetics at Different Phases of Nitriding Process

NASA Astrophysics Data System (ADS)

Özdemir, İ. Bedii; Akar, Firat

2015-08-01

The local dynamics of chemical kinetics at different phases of the nitriding process have been studied. The calculations are performed under the conditions where the temperature and composition data are provided experimentally from an in-service furnace. Results are presented in temporal variations of gas concentrations and the nitrogen coverage on the surface. It is shown that if it is available in the furnace, the adsorption of the N2 gas can seemingly start at temperatures as low as 200 °C. However, at such low temperatures, as the diffusion into the material is very unlikely, this results in the surface poisoning. It becomes clear that, contrary to common knowledge, the nitriding heat treatment with ammonia as a nitrogen-providing medium is possible at temperatures like 400 °C. Under these conditions, however, the presence of excess amounts of product gas N2 in the furnace atmosphere suppresses the forward kinetics in the nitriding process. It seems that the best operating point in the nitriding heat treatment is achieved with a mixture of 6% N2. When the major nitriding species NH3 is substituted by N2 and the N2 fraction increases above 30%, the rate of the forward reaction decreases drastically, so that there is no point to continue the furnace operation any further. Hence, during the initial heating phase, the N2 gas must be purged from the furnace to keep its fraction less than 30% before the furnace reaches the temperature where the reaction starts.

New approach to effective diffusion coefficient evaluation in the nanostructured two-phase media

NASA Astrophysics Data System (ADS)

Lyashenko, Yu. O.; Liashenko, O. Y.; Morozovich, V. V.

2018-03-01

Most widely used basic and combined models for evaluation of the effective diffusion parameters of inhomogeneous two-phase zone are reviewed. A new combined model of effective medium is analyzed for the description of diffusion processes in the two-phase zones. In this model the effective diffusivity depends on the growth kinetic coefficients of each phase, the volume fractions of phases and on the additional parameter that generally characterizes the structure type of the two-phase zone. Our combined model describes two-phase zone evolution in the binary systems based on consideration of the diffusion fluxes through both phases. The Lattice Monte Carlo method was used to test the validity of different phenomenological models for evaluation of the effective diffusivity in nanostructured two-phase zones with different structural morphology.

N2 and CO2 capillary breakthrough experiments on Opalinus Clay

NASA Astrophysics Data System (ADS)

Amann, Alexandra; Busch, Andreas; Krooss, Bernhard M.

2013-04-01

The aim of this project was to identify the critical capillary pressures on the drainage and the imbibition path for clay-rich rocks, at a burial depth of 1500 m (30 MPa confining pressure, 45°C). The experiments were performed on fully water-saturated sample plugs of 38 mm diameter and 5 to 20 mm length. The capillary breakthrough pressure was determined by step-wise increase of the differential pressure (drainage), the capillary snap-off pressure was determined from the final pressure difference at the end of a spontaneous imbibition phase. The confining pressure was kept constant throughout the experiment, which resulted in a continuous change of effective stress. The measurements were performed in a closed system and the pressure response was interpreted in terms of different flow mechanisms (diffusion-controlled vs. viscous flow). In total, four breakthrough experiments with N2 and five experiments with CO2 were conducted. Because of very low flow rates and high critical capillary pressures the experiments took rather long. In some cases the experiments were allowed to run for half a year (drainage experiments). Substantial differences were observed between gas breakthrough (drainage) and snap-off (imbibition) pressures. As expected, breakthrough pressures were always higher than the snap-off pressures. For three samples a pbreakthrough/psnap-off ratio of 1.6 to 1.9 was observed, for one sample a ratio of 4. A clear permeability-capillary pressure relationship could not be identified. Based on (omnidirectional) Hg-injection porosimetry results, and assuming perfectly water wet mineral surfaces, gas breakthrough pressures were predicted to occur at approximately 16 MPa for N2 and 5.7 MPa for CO2. The gas breakthrough experiments, however, produced different results. Even though a relatively homogeneous sample set was chosen, with permeability coefficients ranging between 1E-21 and 6E-21 m², the critical capillary breakthrough pressures for nitrogen ranged between 3.4 and 12.3 MPa and snap-off pressures from 0.5 to 6.4 MPa. The CO2 experiments yielded breakthrough pressures of 14.0 to 17.5 MPa and snap-off pressures of 3.5 to 10 MPa. No significant changes in single-phase water permeability coefficients before and after the gas breakthrough experiments were observed. In our contribution we will discuss the following points: 1. Gas fluxes occurring during gas breakthrough experiments may be extremely low. Therefore an unambigous identification of gas breakthrough is not always possible. Besides viscous or diffusive transport, dissolution of CO2 in the pore water may affect the observed pressure changes in the upstream and downstream compartments. All of these processes occur simultaneously and can only be partly discriminated. Gas fluxes detected during the diffusion-controlled flow regimes result in nominal effective gas permeability coefficients as low as 6E-25 m² to 7E-24m². 2. The application of purely capillary-controlled flow models may not be justified. o Gas breakthrough is controlled by effective stress, i.e. the opening of pores or small fissures. o Assumptions about wettability (completely water-wet mineral surfaces) may be incorrect.

Multicomponent Gas Diffusion and an Appropriate Momentum Boundary Condition

NASA Technical Reports Server (NTRS)

Noever, David A.

1994-01-01

Multicomponent gas diffusion is reviewed with particular emphasis on gas flows near solid boundaries-the so-called Kramers-Kistemaker effect. The aim is to derive an appropriate momentum boundary condition which governs many gaseous species diffusing together. The many species' generalization of the traditional single gas condition, either as slip or stick (no-slip), is not obvious, particularly for technologically important cases of lower gas pressures and very dissimilar molecular weight gases. No convincing theoretical case exists for why two gases should interact with solid boundaries equally but in opposite flow directions, such that the total gas flow exactly vanishes. ln this way, the multicomponent no-slip boundary requires careful treatment The approaches discussed here generally adopt a microscopic model for gas-solid contact. The method has the advantage that the mathematics remain tractable and hence experimentally testable. Two new proposals are put forward, the first building in some molecular collision physics, the second drawing on a detailed view of surface diffusion which does not unphysically extrapolate bulk gas properties to govern the adsorbed molecules. The outcome is a better accounting of previously anomalous experiments. Models predict novel slip conditions appearing even for the case of equal molecular weight components. These approaches become particularly significant in view of a conceptual contradiction found to arise in previous derivations of the appropriate boundary conditions. The analogous case of three gases, one of which is uniformly distributed and hence non-diffusing, presents a further refinement which gives unexpected flow reversals near solid boundaries. This case is investigated alone and for aggregating gas species near their condensation point. In addition to predicting new physics, this investigation carries practical implications for controlling vapor diffusion in the growth of crystals used in medical diagnosis (e.g. mercuric iodide) and semiconductors.

Calculation of gas-flow in plasma reactor for carbon partial oxidation

NASA Astrophysics Data System (ADS)

Bespala, Evgeny; Myshkin, Vyacheslav; Novoselov, Ivan; Pavliuk, Alexander; Makarevich, Semen; Bespala, Yuliya

2018-03-01

The paper discusses isotopic effects at carbon oxidation in low temperature non-equilibrium plasma at constant magnetic field. There is described routine of experiment and defined optimal parameters ensuring maximum enrichment factor at given electrophysical, gas-dynamic, and thermodymanical parameters. It has been demonstrated that at high-frequency generator capacity of 4 kW, supply frequency of 27 MHz and field density of 44 mT the concentration of paramagnetic heavy nuclei 13C in gaseous phase increases up to 1.78 % compared to 1.11 % for natural concentration. Authors explain isotopic effect decrease during plasmachemical separation induced by mixing gas flows enriched in different isotopes at the lack of product quench. With the help of modeling the motion of gas flows inside the plasma-chemical reactor based on numerical calculation of Navier-Stokes equation authors determine zones of gas mixing and cooling speed. To increase isotopic effects and proportion of 13C in gaseous phase it has been proposed to use quench in the form of Laval nozzle of refractory steel. The article represents results on calculation of optimal Laval Nozzle parameters for plasma-chemical reactor of chosen geometry of. There are also given dependences of quench time of products on pressure at the diffuser output and on critical section diameter. Authors determine the location of quench inside the plasma-chemical reactor in the paper.

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter

PubMed Central

2018-01-01

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet–visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance. PMID:29532020

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter.

PubMed

Liu, Pengfei; Li, Yong Jie; Wang, Yan; Bateman, Adam P; Zhang, Yue; Gong, Zhaoheng; Bertram, Allan K; Martin, Scot T

2018-02-28

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet-visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.

A finite element code for modelling tracer transport in a non-isothermal two-phase flow system for CO2 geological storage characterization

NASA Astrophysics Data System (ADS)

Tong, F.; Niemi, A. P.; Yang, Z.; Fagerlund, F.; Licha, T.; Sauter, M.

2011-12-01

This paper presents a new finite element method (FEM) code for modeling tracer transport in a non-isothermal two-phase flow system. The main intended application is simulation of the movement of so-called novel tracers for the purpose of characterization of geologically stored CO2 and its phase partitioning and migration in deep saline formations. The governing equations are based on the conservation of mass and energy. Among the phenomena accounted for are liquid-phase flow, gas flow, heat transport and the movement of the novel tracers. The movement of tracers includes diffusion and the advection associated with the gas and liquid flow. The temperature, gas pressure, suction, concentration of tracer in liquid phase and concentration of tracer in gas phase are chosen as the five primary variables. Parameters such as the density, viscosity, thermal expansion coefficient are expressed in terms of the primary variables. The governing equations are discretized in space using the Galerkin finite element formulation, and are discretized in time by one-dimensional finite difference scheme. This leads to an ill-conditioned FEM equation that has many small entries along the diagonal of the non-symmetric coefficient matrix. In order to deal with the problem of non-symmetric ill-conditioned matrix equation, special techniques are introduced . Firstly, only nonzero elements of the matrix need to be stored. Secondly, it is avoided to directly solve the whole large matrix. Thirdly, a strategy has been used to keep the diversity of solution methods in the calculation process. Additionally, an efficient adaptive mesh technique is included in the code in order to track the wetting front. The code has been validated against several classical analytical solutions, and will be applied for simulating the CO2 injection experiment to be carried out at the Heletz site, Israel, as part of the EU FP7 project MUSTANG.

Physical gills prevent drowning of many wetland insects, spiders and plants.

PubMed

Pedersen, Ole; Colmer, Timothy D

2012-03-01

Insects, spiders and plants risk drowning in their wetland habitats. The slow diffusion of O(2) can cause asphyxiation when underwater, as O(2) supply cannot meet respiratory demands. Some animals and plants have found a common solution to the major challenge: how to breathe underwater with respiratory systems evolved for use in air? Hydrophobic surfaces on their bodies possess gas films that act as a 'physical gill' to collect O(2) when underwater and thus sustain respiration. In aquatic insects, this feature/process has been termed 'plastron respiration'. Here, we demonstrate the similarities in function between underwater respiration of insect (Aphelocheirus aestivalis) plastrons and gas films on leaves of wetland plants (Phalaris arundinacea) and also show the importance of these physical gills by the resulting changes upon their removal. The gas films provide an enlarged gas-water interface to enhance O(2) uptake underwater that is above that if only spiracles (insects) or stomata (plants) provided the gas-phase contact with the water. Body-surface gas films contribute to the survival of many insects, spiders and plants in aquatic and flood-prone environments.

Measurement of the oxygen mass transfer through the air-water interface.

PubMed

Mölder, Erik; Mashirin, Alelxei; Tenno, Toomas

2005-01-01

Gas mass transfer through the liquid-gas interface has enormous importance in various natural and industrial processes. Surfactants or insoluble compounds adsorbed onto an interface will inhibit the gas mass transfer through the liquid-gas surface. This study presents a technique for measuring the oxygen mass transfer through the air-water interface. Experimental data obtained with the measuring device were incorporated into a novel mathematical model, which allowed one to calculate diffusion conduction of liquid surface layer and oxygen mass transfer coefficient in the liquid surface layer. A special measurement cell was constructed. The most important part of the measurement cell is a chamber containing the electrochemical oxygen sensor inside it. Gas exchange between the volume of the chamber and the external environment takes place only through the investigated surface layer. Investigated liquid was deoxygenated, which triggers the oxygen mass transfer from the chamber through the liquid-air interface into the liquid phase. The decrease of oxygen concentration in the cell during time was measured. By using this data it is possible to calculate diffusional parameters of the water surface layer. Diffusion conduction of oxygen through the air-water surface layer of selected wastewaters was measured. The diffusion conduction of different wastewaters was about 3 to 6 times less than in the unpolluted water surface. It was observed that the dilution of wastewater does not have a significant impact on the oxygen diffusion conduction through the wastewater surface layer. This fact can be explained with the presence of the compounds with high surface activity in the wastewater. Surfactants achieved a maximum adsorption and, accordingly, the maximum decrease of oxygen permeability already at a very low concentration of surfactants in the solution. Oxygen mass transfer coefficient of the surface layer of the water is found to be Ds/ls = 0.13 x 10(-3) x cm/s. A simple technique for measuring oxygen diffusion parameters through the air-water solution surface has been developed. Derived equations enable the calculation of diffusion parameters of the surface layer at current conditions. These values of the parameters permit one to compare the resistances of the gas-liquid interface to oxygen mass transfer in the case of adsorption of different substances on the surface layer. This simple technique may be used for a determination of oxygen permeability of different water-solution surface layers. It enables one to measure the resistance to the oxygen permeability of all inflowing wastewater surface layers in the wastewater treatment plant, and to initiate a preliminary cleaning of this wastewater if required. Similarly, we can measure oxygen permeability of natural waterbodies. Especially in the case of pollution, it is important to know to what extent the oxygen permeability of the water surface layer has been decreased. Based on the tehnique presented in this research, fieldwork equipment will be developed.

Acoustic observations of gas bubble streams in the NW Black Sea as a method for estimation of gas flux from vent sites

NASA Astrophysics Data System (ADS)

Artemov, Yu. G.

2003-04-01

Relatively recent discovery of the natural CH_4 gas seepage from the sea bed had action upon the philosophy of CH_4 contribution to global budgets. So far as numerous gas vent sites are known, an acceptable method for released gas quantification is required. In particular, the questions should be answered as follows: 1) how much amount of gas comes into the water column due to a certain bubble stream, 2) how much amount of gas comes into the water column due to a certain seepage area of the see floor, 3) how much amount of gas diffuses into the water and how much gas phase enters the atmosphere. Echo-sounder is the habitual equipment for detecting gas plumes (flares) in the water column. To provide observations of gas seeps with bubbles tracking, single target and volume backscattering strength measurements, we use installed on board the R/V "Professor Vodyanitskiy" dual frequency (38 and 120 kHz) split-beam scientific echo-sounder SIMRAD EK-500. Dedicated software is developed to extract from the raw echo data and to handle the definite information for analyses of gas bubble streams features. This improved hydroacoustic techniques allows to determine gas bubbles size spectrum at different depths through the water column as well as rise velocity of bubbles of different sizes. For instance, bubble of 4.5 mm diameter has rising speed of 25.8 cm/sec at 105 m depth, while bubble of 1.7 mm diameter has rising speed of 16.3 cm/sec at 32 m depth. Using volume backscattering measurements in addition, it is possible to evaluate flux of the gas phase produced by methane bubble streams and to learn of its fate in the water column. Ranking of various gas plumes by flux rate value is available also. In this presentation results of acoustic observations at the shallow NW Black Sea seepage area are given.

Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations.

PubMed

Visser, Ate; Schaap, Joris D; Broers, Hans Peter; Bierkens, Marc F P

2009-01-26

The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2=69%), as well as the 3H (R2=79%) and 3He (R2=76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (+/-2 sigma) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.

Percolation Network Study on the Gas Apparent Permeability of Rock

NASA Astrophysics Data System (ADS)

Wang, Y.; Tang, Y. B.; Li, M.

2017-12-01

We modeled the gas single phase transport behaviors of monomodal porous media using percolation networks. Different from the liquid absolute permeability, which is only related to topology and morphology of pore space, the gas permeability depends on pore pressure as well. A published gas flow conductance model, included usual viscous flow, slip flow and Knudsen diffusion in cylinder pipe, was used to simulated gas flow in 3D, simple cubic, body-center cubic and face-center cubic networks with different hydraulic radius, different coordination number, and different pipe radius distributions under different average pore pressure. The simulation results showed that the gas apparent permeability kapp obey the `universal' scaling law (independence of network lattices), kapp (z-zc)β, where exponent β is related to pore radius distribution, z is coordination number and zc=1.5. Following up on Bernabé et al.'s (2010) study of the effects of pore connectivity and pore size heterogeneity on liquid absolute permeability, gas apparent permeability kapp model and a new joint gas-liquid permeability (i.e., kapp/k∞) model, which could explain the Klinkenberg phenomenon, were proposed. We satisfactorily tested the models by comparison with published experimental data on glass beads and other datasets.

Transport of organic solutes through amorphous teflon AF films.

PubMed

Zhao, Hong; Zhang, Jie; Wu, Nianqiang; Zhang, Xu; Crowley, Katie; Weber, Stephen G

2005-11-02

Fluorous media have great potential for selective extraction (e.g., as applied to organic synthesis). Fluorous polymer films would have significant advantages in fluorous separations. Stable films of Teflon AF 2400 were cast from solution. Films appear defect-free (SEM; AFM). Rigid aromatic solutes are transported (from chloroform solution to chloroform receiving phase) in a size-dependent manner (log permeability is proportional to -0.0067 times critical volume). Benzene's permeability is about 2 orders of magnitude higher than in comparable gas-phase experiments. The films show selectivity for fluorinated solutes in comparison to the hydrogen-containing control. Transport rates are dependent on the solvent making up the source and receiving phases. The effect of solvent is, interestingly, not due to changes in partition ratio, but rather it is due to changes in the solute diffusion coefficient in the film. Solvents plasticize the films. A less volatile compound, -COOH-terminated poly(hexafluoropropylene oxide) (4), plasticizes the films (T(g) = -40 degrees C). Permeabilities are decreased in comparison to 4-free films apparently because of decreased diffusivity of solutes. The slope of dependence of log permeability on critical volume is not changed, however.

Digital micromirror device as amplitude diffuser for multiple-plane phase retrieval

NASA Astrophysics Data System (ADS)

Abregana, Timothy Joseph T.; Hermosa, Nathaniel P.; Almoro, Percival F.

2017-06-01

Previous implementations of the phase diffuser used in the multiple-plane phase retrieval method included a diffuser glass plate with fixed optical properties or a programmable yet expensive spatial light modulator. Here a model for phase retrieval based on a digital micromirror device as amplitude diffuser is presented. The technique offers programmable, convenient and low-cost amplitude diffuser for a non-stagnating iterative phase retrieval. The technique is demonstrated in the reconstructions of smooth object wavefronts.

Modelling the Composition of Outgassing Bubbles at Basaltic Open Vent Volcanoes

NASA Astrophysics Data System (ADS)

Edmonds, M.; Clements, N.; Houghton, B. F.; Oppenheimer, C.; Jones, R. L.; Burton, M. R.

2015-12-01

Basaltic open vent volcanoes exhibit a wide range in eruption styles, from passive outgassing to Strombolian and Hawaiian explosive activity. Transitions between these styles are linked to contrasting two-phase (melt and gas) flow regimes in the conduit system. A wealth of data now exists characterising the fluxes and compositions of gases emitted from these volcanoes, alongside detailed observations of patterns of outgassing at the magma free surfaces. Complex variations in gas composition are apparent from high temporal resolution measurement techniques such as open path spectroscopy. This variability with time is likely a function of individual bubbles' histories of growth during ascent, with variable degrees of kinetic inhibition. Our previous studies at Kilauea and Stromboli have, for example, linked CO2-rich gases with the bursting of bubbles that last equilibrated at some depth beneath the surface. However, very few studies have attempted to reconcile such observations with quantitative models of diffusion-limited bubble growth in magmas prior to eruption. We present here an analytical model that simulates the growth of populations of bubbles by addition of volatile mass during decompression, with growth limited by diffusion. The model simulates a range of behaviors between the end members of separated two-phase flow and homogeneous bubbly flow in the conduit, tied to thermodynamic models of solubility and partitioning of volatile species (carbon, water, sulfur). We explore the effects of the form of bubble populations at depth, melt viscosity, total volatile content, magma decompression rate and other intrinsic parameters on expected gas compositions at the surface and consider implications for transitions between eruption styles. We compare the the model to data suites from Stromboli and Kilauea.

A four-dimensional variational chemistry data assimilation scheme for Eulerian chemistry transport modeling

NASA Astrophysics Data System (ADS)

Eibern, Hendrik; Schmidt, Hauke

1999-08-01

The inverse problem of data assimilation of tropospheric trace gas observations into an Eulerian chemistry transport model has been solved by the four-dimensional variational technique including chemical reactions, transport, and diffusion. The University of Cologne European Air Pollution Dispersion Chemistry Transport Model 2 with the Regional Acid Deposition Model 2 gas phase mechanism is taken as the basis for developing a full four-dimensional variational data assimilation package, on the basis of the adjoint model version, which includes the adjoint operators of horizontal and vertical advection, implicit vertical diffusion, and the adjoint gas phase mechanism. To assess the potential and limitations of the technique without degrading the impact of nonperfect meteorological analyses and statistically not established error covariance estimates, artificial meteorological data and observations are used. The results are presented on the basis of a suite of experiments, where reduced records of artificial "observations" are provided to the assimilation procedure, while other "data" is retained for performance control of the analysis. The paper demonstrates that the four-dimensional variational technique is applicable for a comprehensive chemistry transport model in terms of computational and storage requirements on advanced parallel platforms. It is further shown that observed species can generally be analyzed, even if the "measurements" have unbiased random errors. More challenging experiments are presented, aiming to tax the skill of the method (1) by restricting available observations mostly to surface ozone observations for a limited assimilation interval of 6 hours and (2) by starting with poorly chosen first guess values. In this first such application to a three-dimensional chemistry transport model, success was also achieved in analyzing not only observed but also chemically closely related unobserved constituents.

MUTUAL DIFFUSION OF PAIRS OF RARE GASES AT DIFFERENT TEMPERATURES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, B.N.; Srivastava, K.P.

1959-04-01

The eoefficient of mutual diffusion of the binary gas mixtures Ne--Ar, Ar--Krs and Ne--Kr has been determined at 0, 15, 30s and 45 C. Diffusion is allowed to take place between two diffusion bulbs through a precision capillary tube and samples of gas are withdrawn from one bulb at different times and analyzed by a differential conductivity analyzer. From the experimentally determined values of the diffusion coefficient at different temperatures the unlike interaction parameters for the above gas pairs have been calculated by two different methods on the Lennard-Jones I2:6 model. These values of the force parameters are found tomore » be in good agreement with those obtained from the usual combination rules and also from the thermal diffusion data following the method of Srivastava and Madan. These values are found to reproduce the experimental data on mutual diffusion quite satisfactorily. With Kelvin's method, these data have also been utilized to calculate the self-diffusion coefficient of neon, argons and krypton. (auth)« less

Constraining the Volatility Distributions and Possible Diffusion Limitations of Secondary Organic Aerosols Using Laboratory Dilution Experiments

NASA Astrophysics Data System (ADS)

Ye, Q.; Robinson, E. S.; Mahfouz, N.; Sullivan, R. C.; Donahue, N. M.

2016-12-01

Secondary organic aerosols (SOA) dominate the mass of fine particles in the atmosphere. Their formation involves both oxidation of volatile organics from various sources that produce products with uncertain volatilities, and diffusion of these products into the condensed phase. Therefore, constraining volatility distribution and diffusion timescales of the constituents in SOA are important in predicting size, concentration and composition of SOA, as well as how these properties of SOA evolve in the atmosphere. In this work, we demonstrate how carefully designed laboratory isothermal dilution experiments in smog chambers can shed light into the volatility distribution and any diffusion barriers of common types of SOA over time scales relevant to atmospheric transport and diurnal cycling. We choose SOA made from mono-terpenes (alpha-pinene and limonene) and toluene to represent biogenic and anthropogenic SOA. We look into how moisture content can alter any evaporation behaviors of SOA by varying relative humidity during SOA generation and during dilution process. This provides insight into whether diffusion in the condensed phase is rate limiting in reaching gas/particle equilibrium of semi-volatile organic compounds. Our preliminary results show that SOA from alpha-pinene evaporates continuously over several hours of experiments, and there is no substantial discernible differences over wide ranges of the chamber humidity. SOA from toluene oxidation shows slower evaporation. We fit these experimental data using absorptive partitioning theory and a particle dynamic model to obtain volatility distributions and to predict particle size evolution. This in the end will help us to improve representation of SOA in large scale chemical transport models.

Dissociation of Laboratory-Synthesized Methane Hydrate in Coarse-Grained Sediments by Slow Depressurization

NASA Astrophysics Data System (ADS)

Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.

2016-12-01

We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.

Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

NASA Astrophysics Data System (ADS)

Shibata, T.; Nishiyama, H.

2014-03-01

Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

Onset of Curved Dendrite Growth in an Al-Cu Welding Pool: A Phase Field Study

NASA Astrophysics Data System (ADS)

Wang, Lei; Wei, Yanhong

2018-02-01

A phase field model is developed to predict curved dendrite growth in the gas tungsten arc (GTA) welding pool of an Al-Cu alloy. The equations of temperature gradient, pulling velocity and dendrite growth orientation are proposed to consider the transient solidification process during welding. Solidification microstructures and solute diffusion along the fusion boundary in the welding pool are predicted by using the phase field model coupled with transient solidification conditions. Predicted primary dendrites are curved and point toward the welding direction. Welding experiments are carried out to observe solidification microstructures of the weld. Comparisons of simulation results with experimental measurements are conducted. Predicted dendritic morphology, dendrite growth orientation, primary dendrite arm spacing and initial cell spacing give a good agreement with experimental measurements.

Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

PubMed

Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

2009-12-31

Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

NASA Astrophysics Data System (ADS)

Amalberti, Julien; Burnard, Pete; Laporte, Didier; Tissandier, Laurent; Neuville, Daniel R.

2016-01-01

Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications of the silicate network itself as the glass transition temperature is approached: as the available free volume (available site for diffusive jumps) is modified, noble gas diffusion is no longer solely temperature-activated but also becomes sensitive to the kinetics of network rearrangements. The non-Arrhenian behavior of noble gas diffusion close to Tg is well described by a modified Vogel-Tammann-Fulcher (VTF) equation: Finally, our step heating diffusion experiments suggest that at T close to Tg, noble gas isotopes may suffer kinetic fractionation at a degree larger than that predicted by Graham's law. In the case of 40Ar and 36Ar, the traditional assumption based on Graham's law is that the ratio D40Ar/D36Ar should be equal to 0.95 (the square root of the ratio of the mass of 36Ar over the mass of 40Ar). In our experiment with glass G1, D40Ar/D36Ar rapidly decreased with decreasing temperature, from near unity (0.98 ± 0.14) at T > 1040 K to 0.76 when close to Tg (T = 1003 K). Replicate experiments are needed to confirm the strong kinetic fractionation of heavy noble gases close to the transition temperature.

Turbine exhaust diffuser with region of reduced flow area and outer boundary gas flow

DOEpatents

Orosa, John

2014-03-11

An exhaust diffuser system and method for a turbine engine. The outer boundary may include a region in which the outer boundary extends radially inwardly toward the hub structure and may direct at least a portion of an exhaust flow in the diffuser toward the hub structure. At least one gas jet is provided including a jet exit located on the outer boundary. The jet exit may discharge a flow of gas downstream substantially parallel to an inner surface of the outer boundary to direct a portion of the exhaust flow in the diffuser toward the outer boundary to effect a radially outward flow of at least a portion of the exhaust gas flow toward the outer boundary to balance an aerodynamic load between the outer and inner boundaries.

Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2O 3–FeF 3 Conversion Compounds by Direct Fluorination

DOE PAGES

Zhou, Hui; Ruther, Rose E.; Adcock, Jamie; ...

2015-02-22

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe 2O 3) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe 2O 3-xF 2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELSmore » results showed porous interconnected nanodomains of FeF 3 and Fe 2O 3 coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF 3 + Fe 2O 3 composition, and correlate the results to their electrochemical performance. Finally and further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF 3) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.« less

Experimental studies and model analysis of noble gas fractionation in porous media

USGS Publications Warehouse

Ding, Xin; Kennedy, B. Mack.; Evans, William C.; Stonestrom, David A.

2016-01-01

The noble gases, which are chemically inert under normal terrestrial conditions but vary systematically across a wide range of atomic mass and diffusivity, offer a multicomponent approach to investigating gas dynamics in unsaturated soil horizons, including transfer of gas between saturated zones, unsaturated zones, and the atmosphere. To evaluate the degree to which fractionation of noble gases in the presence of an advective–diffusive flux agrees with existing theory, a simple laboratory sand column experiment was conducted. Pure CO2 was injected at the base of the column, providing a series of constant CO2 fluxes through the column. At five fixed sampling depths within the system, samples were collected for CO2 and noble gas analyses, and ambient pressures were measured. Both the advection–diffusion and dusty gas models were used to simulate the behavior of CO2 and noble gases under the experimental conditions, and the simulations were compared with the measured depth-dependent concentration profiles of the gases. Given the relatively high permeability of the sand column (5 ´ 10−11 m2), Knudsen diffusion terms were small, and both the dusty gas model and the advection–diffusion model accurately predicted the concentration profiles of the CO2 and atmospheric noble gases across a range of CO2 flux from ?700 to 10,000 g m−2 d−1. The agreement between predicted and measured gas concentrations demonstrated that, when applied to natural systems, the multi-component capability provided by the noble gases can be exploited to constrain component and total gas fluxes of non-conserved (CO2) and conserved (noble gas) species or attributes of the soil column relevant to gas transport, such as porosity, tortuosity, and gas saturation.

SNOW LINES AS PROBES OF TURBULENT DIFFUSION IN PROTOPLANETARY DISKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Owen, James E.

2014-07-20

Sharp chemical discontinuities can occur in protoplanetary disks, particularly at ''snow lines'' where a gas-phase species freezes out to form ice grains. Such sharp discontinuities will diffuse out due to the turbulence suspected to drive angular momentum transport in accretion disks. We demonstrate that the concentration gradient—in the vicinity of the snow line—of a species present outside a snow line but destroyed inside is strongly sensitive to the level of turbulent diffusion (provided the chemical and transport timescales are decoupled) and provides a direct measurement of the radial ''Schmidt number'' (the ratio of the angular momentum transport to radial turbulentmore » diffusion). Taking as an example the tracer species N{sub 2}H{sup +}, which is expected to be destroyed inside the CO snow line (as recently observed in TW Hya) we show that ALMA observations possess significant angular resolution to constrain the Schmidt number. Since different turbulent driving mechanisms predict different Schmidt numbers, a direct measurement of the Schmidt number in accretion disks would allow inferences to be made about the nature of the turbulence.« less

A study of the polyethylene membrane used in diffusion chambers for radon gas concentration measurements

NASA Astrophysics Data System (ADS)

Leung, S. Y. Y.; Nikezic, D.; Leung, J. K. C.; Yu, K. N.

2007-10-01

Solid-state nuclear track detectors (SSNTDs) in diffusion chambers have been routinely used for long-term measurements of radon gas concentrations. In usual practice, a filter is added across the top of the diffusion chamber to stop the progeny from entering. Thoron can also be deterred from entering the diffusion chamber by using a polyethylene (PE) membrane. However, the thickness of the PE membrane is rarely specified in the literature. In this paper, we will present our experimental results for a radon exposure that the number of alpha-particle tracks registered by the LR 115 SSNTD in a Karlsruhe diffusion chamber covered with one layer of PE membrane is actually enhanced. This is explained by enhanced deposition of radon progeny on the outside surface of the PE membrane and the insufficient thickness of the PE membrane to stop the alpha particles emitted from these deposited radon progeny to reach the SSNTD. We will present the PE thickness which can stop the alpha particles emitted from the deposited radon or thoron progeny. For the "twin diffusion chambers method", one of the diffusion chambers is covered with PE membranes. The optimal number of thickness of PE membranes will be determined, which allows the largest amount of radon gas to diffuse into the diffusion chamber while at the same time screening out the largest amount of thoron gas.

Copper Gas Diffusers For Purging Line-Focus Laser Welds

NASA Technical Reports Server (NTRS)

Fonteyne, Steve L.; Hosking, Timothy J.; Shelley, D. Mark

1996-01-01

Modified flow diffusers built for inert-gas purging of welds made with 5-kW CO(2) lasers operating with line-focus optics in conduction mode instead of with point-focus optics in customary keyhole mode. Diffusers made of copper components brazed together, robust enough to withstand strong reflections of line-focused laser energy.

The CO Transition from Diffuse Molecular Gas to Dense Clouds

NASA Astrophysics Data System (ADS)

Rice, Johnathan S.; Federman, Steven

2017-06-01

The atomic to molecular transitions occurring in diffuse interstellar gas surrounding molecular clouds are affected by the local physical conditions (density and temperature) and the radiation field penetrating the material. Our optical observations of CH, CH^{+}, and CN absorption from McDonald Observatory and the European Southern Observatory are useful tracers of this gas and provide the velocity structure needed for analyzing lower resolution ultraviolet observations of CO and H_{2} absorption from Far Ultraviolet Spectroscopic Explorer. We explore the changing environment between diffuse and dense gas by using the column densities and excitation temperatures from CO and H_{2} to determine the gas density. The resulting gas densities from this method are compared to densities inferred from other methods such as C_{2} and CN chemistry. The densities allow us to interpret the trends from the combined set of tracers. Groupings of sight lines, such as those toward h and χ Persei or Chameleon provide a chance for further characterization of the environment. The Chameleon region in particular helps illuminate CO-dark gas, which is not associated with emission from H I at 21 cm or from CO at 2.6 mm. Expanding this analysis to include emission data from the GOT C+ survey allows the further characterization of neutral diffuse gas, including CO-dark gas.

Graphical Interface for the Study of Gas-Phase Reaction Kinetics: Cyclopentene Vapor Pyrolysis

NASA Astrophysics Data System (ADS)

Marcotte, Ronald E.; Wilson, Lenore D.

2001-06-01

The undergraduate laboratory experiment on the pyrolysis of gaseous cyclopentene has been modernized to improve safety, speed, and precision and to better reflect the current practice of physical chemistry. It now utilizes virtual instrument techniques to create a graphical computer interface for the collection and display of experimental data. An electronic pressure gauge has replaced the mercury manometer formerly needed in proximity to the 500 °C pyrolysis oven. Students have much better real-time information available to them and no longer require multiple lab periods to get rate constants and acceptable Arrhenius parameters. The time saved on manual data collection is used to give the students a tour of the computer interfacing hardware and software and a hands-on introduction to gas-phase reagent preparation using a research-grade high-vacuum system. This includes loading the sample, degassing it by the freeze-pump-thaw technique, handling liquid nitrogen and working through the logic necessary for each reconfiguration of the diffusion pump section and the submanifolds.

Does shaking increase the pressure inside a bottle of champagne?

PubMed

Vreme, A; Pouligny, B; Nadal, F; Liger-Belair, G

2015-02-01

Colas, beers and sparkling wines are all concentrated solutions of carbon dioxide in aqueous solvents. Any such carbonated liquid is ordinarily conditioned inside a closed bottle or a metal can as a liquid-gas 2-phase system. At thermodynamic equilibrium, the partial pressure of carbon-dioxide in the gas phase and its concentration in the liquid are proportional (Henry's law). In practical conditions and use (transport, opening of the container, exterior temperature change, etc.), Henry's equilibrium can be perturbed. The goal of this paper is to describe and understand how the system responds to such perturbations and evolves towards a new equilibrium state. Formally, we investigate the dynamics around Henry's equilibrium of a closed system, through dedicated experiments and modeling. We focus on the response to a sudden pressure change and to mechanical shaking (the latter point inspired the article's title). Observations are rationalized through basic considerations including molecular diffusion, bubble dynamics (based on Epstein-Plesset theory) and chemi-convective hydrodynamic instabilities. Copyright © 2014 Elsevier Inc. All rights reserved.

Dynamic density functional theory with hydrodynamic interactions: theoretical development and application in the study of phase separation in gas-liquid systems.

PubMed

Kikkinides, E S; Monson, P A

2015-03-07

Building on recent developments in dynamic density functional theory, we have developed a version of the theory that includes hydrodynamic interactions. This is achieved by combining the continuity and momentum equations eliminating velocity fields, so the resulting model equation contains only terms related to the fluid density and its time and spatial derivatives. The new model satisfies simultaneously continuity and momentum equations under the assumptions of constant dynamic or kinematic viscosity and small velocities and/or density gradients. We present applications of the theory to spinodal decomposition of subcritical temperatures for one-dimensional and three-dimensional density perturbations for both a van der Waals fluid and for a lattice gas model in mean field theory. In the latter case, the theory provides a hydrodynamic extension to the recently studied dynamic mean field theory. We find that the theory correctly describes the transition from diffusive phase separation at short times to hydrodynamic behaviour at long times.

Dynamic density functional theory with hydrodynamic interactions: Theoretical development and application in the study of phase separation in gas-liquid systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kikkinides, E. S.; Monson, P. A.

Building on recent developments in dynamic density functional theory, we have developed a version of the theory that includes hydrodynamic interactions. This is achieved by combining the continuity and momentum equations eliminating velocity fields, so the resulting model equation contains only terms related to the fluid density and its time and spatial derivatives. The new model satisfies simultaneously continuity and momentum equations under the assumptions of constant dynamic or kinematic viscosity and small velocities and/or density gradients. We present applications of the theory to spinodal decomposition of subcritical temperatures for one-dimensional and three-dimensional density perturbations for both a van dermore » Waals fluid and for a lattice gas model in mean field theory. In the latter case, the theory provides a hydrodynamic extension to the recently studied dynamic mean field theory. We find that the theory correctly describes the transition from diffusive phase separation at short times to hydrodynamic behaviour at long times.« less

Diffusive sampling of methylene chloride with solid phase microextraction.

PubMed

Chen, Cheng-Yao; Hsiech, Chunming; Lin, Jia-Ming

2006-12-29

This study examined the characteristics of a solid phase microextraction (SPME) assembly as a passive sampler to determine the short-term exposure level (STEL) of methylene chloride. Two types of SPME fibers and six sampling-related factors were chosen and nested in an L(18) Taguchi's orthogonal array. Samples were thermally desorpted and analyzed by gas chromatograph equipped with an electron capture detector (GC/ECD). The use of 85-mum Carboxen/polydimethylsiloxane (Car/PDMS) fibers resulted in greater adsorbed mass, which was highly correlated with the product of concentration and sampling time (r>0.99, p<0.0001), than 85-microm polyacrylate fibers. The sampling rate (SR) of the 85-microm Carboxen/polydimethylsiloxane fibers was not significantly affected by variations in relative humidity (0-80%) and coexistent toluene (none to 100 ppm). Variance of sampling rate was predominantly attributed to the diffusive path length (86.4%) and sampling time (5.7%). With diffusive paths of 3, 10 and 15 mm, the sampling rates of 85-microm Carboxen/polydimethylsiloxane fibers for methylene chloride were 1.4 x 10(-2), 7.7 x 10(-3) and 5.1 x1 0(-3)mL min(-1), respectively. The measured sampling rates were greater than the theoretical values, and decreased with increment of sampling time until they came to constant.

Lung Morphometry with Hyperpolarized 129Xe: Theoretical Background

PubMed Central

Sukstanskii, A.L.; Yablonskiy, D.A.

2011-01-01

The 3He lung morphometry technique, based on MRI measurements of hyperpolarized 3He gas diffusion in lung airspaces, provides unique information on the lung microstructure at the alveolar level. In vivo 3D tomographic images of standard morphological parameters (airspace chord length, lung parenchyma surface-to-volume ratio, number of alveoli per unit volume) can be generated from a rather short (several seconds) MRI scan. The technique is based on a theory of gas diffusion in lung acinar airways and experimental measurements of diffusion attenuated MRI signal. The present work aims at developing the theoretical background of a similar technique based on hyperpolarized 129Xe gas. As the diffusion coefficient and gyromagnetic ratio of 129Xe gas are substantially different from those of 3He gas, the specific details of the theory and experimental measurements with 129Xe should be amended. We establish phenomenological relationships between acinar airway geometrical parameters and the diffusion attenuated MR signal for human and small animal lungs, both normal lungs and lungs with mild emphysema. Optimal diffusion times are shown to be about 5 ms for human and 1.3 ms for small animals. The expected uncertainties in measuring main morphometrical parameters of the lungs are estimated in the framework of Bayesian probability theory. PMID:21713985

Simultaneous Analysis of 22 Volatile Organic Compounds in Cigarette Smoke Using Gas Sampling Bags for High-Throughput Solid-Phase Microextraction

PubMed Central

Sampson, Maureen M.; Chambers, David M.; Pazo, Daniel Y.; Moliere, Fallon; Blount, Benjamin C.; Watson, Clifford H.

2015-01-01

Quantifying volatile organic compounds (VOCs) in cigarette smoke is necessary to establish smoke-related exposure estimates and evaluate emerging products and potential reduced-exposure products. In response to this need, we developed an automated, multi-VOC quantification method for machine-generated, mainstream cigarette smoke using solidphase microextraction gas chromatography–mass spectrometry (SPME-GC–MS). This method was developed to simultaneously quantify a broad range of smoke VOCs (i.e., carbonyls and volatiles, which historically have been measured by separate assays) for large exposure assessment studies. Our approach collects and maintains vapor-phase smoke in a gas sampling bag, where it is homogenized with isotopically labeled analogue internal standards and sampled using gas-phase SPME. High throughput is achieved by SPME automation using a CTC Analytics platform and custom bag tray. This method has successfully quantified 22 structurally diverse VOCs (e.g., benzene and associated monoaromatics, aldehydes and ketones, furans, acrylonitrile, 1,3-butadiene, vinyl chloride, and nitromethane) in the microgram range in mainstream smoke from 1R5F and 3R4F research cigarettes smoked under ISO (Cambridge Filter or FTC) and Intense (Health Canada or Canadian Intense) conditions. Our results are comparable to previous studies with few exceptions. Method accuracy was evaluated with third-party reference samples (≤15% error). Short-term diffusion losses from the gas sampling bag were minimal, with a 10% decrease in absolute response after 24 h. For most analytes, research cigarette inter- and intrarun precisions were ≤20% relative standard deviation (RSD). This method provides an accurate and robust means to quantify VOCs in cigarette smoke spanning a range of yields that is sufficient to characterize smoke exposure estimates. PMID:24933649

Combustion of liquid-fuel droplets in supercritical conditions

NASA Technical Reports Server (NTRS)

Shuen, J. S.; Yang, Vigor; Hsaio, C. C.

1992-01-01

A comprehensive analysis of liquid-fuel droplet combustion in both subcritical and supercritical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates variable thermophysical properties, finite-rate chemical kinetics, and a full treatment of liquid-vapor phase equilibrium at the drop surface. The governing equations and associated interfacial boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures in the range of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the critical pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure.

Model for diffuse interstellar clouds: improvements to the theory of molecular hydrogen photodestruction and to the gas phase chemistry of carbon monoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Federman, S.R.

1979-01-01

A theoretical model has been developed to determine physical processes in conjunction with astrophysical observation. The calculations are based on isobaric, steady-state, plane-parallel conditions. In the model, the cloud is illuminated by ultraviolet radiation from one side. The density and temperature of the gas are derived by invoking energy conservation in terms of thermal balance. The derived values for density and temperature then are used to determine the abundances of approximately fifty atomic and molecular species, including important ionic species and simple carbon and oxygen bearing molecules. Except for molecular hydrogen formation on dust grains, binary gas phase reactions aremore » used to develop the chemistry of the model cloud. The theoretical model has been found to be appropriate for a particular range of physical parameters. The results of the steady-state calculations have been compared to ultraviolet observations, predominantly those made with the Copernicus satellite. The theory of molecular hydrogen photodestruction has been reexamined so that improvements to the model can be made. By analyzing the region where the atomic to molecuar hydrogen transition occurs, several processes have been found to contribute to dissociation.« less

Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

NASA Astrophysics Data System (ADS)

Merino-Garcia, I.; Albo, J.; Irabien, A.

2018-01-01

Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

Combustion of liquid fuel droplets in supercritical conditions

NASA Technical Reports Server (NTRS)

Shuen, J. S.; Yang, Vigor

1991-01-01

A comprehensive analysis of liquid-fuel droplet combustion in both sub- and super-critical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates finite-rate chemical kinetics and a full treatment of liquid-vapor phase equilibrium at the droplet surface. The governing equations and the associated interface boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to the supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influences on the fluid transport, gas/liquid interface thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibits a significant variation near the critical burning pressure, mainly as a result of reduced mass-diffusion rate and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

Inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy

NASA Astrophysics Data System (ADS)

Krieger, Ulrich; Lienhard, Daniel; Bastelberger, Sandra; Steimer, Sarah

2014-05-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a "white light" LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. [1] A. Virtanen et al. (2010): An amorphous solid state of biogenic secondary organic aerosol particles, Nature 467, 824-827. [2] B. Zobrist et al. (2011): Ultra-slow water diffusion in aqueous sucrose glasses, Phys. Chem. Chem. Phys. 13, 3514-3526. [3] D. L. Bones, J. P. Reid, D. M. Lienhard, and U. K. Krieger (2012): Comparing the mechanism of water condensation and evaporation in glassy aerosol, PNAS 109, 11613-11618. [4] O. Peña and U. Pal (2009): Scattering of electromagnetic radiation by a multilayered sphere, Comput. Phys. Commun. 180, 2348-2354.

New Gas Polarographic Hydrogen Sensor

NASA Technical Reports Server (NTRS)

Dominguez, Jesus A.; Barile, Ron

2004-01-01

Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor. is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H+ ions or protons; H+ ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic 02 sensors are commercially available; a gas polarographic 02 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

Inert-Gas Diffuser For Plasma Or Arc Welding

NASA Technical Reports Server (NTRS)

Gilbert, Jeffrey L.; Spencer, Carl N.; Hosking, Timothy J.

1994-01-01

Inert-gas diffuser provides protective gas cover for weld bead as it cools. Follows welding torch, maintaining continuous flow of argon over newly formed joint and prevents it from oxidizing. Helps to ensure welds of consistently high quality. Devised for plasma arc keyhole welding of plates of 0.25-in. or greater thickness, also used in tungsten/inert-gas and other plasma or arc welding processes.

Evidence for minimal oxygen heterogeneity in the healthy human pulmonary acinus

PubMed Central

Tawhai, Merryn H.

2011-01-01

It has been suggested that the human pulmonary acinus operates at submaximal efficiency at rest due to substantial spatial heterogeneity in the oxygen partial pressure (Po2) in alveolar air within the acinus. Indirect measurements of alveolar air Po2 could theoretically mask significant heterogeneity if intra-acinar perfusion is well matched to Po2. To investigate the extent of intra-acinar heterogeneity, we developed a computational model with anatomically based structure and biophysically based equations for gas exchange. This model yields a quantitative prediction of the intra-acinar O2 distribution that cannot be measured directly. Temporal and spatial variations in Po2 in the intra-acinar air and blood are predicted with the model. The model, representative of a single average acinus, has an asymmetric multibranching respiratory airways geometry coupled to a symmetric branching conducting airways geometry. Advective and diffusive O2 transport through the airways and gas exchange into the capillary blood are incorporated. The gas exchange component of the model includes diffusion across the alveolar air-blood membrane and O2-hemoglobin binding. Contrary to previous modeling studies, simulations show that the acinus functions extremely effectively at rest, with only a small degree of intra-acinar Po2 heterogeneity. All regions of the model acinus, including the peripheral generations, maintain a Po2 >100 mmHg. Heterogeneity increases slightly when the acinus is stressed by exercise. However, even during exercise the acinus retains a reasonably homogeneous gas phase. PMID:21071589

Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

NASA Astrophysics Data System (ADS)

Sanibondi, Paolo

2015-09-01

Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

Carbon chemistry in dense molecular clouds: Theory and observational constraints

NASA Technical Reports Server (NTRS)

Blake, Geoffrey A.

1990-01-01

For the most part, gas phase models of the chemistry of dense molecular clouds predict the abundances of simple species rather well. However, for larger molecules and even for small systems rich in carbon these models often fail spectacularly. Researchers present a brief review of the basic assumptions and results of large scale modeling of the carbon chemistry in dense molecular clouds. Particular attention is to the influence of the gas phase C/O ratio in molecular clouds, and the likely role grains play in maintaining this ratio as clouds evolve from initially diffuse objects to denser cores with associated stellar and planetary formation. Recent spectral line surveys at centimeter and millimeter wavelengths along with selected observations in the submillimeter have now produced an accurate inventory of the gas phase carbon budget in several different types of molecular clouds, though gaps in our knowledge clearly remain. The constraints these observations place on theoretical models of interstellar chemistry can be used to gain insights into why the models fail, and show also which neglected processes must be included in more complete analyses. Looking toward the future, larger molecules are especially difficult to study both experimentally and theoretically in such dense, cold regions, and some new methods are therefore outlined which may ultimately push the detectability of small carbon chains and rings to much heavier species.

Fluorescence probe of polypeptide conformational dynamics in gas phase and in solution

NASA Astrophysics Data System (ADS)

Iavarone, Anthony T.; Meinen, Jan; Schulze, Susanne; Parks, Joel H.

2006-07-01

Fluorescence measurements of polypeptides derivatized with the fluorescent dye BODIPY TMR have been used to probe the polypeptide conformational dynamics as a function of temperature and charge state. Measurements of (BODIPY TMR)-[Pro]n-Arg-Trp and (BODIPY TMR)-[Gly-Ser]m-Arg-Trp have been performed for charge states 1+ and 2+ of n = 4 and 10 and m = 2 and 5. The 2+ charge states of both of these polypeptides exhibit similar temperature dependences for equal chain lengths (n = 4, m = 2 and n = 10, m = 5) and suggest conformations dominated by Coulomb repulsion. In the absence of such Coulomb repulsion, the 1+ charge state conformations appear to be characterized by the flexibility of the polypeptide chain for which [Gly-Ser]m > [Pro]n. Comparisons of these gas phase polypeptide measurements with corresponding measurements in solution provide a direct measure of the effects of solvent on the conformational dynamics. The change in fluorescence as a function of temperature in the gas phase is two orders of magnitude greater than that in solution, a dramatic result we attribute to the restrictions on intramolecular dynamics imposed by diffusion-limited kinetics and the lack of shielding by solvent. Measurements were also made of unsolvated Pron peptides without the tryptophan (Trp) residue to isolate the interaction of the fluorescent dye with charges.

Origin and z-distribution of Galactic diffuse [C II] emission

NASA Astrophysics Data System (ADS)

Velusamy, T.; Langer, W. D.

2014-12-01

Context. The [C ii] emission is an important probe of star formation in the Galaxy and in external galaxies. The GOT C+ survey and its follow up observations of spectrally resolved 1.9 THz [C ii] emission using Herschel HIFI provides the data needed to quantify the Galactic interstellar [C ii] gas components as tracers of star formation. Aims: We determine the source of the diffuse [C ii] emission by studying its spatial (radial and vertical) distributions by separating and evaluating the fractions of [C ii] and CO emissions in the Galactic ISM gas components. Methods: We used the HIFI [C ii] Galactic survey (GOT C+), along with ancillary H i, 12CO, 13CO, and C18O data toward 354 lines of sight, and several HIFI [C ii] and [C i] position-velocity maps. We quantified the emission in each spectral line profile by evaluating the intensities in 3 km s-1 wide velocity bins, "spaxels". Using the detection of [C ii] with CO or [C i], we separated the dense and diffuse gas components. We derived 2D Galactic disk maps using the spaxel velocities for kinematic distances. We separated the warm and cold H2 gases by comparing CO emissions with and without associated [C ii]. Results: We find evidence of widespread diffuse [C ii] emission with a z-scale distribution larger than that for the total [C ii] or CO. The diffuse [C ii] emission consists of (i) diffuse molecular (CO-faint) H2 clouds and (ii) diffuse H i clouds and/or WIM. In the inner Galaxy we find a lack of [C ii] detections in a majority (~62%) of H i spaxels and show that the diffuse component primarily comes from the WIM (~21%) and that the H i gas is not a major contributor to the diffuse component (~6%). The warm-H2 radial profile shows an excess in the range 4 to 7 kpc, consistent with enhanced star formation there. Conclusions: We derive, for the first time, the 2D [C ii] spatial distribution in the plane and the z-distributions of the individual [C ii] gas component. From the GOT C+ detections we estimate the fractional [C ii] emission tracing (i) H2 gas in dense and diffuse molecular clouds as ~48% and ~14%, respectively, (ii) in the H i gas ~18%, and (iii) in the WIM ~21%. Including non-detections from H i increases the [C ii] in H i to ~27%. The z-scale distributions FWHM from smallest to largest are [C ii] sources with CO, ~130 pc, (CO-faint) diffuse H2 gas, ~200 pc, and the diffuse H i and WIM, ~330 pc. When combined with [C ii], CO observations probe the warm-H2 gas, tracing star formation. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Gaseous diffusion system

DOEpatents

Garrett, George A.; Shacter, John

1978-01-01

1. A gaseous diffusion system comprising a plurality of diffusers connected in cascade to form a series of stages, each of said diffusers having a porous partition dividing it into a high pressure chamber and a low pressure chamber, and means for combining a portion of the enriched gas from a succeeding stage with a portion of the enriched gas from the low pressure chamber of each stage and feeding it into one extremity of the high pressure chamber thereof.

Apparatus and process for the separation of gases using supersonic expansion and oblique wave compression

DOE Office of Scientific and Technical Information (OSTI.GOV)

VanOsdol, John G.

The disclosure provides an apparatus and method for gas separation through the supersonic expansion and subsequent deceleration of a gaseous stream. The gaseous constituent changes phase from the gaseous state by desublimation or condensation during the acceleration producing a collectible constituent, and an oblique shock diffuser decelerates the gaseous stream to a subsonic velocity while maintain the collectible constituent in the non-gaseous state. Following deceleration, the carrier gas and the collectible constituent at the subsonic velocity are separated by a separation means, such as a centrifugal, electrostatic, or impingement separator. In an embodiment, the gaseous stream issues from a combustionmore » process and is comprised of N.sub.2 and CO.sub.2.« less

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Xiong, Yongliang; Criscenti, Louise J.

The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability ofmore » the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3 - 35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. We have successfully established experimental capabilities for measuring gas sorption and desorption on shale and model materials under a wide range of physical and chemical conditions. Both low and high pressure measurements show significant sorption of CH 4 and CO 2 onto clays, implying that methane adsorbed on clay minerals could contribute a significant portion of gas-in-place in an unconventional reservoir. We have also studied the potential impact of the interaction of shale with hydrofracking fluid on gas sorption. We have found that the CH 4-CO 2 sorption capacity for the reacted sample is systematically lower (by a factor of ~2) than that for the unreacted (raw) sample. This difference in sorption capacity may result from a mineralogical or surface chemistry change of the shale sample induced by fluid-rock interaction. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs.« less

Influence of physical state on the ozonolysis of shikimic acid

NASA Astrophysics Data System (ADS)

Steimer, Sarah; Krieger, Ulrich; Lampimäki, Markus; Peter, Thomas; Ammann, Markus

2014-05-01

Atmospheric aerosols are an important focus of environmental research due to their effect on climate, air quality and human health. They undergo continuous transformation, changing their physical and chemical properties. Recent findings show that secondary organic aerosol (SOA) particles can form amorphous solids and semi-solids under atmospheric conditions [1]. Since such physical states are highly viscous, diffusivity within the bulk decreases. The decrease in mass transport could slow down chemical reactions, thereby increasing the lifetime of the organic compounds involved. First indications of such behavior were recently shown for reaction of thin protein films with ozone [2], formation of organonitrogen from ammonia uptake to α-pinene secondary organic material [3] and reaction of SOA-coated benzo[a]pyrene with ozone [4]. In this study, we investigated the influence of physical state on the ozonolysis of shikimic acid. Said carboxylic acid is a constituent of biomass burning aerosols and used here as a proxy for oxygenated organic material. Its viscosity was adjusted by varying the humidity of the system between 0% and 92% RH, assuming correlation between the two parameters since water acts as a plasticizer. The system was probed with three complementary techniques: an electrodynamic balance (EDB), measuring the response of single particles to changes in humidity, coated wall flow tube measurements, where uptake of ozone is measured via loss from the gas phase and in situ X-ray microspectroscopy on single particles, where oxidation of the bulk can be observed. Additionally, a kinetic model was used to facilitate data analysis. EDB measurements showed clear evidence of humidity dependent glass formation and correlation of water content and water diffusivity. The dependence of the ozonolysis on relative humidity was observed with both flow tube and microspectroscopy measurements. The coated wall flow tube experiments showed a long term, gradually changing ozone uptake over more than 15 hours, the magnitude of which varied over nearly two orders between lowest and highest humidity. It was possible to separate the uptake into two distinct kinetic regimes, the first of which displayed a Langmuir-Hinshelwood type behavior regarding the ozone gas phase concentration. Microspectroscopy showed that the speed at which the characteristic double bond peak of shikimic acid disappeared was humidity dependent. The measured dependence of the reaction kinetics on humidity supports the hypothesis that the uptake coefficient is highly dependent on the diffusion coefficients of ozone and/or shikimic acid in the organic film. [1] Virtanen, A., et al., An amorphous solid state of biogenic secondary organic aerosol particles. Nature, 2010. 467(7317): p. 824-827. [2] Shiraiwa, M., et al., Gas uptake and chemical aging of semisolid organic aerosol particles. Proceedings of the National Academy of Sciences of the United States of America, 2011. 108(27): p. 11003-11008. [3] Kuwata, M. and Martin, S. T., Phase of atmospheric secondary organic material affects its reactivity. Proceedings of the National Academy of Sciences of the United States of America, 109(43): p. 17354-17359. [4] Zhou, S., et al., Kinetic limitations in gas-particle reactions arising from slow diffusion in secondary organic aerosol. Faraday Discussions, 2013. 165: p. 391-406.

Flood effects on efflux and net production of nitrous oxide in river floodplain soils

NASA Astrophysics Data System (ADS)

Riaz, Muhammad; Bruderer, Christian; Niklaus, Pascal A.; Luster, Jörg

2016-04-01

Floodplain soils are often rich in nutrients and exhibit high spatial heterogeneity in terms of geomorphology, soil environmental conditions and substrate availability for processes involved in carbon and nutrient cycling. In addition, fluctuating water tables lead to temporally changing redox conditions. In such systems, there are ideal conditions for the occurrence of hot spots and moments of nitrous oxide emissions, a potent greenhouse gas. The factors that govern the spatial heterogeneity and dynamics of N2O formation in floodplain soils and the surface efflux of this gas are not fully understood. A particular issue is the contribution of N2O formation in the subsoil to surface efflux. We studied this question in the floodplain of a restored section of the Thur river (NE Switzerland) which is characterized by a flashy flow regime. As a consequence, the floodplain soils are unsaturated most of the time. We showed earlier that saturation during flood pulses leads to short phases of generally anoxic conditions followed by a drying phase with anoxic conditions within aggregates and oxic conditions in larger soil pores. The latter conditions are conducive for spatially closely-coupled nitrification-denitrification and related hot moments of nitrous oxide formation. In a floodplain zone characterized by about one meter of young, sandy sediments, that are mostly covered by the tall grass Phalaris arundinacea, we measured at several time points before and after a small flood event N2O surface efflux with the closed-chamber method, and assessed N2O concentrations in the soil air at four different depths using gas-permeable tubings. In addition, we calculated the N2O diffusivity in the soil from Radon diffusivity. The latter was estimated in-situ from the recovery of Radon concentration in the gas-permeable tubings after purging with ambient air. All these data were then used to calculate net N2O production rates at different soil depths with the gradient method. In addition, temperature, volumetric water content, as well as ammonium, nitrate and dissolved organic carbon in the soil solution were monitored at different depths in the observation plots. During not flood-affected conditions we observed weak diffusive gradients between subsoil and top soil, and net N2O production was maximum in the top soil. During the drying phase after a flood, diffusive gradients between subsoil and topsoil were more pronounced, and net N2O production in the subsoil increased. At all conditions, N2O efflux was more strongly correlated with N2O concentrations in the subsoil than those in the top soil. The complex interactions between soil moisture on one hand, and C and N substrate limitation on the other hand in determining N2O production at different soil depths will be discussed. Finally, the results will be put into the context of our earlier and ongoing studies that aim at elucidating the governing factors of spatial heterogeneity and dynamics of N2O emissions in floodplain soils.

Validation of a Computational Model for the SLS Core Stage Oxygen Tank Diffuser Concept and the Low Profile Diffuser - An Advanced Development Design for the SLS

NASA Technical Reports Server (NTRS)

Brodnick, Jacob; Richardson, Brian; Ramachandran, Narayanan

2015-01-01

The Low Profile Diffuser (LPD) project originated as an award from the Marshall Space Flight Center (MSFC) Advanced Development (ADO) office to the Main Propulsion Systems Branch (ER22). The task was created to develop and test an LPD concept that could produce comparable performance to a larger, traditionally designed, ullage gas diffuser while occupying a smaller volume envelope. Historically, ullage gas diffusers have been large, bulky devices that occupy a significant portion of the propellant tank, decreasing the tank volume available for propellant. Ullage pressurization of spacecraft propellant tanks is required to prevent boil-off of cryogenic propellants and to provide a positive pressure for propellant extraction. To achieve this, ullage gas diffusers must slow hot, high-pressure gas entering a propellant tank from supersonic speeds to only a few meters per second. Decreasing the incoming gas velocity is typically accomplished through expansion to larger areas within the diffuser which has traditionally led to large diffuser lengths. The Fluid Dynamics Branch (ER42) developed and applied advanced Computational Fluid Dynamics (CFD) analysis methods in order to mature the LPD design from and initial concept to an optimized test prototype and to provide extremely accurate pre-test predictions of diffuser performance. Additionally, the diffuser concept for the Core Stage of the Space Launch System (SLS) was analyzed in a short amount of time to guide test data collection efforts of the qualification of the device. CFD analysis of the SLS diffuser design provided new insights into the functioning of the device and was qualitatively validated against hot wire anemometry of the exterior flow field. Rigorous data analysis of the measurements was performed on static and dynamic pressure data, data from two microphones, accelerometers and hot wire anemometry with automated traverse. Feasibility of the LPD concept and validation of the computational model were demonstrated by the test data.

Diffusion limit of Lévy-Lorentz gas is Brownian motion

NASA Astrophysics Data System (ADS)

Magdziarz, Marcin; Szczotka, Wladyslaw

2018-07-01

In this paper we analyze asymptotic behaviour of a stochastic process called Lévy-Lorentz gas. This process is aspecial kind of continuous-time random walk in which walker moves in the fixed environment composed of scattering points. Upon each collision the walker performs a flight to the nearest scattering point. This type of dynamics is observed in Lévy glasses or long quenched polymers. We show that the diffusion limit of Lévy-Lorentz gas with finite mean distance between scattering centers is the standard Brownian motion. Thus, for long times the behaviour of the Lévy-Lorentz gas is close to the diffusive regime.

Small particle transport across turbulent nonisothermal boundary layers

NASA Technical Reports Server (NTRS)

Rosner, D. E.; Fernandez De La Mora, J.

1982-01-01

The interaction between turbulent diffusion, Brownian diffusion, and particle thermophoresis in the limit of vanishing particle inertial effects is quantitatively modeled for applications in gas turbines. The model is initiated with consideration of the particle phase mass conservation equation for a two-dimensional boundary layer, including the thermophoretic flux term directed toward the cold wall. A formalism of a turbulent flow near a flat plate in a heat transfer problem is adopted, and variable property effects are neglected. Attention is given to the limit of very large Schmidt numbers and the particle concentration depletion outside of the Brownian sublayer. It is concluded that, in the parameter range of interest, thermophoresis augments the high Schmidt number mass-transfer coefficient by a factor equal to the product of the outer sink and the thermophoretic suction.

Numerical and Experimental Study on the Residual Stresses in the Nitrided Steel

NASA Astrophysics Data System (ADS)

Song, X.; Zhang, Zhi-Qian; Narayanaswamy, S.; Huang, Y. Z.; Zarinejad, M.

2016-09-01

In the present work, residual stresses distribution in the gas nitrided AISI 4140 sample has been studied using finite element (FE) simulation. The nitrogen concentration profile is obtained from the diffusion-controlled compound layer growth model, and nitrogen concentration controls the material volume change through phase transformation and lattice interstitials which results in residual stresses. Such model is validated through residual stress measurement technique—micro-ring-core method, which is applied to the nitriding process to obtain the residual stresses profiles in both the compound and diffusion layer. The numerical and experimental results are in good agreement with each other; they both indicate significant stress variation in the compound layer, which was not captured in previous research works due to the resolution limit of the traditional methods.

Two reference time scales for studying the dynamic cavitation of liquid films

NASA Technical Reports Server (NTRS)

Sun, D. C.; Brewe, D. E.

1992-01-01

Two formulas, one for the characteristic time of filling a void with the vapor of the surrounding liquid, and one of filling the void by diffusion of the dissolved gas in the liquid, are derived. By comparing these time scales with that of the dynamic operation of oil film bearings, it is concluded that the evaporation process is usually fast enough to fill the cavitation bubble with oil vapor; whereas the diffusion process is much too slow for the dissolved air to liberate itself and enter the cavitation bubble. These results imply that the formation of a two phase fluid in dynamically loaded bearings, as often reported in the literature, is caused by air entrainment. They further indicate a way to simplify the treatment of the dynamic problem of bubble evolution.

Acoustic instability driven by cosmic-ray streaming

NASA Technical Reports Server (NTRS)

Begelman, Mitchell C.; Zweibel, Ellen G.

1994-01-01

We study the linear stability of compressional waves in a medium through which cosmic rays stream at the Alfven speed due to strong coupling with Alfven waves. Acoustic waves can be driven unstable by the cosmic-ray drift, provided that the streaming speed is sufficiently large compared to the thermal sound speed. Two effects can cause instability: (1) the heating of the thermal gas due to the damping of Alfven waves driven unstable by cosmic-ray streaming; and (2) phase shifts in the cosmic-ray pressure perturbation caused by the combination of cosmic-ray streaming and diffusion. The instability does not depend on the magnitude of the background cosmic-ray pressure gradient, and occurs whether or not cosmic-ray diffusion is important relative to streaming. When the cosmic-ray pressure is small compared to the gas pressure, or cosmic-ray diffusion is strong, the instability manifests itself as a weak overstability of slow magnetosonic waves. Larger cosmic-ray pressure gives rise to new hybrid modes, which can be strongly unstable in the limits of both weak and strong cosmic-ray diffusion and in the presence of thermal conduction. Parts of our analysis parallel earlier work by McKenzie & Webb (which were brought to our attention after this paper was accepted for publication), but our treatment of diffusive effects, thermal conduction, and nonlinearities represent significant extensions. Although the linear growth rate of instability is independent of the background cosmic-ray pressure gradient, the onset of nonlinear eff ects does depend on absolute value of DEL (vector differential operator) P(sub c). At the onset of nonlinearity the fractional amplitude of cosmic-ray pressure perturbations is delta P(sub C)/P(sub C) approximately (kL) (exp -1) much less than 1, where k is the wavenumber and L is the pressure scale height of the unperturbed cosmic rays. We speculate that the instability may lead to a mode of cosmic-ray transport in which plateaus of uniform cosmic-ray pressure are separated by either laminar or turbulent jumps in which the thermal gas is subject to intense heating.

Low Stretch Solid-Fuel Flame Transient Response to a Step Change in Gravity

NASA Technical Reports Server (NTRS)

Armstrong, J. B.; Olson, S. L.; T'ien, J. S.

2003-01-01

The effect of a step change in gravity level on the stability of low stretch diffusion flames over a solid fuel is studied both numerically and experimentally. Drop tower experiments have been conducted in NASA Glenn Research Center's 5.2 Zero Gravity Facility. In the experiments burning PMMA cylinders, a dynamic transition is observed when the steadily burning 1g flame is dropped and becomes a 0g flame. To understand the physics behind this dynamic transition, a transient stagnation point model has been developed which includes gas-phase radiation and solid phase coupling to describe this dynamic process. In this paper, the experimental results are compared with the model predictions. Both model and experiment show that the interior of the solid phase does not have time to change significantly in the few seconds of drop time, so the experimental results are pseudo-steady in the gas-phase, but the solid is inherently unsteady over long time scales. The model is also used to examine the importance of fractional heat losses on extinction, which clearly demonstrates that as the feedback from the flame decreases, the importance of the ongoing heat losses becomes greater, and extinction is observed when these losses represent 80% or more of the flame feedback.

Particle growth kinetics over the Amazon rainforest

NASA Astrophysics Data System (ADS)

Pinterich, T.; Andreae, M. O.; Artaxo, P.; Kuang, C.; Longo, K.; Machado, L.; Manzi, A. O.; Martin, S. T.; Mei, F.; Pöhlker, C.; Pöhlker, M. L.; Poeschl, U.; Shilling, J. E.; Shiraiwa, M.; Tomlinson, J. M.; Zaveri, R. A.; Wang, J.

2016-12-01

Aerosol particles larger than 100 nm play a key role in global climate by acting as cloud condensation nuclei (CCN). Most of these particles, originated from new particle formation or directly emitted into the atmospheric, are initially too small to serve as CCN. These small particles grow to CCN size mainly through condensation of secondary species. In one extreme, the growth is dictated by kinetic condensation of very low-volatility compounds, favoring the growth of the smallest particles; in the other extreme, the process is driven by Raoult's law-based equilibrium partitioning of semi-volatile organic compound, favoring the growth of larger particles. These two mechanisms can lead to very different production rates of CCN. The growth of particles depends on a number of parameters, including the volatility of condensing species, particle phase, and diffusivity inside the particles, and this process is not well understood in part due to lack of ambient data. Here we examine atmospheric particle growth using high-resolution size distributions measured onboard the DOE G-1 aircraft during GoAmazon campaign, which took place from January 2014 to December 2015 near Manaus, Brazil, a city surrounded by natural forest for over 1000 km in every direction. City plumes are clearly identified by the strong enhancement of nucleation and Aitken mode particle concentrations over the clean background. As the plume traveled downwind, particle growth was observed, and is attributed to condensation of secondary species and coagulation (Fig.1). Observed aerosol growth is modeled using MOSAIC (Model for Simulating Aerosol Interactions and Chemistry), which dynamically partitions multiple compounds to all particle size bins by taking into account compound volatility, gas-phase diffusion, interfacial mass accommodation, particle-phase diffusion, and particle-phase reaction. The results from both wet and dry seasons will be discussed.

Experimental and Computational Study of Trapped Vortex Combustor Sector Rig with Tri-pass Diffuser

NASA Technical Reports Server (NTRS)

Hendricks, Robert C.; Shouse, D. T.; Roquemore, W. M.; Burrus, D. L.; Duncan, B. S.; Ryder, R. C.; Brankovic, A.; Liu, N.-S.; Gallagher, J. R.; Hendricks, J. A.

2001-01-01

The Trapped Vortex Combustor (TVC) potentially offers numerous operational advantages over current production gas turbine engine combustors. These include lower weight, lower pollutant emissions, effective flame stabilization, high combustion efficiency, excellent high altitude relight capability, and operation in the lean burn or RQL (Rich burn/Quick mix/Lean burn) modes of combustion. The present work describes the operational principles of the TVC, and provides detailed performance data on a configuration featuring a tri-pass diffusion system. Performance data include EINOx (NO(sub x) emission index) results for various fuel-air ratios and combustor residence times, combustion efficiency as a function of combustor residence time, and combustor lean blow-out (LBO) performance. Computational fluid dynamics (CFD) simulations using liquid spray droplet evaporation and combustion modeling are performed and related to flow structures observed in photographs of the combustor. The CFD results are used to understand the aerodynamics and combustion features under different fueling conditions. Performance data acquired to date are favorable in comparison to conventional gas turbine combustors. Further testing over a wider range of fuel-air ratios, fuel flow splits, and pressure ratios is in progress to explore the TVC performance. In addition, alternate configurations for the upstream pressure feed, including bi-pass diffusion schemes, as well as variations on the fuel injection patterns, are currently in test and evaluation phases.

Gas depletion through single gas bubble diffusive growth and its effect on subsequent bubbles

NASA Astrophysics Data System (ADS)

Moreno Soto, Alvaro; Prosperetti, Andrea; Lohse, Detlef; van der Meer, Devaraj; Physics of Fluid Group Collaboration; MCEC Netherlands CenterMultiscale Catalytic Energy Conversion Collaboration

2016-11-01

In weakly supersaturated mixtures, bubbles are known to grow quasi-statically as diffusion-driven mass transfer governs the process. In the final stage of the evolution, before detachment, there is an enhancement of mass transfer, which changes from diffusion to natural convection. Once the bubble detaches, it leaves behind a gas-depleted area. The diffusive mass transfer towards that region cannot compensate for the amount of gas which is taken away by the bubble. Consequently, the consecutive bubble will grow in an environment which contains less gas than for the previous one. This reduces the local supersaturation of the mixture around the nucleation site, leading to a reduced bubble growth rate. We present quantitative experimental data on this effect and the theoretical model for depletion during the bubble growth rate. This work was supported by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the government of the Netherlands.

CO2 dynamics in the Amargosa Desert: Fluxes and isotopic speciation in a deep unsaturated zone

USGS Publications Warehouse

Walvoord, Michelle Ann; Striegl, Robert G.; Prudic, David E.; Stonestrom, David A.

2005-01-01

Natural unsaturated-zone gas profiles at the U.S. Geological Survey's Amargosa Desert Research Site, near Beatty, Nevada, reveal the presence of two physically and isotopically distinct CO2 sources, one shallow and one deep. The shallow source derives from seasonally variable autotrophic and heterotrophic respiration in the root zone. Scanning electron micrograph results indicate that at least part of the deep CO2 source is associated with calcite precipitation at the 110-m-deep water table. We use a geochemical gas-diffusion model to explore processes of CO2 production and behavior in the unsaturated zone. The individual isotopic species 12CO2, 13CO2, and 14CO2 are treated as separate chemical components that diffuse and react independently. Steady state model solutions, constrained by the measured δ13C (in CO2), and δ14C (in CO2) profiles, indicate that the shallow CO2 source from root and microbial respiration composes ∼97% of the annual average total CO2 production at this arid site. Despite the small contribution from deep CO2 production amounting to ∼0.1 mol m−2 yr−1, upward diffusion from depth strongly influences the distribution of CO2 and carbon isotopes in the deep unsaturated zone. In addition to diffusion from deep CO2 production, 14C exchange with a sorbed CO2 phase is indicated by the modeled δ14C profiles, confirming previous work. The new model of carbon-isotopic profiles provides a quantitative approach for evaluating fluxes of carbon under natural conditions in deep unsaturated zones.

Mathematical model for the growth of phases in binary multiphase systems upon isothermic annealing

NASA Astrophysics Data System (ADS)

Molokhina, L. A.; Rogalin, V. E.; Filin, S. A.; Kaplunov, I. A.

2017-09-01

A phenomenological mathematical model of the formation and growth of phases in a binary multiphase system with allowance for factors influencing the process of diffusion in a binary system is presented. It is shown that phases can grow for a certain time at different ratios between diffusion parameters according to a parabolic law that depends on the duration of isothermic annealing. They then slow their growth after successor phases appear at their interface with one component and can completely disappear from a diffusion layer or begin to grow again, but only at a rate slower than during their initial formation. The dependence of the thickness of each phase layer in a multiphase diffusion zone on the duration of isothermic annealing and the ratio between the diffusion parameters in neighboring phases is obtained. It is established that a certain ratio between the phase growth and rates of dissolution with allowance for the coefficients of diffusion in each phase and the periods of incubation can result in the complete disappearance of one phase as early as the onset of the growth of phase nuclei and be interpreted as a process of reaction diffusion.

Theoretical Basis for Estimated Test Times and Conditions for Drop Tower and Space-Based Droplet Burning Experiments With Methanol and N-Heptane

NASA Technical Reports Server (NTRS)

Marchese, Anthony J.; Dryer, Fredrick L.; Choi, Mun Y.

1994-01-01

In order to develop an extensive envelope of test conditions for NASA's space-based Droplet Combustion Experiment (DCE) as well those droplet experiments which can be performed using a drop tower, the transient vaporization and combustion of methanol and n-heptane droplets were simulated using a recently developed fully time-dependent, spherically symmetric droplet combustion model. The transient vaporization of methanol and n-heptane was modeled to characterize the instantaneous gas phase composition surrounding the droplet prior to the introduction of an ignition source. The results for methanol/air showed that the entire gas phase surrounding a 2 mm methanol droplet deployed in zero-g .quickly falls outside the lean flammability limit. The gas phase surrounding an identically-sized n-heptane droplet, on the other hand, remains flammable. The combustion of methanol was then modeled considering a detailed gas phase chemical kinetic mechanism (168 steps, 26 species) and the effect of the dissolution of flame-generated water into the liquid droplet. These results were used to determine the critical ignition diameter required to achieve quasi-steady droplet combustion in a given oxidizing environment. For droplet diameters greater than the critical ignition diameter, the model predicted a finite diameter at which the flame would extinguish. These extinction diameters were found to vary significantly with initial droplet diameter. This phenomenon appears to be unique to the transient heat transfer, mass transfer and chemical kinetics of the system and thus has not been reported elsewhere to date. The extinction diameter was also shown to vary significantly with the liquid phase Lewis number since the amount of water present in the droplet at extinction is largely governed by the rate at which water is transported into the droplet via mass diffusion. Finally, the numerical results for n-heptane combustion were obtained using both 2 step and 96 step semi-emperical chemical kinetic mechanisms. Neither mechanism exhibited the variation of extinction diameter with initial diameter.

Airfoil for a turbine of a gas turbine engine

DOEpatents

Liang, George

2010-12-21

An airfoil for a turbine of a gas turbine engine is provided. The airfoil comprises a main body comprising a wall structure defining an inner cavity adapted to receive a cooling air. The wall structure includes a first diffusion region and at least one first metering opening extending from the inner cavity to the first diffusion region. The wall structure further comprises at least one cooling circuit comprising a second diffusion region and at least one second metering opening extending from the first diffusion region to the second diffusion region. The at least one cooling circuit may further comprise at least one third metering opening, at least one third diffusion region and a fourth diffusion region.

Diffusion of oxygen through cork stopper: is it a Knudsen or a Fickian mechanism?

PubMed

Lagorce-Tachon, Aurélie; Karbowiak, Thomas; Simon, Jean-Marc; Gougeon, Régis; Bellat, Jean-Pierre

2014-09-17

The aim of this work is to identify which law governs oxygen transfer through cork: Knudsen or Fickian mechanism. This is important to better understand wine oxidation during post-bottling aging. Oxygen transfer through cork wafers is measured at 298 K using a manometric permeation technique. Depending on the mechanism, we can extract the transport coefficients. Increasing the initial pressure of oxygen from 50 to 800 hPa leads to a change in the values of the transport coefficients. This implies that oxygen transport through cork does not obey the Knudsen law. From these results, we conclude that the limiting step of oxygen transport through cork occurs in the cell wall following Fickian law. From the diffusion dependence's coefficients with pressure, we also extract by applying transition state theory an apparent activation volume of 45 ± 4 nm(3). This high value indicates that oxygen molecules also diffuse from one site to another by passing through a gas phase.

Thermal-Diffusivity Measurements of Mexican Citrus Essential Oils Using Photoacoustic Methodology in the Transmission Configuration

NASA Astrophysics Data System (ADS)

Muñoz, G. A. López; González, R. F. López; López, J. A. Balderas; Martínez-Pérez, L.

2011-05-01

Photoacoustic methodology in the transmission configuration (PMTC) was used to study the thermophysical properties and their relation with the composition in Mexican citrus essential oils providing the viability of using photothermal techniques for quality control and for authentication of oils and their adulteration. Linear relations for the amplitude (on a semi-log scale) and phase, as functions of the sample's thickness, for the PMTC was obtained through a theoretical model fit to the experimental data for thermal-diffusivity measurements in Mexican orange, pink grapefruit, mandarin, lime type A, centrifuged essential oils, and Mexican distilled lime essential oil. Gas chromatography for distilled lime essential oil and centrifuged lime essential oil type A is reported to complement the study. Experimental results showed close thermal-diffusivity values between Mexican citrus essential oils obtained by centrifugation, but a significant difference of this physical property for distilled lime oil and the corresponding value obtained by centrifugation, which is due to their different chemical compositions involved with the extraction processes.

Perspective: C60+ and laboratory spectroscopy related to diffuse interstellar bands

NASA Astrophysics Data System (ADS)

Campbell, E. K.; Maier, J. P.

2017-04-01

In the last 30 years, our research has focused on laboratory measurements of the electronic spectra of organic radicals and ions. Many of the species investigated were selected based on their potential astrophysical relevance, particularly in connection with the identification of appealing candidate molecules for the diffuse interstellar absorptions. Notably, carbon chains and derivatives containing hydrogen and nitrogen atoms in their neutral and ionic forms were studied. These data could be obtained after developing appropriate techniques to record spectra at low temperatures relevant to the interstellar medium. The measurement of gas phase laboratory spectra has enabled direct comparisons with astronomical data to be made and though many species were found to have electronic transitions in the visible where the majority of diffuse bands are observed, none of the absorptions matched the prominent interstellar features. In 2015, however, the first carrier molecule was identified: C60 + . This was achieved after the measurement of the electronic spectrum of C60 + -He at 6K in a radiofrequency ion trap.

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

NASA Astrophysics Data System (ADS)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

Acoustic measurements of the 1999 basaltic eruption of Shishaldin volcano, Alaska 2. Precursor to the Subplinian phase

USGS Publications Warehouse

Vergniolle, S.; Caplan-Auerbach, J.

2004-01-01

The 1999 eruption of Shishaldin volcano (Alaska, USA) displayed both Strombolian and Subplinian basaltic activity. The Subplinian phase was preceded by a signal of low amplitude and constant frequency (??? 2 Hz) lasting 13 h. This "humming signal" is interpreted as the coalescence of the very shallow part of a foam building up in the conduit, which produces large gas bubbles before bursting. The acoustic waveform of the hum event is modelled by a Helmholtz resonator: gas is trapped into a rigid cavity and can only escape through a tiny upper hole producing sound waves. At Shishaldin, the radius of the hole (??? 5 m) is close to that of the conduit (??? 6 m), the cavity has a length of ??? 60 m, and gas presents only a small overpressure between (??? 1.2 ?? 10-3 and 4.5 ?? 10-3 MPa). Such an overpressure is obtained by the partial coalescence of a foam formed by bubbles with a diameter from ??? 2.3 mm at the beginning of the episode towards ??? 0.64 mm very close to the end of the phase. The intermittency between hum events is explained by the ripening of the foam induced by the H2O diffusion through the liquid films. The two extreme values, from 600 to 10 s, correspond to a bubble diameter from 2.2 to 0.3 mm at the beginning and end of the pre-Subplinian phase, respectively. The extremely good agreement between two independent estimates of bubble diameters in the shallow foam reinforces the validity of such an interpretation. The total gas volume lost at the surface during the humming events is at most 5.9 ?? 106 m3. At the very end of the pre-Subplinian phase, there is a single large bubble with an overpressure of ???0.42 MPa. The large overpressure suggests that it comes from significant depth, unlike other bubbles in the pre-Subplinian phase. This deep bubble may be responsible for the entire foam collapse, resulting in the Subplinian phase. ?? 2004 Elsevier B.V. All rights reserved.

Purging of a multilayer insulation with dacron tuft spacer by gas diffusion

NASA Technical Reports Server (NTRS)

Sumner, I. E.; Fisk, W. J.

1976-01-01

The time and purge gas usage required to purge a multilayer insulation (MLI) panel with gaseous helium by means of gas diffusion to obtain a condensable gas (nitrogen) concentration of less than 1 percent within the panel are stipulated. Two different, flat, rectangular MLI panels, one incorporating a butt joint, were constructed of of 11 double-aluminized Mylar (DAM) radiation shields separated by Dacron tuft spacers. The DAM/Dacron tuft concept is known commercially as Superfloc. The nitrogen gas concentration as a function of time within the MLI panel could be adequately predicted by using a simple, one dimensional gas diffusion model in which the boundary conditions at the edge of the MLI panel were time dependent. The time and purge gas usage required to achieve 1 percent nitrogen gas concentration within the MLI panel varied from 208 to 86 minutes and 34.1 to 56.5 MLI panel purge volumes, respectively, for gaseous helium purge rates from 10 to 40 MLI panel volumes per hour.

Fuel cell assembly unit for promoting fluid service and electrical conductivity

DOEpatents

Jones, Daniel O.

1999-01-01

Fluid service and/or electrical conductivity for a fuel cell assembly is promoted. Open-faced flow channel(s) are formed in a flow field plate face, and extend in the flow field plate face between entry and exit fluid manifolds. A resilient gas diffusion layer is located between the flow field plate face and a membrane electrode assembly, fluidly serviced with the open-faced flow channel(s). The resilient gas diffusion layer is restrained against entering the open-faced flow channel(s) under a compressive force applied to the fuel cell assembly. In particular, a first side of a support member abuts the flow field plate face, and a second side of the support member abuts the resilient gas diffusion layer. The support member is formed with a plurality of openings extending between the first and second sides of the support member. In addition, a clamping pressure is maintained for an interface between the resilient gas diffusion layer and a portion of the membrane electrode assembly. Preferably, the support member is spikeless and/or substantially flat. Further, the support member is formed with an electrical path for conducting current between the resilient gas diffusion layer and position(s) on the flow field plate face.

Gas-induced friction and diffusion of rigid rotors

NASA Astrophysics Data System (ADS)

Martinetz, Lukas; Hornberger, Klaus; Stickler, Benjamin A.

2018-05-01

We derive the Boltzmann equation for the rotranslational dynamics of an arbitrary convex rigid body in a rarefied gas. It yields as a limiting case the Fokker-Planck equation accounting for friction, diffusion, and nonconservative drift forces and torques. We provide the rotranslational friction and diffusion tensors for specular and diffuse reflection off particles with spherical, cylindrical, and cuboidal shape, and show that the theory describes thermalization, photophoresis, and the inverse Magnus effect in the free molecular regime.

CO Depletion: A Microscopic Perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cazaux, S.; Martín-Doménech, R.; Caro, G. M. Muñoz

In regions where stars form, variations in density and temperature can cause gas to freeze out onto dust grains forming ice mantles, which influences the chemical composition of a cloud. The aim of this paper is to understand in detail the depletion (and desorption) of CO on (from) interstellar dust grains. Experimental simulations were performed under two different (astrophysically relevant) conditions. In parallel, Kinetic Monte Carlo simulations were used to mimic the experimental conditions. In our experiments, CO molecules accrete onto water ice at temperatures below 27 K, with a deposition rate that does not depend on the substrate temperature.more » During the warm-up phase, the desorption processes do exhibit subtle differences, indicating the presence of weakly bound CO molecules, therefore highlighting a low diffusion efficiency. IR measurements following the ice thickness during the TPD confirm that diffusion occurs at temperatures close to the desorption. Applied to astrophysical conditions, in a pre-stellar core, the binding energies of CO molecules, ranging between 300 and 850 K, depend on the conditions at which CO has been deposited. Because of this wide range of binding energies, the depletion of CO as a function of A{sub V} is much less important than initially thought. The weakly bound molecules, easily released into the gas phase through evaporation, change the balance between accretion and desorption, which result in a larger abundance of CO at high extinctions. In addition, weakly bound CO molecules are also more mobile, and this could increase the reactivity within interstellar ices.« less

Reduced xenon diffusion for quantitative lung study--the role of SF(6)

NASA Technical Reports Server (NTRS)

Mair, R. W.; Hoffmann, D.; Sheth, S. A.; Wong, G. P.; Butler, J. P.; Patz, S.; Topulos, G. P.; Walsworth, R. L.

2000-01-01

The large diffusion coefficients of gases result in significant spin motion during the application of gradient pulses that typically last a few milliseconds in most NMR experiments. In restricted environments, such as the lung, this rapid gas diffusion can lead to violations of the narrow pulse approximation, a basic assumption of the standard Stejskal-Tanner NMR method of diffusion measurement. We therefore investigated the effect of a common, biologically inert buffer gas, sulfur hexafluoride (SF(6)), on (129)Xe NMR and diffusion. We found that the contribution of SF(6) to (129)Xe T(1) relaxation in a 1:1 xenon/oxygen mixture is negligible up to 2 bar of SF(6) at standard temperature. We also measured the contribution of SF(6) gas to (129)Xe T(2) relaxation, and found it to scale inversely with pressure, with this contribution approximately equal to 1 s for 1 bar SF(6) pressure and standard temperature. Finally, we found the coefficient of (129)Xe diffusion through SF(6) to be approximately 4.6 x 10(-6) m(2)s(-1) for 1 bar pressure of SF(6) and standard temperature, which is only 1.2 times smaller than the (129)Xe self diffusion coefficient for 1 bar (129)Xe pressure and standard temperature. From these measurements we conclude that SF(6) will not sufficiently reduce (129)Xe diffusion to allow accurate surface-area/volume ratio measurements in human alveoli using time-dependent gas diffusion NMR.

Diffusivity Measurements of Volatile Organics in Levitated Viscous Aerosol Particles

NASA Astrophysics Data System (ADS)

Bastelberger, Sandra; Krieger, Ulrich; Luo, Beiping; Peter, Thomas

2017-04-01

Field measurements indicating that atmospheric secondary aerosol (SOA) particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low water diffusivities in glassy aerosols, focusing on kinetic limitations to hygroscopic growth and the plasticizing effect of water. Less is known about diffusion limitations of organic molecules and oxidants in viscous matrices and how these might affect atmospheric chemistry and gas-particle phase partitioning of complex mixtures with constituents of different volatility. Often viscosity data has been used to infer diffusivity via the Stokes- Einstein relationship even though strong deviations from this relationship have been observed for matrices of high viscosity. In this study, we provide a quantitative estimate for the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and a small quantity of volatile tetraethylene glycol (PEG-4) is investigated in an electrodynamic balance at controlled relative humidity (RH) and temperature conditions, thereby varying the viscosity of the sucrose matrix. The evaporative loss of tetraethylene glycol as determined by Mie resonance spectroscopy is used in conjunction with a diffusion model to retrieve translational diffusion coefficients of tetraethylene glycol. The evaporation of PEG-4 shows a pronounced RH and temperature dependence and is severely depressed for RH 30% corresponding to diffusivities < 10-14 cm2/s at temperatures as high as 15 °C, implying that atmospheric volatile organic compounds (VOC) can be subject to severe diffusion limitations in glassy SOA. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes-Einstein relationship.

3He Diffusion MRI of the Lung

PubMed Central

Conradi, Mark S.; Yablonskiy, Dmitriy A.; Woods, Jason C.; Gierada, David S.; Jacob, Richard E.; Chang, Yulin V.; Choong, Cliff K.; Sukstanskii, Alex L.; Tanoli, Tariq; Lefrak, Stephen S.; Cooper, Joel D.

2007-01-01

Rationale and Objectives MR imaging of the restricted diffusion of laser-polarized 3He gas provides unique insights into the changes in lung microstructure in emphysema. Results We discuss measurements of ventilation (spin density), mean diffusivity, and the anisotropy of diffusion, which yields the mean acinar airway radius. In addition, the use of spatially modulated longitudinal magnetization allows diffusion to be measured over longer distances and times, with sensitivity to collateral ventilation paths. Early results are also presented for spin density and diffusivity maps made with a perfluorinated inert gas, C3F8. Methods Techniques for purging and imaging excised lungs are discussed. PMID:16253852

Transport rather than diffusion-dependent route for nitric oxide gas activity in alveolar epithelium.

PubMed

Brahmajothi, Mulugu V; Mason, S Nicholas; Whorton, A Richard; McMahon, Timothy J; Auten, Richard L

2010-07-15

The pathway by which inhaled NO gas enters pulmonary alveolar epithelial cells has not been directly tested. Although the expected mechanism is diffusion, another route is the formation of S-nitroso-L-cysteine, which then enters the cell through the L-type amino acid transporter (LAT). To determine if NO gas also enters alveolar epithelium this way, we exposed alveolar epithelial-rat type I, type II, L2, R3/1, and human A549-cells to NO gas at the air liquid interface in the presence of L- and D-cysteine+/-LAT competitors. NO gas exposure concentration dependently increased intracellular NO and S-nitrosothiol levels in the presence of L- but not D-cysteine, which was inhibited by LAT competitors, and was inversely proportional to diffusion distance. The effect of L-cysteine on NO uptake was also concentration dependent. Without preincubation with L-cysteine, NO uptake was significantly reduced. We found similar effects using ethyl nitrite gas in place of NO. Exposure to either gas induced activation of soluble guanylyl cylase in a parallel manner, consistent with LAT dependence. We conclude that NO gas uptake by alveolar epithelium achieves NO-based signaling predominantly by forming extracellular S-nitroso-L-cysteine that is taken up through LAT, rather than by diffusion. Augmenting extracellular S-nitroso-L-cysteine formation may augment pharmacological actions of inhaled NO gas. Copyright 2010 Elsevier Inc. All rights reserved.

NUMERICAL ANALYSES FOR TREATING DIFFUSION IN SINGLE-, TWO-, AND THREE-PHASE BINARY ALLOY SYSTEMS

NASA Technical Reports Server (NTRS)

Tenney, D. R.

1994-01-01

This package consists of a series of three computer programs for treating one-dimensional transient diffusion problems in single and multiple phase binary alloy systems. An accurate understanding of the diffusion process is important in the development and production of binary alloys. Previous solutions of the diffusion equations were highly restricted in their scope and application. The finite-difference solutions developed for this package are applicable for planar, cylindrical, and spherical geometries with any diffusion-zone size and any continuous variation of the diffusion coefficient with concentration. Special techniques were included to account for differences in modal volumes, initiation and growth of an intermediate phase, disappearance of a phase, and the presence of an initial composition profile in the specimen. In each analysis, an effort was made to achieve good accuracy while minimizing computation time. The solutions to the diffusion equations for single-, two-, and threephase binary alloy systems are numerically calculated by the three programs NAD1, NAD2, and NAD3. NAD1 treats the diffusion between pure metals which belong to a single-phase system. Diffusion in this system is described by a one-dimensional Fick's second law and will result in a continuous composition variation. For computational purposes, Fick's second law is expressed as an explicit second-order finite difference equation. Finite difference calculations are made by choosing the grid spacing small enough to give convergent solutions of acceptable accuracy. NAD2 treats diffusion between pure metals which form a two-phase system. Diffusion in the twophase system is described by two partial differential equations (a Fick's second law for each phase) and an interface-flux-balance equation which describes the location of the interface. Actual interface motion is obtained by a mass conservation procedure. To account for changes in the thicknesses of the two phases as diffusion progresses, a variable grid technique developed by Murray and Landis is employed. These equations are expressed in finite difference form and solved numerically. Program NAD3 treats diffusion between pure metals which form a two-phase system with an intermediate third phase. Diffusion in the three-phase system is described by three partial differential expressions of Fick's second law and two interface-flux-balance equations. As with the two-phase case, a variable grid finite difference is used to numerically solve the diffusion equations. Computation time is minimized without sacrificing solution accuracy by treating the three-phase problem as a two-phase problem when the thickness of the intermediate phase is less than a preset value. Comparisons between these programs and other solutions have shown excellent agreement. The programs are written in FORTRAN IV for batch execution on the CDC 6600 with a central memory requirement of approximately 51K (octal) 60 bit words.