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Sample records for surface reaction zone

  1. A library of prompt detonation reaction zone data

    Energy Technology Data Exchange (ETDEWEB)

    Souers, P. C., LLNL

    1998-06-01

    Tables are given listing literature data that allows calculation of sonic reaction zones at or near steady-state for promptly detonating explosive cylinders. The data covers homogeneous, heterogeneous, composite, inorganic and binary explosives and allows comparison across the entire explosive field. Table 1 lists detonation front curvatures. Table 2 lists Size Effect data, i.e. the change of detonation velocity with cylinder radius. Table 3 lists failure radii and detonation velocities. Table 4 lists explosive compositions. A total of 51 references dating back into the 1950`s are given. Calculated reaction zones, radii of curvature and growth rate coefficients are listed.

  2. Surface modification by preparation of buffer zone in glow-discharge plasma

    International Nuclear Information System (INIS)

    Cho, D.L.

    1986-01-01

    Reactive species, energetic particles, and uv radiation in the plasma created by a glow discharge strongly interact with solid surfaces under the influence of the plasma. As a result of the strong interaction, various physical and chemical reactions, unique and advantageous for the surface modification of solid materials, occur on the solid surfaces. The surface modification is carried out through formation of a thin buffering layer on the solid surface. The preparation of a buffer zone on solid surfaces for surface modification is described. Two kinds of a buffer zone are prepared by plasma polymerization, or simultaneous sputter deposition of electrode material with plasma polymerization: a transitional buffer zone and a graded buffer zone. Important factors for preparation of the buffer zone (pre-conditioning of a substrate surface, thin-film deposition, post-treatment of the film, magnetron discharge, energy input, geometry of a substrate and a plasma) are discussed

  3. Surface-Activated Coupling Reactions Confined on a Surface.

    Science.gov (United States)

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  4. Surface deformation in volcanic rift zones

    Science.gov (United States)

    Pollard, D.D.; Delaney, P.T.; Duffield, W.A.; Endo, E.T.; Okamura, A.T.

    1983-01-01

    The principal conduits for magma transport within rift zones of basaltic volcanoes are steeply dipping dikes, some of which feed fissure eruptions. Elastic displacements accompanying a single dike emplacement elevate the flanks of the rift relative to a central depression. Concomitant normal faulting may transform the depression into a graben thus accentuating the topographic features of the rift. If eruption occurs the characteristic ridge-trough-ridge displacement profile changes to a single ridge, centered at the fissure, and the erupted lava alters the local topography. A well-developed rift zone owes its structure and topography to the integrated effects of many magmatic rifting events. To investigate this process we compute the elastic displacements and stresses in a homogeneous, two-dimensional half-space driven by a pressurized crack that may breach the surface. A derivative graphical method permits one to estimate the three geometric parameters of the dike (height, inclination, and depth-to-center) and the mechanical parameter (driving pressure/rock stiffness) from a smoothly varying displacement profile. Direct comparison of measured and theoretical profiles may be used to estimate these parameters even if inelastic deformation, notably normal faulting, creates discontinuities in the profile. Geological structures (open cracks, normal faults, buckles, and thrust faults) form because of stresses induced by dike emplacement and fissure eruption. Theoretical stress states associated with dilation of a pressurized crack are used to interpret the distribution and orientation of these structures and their role in rift formation. ?? 1983.

  5. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

    2003-02-21

    The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  6. Specifications for surface reaction analysis apparatus

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2001-03-01

    A surface reaction analysis apparatus was installed at the JAERI soft x-ray beamline in the SPring-8 as an experimental end-station for the study of surface chemistry. The apparatus is devoted to the study concerning the influence of translational kinetic energy of incident molecules to chemical reactions on solid surfaces with gas molecules. In order to achieve the research purpose, reactive molecular scattering experiments and photoemission spectroscopic measurements using synchrotron radiation are performed in that apparatus via a supersonic molecular beam generator, an electron energy analyzer and a quadrupole mass analyzer. The detail specifications for the apparatus are described in this report. (author)

  7. Investigation of (n,γ) reaction in hybrid reactor zones

    Energy Technology Data Exchange (ETDEWEB)

    Guenay, Mehtap [Inoenue Univ., Malatya (Turkey). Physics Dept.

    2014-12-15

    In this study, the fluids were composed with increased mole fractions of a mixture of molten salt: heavy metals 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-Pu, 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-PuF{sub 4}, 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-PuO{sub 2}. In this study, the effect on conversion of each isotope ({sup 238-242}Pu) in spent fuel grade plutonium by (n,γ) reactions was investigated in liquid first wall, blanket and shield zones of the designed hybrid reactor system. Beryllium (Be) is the neutron multiplier by (n,2n) reactions. The Be zone used was 3 cm thick. 9Cr2WVT, a ferritic steel, is used as structural material. Three-dimensional nucleonic calculations were performed by using the most recent versions of the MCNPX-2.7.0 Monte Carlo code and the nuclear data library ENDF/B-VII.0.

  8. Investigation of (n,γ) reaction in hybrid reactor zones

    International Nuclear Information System (INIS)

    Guenay, Mehtap

    2014-01-01

    In this study, the fluids were composed with increased mole fractions of a mixture of molten salt: heavy metals 99-95 % Li 20 Sn 80 - 1-5 % SFG-Pu, 99-95 % Li 20 Sn 80 - 1-5 % SFG-PuF 4 , 99-95 % Li 20 Sn 80 - 1-5 % SFG-PuO 2 . In this study, the effect on conversion of each isotope ( 238-242 Pu) in spent fuel grade plutonium by (n,γ) reactions was investigated in liquid first wall, blanket and shield zones of the designed hybrid reactor system. Beryllium (Be) is the neutron multiplier by (n,2n) reactions. The Be zone used was 3 cm thick. 9Cr2WVT, a ferritic steel, is used as structural material. Three-dimensional nucleonic calculations were performed by using the most recent versions of the MCNPX-2.7.0 Monte Carlo code and the nuclear data library ENDF/B-VII.0.

  9. Low Energy Nuclear Reaction Products at Surfaces

    Science.gov (United States)

    Nagel, David J.

    2008-03-01

    This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

  10. RADIATION ACCESS ZONE AND VENTILATION CONFINEMENT ZONE CRITERIA FOR THE MGR SURFACE FACILITIES

    International Nuclear Information System (INIS)

    D. A. Padula

    2000-01-01

    The objectives of this technical report are to: (1) Establish the criteria for Radiation Access Zone (RAZ) designation. (2) Establish the criteria for the Ventilation Confinement Zone (VCZ) designation. The scope will be to formulate the RAZ and VCZ zoning designation for the Monitored Geologic Repository (MGR) surface facilities and to apply the zoning designations to the current Waste Handling Building (WHB), Waste Treatment Building (WTB), and Carrier Preparation Building (CPB) configurations

  11. Aquifer/aquitard interfaces: mixing zones that enhance biogeochemical reactions

    Science.gov (United States)

    McMahon, P. B.

    2001-01-01

    Several important biogeochemical reactions are known to occur near the interface between aquifer and aquitard sediments. These reactions include O2 reduction; denitrification; and Fe3+, SO42-, and CO2 (methanogenesis) reduction. In some settings, these reactions occur on the aquitard side of the interface as electron acceptors move from the aquifer into the electron-donor-enriched aquitard. In other settings, these reactions occur on the aquifer side of the interface as electron donors move from the aquitard into the electron-acceptor-enriched, or microorganism-enriched, aquifer. Thus, the aquifer/aquitard interface represents a mixing zone capable of supporting greater microbial activity than either hydrogeologic unit alone. The extent to which biogeochemical reactions proceed in the mixing zone and the width of the mixing zone depend on several factors, including the abundance and solubility of electron acceptors and donors on either side of the interface and the rate at which electron acceptors and donors react and move across the interface. Biogeochemical reactions near the aquifer/aquitard interface can have a substantial influence on the chemistry of water in aquifers and on the chemistry of sediments near the interface. Résumé. Il se produit au voisinage de l'interface entre les aquifères et les imperméables plusieurs réactions biogéochimiques importantes. Il s'agit des réactions de réduction de l'oxygène, de la dénitrification et de la réduction de Fe3+, SO42- et CO2 (méthanogenèse). Dans certaines situations, ces réactions se produisent du côté imperméable de l'interface, avec des accepteurs d'électrons qui vont de l'aquifère vers l'imperméable riche en donneurs d'électrons. Dans d'autres situations, ces réactions se produisent du côté aquifère de l'interface, avec des donneurs d'électrons qui se déplacent de l'imperméable vers l'aquifère riche en accepteurs d'électrons ou en microorganismes. Ainsi, l'interface aquif

  12. Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

    Science.gov (United States)

    Wang, H; Morrison, G

    2010-06-01

    Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

  13. Surface Wave Focusing and Acoustic Communications in the Surf Zone

    National Research Council Canada - National Science Library

    Preisig, James

    2004-01-01

    The forward scattering of acoustic signals off of shoaling surface gravity waves in the surf zone results in a time-varying channel impulse response that is characterized by intense, rapidly fluctuating arrivals...

  14. Dilution in Transition Zone between Rising Plumes and Surface Plumes

    DEFF Research Database (Denmark)

    Larsen, Torben

    2004-01-01

    The papers presents some physical experiments with the dilution of sea outfall plumes with emphasize on the transition zone where the relative fast flowing vertical plume turns to a horizontal surface plume following the slow sea surface currents. The experiments show that a considerable dilution...

  15. Relativistic nucleus-nucleus collisions: Zone of reactions and space-time structure of fireball

    International Nuclear Information System (INIS)

    Anchishkin, D.; Muskeyev, A.; Yezhov, S.

    2010-01-01

    A zone of reactions is determined and then exploited as a tool in studying the space-time structure of an interacting system formed in a collision of relativistic nuclei. The time dependence of the reaction rates integrated over spatial coordinates is also considered. Evaluations are made with the help of the microscopic transport model UrQMD. The relation of the boundaries of different zones of reactions and the hypersurfaces of sharp chemical and kinetic freeze-outs is discussed.

  16. Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flytzani-Stephanopoulos, M; Schmidt, L D

    1979-01-01

    Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

  17. Definition of a critical confining zone using surface geophysical methods

    International Nuclear Information System (INIS)

    Eddy-Dilek, C.A.; Hoekstra, P.; Harthill, N.; Blohm, M.; Phillips, D.R.

    1996-01-01

    Definition of the hydrogeologic framework in layered sediments of fluvial and deltaic origin is a difficult challenge for environmental characterization and remediation programs due to the lithologic and stratigraphic heterogeneities inherent in these settings. These heterogeneties often control contaminant transport and the effectiveness of remediation alternatives, Surface geophysical surveys can be cost-effective methods for characterization, but individual methods have inherent limitations in resolution and sensitivity. A synergistic approach, utilizing two geophysical survey methods was applied, to define and examine the nature and extent of a deep confining zone of regulatory importance, the Crouch Branch Confining Unit, in Coastal Plain sediments at the Savannah River Site. TDEM accurately maps the overall conductance (product of thickness and electrical conductivity) of a confining zone clay facies; from variation in conductance, changes in lithology of the conforming zone can be inferred. Shear wave seismic reflection surveys map the depth to the clay layers, and the clay layer thickness, but provides little information on the lithologic nature of the confining zone. Integrated interpretation of the combined data set (including all available borehole logs) allows for delineation of the lateral and vertical extent of clay-dominated zones, sand-dominated zones, key stratigraphic horizons, and erosional features associated with unconformities. This approach has resulted in the collection of critical information that will be used to optimize remedial system design, representing a significant cost savings to environmental restoration programs at the Savannah River Site

  18. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  19. Photocatalytic surface reactions on indoor wall paint.

    Science.gov (United States)

    Salthammer, T; Fuhrmann, F

    2007-09-15

    The reduction of indoor air pollutants by air cleaning systems has received considerable interest, and a number of techniques are now available. So far, the method of photocatalysis was mainly applied by use of titanium dioxide (TiO2) in flow reactors under UV light of high intensity. Nowadays, indoor wall paints are equipped with modified TiO2 to work as a catalyst under indoor daylight or artificial light. In chamber experiments carried out under indoor related conditions itwas shown thatthe method works for nitrogen dioxide with air exchange and for formaldehyde without air exchange at high concentrations. In further experiments with volatile organic compounds (VOCs), a small effect was found for terpenoids with high kOH rate constants. For other VOCs and carbon monoxide there was no degradation at all or the surface acted as a reversible sink. Secondary emissions from the reaction of paint constituents were observed on exposure to light. From the results it is concluded that recipes of photocatalytic wall paints need to be optimized for better efficiency under indoor conditions.

  20. Investigation of zones with increased ground surface gamma radiation

    International Nuclear Information System (INIS)

    Butkus, D.V.; Morkunas, G.S.; Styro, B.I.

    1989-01-01

    Measurements of the increased gamma radiation zones of soils were conducted in the South-Western part of the Litvinian. The shores of lakes in the north-eastern part of the Suduva high land were investigated. the maximum values of the gamma radiation dose rates were distributed along the lake shores at a distance of 1 m from the water surface, while farther than 1.5 m from it the dose rate was close to the natural value. The increased gamma radiation intensity zones on the ground surface were found only at the northern (Lake Reketija) or the western shore (other lakes under investigation). The highest values of the gamma radiation dose 200-600 μR/h (0.5-1.5 nGy/s) were observed in the comparatively small areas (up to several square metres). The gamma radiation intensity of soil surface increased strongly moving towards the point where the maximum intensity was obsered. 10 figs

  1. Surface chemical reactions probed with scanning force microscopy

    NARCIS (Netherlands)

    Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

    1997-01-01

    In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

  2. On surface reactions of iron tungstate with ethane

    International Nuclear Information System (INIS)

    Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

    1980-01-01

    Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

  3. Electronic dissipation processes during chemical reactions on surfaces

    CERN Document Server

    Stella, Kevin

    2012-01-01

    Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

  4. Monitoring the Vadose Zone Moisture Regime Below a Surface Barrier

    Science.gov (United States)

    Zhang, Z. F.; Strickland, C. E.; Field, J. G.

    2009-12-01

    A 6000 m2 interim surface barrier has been constructed over a portion of the T Tank Farm in the Depart of Energy’s Hanford site. The purpose of using a surface barrier was to reduce or eliminate the infiltration of meteoric precipitation into the contaminated soil zone due to past leaks from Tank T-106 and hence to reduce the rate of movement of the plume. As part of the demonstration effort, vadose zone moisture is being monitored to assess the effectiveness of the barrier on the reduction of soil moisture flow. A vadose zone monitoring system was installed to measure soil water conditions at four horizontal locations (i.e., instrument Nests A, B, C, and D) outside, near the edge of, and beneath the barrier. Each instrument nest consists of a capacitance probe with multiple sensors, multiple heat-dissipation units, and a neutron probe access tube used to measure soil-water content and soil-water pressure. Nest A serves as a control by providing subsurface conditions outside the influence of the surface barrier. Nest B provides subsurface measurements to assess barrier edge effects. Nests C and D are used to assess the impact of the surface barrier on soil-moisture conditions beneath it. Monitoring began in September 2006 and continues to the present. To date, the monitoring system has provided high-quality data. Results show that the soil beneath the barrier has been draining from the shallower depth. The lack of climate-caused seasonal variation of soil water condition beneath the barrier indicates that the surface barrier has minimized water exchange between the soil and the atmosphere.

  5. Width of surface rupture zone for thrust earthquakes: implications for earthquake fault zoning

    Science.gov (United States)

    Boncio, Paolo; Liberi, Francesca; Caldarella, Martina; Nurminen, Fiia-Charlotta

    2018-01-01

    The criteria for zoning the surface fault rupture hazard (SFRH) along thrust faults are defined by analysing the characteristics of the areas of coseismic surface faulting in thrust earthquakes. Normal and strike-slip faults have been deeply studied by other authors concerning the SFRH, while thrust faults have not been studied with comparable attention. Surface faulting data were compiled for 11 well-studied historic thrust earthquakes occurred globally (5.4 ≤ M ≤ 7.9). Several different types of coseismic fault scarps characterize the analysed earthquakes, depending on the topography, fault geometry and near-surface materials (simple and hanging wall collapse scarps, pressure ridges, fold scarps and thrust or pressure ridges with bending-moment or flexural-slip fault ruptures due to large-scale folding). For all the earthquakes, the distance of distributed ruptures from the principal fault rupture (r) and the width of the rupture zone (WRZ) were compiled directly from the literature or measured systematically in GIS-georeferenced published maps. Overall, surface ruptures can occur up to large distances from the main fault ( ˜ 2150 m on the footwall and ˜ 3100 m on the hanging wall). Most of the ruptures occur on the hanging wall, preferentially in the vicinity of the principal fault trace ( > ˜ 50 % at distances guidelines). In the absence of such a very detailed study (basic SM, i.e. Level 1 SM of Italian guidelines) a width of ˜ 840 m (90 % probability from "simple thrust" database of distributed ruptures, excluding B-M, F-S and Sy fault ruptures) is suggested to be sufficiently precautionary. For more detailed SM, where the fault is carefully mapped, one must consider that the highest SFRH is concentrated in a narrow zone, ˜ 60 m in width, that should be considered as a fault avoidance zone (more than one-third of the distributed ruptures are expected to occur within this zone). The fault rupture hazard zones should be asymmetric compared to the trace

  6. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  7. Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

    Science.gov (United States)

    Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

    1998-01-01

    The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

  8. Defining the Brittle Failure Envelopes of Individual Reaction Zones Observed in CO2-Exposed Wellbore Cement.

    Science.gov (United States)

    Hangx, Suzanne J T; van der Linden, Arjan; Marcelis, Fons; Liteanu, Emilia

    2016-01-19

    To predict the behavior of the cement sheath after CO2 injection and the potential for leakage pathways, it is key to understand how the mechanical properties of the cement evolves with CO2 exposure time. We performed scratch-hardness tests on hardened samples of class G cement before and after CO2 exposure. The cement was exposed to CO2-rich fluid for one to six months at 65 °C and 8 MPa Ptotal. Detailed SEM-EDX analyses showed reaction zones similar to those previously reported in the literature: (1) an outer-reacted, porous silica-rich zone; (2) a dense, carbonated zone; and (3) a more porous, Ca-depleted inner zone. The quantitative mechanical data (brittle compressive strength and friction coefficient) obtained for each of the zones suggest that the heterogeneity of reacted cement leads to a wide range of brittle strength values in any of the reaction zones, with only a rough dependence on exposure time. However, the data can be used to guide numerical modeling efforts needed to assess the impact of reaction-induced mechanical failure of wellbore cement by coupling sensitivity analysis and mechanical predictions.

  9. Width of surface rupture zone for thrust earthquakes: implications for earthquake fault zoning

    Directory of Open Access Journals (Sweden)

    P. Boncio

    2018-01-01

    Full Text Available The criteria for zoning the surface fault rupture hazard (SFRH along thrust faults are defined by analysing the characteristics of the areas of coseismic surface faulting in thrust earthquakes. Normal and strike–slip faults have been deeply studied by other authors concerning the SFRH, while thrust faults have not been studied with comparable attention. Surface faulting data were compiled for 11 well-studied historic thrust earthquakes occurred globally (5.4 ≤ M ≤ 7.9. Several different types of coseismic fault scarps characterize the analysed earthquakes, depending on the topography, fault geometry and near-surface materials (simple and hanging wall collapse scarps, pressure ridges, fold scarps and thrust or pressure ridges with bending-moment or flexural-slip fault ruptures due to large-scale folding. For all the earthquakes, the distance of distributed ruptures from the principal fault rupture (r and the width of the rupture zone (WRZ were compiled directly from the literature or measured systematically in GIS-georeferenced published maps. Overall, surface ruptures can occur up to large distances from the main fault ( ∼ 2150 m on the footwall and  ∼  3100 m on the hanging wall. Most of the ruptures occur on the hanging wall, preferentially in the vicinity of the principal fault trace ( >   ∼  50 % at distances  <   ∼  250 m. The widest WRZ are recorded where sympathetic slip (Sy on distant faults occurs, and/or where bending-moment (B-M or flexural-slip (F-S fault ruptures, associated with large-scale folds (hundreds of metres to kilometres in wavelength, are present. A positive relation between the earthquake magnitude and the total WRZ is evident, while a clear correlation between the vertical displacement on the principal fault and the total WRZ is not found. The distribution of surface ruptures is fitted with probability density functions, in order to define a criterion to

  10. FLUID EVOLUTION AND MINERAL REACTIONS DURING SHEAR ZONE FORMATION AT NUSFJORD, LOFOTEN, NORWAY (Invited)

    Science.gov (United States)

    Kullerud, K.

    2009-12-01

    At Nusfjord in Lofoten, Norway, three 0.3 - 3 m thick shear zones occur in a gabbro-anorthosite. During deformation, the shear zones were infiltrated by a hydrous fluid enriched in Cl. In the central parts of the shear zones, fluid-rock interaction resulted in complete break-down of the primary mafic silicates. Complete hydration of these minerals to Cl-free amphibole and biotite suggests that the hydrous fluid was present in excess during deformation in these parts of the shear zones. Along the margins of the shear zones, however, the igneous mafic silicates (Cpx, Bt, Opx) were only partly overgrown by hydrous minerals. Here, Cl-enriched minerals (Amph, Bt, Scp, Ap) can be observed. Amphibole shows compositions covering the range 0.1 - 4.0 wt % Cl within single thin sections. Mineral textures and extreme compositional variations of the Cl-bearing minerals indicate large chemical gradients of the fluid phase. Relics of primary mafic silicates and compositionally zoned reaction coronas around primary mafic silicates suggest that the free fluid was totally consumed before the alteration of the primary phases were completed. The extreme variations in the Cl-content of amphibole are inferred to monitor a gradual desiccation of the Cl-bearing grain-boundary fluid during fluid-mineral reactions accordingly: 1) The first amphibole that formed during the reactions principally extracted water from the fluid, resulting in a slight increase in the Cl content of the fluid. 2) Continued amphibole-forming reactions resulted in gradual consumption of the free fluid phase, principally by extracting water from the fluid, resulting in an increase in its Cl-content. Higher Cl-content of the fluid resulted in higher Cl-content of the equilibrium amphibole. 3) The most Cl-enriched amphibole (4 wt % Cl) formed in equilibrium with the last volumes of the grain-boundary fluid, which had evolved to a highly saline solution. Mineral reactions within a 1-2 thick zone of the host rock along

  11. Characterisation of weld zone reactions in dissimilar glass-to-aluminium pulsed picosecond laser welds

    Energy Technology Data Exchange (ETDEWEB)

    Ciuca, Octav P., E-mail: octav.ciuca@manchester.ac.uk [School of Materials, University of Manchester, Manchester, M13 9PL (United Kingdom); Carter, Richard M. [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh, EH14 4AS (United Kingdom); Prangnell, Philip B. [School of Materials, University of Manchester, Manchester, M13 9PL (United Kingdom); Hand, Duncan P. [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh, EH14 4AS (United Kingdom)

    2016-10-15

    Precision welded joints, produced between fused silica glass and aluminium by a newly-developed picosecond-pulse laser technique, have been analysed for the first time using a full range of electron microscopy methods. The welds were produced as lap joints by focusing a 1.2 μm diameter laser beam through the transparent glass top sheet, slightly below the surface of the metal bottom sheet. Despite the extremely short interaction time, extensive reaction was observed in the weld zone, which involved the formation of nanocrystalline silicon and at least two transitional alumina phases, γ- and δ-Al{sub 2}O{sub 3}. The weld formation process was found to be complex and involved: the formation of a constrained plasma cavity at the joint interface, non-linear absorption in the glass, and the creation of multiple secondary keyholes in the metal substrate by beam scattering. The joint area was found to expand outside of the main interaction volume, as the energy absorbed into the low conductivity and higher melting point silica glass sheet melted the aluminium surface across a wider contact area. The reasons for the appearance of nanocrystalline Si and transitional alumina reaction products within the welds are discussed. - Highlights: •Pulsed laser welding of dissimilar materials causes extensive chemical reactivity. •Metastable Al{sub 2}O{sub 3} phases form due to laser-induced highly-transient thermal regime. •Fused silica is reduced by Al to form nanocrystalline Si. •Mechanism of joint formation is discussed.

  12. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  13. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

  14. Multifractal scaling analysis of autopoisoning reactions over a rough surface

    International Nuclear Information System (INIS)

    Chaudhari, Ajay; Yan, Ching-Cher Sanders; Lee, S.-L.

    2003-01-01

    Decay type diffusion-limited reactions (DLR) over a rough surface generated by a random deposition model were performed. To study the effect of the decay profile on the reaction probability distribution (RPD), multifractal scaling analysis has been carried out. The dynamics of these autopoisoning reactions are controlled by the two parameters in the decay function, namely, the initial sticking probability (P ini ) of every site and the decay rate (m). The smaller the decay rate, the narrower is the range of α values in the α-f(α) multifractal spectrum. The results are compared with the earlier work of DLR over a surface of diffusion-limited aggregation (DLA). We also considered here the autopoisoning reactions over a smooth surface for comparing our results, which show clearly how the roughness affects the chemical reactions. The q-τ(q) multifractal curves for the smooth surface are linear whereas those for the rough surface are nonlinear. The range of α values in the case of a rough surface is wider than that of the smooth surface

  15. Surface sampling concentration and reaction probe

    Science.gov (United States)

    Van Berkel, Gary J; Elnaggar, Mariam S

    2013-07-16

    A method of analyzing a chemical composition of a specimen is described. The method can include providing a probe comprising an outer capillary tube and an inner capillary tube disposed co-axially within the outer capillary tube, where the inner and outer capillary tubes define a solvent capillary and a sampling capillary in fluid communication with one another at a distal end of the probe; contacting a target site on a surface of a specimen with a solvent in fluid communication with the probe; maintaining a plug volume proximate a solvent-specimen interface, wherein the plug volume is in fluid communication with the probe; draining plug sampling fluid from the plug volume through the sampling capillary; and analyzing a chemical composition of the plug sampling fluid with an analytical instrument. A system for performing the method is also described.

  16. Surface reactivity and layer analysis of chemisorbed reaction films in ...

    Indian Academy of Sciences (India)

    Administrator

    Surface reactivity and layer analysis of chemisorbed reaction films in ... in the nitrogen environment. Keywords. Surface reactivity ... sium (Na–K) compounds in the coating or core of the ..... Barkshire I R, Pruton M and Smith G C 1995 Appl. Sur.

  17. Investigation of heterogeneous reactions of NO2 on aqueous surfaces

    International Nuclear Information System (INIS)

    Mertes, S.

    1992-01-01

    A microjet apparatus was developed for the purpose of measuring the loss in the gaseous phase and the uptake in the liquid phase of nitrogen on the basis of heterogeneous processes on a liquid surface. The measurements were to provide information on the mass accomodation coefficient α and on assumed surface reactions of NO 2 . (orig./BBR) [de

  18. Supersonic molecular beam experiments on surface chemical reactions.

    Science.gov (United States)

    Okada, Michio

    2014-10-01

    The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Basic reactions of osteoblasts on structured material surfaces

    Directory of Open Access Journals (Sweden)

    U. Meyer

    2005-04-01

    Full Text Available In order to assess how bone substitute materials determine bone formation in vivo it is useful to understand the mechanisms of the material surface/tissue interaction on a cellular level. Artificial materials are used in two applications, as biomaterials alone or as a scaffold for osteoblasts in a tissue engineering approach. Recently, many efforts have been undertaken to improve bone regeneration by the use of structured material surfaces. In vitro studies of bone cell responses to artificial materials are the basic tool to determine these interactions. Surface properties of materials surfaces as well as biophysical constraints at the biomaterial surface are of major importance since these features will direct the cell responses. Studies on osteoblast-like cell reactivity towards materials will have to focus on the different steps of protein and cell reactions towards defined surface properties. The introduction of new techniques allows nowadays the fabrication of materials with ordered surface structures. This paper gives a review of present knowledge on the various stages of osteoblast reactions on material surfaces, focused on basic cell events under in vitro conditions. Special emphasis is given to cellular reactions towards ordered nano-sized topographies.

  20. Chemical reactions in the presence of surface modulation and stirring

    OpenAIRE

    Kamhawi, Khalid; Náraigh, Lennon Ó

    2009-01-01

    We study the dynamics of simple reactions where the chemical species are confined on a general, time-modulated surface, and subjected to externally-imposed stirring. The study of these inhomogeneous effects requires a model based on a reaction-advection-diffusion equation, which we derive. We use homogenization methods to show that up to second order in a small scaling parameter, the modulation effects on the concentration field are asymptotically equivalent for systems with or without stirri...

  1. Experimental investigations of different steel resistances in the sodium-steam reaction zone

    International Nuclear Information System (INIS)

    Mazanov, A.S.; Kulpin, B.V.; Petukhov, V.P.; Ledovskikh, N.M.

    1975-01-01

    The results are stated on the experimental investigations of IX2M, IXI8HIOT, OXI2H2M and Sanikro-31 steel resistance in the sodium-steam reaction zone. A target in the form of a pipe was used in the experiments within which the excessive pressure of 95 atm. was produced with an inert gas. Steam was supplied through the nozzle to the sodium tank in which there was a movable target unit. The dependence of time-to failure and failure rate on the distance of the nozzle and target wall thickness was estimated for these steels. It was shown that the resistance of Sanikro-31 in the sodium steam reaction zone was 2.5, 3.5 and 6 times that of IXI8HIOT, OXI2H2M, IX2M steels, respectively. The failure curves were obtained on thin targets for two steels (author)

  2. Fracture zones constrained by neutral surfaces in a fault-related fold: Insights from the Kelasu tectonic zone, Kuqa Depression

    Science.gov (United States)

    Sun, Shuai; Hou, Guiting; Zheng, Chunfang

    2017-11-01

    Stress variation associated with folding is one of the controlling factors in the development of tectonic fractures, however, little attention has been paid to the influence of neutral surfaces during folding on fracture distribution in a fault-related fold. In this study, we take the Cretaceous Bashijiqike Formation in the Kuqa Depression as an example and analyze the distribution of tectonic fractures in fault-related folds by core observation and logging data analysis. Three fracture zones are identified in a fault-related fold: a tensile zone, a transition zone and a compressive zone, which may be constrained by two neutral surfaces of fold. Well correlation reveals that the tensile zone and the transition zone reach the maximum thickness at the fold hinge and get thinner in the fold limbs. A 2D viscoelastic stress field model of a fault-related fold was constructed to further investigate the mechanism of fracturing. Statistical and numerical analysis reveal that the tensile zone and the transition zone become thicker with decreasing interlimb angle. Stress variation associated with folding is the first level of control over the general pattern of fracture distribution while faulting is a secondary control over the development of local fractures in a fault-related fold.

  3. Theoretical Study of Sodium-Water Surface Reaction Mechanism

    Science.gov (United States)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

  4. Theoretical study of sodium-water surface reaction mechanism

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    2012-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  5. Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

    Science.gov (United States)

    Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

    2016-09-01

    It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

  6. Reaction of water vapor with a clean liquid uranium surface

    International Nuclear Information System (INIS)

    Siekhaus, W.

    1985-01-01

    To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

  7. Reactions between monolayer Fe and Si(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, M; Kobayashi, N; Hayashi, N [Electrotechnical Lab., Tsukuba, Ibaraki (Japan)

    1997-03-01

    Reactions between 1.5 monolayer(ML) Fe deposited on Si(001)-2x1 and -dihydride surfaces were studied in situ by reflection high-energy electron diffraction and time-of-flight ion scattering spectrometry with the use of 25 keV H ions. The reactions between Fe and Si which were successively deposited on Si(001)-dihydride surface were also studied. After the room temperature deposition Fe reacted with Si(001)-2x1 substrate resulting in the formation of polycrystalline Fe5Si3. By annealing to 560-650degC composite heteroepitaxial layer of both type A and type B {beta}-FeSi2 was formed. On the dihydride surface polycrystalline Fe was observed after 1.5ML Fe deposition at room temperature, and reaction between Fe and Si(001)-dihydride surface is not likely at room temperature. We observed 3D rough surface when we deposited only Fe layer on the dihydride surface and annealed above 700degC. The hydrogen termination of Si(001) surface prevents the deposited Fe from diffusing into the substrate below 500degC, however the annealing above 710degC leads to the diffusion. We obtained 2D ordered surface, which showed 3x3 RHEED pattern as referenced to the primitive unreconstructed Si(001) surface net, when we deposited 2.5ML Fe and 5.8ML Si successively onto Si(001)-dihydride surface and annealed to 470degC. (author)

  8. Chemical reaction on solid surface observed through isotope tracer technique

    International Nuclear Information System (INIS)

    Tanaka, Ken-ichi

    1983-01-01

    In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

  9. Self-activated, self-limiting reactions on Si surfaces

    DEFF Research Database (Denmark)

    Morgen, Per; Hvam, Jeanette; Bahari, Ali

    The direct thermally activated reactions of oxygen and ammonia with Si surfaces in furnaces have been used for a very long time in the semiconductor industry for the growth of thick oxides and nitride layers respectively. The oxidation mechanism was described in the Deal-Grove model as a diffusion...... mechanism for the direct growth of ultrathin films (0-3 nm) of oxides and nitrides under ultrahigh vacuum conditions. Neutral oxygen and a microwave excited nitrogen plasma interact directly with Si surfaces kept at different temperatures during the reaction. The gas pressures are around 10-6 Torr...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...

  10. Spatial distributions of biogeochemical reactions in freshwater-saltwater mixing zones of sandy beach aquifers

    Science.gov (United States)

    Kim, K. H.; Michael, H. A.; Ullman, W. J.; Cai, W. J.

    2017-12-01

    Beach aquifers host biogeochemically dynamic mixing zones between fresh and saline groundwaters of contrasting origins, histories, and compositions. Seawater, driven up the beachface by waves and tides, infiltrates into the sand and meets the seaward-discharging fresh groundwater, creating and maintaining a highly reactive intertidal circulation cell well-defined by salinity. Seawater supplies oxygen and reactive carbon to the circulation cell, supporting biogeochemical reactions within the cell that transform and attenuate dissolved nutrient fluxes from terrestrial sources. We investigated the spatial distribution of chemical reaction zones within the intertidal circulation cell at Cape Shores, Lewes, Delaware. Porewater samples were collected from multi-level wells along a beach-perpendicular transect. Samples were analyzed for particulate carbon and reactive solutes, and incubated to obtain rates of oxic respiration and denitrification. High rates of oxic respiration were observed higher on the beach, in the landward freshwater-saline water mixing zone, where dissolved oxygen availability was high. Denitrification was dominant in lower areas of the beach, below the intertidal discharge point. High respiration rates did not correlate with particulate carbon concentrations entrained within porewater, suggesting that dissolved organic carbon or immobile particulate carbon trapped within the sediment can contribute to and alter bulk reactivity. A better understanding of the sources and sinks of carbon within the beach will improve our ability to predict nutrient fluxes to estuaries and oceans, aiding the management of coastal environments and ecosystems.

  11. Surface Intermediate Zone of Submerged Turbulent Buoyant Jet in Current

    DEFF Research Database (Denmark)

    Chen, H. B.; Larsen, Torben

    1995-01-01

    This paper deals with the intermediate zone between the jet and plume stages of a submerged buoyant discharge from sea outfall in current. The stability criteria, plume width and height after the intermediate zone and the dilution within the intermediate region have been studied theoretically and...

  12. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Science.gov (United States)

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  13. Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

    2015-10-15

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

  14. Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

    International Nuclear Information System (INIS)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

    2015-01-01

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

  15. Time variation in the reaction-zone structure of two-phase spray detonations.

    Science.gov (United States)

    Pierce, T. H.; Nicholls, J. A.

    1973-01-01

    A detailed theoretical analysis of the time-varying detonation structure in a monodisperse spray is presented. The theory identifies experimentally observed reaction-zone overpressures as deriving from blast waves formed therein by the explosive ignition of the spray droplets, and follows in time the motion, change in strength, and interactions of these blast waves with one another, and with the leading shock. The results are compared with experimental data by modeling the motion of a finite-size circular pressure transducer through the theoretical data field in an x-t space.

  16. A field ion microscope study of the surface reaction of tungsten with n-octanol under an applied positive voltage: reaction conditions for the 'splitting' of (110) plane

    International Nuclear Information System (INIS)

    Terao, T.; Iwatsu, F.; Morikawa, H.

    1993-01-01

    Field ion microscopy is a powerful tool for the study of surface phenomena on an atomic scale, especially when they are crystal plane dependent, because the microscope shows many crystal planes of the sample tip simultaneously. Although a large number of FIM studies on vapor deposition, surface diffusion and surface reactions at a metal-gas interface have been reported, those on reactions at a metal-liquid interface are few. The authors have studied the corrosion or tungsten with aqueous solutions and found that water corroded the tungsten tips very severely to reduce the radius of curvature of the tip cap drastically. The reaction was so severe that it was not possible to trace it back to the very initial stages. They adopted, as a weaker reagent, one of the higher alcohols, n-octanol(C 8 H 17 OH), and found that it reacted with tungsten tips when an electrical pulse with a positive voltage between 5 and 10V was applied to the tip, giving very interesting field ion images in which the central (110) plane was divided into two parts located side by side across the [001] zone line. This means that some anisotropic surface reaction occurred which made a groove along the [001] zone line going through the (110) plane, usually the most stable plane chemically for bcc metals. They named this phenomenon 'splitting'. This reaction was less severe than that with water and some results on the morphology of the groove and on the reaction sequence have been reported. In the present paper more detailed reaction conditions which give rise to the splitting are described

  17. Recyclable surfaces for amine conjugation chemistry via redox reaction

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2017-02-15

    In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

  18. Reaction and Aggregation Dynamics of Cell Surface Receptors

    Science.gov (United States)

    Wang, Michelle Dong

    This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

  19. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  20. Investigations Of Surface-Catalyzed Reactions In A Mars Mixture

    Science.gov (United States)

    Dougherty, Max; Owens, W.; Meyers, J.; Fletcher, D. G.

    2011-05-01

    In the design of a thermal protection system (TPS) for a planetary entry vehicle, accurate modeling of the trajectory aero-heating poses a significant challenge owing to large uncertainties in chemical processes taking place at the surface. Even for surface-catalyzed reactions, which have been investigated extensively, there is no consensus on how they should be modeled; or, in some cases, on which reactions are likely to occur. Current TPS designs for Mars missions rely on a super-catalytic boundary condition, which assumes that all dissociated species recombine to the free stream composition.While this is recognized to be the the most conservative approach, discrepancies in aero-heating measurements in ground test facilities preclude less conservative design options, resulting in an increased TPS mass at the expense of scientific pay- load.Using two-photon absorption laser induced fluorescence in a 30 kW inductively coupled plasma torch facility, preliminary studies have been performed to obtain spatially-resolved measurements of the dominant species in a plasma boundary layer for a Martian atmosphere mixture over catalytic and non-catalytic surfaces.

  1. Microanalysis of solid surfaces by nuclear reactions and elastic scattering

    International Nuclear Information System (INIS)

    Agius, B.

    1975-01-01

    The principles involved in the use of monokinetic light ions beams, of about 1MeV, to the study of surface phenomena are presented. Two complementary techniques are described: the use of elastic scattering, which allows the analysis of impurity elements heavier than the substrate components and the use of nuclear reactions specific of light elements. Typical sensitivities are of the order of 10 11 at/cm 2 in good cases. The depth resolution varies, according to the cases, from about a hundred angstroems to a few thousand angstroems [fr

  2. Unravelling Diurnal Asymmetry of Surface Temperature in Different Climate Zones.

    Science.gov (United States)

    Vinnarasi, R; Dhanya, C T; Chakravorty, Aniket; AghaKouchak, Amir

    2017-08-04

    Understanding the evolution of Diurnal Temperature Range (DTR), which has contradicting global and regional trends, is crucial because it influences environmental and human health. Here, we analyse the regional evolution of DTR trend over different climatic zones in India using a non-stationary approach known as the Multidimensional Ensemble Empirical Mode Decomposition (MEEMD) method, to explore the generalized influence of regional climate on DTR, if any. We report a 0.36 °C increase in overall mean of DTR till 1980, however, the rate has declined since then. Further, arid deserts and warm-temperate grasslands exhibit negative DTR trends, while the west coast and sub-tropical forest in the north-east show positive trends. This transition predominantly begins with a 0.5 °C increase from the west coast and spreads with an increase of 0.25 °C per decade. These changes are more pronounced during winter and post-monsoon, especially in the arid desert and warm-temperate grasslands, the DTR decreased up to 2 °C, where the rate of increase in minimum temperature is higher than the maximum temperature. We conclude that both maximum and minimum temperature increase in response to the global climate change, however, their rates of increase are highly local and depend on the underlying climatic zone.

  3. Using the Vertical Component of the Surface Velocity Field to Map the Locked Zone at Cascadia Subduction Zone

    Science.gov (United States)

    Moulas, E.; Brandon, M. T.; Podladchikov, Y.; Bennett, R. A.

    2014-12-01

    At present, our understanding of the locked zone at Cascadia subduction zone is based on thermal modeling and elastic modeling of horizontal GPS velocities. The thermal model by Hyndman and Wang (1995) provided a first-order assessment of where the subduction thrust might be cold enough for stick-slip behavior. The alternative approach by McCaffrey et al. (2007) is to use a Green's function that relates horizontal surface velocities, as recorded by GPS, to interseismic elastic deformation. The thermal modeling approach is limited by a lack of information about the amount of frictional heating occurring on the thrust (Molnar and England, 1990). The GPS approach is limited in that the horizontal velocity component is fairly insensitive to the structure of the locked zone. The vertical velocity component is much more useful for this purpose. We are fortunate in that vertical velocities can now be measured by GPS to a precision of about 0.2 mm/a. The dislocation model predicts that vertical velocities should range up to about 20 percent of the subduction velocity, which means maximum values of ~7 mm/a. The locked zone is generally entirely offshore at Cascadia, except for the Olympic Peninsula region, where the underlying Juan De Fuca plate has an anomalously low dip. Previous thermal and GPS modeling, as well as tide gauge data and episodic tremors indicate the locked zone there extends about 50 to 75 km onland. This situation provides an opportunity to directly study the locked zone. With that objective in mind, we have constructed a full 3D geodynamic model of the Cascadia subduction zone. At present, the model provides a full representation of the interseismic elastic deformation due to variations of slip on the subduction thrust. The model has been benchmarked against the Savage (2D) and Okada (3D) analytical solutions. This model has an important advantage over traditional dislocation modeling in that we include temperature-sensitive viscosity for the upper and

  4. Reaction dynamics of small molecules at metal surfaces

    International Nuclear Information System (INIS)

    Samson, P.A.

    1999-09-01

    The dissociation-desorption dynamics of D 2 upon the Sn/Pt(111) surface alloy are dependent on the surface concentration of Sn. The p(2 x 2) Sn/Pt(111) alloy surface (Θ Sn = 0.25 ML), is initially ∼30 times less reactive towards D 2 adsorption than clean Pt(111). On the (√3 x √3) R30 deg Sn/Pt(111) alloy surface (Θ Sn = 0.33 ML), increased inhibition of D 2 adsorption is reported, with S o ∼ 10 -5 at low energy, coinciding with the loss of stable Pt 3 hollow sites and a significant reduction in the D atom binding energy. Sticking on the √3 alloy is activated with an increased energy threshold of ∼280 meV, with no evidence that vibration enhances dissociation. The barrier to dissociation remains in the entrance channel before the D 2 bond begins to stretch. Vibrational excitation is, however, observed in nitrogen desorption from the catalytic reaction of NO + H 2 over Pd(110). For a surface at 600 K, N 2 vibrational state population ratios of P(v=1/v=0) = 0.50 ± 0.05 and P(v=2/v=0) = 0.60 ± 0.20 are reported. Desorption occurs via the N(ad) + N(ad) recombination channel with little energy released into translation and rotation. The translational energy release observed is dependent on the N 2 vibrational state, with translational temperatures of 425 K, 315 K and 180 K reported for the v=0, 1 and 2 states respectively. Sub-thermal energy releases and normally directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d NN responsible for the product vibrational excitation. Although N 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (∼10 -6 to 10 -7 ). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe 4 N. Scanning tunnelling

  5. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  6. Laser surface pretreatment of 100Cr6 bearing steel – Hardening effects and white etching zones

    International Nuclear Information System (INIS)

    Buling, Anna; Sändker, Hendrik; Stollenwerk, Jochen; Krupp, Ulrich; Hamann-Steinmeier, Angela

    2016-01-01

    Highlights: • Laser surface pretreatment of the bearing steel 100Cr6 is performed. • Microstructural changes of the surface are examined by light microscopy and SEM. • Topographical changes are observed using white light interferometry. • Micro-hardness testing show the existence of very hard white etching zones (WEZ). • WEZ are attributed to near-surface reaustenitization and rapid quenching. • Dark etching zones (DEZ) are found at the laser path edges after laser pretreatment. - Abstract: In order to achieve a surface pretreatment of the bearing steel 100Cr6 (1–1.5 wt.% Cr) a laser-based process was used. The obtained modification may result in an optimization of the adhesive properties of the surface with respect to an anticorrosion polymer coating on the basis of PEEK (poly-ether-ether-ketone), which is applied on the steel surface by a laser melting technique. This work deals with the influence of the laser-based pretreatment regarding the surface microstructure and the micro-hardness of the steel, which has been examined by scanning electron microscopy (SEM), light microscopy and automated micro-hardness testing. The most suitable parameter set for the laser-based pretreatment leads to the formation of very hard white etching zones (WEZ) with a thickness of 23 μm, whereas this pretreatment also induces topographical changes. The occurrence of the white etching zones is attributed to near-surface re-austenitization and rapid quenching. Moreover, dark etching zones (DEZ) with a thickness of 32 μm are found at the laser path edges as well as underneath the white etching zones (WEZ). In these areas, the hardness is decreased due to the formation of oxides as a consequence of re-tempering.

  7. Laser surface pretreatment of 100Cr6 bearing steel – Hardening effects and white etching zones

    Energy Technology Data Exchange (ETDEWEB)

    Buling, Anna, E-mail: a.buling@hs-osnabrueck.de [Faculty of Engineering and Computer Science, University of Applied Sciences, 49009 Osnabrück (Germany); Sändker, Hendrik; Stollenwerk, Jochen [Fraunhofer Institute for Laser Technology ILT, Steinbachstrasse 15, 52074 Aachen (Germany); Krupp, Ulrich; Hamann-Steinmeier, Angela [Faculty of Engineering and Computer Science, University of Applied Sciences, 49009 Osnabrück (Germany)

    2016-08-15

    Highlights: • Laser surface pretreatment of the bearing steel 100Cr6 is performed. • Microstructural changes of the surface are examined by light microscopy and SEM. • Topographical changes are observed using white light interferometry. • Micro-hardness testing show the existence of very hard white etching zones (WEZ). • WEZ are attributed to near-surface reaustenitization and rapid quenching. • Dark etching zones (DEZ) are found at the laser path edges after laser pretreatment. - Abstract: In order to achieve a surface pretreatment of the bearing steel 100Cr6 (1–1.5 wt.% Cr) a laser-based process was used. The obtained modification may result in an optimization of the adhesive properties of the surface with respect to an anticorrosion polymer coating on the basis of PEEK (poly-ether-ether-ketone), which is applied on the steel surface by a laser melting technique. This work deals with the influence of the laser-based pretreatment regarding the surface microstructure and the micro-hardness of the steel, which has been examined by scanning electron microscopy (SEM), light microscopy and automated micro-hardness testing. The most suitable parameter set for the laser-based pretreatment leads to the formation of very hard white etching zones (WEZ) with a thickness of 23 μm, whereas this pretreatment also induces topographical changes. The occurrence of the white etching zones is attributed to near-surface re-austenitization and rapid quenching. Moreover, dark etching zones (DEZ) with a thickness of 32 μm are found at the laser path edges as well as underneath the white etching zones (WEZ). In these areas, the hardness is decreased due to the formation of oxides as a consequence of re-tempering.

  8. Metasomatic Reaction Zones as Monitors of Trace Element Transfer at the Slab-Mantle Interface: the Case of the Hochwart Peridotite (Ulten Zone, Italy)

    Science.gov (United States)

    Marocchi, M.; Hermann, J.; Bargossi, G. M.; Mair, V.; Morten, L.

    2006-12-01

    phases (phlogopite and amphibole) in different metasomatic zones indicate mobility of many elements, including elements such as Ta which are considered to have scarce mobility in fluids. Trace element composition of accessory minerals in the phlogopite-rich zone suggests that the trace element signature of subduction zone fluids may be fractionated in this zone. The progressive depletion in some trace elements (LREE) and enrichment in LILE and Li from the peridotite towards the gneiss suggests a strong influence of bulk composition on the trace element budget of hydrous minerals. Since the ultramafic blocks can be representative of metasomatic processes occurring at the slab-mantle interface, we can infer that metasomatic reactions between slab-derived fluids and ultramafic mantle wedge will follow a specific series of reactions, creating mineral zonation similar to those observed in this study. Our results further favour the evidence that the primary composition of subduction zone fluids is modified substantially by metasomatic reactions occurring in the mantle wedge.

  9. Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

    Science.gov (United States)

    Hudson, R.; Loeffler, M. J.; Gerakines, P.

    2017-12-01

    The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

  10. Definition of a critical confining zone using surface geophysical methods

    International Nuclear Information System (INIS)

    Eddy-Dilek, C.A.; Looney, B.B.; Hoekstra, P.; Harthill, N.; Blohm, M.; Phillips, D.R.

    1997-01-01

    Definition of the hydrologic framework in layered sediments of fluvial and deltaic origin is a difficult challenge for environmental characterization and remediation programs due to the lithologic and stratigraphic heterogeneities inherent in these settings. The authors set out to use complementary geophysical surveys to determine the nature and extent of a deep confining unit at the Savannah River Site, South Carolina. Time Domain Electromagnetic (TDEM) soundings were used to define the electrical conductance of the clayey confining unit (aquitard), and shear-wave reflection seismic was used to define the stratigraphic framework. Based on correlations with borehole geophysical logs and sieve data, the shear-wave seismic proved capable of defining relatively fine layering in the coastal plain sediments, the upper and lower surfaces of a critical confining unit, and erosional features on the surface of the confining unit. The TDEM surveys defined the presence or absence of the clay facies of the confining unit. Moreover, by constraining the interpretation of the TDEM data with the thickness of the confining unit derived from the seismic data, the authors mapped the extent of the unit, showing where the clay is thicker, where it probably was never deposited, and where it was eroded by downcutting channels. These results have significant implications on the design and optimization of remedial systems

  11. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  12. Local stresses, dyke arrest and surface deformation in volcanic edificesand rift zones

    Directory of Open Access Journals (Sweden)

    L. S. Brenner

    2004-06-01

    Full Text Available Field studies indicate that nearly all eruptions in volcanic edifices and rift zones are supplied with magma through fractures (dykes that are opened by magmatic overpressure. While (inferred dyke injections are frequent during unrest periods, volcanic eruptions are, in comparison, infrequent, suggesting that most dykes become arrested at certain depths in the crust, in agreement with field studies. The frequency of dyke arrest can be partly explained by the numerical models presented here which indicate that volcanic edifices and rift zones consisting of rocks of contrasting mechanical properties, such as soft pyroclastic layers and stiff lava flows, commonly develop local stress fields that encourage dyke arrest. During unrest, surface deformation studies are routinely used to infer the geometries of arrested dykes, and some models (using homogeneous, isotropic half-spaces infer large grabens to be induced by such dykes. Our results, however, show that the dyke-tip tensile stresses are normally much greater than the induced surface stresses, making it difficult to explain how a dyke can induce surface stresses in excess of the tensile (or shear strength while the same strength is not exceeded at the (arrested dyke tip. Also, arrested dyke tips in eroded or active rift zones are normally not associated with dyke-induced grabens or normal faults, and some dykes arrested within a few metres of the surface do not generate faults or grabens. The numerical models show that abrupt changes in Young's moduli(stiffnesses, layers with relatively high dyke-normal compressive stresses (stress barriers, and weak horizontal contacts may make the dyke-induced surface tensile stresses too small for significant fault or graben formation to occur in rift zones or volcanic edifices. Also, these small surface stresses may have no simple relation to the dyke geometry or the depth to its tip. Thus, for a layered crust with weak contacts, straightforward

  13. Pd-catalyzed coupling reaction on the organic monolayer: Sonogashira reaction on the silicon (1 1 1) surfaces

    International Nuclear Information System (INIS)

    Qu Mengnan; Zhang Yuan; He Jinmei; Cao Xiaoping; Zhang Junyan

    2008-01-01

    Iodophenyl-terminated organic monolayers were prepared by thermally induced hydrosilylation on hydrogen-terminated silicon (1 1 1) surfaces. The films were characterized by ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy (XPS). To modify the surface chemistry and the structure of the monolayers, the Sonogashira coupling reaction was performed on the as-prepared monolayers. The iodophenyl groups on the film surfaces reacted with 1-ethynyl-4-fluorobenzene or the 1-chloro-4-ethynylbenzene under the standard Sonogashira reaction conditions for attaching conjugated molecules via the formation of C-C bonds. It is expected that this surface coupling reaction will present a new method to modify the surface chemistry and the structure of monolayers

  14. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  15. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

  16. TECHNICAL BASIS FOR EVALUATING SURFACE BARRIERS TO PROTECT GROUNDWATER FROM DEEP VADOSE ZONE CONTAMINATION

    International Nuclear Information System (INIS)

    Fayer, J.M.; Freedman, V.L.; Ward, A.L.; Chronister, G.B.

    2010-01-01

    The U.S. DOE and its predecessors released nearly 2 trillion liters (450 billion gallons) of contaminated liquid into the vadose zone at the Hanford Site. Some of the contaminants currently reside in the deeper parts of the vadose zone where they are much less accessible to characterization, monitoring, and typical remediation activities. The DOE Richland Operations Office (DOE-RL) prepared a treatability test plan in 2008 to examine remediation options for addressing contaminants in the deep vadose zone; one of the technologies identified was surface barriers (also known as engineered barriers, covers, and caps). In the typical configuration, the contaminants are located relatively close to the surface, generally within 15 m, and thus they are close to the base of the surface barrier. The proximity of the surface barrier under these conditions yielded few concerns about the effectiveness of the barrier at depth, particularly for cases in which the contaminants were in a lined facility. At Hanford, however, some unlined sites have contaminants located well below depths of 15 m. The issue raised about these sites is the degree of effectiveness of a surface barrier in isolating contaminants in the deep vadose zone. Previous studies by Hanford Site and PNNL researchers suggest that surface barriers have the potential to provide a significant degree of isolation of deep vadose zone contaminants. The studies show that the actual degree of isolation is site-specific and depends on many factors, including recharge rates, barrier size, depth of contaminants, geohydrologic properties ofthe sediments, and the geochemical interactions between the contaminants and the sediments. After the DOE-RL treatability test plan was published, Pacific Northwest National Laboratory was contracted to review the information available to support surface barrier evaluation for the deep vadose zone, identify gaps in the information and outcomes necessary to fill the data gaps, and outline

  17. INDICATION OF INSENSITIVITY OF PLANETARY WEATHERING BEHAVIOR AND HABITABLE ZONE TO SURFACE LAND FRACTION

    International Nuclear Information System (INIS)

    Abbot, Dorian S.; Ciesla, Fred J.; Cowan, Nicolas B.

    2012-01-01

    It is likely that unambiguous habitable zone terrestrial planets of unknown water content will soon be discovered. Water content helps determine surface land fraction, which influences planetary weathering behavior. This is important because the silicate-weathering feedback determines the width of the habitable zone in space and time. Here a low-order model of weathering and climate, useful for gaining qualitative understanding, is developed to examine climate evolution for planets of various land-ocean fractions. It is pointed out that, if seafloor weathering does not depend directly on surface temperature, there can be no weathering-climate feedback on a waterworld. This would dramatically narrow the habitable zone of a waterworld. Results from our model indicate that weathering behavior does not depend strongly on land fraction for partially ocean-covered planets. This is powerful because it suggests that previous habitable zone theory is robust to changes in land fraction, as long as there is some land. Finally, a mechanism is proposed for a waterworld to prevent complete water loss during a moist greenhouse through rapid weathering of exposed continents. This process is named a 'waterworld self-arrest', and it implies that waterworlds can go through a moist greenhouse stage and end up as planets like Earth with partial ocean coverage. This work stresses the importance of surface and geologic effects, in addition to the usual incident stellar flux, for habitability.

  18. INDICATION OF INSENSITIVITY OF PLANETARY WEATHERING BEHAVIOR AND HABITABLE ZONE TO SURFACE LAND FRACTION

    Energy Technology Data Exchange (ETDEWEB)

    Abbot, Dorian S.; Ciesla, Fred J. [Department of the Geophysical Sciences, University of Chicago, 5734 South Ellis Avenue, Chicago, IL 60637 (United States); Cowan, Nicolas B., E-mail: abbot@uchicago.edu [Center for Interdisciplinary Exploration and Research in Astrophysics (CIERA) and Department of Physics and Astronomy, Northwestern University, 2131 Tech Drive, Evanston, IL 60208 (United States)

    2012-09-10

    It is likely that unambiguous habitable zone terrestrial planets of unknown water content will soon be discovered. Water content helps determine surface land fraction, which influences planetary weathering behavior. This is important because the silicate-weathering feedback determines the width of the habitable zone in space and time. Here a low-order model of weathering and climate, useful for gaining qualitative understanding, is developed to examine climate evolution for planets of various land-ocean fractions. It is pointed out that, if seafloor weathering does not depend directly on surface temperature, there can be no weathering-climate feedback on a waterworld. This would dramatically narrow the habitable zone of a waterworld. Results from our model indicate that weathering behavior does not depend strongly on land fraction for partially ocean-covered planets. This is powerful because it suggests that previous habitable zone theory is robust to changes in land fraction, as long as there is some land. Finally, a mechanism is proposed for a waterworld to prevent complete water loss during a moist greenhouse through rapid weathering of exposed continents. This process is named a 'waterworld self-arrest', and it implies that waterworlds can go through a moist greenhouse stage and end up as planets like Earth with partial ocean coverage. This work stresses the importance of surface and geologic effects, in addition to the usual incident stellar flux, for habitability.

  19. Microstructure of Reaction Zone Formed During Diffusion Bonding of TiAl with Ni/Al Multilayer

    Science.gov (United States)

    Simões, Sónia; Viana, Filomena; Koçak, Mustafa; Ramos, A. Sofia; Vieira, M. Teresa; Vieira, Manuel F.

    2012-05-01

    In this article, the characterization of the interfacial structure of diffusion bonding a TiAl alloy is presented. The joining surfaces were modified by Ni/Al reactive multilayer deposition as an alternative approach to conventional diffusion bonding. TiAl substrates were coated with alternated Ni and Al nanolayers. The nanolayers were deposited by dc magnetron sputtering with 14 nm of period (bilayer thickness). Joining experiments were performed at 900 °C for 30 and 60 min with a pressure of 5 MPa. Cross sections of the joints were prepared for characterization of their interfaces by scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), high resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). Several intermetallic compounds form at the interface, assuring the bonding of the TiAl. The interface can be divided into three distinct zones: zone 1 exhibits elongated nanograins, very small equiaxed grains are observed in zone 2, while zone 3 has larger equiaxed grains. EBSD analysis reveals that zone 1 corresponds to the intermetallic Al2NiTi and AlNiTi, and zones 2 and 3 to NiAl.

  20. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  1. 30 CFR 761.15 - Procedures for waiving the prohibition on surface coal mining operations within the buffer zone...

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Procedures for waiving the prohibition on surface coal mining operations within the buffer zone of an occupied dwelling. 761.15 Section 761.15... surface coal mining operations within the buffer zone of an occupied dwelling. (a) This section does not...

  2. Quantitative surface analysis using deuteron-induced nuclear reactions

    International Nuclear Information System (INIS)

    Afarideh, Hossein

    1991-01-01

    The nuclear reaction analysis (NRA) technique consists of looking at the energies of the reaction products which uniquely define the particular elements present in the sample and it analysis the yield/energy distribution to reveal depth profiles. A summary of the basic features of the nuclear reaction analysis technique is given, in particular emphasis is placed on quantitative light element determination using (d,p) and (d,alpha) reactions. The experimental apparatus is also described. Finally a set of (d,p) spectra for the elements Z=3 to Z=17 using 2 MeV incident deutrons is included together with example of more applications of the (d,alpha) spectra. (author)

  3. Energy Accommodation from Surface Catalyzed Reactions in Air Plasmas

    Data.gov (United States)

    National Aeronautics and Space Administration — Understanding energy transport at the gas-surface interface between catalytic/reacting surfaces exposed to highly dissociated plasmas remains a significant research...

  4. Capability of LEP-type surfaces to describe noncollinear reactions 2 - Polyatomic systems

    CERN Document Server

    Espinosa-Garcia, Joaquin

    2001-01-01

    In this second article of the series, the popular LEP-type surface for collinear reaction paths and a "bent" surface, which involves a saddle point geometry with a nonlinear central angle, were used to examine the capacity of LEP-type surfaces to describe the kinetics and dynamics of noncollinear reaction paths in polyatomic systems. Analyzing the geometries, vibrational frequencies, curvature along the reaction path (to estimate the tunneling effect and the reaction coordinate-bound modes coupling), and the variational transition- state theory thermal rate constants for the NH//3 + O(**3P) reaction, we found that the "collinear" LEP-type and the "bent" surfaces for this polyatomic system show similar behavior, thus allowing a considerable saving in time and computational effort. This agreement is especially encouraging for this polyatomic system because in the Cs symmetry the reaction proceeds via two electronic states of symmetries **3A prime and **3A double prime , which had to be independently calibrated....

  5. A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

    Science.gov (United States)

    Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

    2012-12-21

    Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

  6. Hydrodynamic Characterization of a Surface Storage Zone in a Natural Stream

    Science.gov (United States)

    Sandoval Ulloa, J. C.; Escauriaza, C. R.; Mignot, E.; Mao, L.

    2015-12-01

    Flow developed in surface storage zones in rivers is very important for many physical and biogeochemical processes. These regions are characterized by low velocities compared to the flow in the main channel and long residence times that favor the deposition of contaminants, nutrient uptake and interactions with reactive sediments. The dynamics of the turbulent flows in these zones is very complex, typically characterized by a shear layer that induces a recirculating area, with multiple large-scale coherent structures of different temporal and spatial scales. In this work we present the methodology and analysis of measurements in a natural surface storage zone. We report detailed information of a field campaign carried out in the Lluta River, located in northern Chile in the high altitude Andean environment known as the Altiplano (~4,000 masl). The area of study has great interest for the river ecosystem, since the water has high concentration levels of arsenic and other metals. The Lluta River is also a water source for many agricultural communities and urban centers located in the lower parts of the watershed. Field information obtained was: detailed topography, 3D velocity components in several points, and sediment arsenic concentration in the main channel and in the recirculating region of the natural surface storage zone. Topography was obtained through DGPS and digital image processing. The 3D velocity field was measured with an acoustic Doppler velocimeter (ADV) and surface velocity data was obtained through the LSPIV technique. Arsenic concentration was obtained by sediment sampling analysis. With this data we analyze the flow topology and characteristics features of the velocity, which constitute the controlling mechanisms of contaminant transport in the field. In addition, we contrast with preliminary results of a three-dimensional (3D) numerical simulation, to determine the influence of different parameters on the transport and mixing processes in natural

  7. Potential surfaces in symmetric heavy-ion reactions

    International Nuclear Information System (INIS)

    Royer, G.; Piller, C.; Mignen, J.; Raffray, Y.

    1989-01-01

    The entrance channel in symmetric heavy-ion reactions is studied in the liquid-drop model approach including the nuclear proximity energy and allowing ellipsoidal deformations of the colliding nuclei. In the whole mass range a sudden transition occurs from oblate to prolate shapes when the proximity forces become important. This strongly affects the effective moment of inertia. The ellipsoidal deformations reduce the fusion barrier width for light systems and lower the potential barrier height for medium and heavy nuclei. The results are in agreement with the empirical effective barrier shift determined by Aguiar et al for the 58 Ni + 58 Ni, 74 Ge + 74 Ge and 80 Se + 80 Se systems. The sub-barrier fusion enhancement in heavy-ion reactions might be explained by the slowness of the process. Below the static fusion barrier, the reaction time is long; allowing some adiabaticity and deformations of the colliding ions. Above the barrier, the reaction is more sudden and the deformation degree of freedom is frozen

  8. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    The flow paths were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap - created using a spacer. The aqueous liquid moves between the surfaces by capillary ...

  9. Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

    Science.gov (United States)

    Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

    We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

  10. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  11. Imbalance in Groundwater-Surface Water Interactions and its Relationship to the Coastal Zone Hazards

    Science.gov (United States)

    Kontar, Y. A.; Ozorovich, Y. R.; Salokhiddinov, A. T.

    2011-12-01

    We report here some efforts and results in studying the imbalance in groundwater-surface water interactions and processes of groundwater-surface water interactions and groundwater flooding creating hazards in the coastal zones. Hazards, hydrological and geophysical risk analysis related to imbalance in groundwater-surface water interactions and groundwater flooding have been to a large extent under-emphasized for coastal zone applications either due to economical limitations or underestimation of significance of imbalance in groundwater-surface water interactions. This is particularly true for tsunamis creating salt water intrusion to coastal aquifers, even though most tsunami hazard assessments have in the past relied on scenario or deterministic type models, and to increasing mineralization of potable water because of intensive water diversions and also the abundance of highly toxic pollutants (mainly pesticides) in water, air and food, which contribute to the deterioration of the coastal population's health. In the wake of pressing environmental and economic issues, it is of prime importance for the scientific community to shed light onto the great efforts by hydrologists and geophysicists to quantify conceptual uncertainties and to provide quality assurances of potential coastal zone hazard evaluation and prediction under conditions of imbalance in groundwater-surface water interactions. This paper proposes consideration of two case studies which are important and significant for future understanding of a concept of imbalance in groundwater-surface water interactions and development and essential for feasibility studies of hazards in the coastal zone. The territory of the Aral Sea Region in Central Asia is known as an ecological disaster coastal zone. It is now obvious that, in order to provide reasonable living conditions to the coastal zone population, it is first of all necessary to drastically improve the quality of the water dedicated to human needs. Due

  12. Fluctuation-Induced Pattern Formation in a Surface Reaction

    DEFF Research Database (Denmark)

    Starke, Jens; Reichert, Christian; Eiswirth, Markus

    2006-01-01

    Spontaneous nucleation, pulse formation, and propagation failure have been observed experimentally in CO oxidation on Pt(110) at intermediate pressures ($\\approx 10^{-2}$mbar). This phenomenon can be reproduced with a stochastic model which includes temperature effects. Nucleation occurs randomly...... due to fluctuations in the reaction processes, whereas the subsequent damping out essentially follows the deterministic path. Conditions for the occurence of stochastic effects in the pattern formation during CO oxidation on Pt are discussed....

  13. Surface Defect Passivation and Reaction of c-Si in H2S.

    Science.gov (United States)

    Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

    2017-12-26

    A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

  14. Modeling of pollutant formation in fully premixing surface burners using a verified practice-oriented experimental reaction-kinetic calculation method. Final report

    International Nuclear Information System (INIS)

    Ruy, C.; Kremer, H.

    1996-01-01

    The intent of the present study was to simulate quantitatively pollutant formation in premixing surface burners and to describe qualitatively the share of the premixing flame in pollut emissions from atmospheric burners. For this purpose reaction-kinetic programmes for one-dimensional premixing flames were extended by a terms describing heat discharge through gas radiation. Furthermore, the calculation range for the flame was extended far into the secondary reaction zone. Temperature, CO, and NO x profiles were measured in the secondary reaction zone of premixing burners at standard pressure. The air-fuel ratio was calculated within the practically relevant range between 0.5 and 1.5, as was load behaviour. (DG) [de

  15. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    Science.gov (United States)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  16. Acid-base status of soils in groundwater discharge zones — relation to surface water acidification

    Science.gov (United States)

    Norrström, Ann Catrine

    1995-08-01

    Critical load calculations have suggested that groundwater at depth of 2 m in Sweden is very sensitive to acid load. As environmental isotope studies have shown that most of the runoff in streams has passed through the soil, there is a risk in the near future of accelerated acidification of surface waters. To assess the importance of the last soil horizon of contact before discharge, the upper 0-0.2m of soils in seven discharge zones were analysed for pools of base cations, acidity and base saturation. The sites were about 3-4 m 2 in size and selected from two catchments exposed to different levels of acid deposition. The soils in the seven sites had high concentrations of exchangeable base cations and consequently high base saturation. The high correlation ( r2 = 0.74) between base saturation in the soils of the discharge zones and mean pH of the runoff waters suggested that the discharge zone is important for surface water acidification. The high pool of exchangeable base cations will buffer initially against the acid load. As the cation exchange capacity (meq dm -3) and base saturation were lower in the sites from the catchment receiving lower deposition, these streams may be more vulnerable to acidification in the near future. The high concentration of base cations in non-exchangeable fractions may also buffer against acidification as it is likely that some of these pools will become exchangeable with time.

  17. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  18. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

    2013-05-15

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  19. Controls of faulting and reaction kinetics on serpentinization and double Benioff zones

    OpenAIRE

    Iyer, Karthik; Rüpke, Lars H.; Phipps Morgan, Jason; Grevemeyer, Ingo

    2012-01-01

    The subduction of partially serpentinized oceanic mantle may potentially be the key geologic process leading to the regassing of Earth's mantle and also has important consequences for subduction zone processes such as element cycling, slab deformation, and intermediate-depth seismicity. However, little is known about the quantity of water that is retained in the slab during mantle serpentinization and the pattern of serpentinization that may occur during bending-related faulting; an initial s...

  20. Structure of the Cascadia Subduction Zone Imaged Using Surface Wave Tomography

    Science.gov (United States)

    Schaeffer, A. J.; Audet, P.

    2017-12-01

    Studies of the complete structure of the Cascadia subduction zone from the ridge to the arc have historically been limited by the lack of offshore ocean bottom seismograph (OBS) infrastructure. On land, numerous dense seismic deployments have illuminated detailed structures and dynamics associated with the interaction between the subducting oceanic plate and the overriding continental plate, including cycling of fluids, serpentinization of the overlying forearc mantle wedge, and the location of the upper surface of the Juan de Fuca plate as it subducts beneath the Pacific Northwest. In the last half-decade, the Cascadia Initiative (CI), along with Neptune (ONC) and several other OBS initiatives, have instrumented both the continental shelf and abyssal plains off shore of the Cascadia subduction zone, facilitating the construction of a complete picture of the subduction zone from ridge to trench and volcanic arc. In this study, we present a preliminary azimuthally anisotropic surface-wave phase-velocity based model of the complete system, capturing both the young, unaltered Juan de Fuca plate from the ridge, to its alteration as it enters the subduction zone, in addition to the overlying continent. This model is constructed from a combination of ambient noise cross-correlations and teleseismic two station interferometry, and combines together concurrently running offshore OBS and onshore stations. We furthermore perform a number of representative 1D depth inversions for shear velocity to categorize the pristine oceanic, subducted oceanic, and continental crust and lithospheric structure. In the future the dispersion dataset will be jointly inverted with receiver functions to constrain a 3D shear-velocity model of the complete region.

  1. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  2. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    International Nuclear Information System (INIS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  3. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  4. Near-surface analysis with nuclear reactions and scattering

    International Nuclear Information System (INIS)

    Dunning, K.L.; Hirvonen, J.K.

    1974-01-01

    Very useful information about the elemental composition of solids in the surface and near-surface regions can be obtained with small accelerators and suitable auxiliary apparatus. Two methods which produce data from which quantitative concentration depth profiles can be constructed and which have been used extensively at this laboratory are: nuclear resonance profiling and Rutherford backscattering. The first method is described in detail. Data are given on profiles of Al and Al + Na films implanted on silicon substrates. Rutherford backscattering spectra for chromium implanted into silicon dioxide are used to illustrate the improved depth sensitivity that can be obtained with a magnetic spectrometer in depth concentration profiles of heavy impurities relative to that obtainable with a conventional semiconductor detector

  5. Electrochemical Characterization of Surface Reactions on Biomedical Titanium alloys

    OpenAIRE

    Alkhateeb, Emad Hashim

    2008-01-01

    Titanium and its alloys are successfully used as implant materials for dental, orthopedic and osteosynthesis applications. The processes that take place at the implant tissue interface are important for the acceptance and integration of the implant. This thesis is divided into two parts: the first part deals with surface modification of titanium to improve the osseointegration, and the second part studies metastable pitting of titanium and its alloys. The weakly attached layer of a bone-like ...

  6. Evidence concerning oxidation as a surface reaction in Baltic amber

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

    , obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part...... of cross-sections from samples subjected to long-term thermal ageing, confirming that oxidation of Baltic amber starts from the surface....

  7. Adsorption of water vapour and the specific surface area of arctic zone soils (Spitsbergen)

    Science.gov (United States)

    Cieśla, Jolanta; Sokołowska, Zofia; Witkowska-Walczak, Barbara; Skic, Kamil

    2018-01-01

    Water vapour/nitrogen adsorption were investigated and calculated the specific surface areas of arctic-zone soil samples (Turbic Cryosols) originating from different micro-relief forms (mud boils, cell forms and sorted circles) and from different depths. For the characterisation of the isotherms obtained for arctic soils, the Brunauer-Emmet-Teller model was then compared with the two other models (Aranovich-Donohue and Guggenheim-Anderson-de Boer) which were developed from Brunauer-Emmet-Teller. Specific surface area was calculated using the Brunauer-Emmet-Teller model at p p0-1 range of 0.05-0.35 for the water vapour desorption and nitrogen adsorption isotherms. The values of total specific surface area were the highest in Cryosols on mud boils, lower on cell forms, and the lowest on sorted circles. Such tendency was observed for the results obtained by both the water vapour and nitrogen adsorption. The differences in the values of specific surface area at two investigated layers were small. High determination coefficients were obtained for relationships between the specific surface areas and contents of clay and silt fraction in Cryosols. No statistically significant correlation between the total carbon amount and the values of specific surface area in Cryosols has been found.

  8. Width of the Surface Rupture Zone for Thrust Earthquakes and Implications for Earthquake Fault Zoning: Chi-Chi 1999 and Wenchuan 2008 Earthquakes

    Science.gov (United States)

    Boncio, P.; Caldarella, M.

    2016-12-01

    We analyze the zones of coseismic surface faulting along thrust faults, whit the aim of defining the most appropriate criteria for zoning the Surface Fault Rupture Hazard (SFRH) along thrust faults. Normal and strike-slip faults were deeply studied in the past, while thrust faults were not studied with comparable attention. We analyze the 1999 Chi-Chi, Taiwan (Mw 7.6) and 2008 Wenchuan, China (Mw 7.9) earthquakes. Several different types of coseismic fault scarps characterize the two earthquakes, depending on the topography, fault geometry and near-surface materials. For both the earthquakes, we collected from the literature, or measured in GIS-georeferenced published maps, data about the Width of the coseismic Rupture Zone (WRZ). The frequency distribution of WRZ compared to the trace of the main fault shows that the surface ruptures occur mainly on and near the main fault. Ruptures located away from the main fault occur mainly in the hanging wall. Where structural complexities are present (e.g., sharp bends, step-overs), WRZ is wider then for simple fault traces. We also fitted the distribution of the WRZ dataset with probability density functions, in order to define a criterion to remove outliers (e.g., by selecting 90% or 95% probability) and define the zone where the probability of SFRH is the highest. This might help in sizing the zones of SFRH during seismic microzonation (SM) mapping. In order to shape zones of SFRH, a very detailed earthquake geologic study of the fault is necessary. In the absence of such a very detailed study, during basic (First level) SM mapping, a width of 350-400 m seems to be recommended (95% of probability). If the fault is carefully mapped (higher level SM), one must consider that the highest SFRH is concentrated in a narrow zone, 50 m-wide, that should be considered as a "fault-avoidance (or setback) zone". These fault zones should be asymmetric. The ratio of footwall to hanging wall (FW:HW) calculated here ranges from 1:5 to 1:3.

  9. The SMAP Level 4 Surface and Root-zone Soil Moisture (L4_SM) Product

    Science.gov (United States)

    Reichle, Rolf; Crow, Wade; Koster, Randal; Kimball, John

    2010-01-01

    The Soil Moisture Active and Passive (SMAP) mission is being developed by NASA for launch in 2013 as one of four first-tier missions recommended by the U.S. National Research Council Committee on Earth Science and Applications from Space in 2007. The primary science objectives of SMAP are to enhance understanding of land surface controls on the water, energy and carbon cycles, and to determine their linkages. Moreover, the high resolution soil moisture mapping provided by SMAP has practical applications in weather and seasonal climate prediction, agriculture, human health, drought and flood decision support. In this paper we describe the assimilation of SMAP observations for the generation of the planned SMAP Level 4 Surface and Root-zone Soil Moisture (L4_SM) product. The SMAP mission makes simultaneous active (radar) and passive (radiometer) measurements in the 1.26-1.43 GHz range (L-band) from a sun-synchronous low-earth orbit. Measurements will be obtained across a 1000 km wide swath using conical scanning at a constant incidence angle (40 deg). The radar resolution varies from 1-3 km over the outer 70% of the swath to about 30 km near the center of the swath. The radiometer resolution is 40 km across the entire swath. The radiometer measurements will allow high-accuracy but coarse resolution (40 km) measurements. The radar measurements will add significantly higher resolution information. The radar is however very sensitive to surface roughness and vegetation structure. The combination of the two measurements allows optimal blending of the advantages of each instrument. SMAP directly observes only surface soil moisture (in the top 5 cm of the soil column). Several of the key applications targeted by SMAP, however, require knowledge of root zone soil moisture (approximately top 1 m of the soil column), which is not directly measured by SMAP. The foremost objective of the SMAP L4_SM product is to fill this gap and provide estimates of root zone soil moisture

  10. Molecular-dynamics analysis of mobile helium cluster reactions near surfaces of plasma-exposed tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Lin; Maroudas, Dimitrios, E-mail: maroudas@ecs.umass.edu [Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003-9303 (United States); Hammond, Karl D. [Department of Chemical Engineering, University of Missouri, Columbia, Missouri 65211 (United States); Wirth, Brian D. [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States)

    2015-10-28

    We report the results of a systematic atomic-scale analysis of the reactions of small mobile helium clusters (He{sub n}, 4 ≤ n ≤ 7) near low-Miller-index tungsten (W) surfaces, aiming at a fundamental understanding of the near-surface dynamics of helium-carrying species in plasma-exposed tungsten. These small mobile helium clusters are attracted to the surface and migrate to the surface by Fickian diffusion and drift due to the thermodynamic driving force for surface segregation. As the clusters migrate toward the surface, trap mutation (TM) and cluster dissociation reactions are activated at rates higher than in the bulk. TM produces W adatoms and immobile complexes of helium clusters surrounding W vacancies located within the lattice planes at a short distance from the surface. These reactions are identified and characterized in detail based on the analysis of a large number of molecular-dynamics trajectories for each such mobile cluster near W(100), W(110), and W(111) surfaces. TM is found to be the dominant cluster reaction for all cluster and surface combinations, except for the He{sub 4} and He{sub 5} clusters near W(100) where cluster partial dissociation following TM dominates. We find that there exists a critical cluster size, n = 4 near W(100) and W(111) and n = 5 near W(110), beyond which the formation of multiple W adatoms and vacancies in the TM reactions is observed. The identified cluster reactions are responsible for important structural, morphological, and compositional features in the plasma-exposed tungsten, including surface adatom populations, near-surface immobile helium-vacancy complexes, and retained helium content, which are expected to influence the amount of hydrogen re-cycling and tritium retention in fusion tokamaks.

  11. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  12. Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone, New Hampshire, USA

    Science.gov (United States)

    McAleer, Ryan J.; Bish, David L.; Kunk, Michael J.; Sicard, Karri R.; Valley, Peter M.; Walsh, Gregory J.; Wathen, Bryan A.; Wintsch, R.P.

    2016-01-01

    We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na-poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric-forming Na-rich muscovite is also progressively replaced by fabric-forming Na-poor muscovite. The mineralogy of the new phyllonitic fault-rock produced is dominated by Na-poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric-forming Na-rich muscovite is selectively replaced at high-strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high-grade porphyroblasts by weaker Na-poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na-rich muscovite-defined foliation destroys not only the metastable high-grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.

  13. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

    2017-02-01

    Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  14. Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Lara-Romero, Javier; Maya-Yescas, Rafael; Rico-Cerda, Jose Luis; Rivera-Rojas, Jose Luis; Castillo, Fernando Chinas; Kaltchev, Matey; Tysoe, Wilfred T.

    2006-01-01

    The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl 2 and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used

  15. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  16. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  17. Making the most of CZ seismics: Improving shallow critical zone characterization using surface-wave analysis

    Science.gov (United States)

    Pasquet, S.; Wang, W.; Holbrook, W. S.; Bodet, L.; Carr, B.; Flinchum, B. A.

    2017-12-01

    Estimating porosity and saturation in the shallow subsurface over large lateral scales is vitally important for understanding the development and evolution of the Critical Zone (CZ). Because elastic properties (P- and S-wave velocities) are particularly sensitive to porosity and saturation, seismic methods (in combination with petrophysical models) are effective tools for mapping CZ architecture and processes. While many studies employ P-wave refraction methods, fewer use the surface waves that are typically also recorded in those same surveys. Here we show the value of exploiting surface waves to extract supplementary shear-wave velocity (Vs) information in the CZ. We use a new, user-friendly, open-source MATLAB-based package (SWIP) to invert surface-wave data and estimate lateral variations of Vs in the CZ. Results from synthetics show that this approach enables the resolution of physical property variations in the upper 10-15 m below the surface with lateral scales of about 5 m - a vast improvement compared to P-wave tomography alone. A field example at a Yellowstone hydrothermal system also demonstrates the benefits of including Vs in the petrophysical models to estimate not only porosity but also saturation, thus highlighting subsurface gas pathways. In light of these results, we strongly suggest that surface-wave analysis should become a standard approach in CZ seismic surveys.

  18. Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

    International Nuclear Information System (INIS)

    Zhang Weiguo; Feng Huan; Chang Jinna; Qu Jianguo; Xie Hongxia; Yu Lizhong

    2009-01-01

    Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg -1 dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I geo ) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn. - Surface sediment metal enrichment is evidenced for Cd, Cr and Ni in the Yangtze River intertidal zone.

  19. Kinetics of two simultaneous second-order reactions occurring in different zones

    International Nuclear Information System (INIS)

    Dole, M.; Hsu, C.S.; Patel, V.M.; Patel, G.N.

    1975-01-01

    Equations have been derived for the case of free radicals recombining according to the second-order kinetics with or without diffusion control under the conditions that there are two simultaneous spatially separated recombination reactions but that only the overall free-radical concentration can be observed. The properties of these equations are discussed and methods for determining the three independent parameters in the first case and five in the second developed. The resulting equations have been applied to the interpretation of data obtained in studying the decay of allyl chain free radicals in irradiated extended chain crystalline polyethylene

  20. Monitorizing nitinol alloy surface reactions for biofouling studies

    International Nuclear Information System (INIS)

    Dinu, C.Z.; Dinca, V.C.; Soare, S.; Moldovan, A.; Smarandache, D.; Scarisoareanu, N.; Barbalat, A.; Birjega, R.; Dinescu, M.; DiStefano, V. Ferrari

    2007-01-01

    Growth and deposition of unwanted bacteria on implant metal alloys affect their use as biomedical samples. Monitoring any bacterial biofilm accumulation will provide early countermeasures. For a reliable antifouling strategy we prepared nitinol (NiTi) thin films on Ti-derived substrates by using a pulsed laser deposition (PLD) method. As the microstructure of Ti-alloy is dictated by the tensile strength, fatigue and the fracture toughness we tested the use of hydrogen as an alloying element. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM) investigated the crystalline structure, chemical composition and respectively the surface morphology of the nitinol hydrogen and hydrogen-free samples. Moreover, the alloys were integrated and tested using a cellular metric and their responses were systematic evaluated and quantified. Our attractive approach is meant to select the suitable components for an effective and trustworthy anti-fouling strategy. A greater understanding of such processes should lead to novel and effective control methods that would improve in the future implant stability and capabilities

  1. Coastal Zone Hazards Related to Groundwater-Surface Water Interactions and Groundwater Flooding

    Science.gov (United States)

    Kontar, Y. A.; Ozorovich, Y. R.; Salokhiddinov, A. T.

    2009-12-01

    Worldwide, as many as half a million people have died in natural and man-made disasters since the turn of the 21st century (Wirtz, 2008). Further, natural and man-made hazards can lead to extreme financial losses (Elsner et al, 2009). Hazards, hydrological and geophysical risk analysis related to groundwater-surface water interactions and groundwater flooding have been to a large extent under-emphasized for coastal zone applications either due to economical limitations or underestimation of its significance. This is particularly true for tsunamis creating salt water intrusion to coastal aquifers, even though most tsunami hazard assessments have in the past relied on scenario or deterministic type models (Geist and Parsons, 2006), and to increasing mineralization of potable water because of intensive water diversions and also the abundance of highly toxic pollutants (mainly pesticides) in water, air and food, which contribute to the deterioration of the coastal population's health (Glantz, 2007). In the wake of pressing environmental and economic issues, it is of prime importance for the scientific community to shed light onto the great efforts by hydrologists and geophysicists to quantify conceptual uncertainties and to provide quality assurances of potential coastal zone hazard evaluation and prediction. This paper proposes consideration of two case studies which are important and significant for future development and essential for feasibility studies of hazards in the coastal zone. The territory of the Aral Sea Region in Central Asia is known as an ecological disaster coastal zone (Zavialov, 2005). It is now obvious that, in order to provide reasonable living conditions to the coastal zone population, it is first of all necessary to drastically improve the quality of the water dedicated to human needs. Due to their intensive pollution by industrial wastes and by drainage waters from irrigated fields, the Syr Darya and Amu Darya rivers can no longer be considered

  2. To address surface reaction network complexity using scaling relations machine learning and DFT calculations

    International Nuclear Information System (INIS)

    Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

    2017-01-01

    Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

  3. Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

    Science.gov (United States)

    Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

    2015-03-25

    Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

  4. Assessment of the SMAP Level-4 Surface and Root-Zone Soil Moisture Product Using In Situ Measurements

    NARCIS (Netherlands)

    Reichle, Rolf H.; De Lannoy, Gabrielle J. M.; Liu, Qing; Ardizzone, Joseph V.; Colliander, Andreas; Conaty, Austin; Crow, Wade; Jackson, Thomas J.; Jones, Lucas A.; Kimball, John S.; Koster, Randal D.; Mahanama, Sarith P.; Smith, Edmond B.; Berg, Aaron; Bircher, Simone; Bosch, David; Caldwell, Todd G.; Cosh, Michael; Holifield Collins, Chandra D.; Jensen, Karsten H.; Livingston, Stan; Lopez-baeza, Ernesto; Martínez-fernández, José; Mcnairn, Heather; Moghaddam, Mahta; Pacheco, Anna; Pellarin, Thierry; Prueger, John; Rowlandson, Tracy; Seyfried, Mark; Starks, Patrick; Su, Bob; Thibeault, Marc; Van Der Velde, Rogier; Walker, Jeffrey; Wu, Xiaoling; Zeng, Yijian

    2017-01-01

    The Soil Moisture Active Passive (SMAP) mission Level-4 Surface and Root-Zone Soil Moisture (L4_SM) data product is generated by assimilating SMAP L-band brightness temperature observations into the NASA Catchment land surface model. The L4_SM product is available from 31 March 2015 to present

  5. The effect of surface anisotropy in the slippery zone of Nepenthes alata pitchers on beetle attachment

    Directory of Open Access Journals (Sweden)

    Elena V. Gorb

    2011-06-01

    Full Text Available The slippery zone in pitchers of the carnivorous plant Nepenthes alata bears scattered prominent lunate cells and displays continuous epicuticular crystalline wax coverage. The aim of this study was to examine the influence of the surface anisotropy, caused by the shape of lunate cells, on insect attachment ability. Traction tests with ladybird beetles Coccinella septempunctata were performed in two types of experiments, where surface samples of (1 intact pitchers, (2 chemically de-waxed pitchers, and (3 their polymer replicas were placed horizontally. Beetle traction forces were measured when they walked on test surfaces in either an upward (towards the peristome or downward (towards the pitcher bottom direction, corresponding to the upright or inverted positions of the pitcher. On intact pitcher surfaces covered with both lunate cells and wax crystals, experiments showed significantly higher forces in the direction towards the pitcher bottom. To distinguish between the contributions, from claw interlocking and pad adhesion, to insect attachment on the pitcher surfaces, intact versus claw-ablated beetles were used in the second type of experiment. On both de-waxed plant samples and their replicas, intact insects generated much higher forces in the downward direction compared to the upward one, whereas clawless insects did not. These results led to the conclusion that, (i due to the particular shape of lunate cells, the pitcher surface has anisotropic properties in terms of insect attachment, and (ii claws were mainly responsible for attachment enhancement in the downward pitcher direction, since, in this direction, they could interlock with overhanging edges of lunate cells.

  6. Theory of the reaction dynamics of small molecules on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

    2016-09-09

    The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H2, H2O and CH4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

  7. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    International Nuclear Information System (INIS)

    Osborn, David L.

    2017-01-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  8. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    Science.gov (United States)

    Osborn, David L.

    2017-05-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  9. Surface reaction rate and probability of ozone and alpha-terpineol on glass, polyvinyl chloride, and latex paint surfaces.

    Science.gov (United States)

    Shu, Shi; Morrison, Glenn C

    2011-05-15

    Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.

  10. Mapping Deep Low Velocity Zones in Alaskan Arctic Coastal Permafrost using Seismic Surface Waves

    Science.gov (United States)

    Dou, S.; Ajo Franklin, J. B.; Dreger, D. S.

    2012-12-01

    Surface Waves (MASW) suggests the existence of pronounced low shear wave velocity zones that span the depth range of 2 - 30 meters; this zone has shear velocity values comparable to partially thawed soils. Such features coincide with previous findings of very low electrical resistivity structure (as low as ~10 Ohm*m at some locations) from measurements obtained in the first NGEE-Arctic geophysical field campaign (conducted in the week of September 24 - October 1, 2011). These low shear velocity zones are likely representative of regions with high unfrozen water content and thus have important implications on the rate of microbial activity and the vulnerability of deep permafrost carbon pools. Analysis of this dataset required development of a novel inversion approach based on waveform inversion. The existence of multiple closely spaced Rayleigh wave modes made traditional inversion based on mode picking virtually impossible; As a result, we selected a direct misfit evaluation based on comparing dispersion images in the phase velocity/frequency domain. The misfit function was optimized using a global search algorithm, in this case Huyer and Neumaier's Multi Coordinate Search algorithm (MCS). This combination of MCS and waveform misfit allowed recovery of the low velocity region despite the existence of closely spaced modes.

  11. Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

    International Nuclear Information System (INIS)

    Iwaki, T.; Katsuta, K.; Miura, M.

    1981-01-01

    The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

  12. [Ciliate diversity and spatiotemporal variation in surface sediments of Yangtze River estuary hypoxic zone].

    Science.gov (United States)

    Feng, Zhao; Kui-Dong, Xu; Zhao-Cui, Meng

    2012-12-01

    By using denaturing gradient gel electrophoresis (DGGE) and sequencing as well as Ludox-QPS method, an investigation was made on the ciliate diversity and its spatiotemporal variation in the surface sediments at three sites of Yangtze River estuary hypoxic zone in April and August 2011. The ANOSIM analysis indicated that the ciliate diversity had significant difference among the sites (R = 0.896, P = 0.0001), but less difference among seasons (R = 0.043, P = 0.207). The sequencing of 18S rDNA DGGE bands revealed that the most predominant groups were planktonic Choreotrichia and Oligotrichia. The detection by Ludox-QPS method showed that the species number and abundance of active ciliates were maintained at a higher level, and increased by 2-5 times in summer, as compared with those in spring. Both the Ludox-QPS method and the DGGE technique detected that the ciliate diversity at the three sites had the similar variation trend, and the Ludox-QPS method detected that there was a significant variation in the ciliate species number and abundance between different seasons. The species number detected by Ludox-QPS method was higher than that detected by DGGE bands. Our study indicated that the ciliates in Yangtze River estuary hypoxic zone had higher diversity and abundance, with the potential to supply food for the polyps of jellyfish.

  13. Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

    International Nuclear Information System (INIS)

    Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

    2002-01-01

    Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

  14. Land Surface Temperature Differences within Local Climate Zones, Based on Two Central European Cities

    Czech Academy of Sciences Publication Activity Database

    Geletič, Jan; Lehnert, M.; Dobrovolný, Petr

    2016-01-01

    Roč. 8, č. 10 (2016), č. článku 788. ISSN 2072-4292 R&D Projects: GA MŠk(CZ) LO1415 Grant - others:UrbanAdapt(XE) EHP-CZ02-OV-1-036-2015 Program:CZ02 Biodiverzita a ekosystémové služby / Monitorování a integrované plánování a kontrola v životním prostředí/ Adaptace na změnu klimatu Institutional support: RVO:67179843 Keywords : land surface temperature * local climate zones * ASTER * LANDSAT * analysis of variance * Prague * Brno * Czech Republic Subject RIV: EH - Ecology, Behaviour Impact factor: 3.244, year: 2016

  15. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-03-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

  16. T-TY Tank Farm Interim Surface Barrier Demonstration - Vadose Zone Monitoring Plan

    International Nuclear Information System (INIS)

    Zhang, Z.F.; Strickland, Christopher E.; Field, Jim G.; Parker, Danny L.

    2010-01-01

    The Hanford Site has 149 underground single-shell tanks that store hazardous radioactive waste. Many of these tanks and their associated infrastructure (e.g., pipelines, diversion boxes) have leaked. Some of the leaked waste has entered the groundwater. The largest known leak occurred from the T-106 Tank of the 241-T Tank Farm in 1973. Five tanks are assumed to have leaked in the TY Farm. Many of the contaminants from those leaks still reside within the vadose zone within the T and TY Tank Farms. The Department of Energy's Office of River Protection seeks to minimize the movement of these contaminant plumes by placing interim barriers on the ground surface. Such barriers are expected to prevent infiltrating water from reaching the plumes and moving them further. The soil water regime is monitored to determine the effectiveness of the interim surface barriers. Soil-water content and water pressure are monitored using off-the-shelf equipment that can be installed by the hydraulic hammer technique. Four instrument nests were installed in the T Farm in fiscal year (FY) 2006 and FY2007; two nests were installed in the TY Farm in FY2010. Each instrument nest contains a neutron probe access tube, a capacitance probe, and four heat-dissipation units. A meteorological station has been installed at the north side of the fence of the T Farm. This document summarizes the monitoring methods, the instrument calibration and installation, and the vadose zone monitoring plan for interim barriers in T farm and TY Farm.

  17. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  18. Spatio-Temporal Modelling of Dust Transport over Surface Mining Areas and Neighbouring Residential Zones

    Directory of Open Access Journals (Sweden)

    Eva Gulikova

    2008-06-01

    Full Text Available Projects focusing on spatio-temporal modelling of the living environment need to manage a wide range of terrain measurements, existing spatial data, time series, results of spatial analysis and inputs/outputs from numerical simulations. Thus, GISs are often used to manage data from remote sensors, to provide advanced spatial analysis and to integrate numerical models. In order to demonstrate the integration of spatial data, time series and methods in the framework of the GIS, we present a case study focused on the modelling of dust transport over a surface coal mining area, exploring spatial data from 3D laser scanners, GPS measurements, aerial images, time series of meteorological observations, inputs/outputs form numerical models and existing geographic resources. To achieve this, digital terrain models, layers including GPS thematic mapping, and scenes with simulation of wind flows are created to visualize and interpret coal dust transport over the mine area and a neighbouring residential zone. A temporary coal storage and sorting site, located near the residential zone, is one of the dominant sources of emissions. Using numerical simulations, the possible effects of wind flows are observed over the surface, modified by natural objects and man-made obstacles. The coal dust drifts with the wind in the direction of the residential zone and is partially deposited in this area. The simultaneous display of the digital map layers together with the location of the dominant emission source, wind flows and protected areas enables a risk assessment of the dust deposition in the area of interest to be performed. In order to obtain a more accurate simulation of wind flows over the temporary storage and sorting site, 3D laser scanning and GPS thematic mapping are used to create a more detailed digital terrain model. Thus, visualization of wind flows over the area of interest combined with 3D map layers enables the exploration of the processes of coal dust

  19. Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

    Science.gov (United States)

    Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

    2006-01-01

    Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

  20. Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

    Science.gov (United States)

    Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

    2013-09-01

    In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

  1. Analysis of surface roughness and surface heat affected zone of steel S355J0 after plasma arc cutting

    International Nuclear Information System (INIS)

    Hatala, Michal; Chep, Robert; Pandilov, Zoran

    2010-01-01

    This paper deals with thermal cutting technology of materials with plasma arc. In the first part of this paper the theoretical knowledge of the principles of plasma arc cutting and current use of this technology in industry are presented. The cut of products with this technology is perpendicular and accurate, but the use of this technology affects micro-structural changes and depth of the heat affected zone (HAZ). This article deals with the experimental evaluation of plasma arc cutting technological process. The influence of technological factors on the roughness parameter Ra of the steel surface EN S355J0 has been evaluated by using planned experiments. By using the factor experiment, the significance of the four process factors such as plasma burner feed speed, plasma gas pressure, nozzle diameter, distance between nozzle mouth and material has been analyzed. Regression models obtained by multiple linear regression indicate the quality level of observed factors function. The heat from plasma arc cutting affects the micro-structural changes of the material, too.

  2. Assessing the relationship between surface urban heat islands and landscape patterns across climatic zones in China.

    Science.gov (United States)

    Yang, Qiquan; Huang, Xin; Li, Jiayi

    2017-08-24

    The urban heat island (UHI) effect exerts a great influence on the Earth's environment and human health and has been the subject of considerable attention. Landscape patterns are among the most important factors relevant to surface UHIs (SUHIs); however, the relationship between SUHIs and landscape patterns is poorly understood over large areas. In this study, the surface UHI intensity (SUHII) is defined as the temperature difference between urban and suburban areas, and the landscape patterns are quantified by the urban-suburban differences in several typical landscape metrics (ΔLMs). Temperature and land-cover classification datasets based on satellite observations were applied to analyze the relationship between SUHII and ΔLMs in 332 cities/city agglomerations distributed in different climatic zones of China. The results indicate that SUHII and its correlations with ΔLMs are profoundly influenced by seasonal, diurnal, and climatic factors. The impacts of different land-cover types on SUHIs are different, and the landscape patterns of the built-up and vegetation (including forest, grassland, and cultivated land) classes have the most significant effects on SUHIs. The results of this study will help us to gain a deeper understanding of the relationship between the SUHI effect and landscape patterns.

  3. Urban Imperviousness Effects on Summer Surface Temperatures Nearby Residential Buildings in Different Urban Zones of Parma

    Directory of Open Access Journals (Sweden)

    Marco Morabito

    2017-12-01

    Full Text Available Rapid and unplanned urban growth is responsible for the continuous conversion of green or generally natural spaces into artificial surfaces. The high degree of imperviousness modifies the urban microclimate and no studies have quantified its influence on the surface temperature (ST nearby residential building. This topic represents the aim of this study carried out during summer in different urban zones (densely urbanized or park/rural areas of Parma (Northern Italy. Daytime and nighttime ASTER images, the local urban cartography and the Italian imperviousness databases were used. A reproducible/replicable framework was implemented named “Building Thermal Functional Area” (BTFA useful to lead building-proxy thermal analyses by using remote sensing data. For each residential building (n = 8898, the BTFA was assessed and the correspondent ASTER-LST value (ST_BTFA and the imperviousness density were calculated. Both daytime and nighttime ST_BTFA significantly (p < 0.001 increased when high levels of imperviousness density surrounded the residential buildings. These relationships were mostly consistent during daytime and in densely urbanized areas. ST_BTFA differences between urban and park/rural areas were higher during nighttime (above 1 °C than daytime (about 0.5 °C. These results could help to identify “urban thermal Hot-Spots” that would benefit most from mitigation actions.

  4. T Tank Farm Interim Surface Barrier Demonstration--Vadose Zone Monitoring Plan

    International Nuclear Information System (INIS)

    Zhang, Z. F.; Keller, Jason M.; Strickland, Christopher E.

    2007-01-01

    The Hanford Site has 149 underground single-shell tanks that store hazardous radioactive waste. Many of these tanks and their associated infrastructure (e.g., pipelines, diversion boxes) have leaked. Some of the leaked waste has entered the groundwater. The largest known leak occurred from the T-106 Tank in 1973. Many of the contaminants from that leak still reside within the vadose zone beneath the T Tank Farm. CH2M Hill Hanford Group, Inc. seeks to minimize movement of this residual contaminant plume by placing an interim barrier on the surface. Such a barrier is expected to prevent infiltrating water from reaching the plume and moving it further. A plan has been prepared to monitor and determine the effectiveness of the interim surface barrier. Soil water content and water pressure will be monitored using off-the-shelf equipment that can be installed by the hydraulic hammer technique. In fiscal year 2006, two instrument nests were installed. Each instrument nest contains a neutron probe access tube, a capacitance probe, four heat-dissipation units, and a drain gauge to measure soil water flux. A meteorological station has been installed outside of the fence. In fiscal year 2007, two additional instrument nests are planned to be installed beneath the proposed barrier.

  5. Surface runoff water quality in a managed three zone riparian buffer.

    Science.gov (United States)

    Lowrance, Richard; Sheridan, Joseph M

    2005-01-01

    Managed riparian forest buffers are an important conservation practice but there are little data on the water quality effects of buffer management. We measured surface runoff volumes and nutrient concentrations and loads in a riparian buffer system consisting of (moving down slope from the field) a grass strip, a managed forest, and an unmanaged forest. The managed forest consisted of sections of clear-cut, thinned, and mature forest. The mature forest had significantly lower flow-weighted concentrations of nitrate, ammonium, total Kjeldahl N (TKN), sediment TKN, total N (nitrate + TKN), dissolved molybdate reactive P (DMRP), total P, and chloride. The average buffer represented the conditions along a stream reach with a buffer system in different stages of growth. Compared with the field output, flow-weighted concentrations of nitrate, ammonium, DMRP, and total P decreased significantly within the buffer and flow-weighted concentrations of TKN, total N, and chloride increased significantly within the buffer. All loads decreased significantly from the field to the middle of the buffer, but most loads increased from the middle of the buffer to the sampling point nearest the stream because surface runoff volume increased near the stream. The largest percentage reduction of the incoming nutrient load (at least 65% for all nutrient forms) took place in the grass buffer zone because of the large decrease (68%) in flow. The average buffer reduced loadings for all nutrient species, from 27% for TKN to 63% for sediment P. The managed forest and grass buffer combined was an effective buffer system.

  6. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  7. Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

    Science.gov (United States)

    Dulnee, Siriwan; Scheinost, Andreas C

    2014-08-19

    To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

  8. Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

    Science.gov (United States)

    Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

    2003-10-01

    The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

  9. Research project AUS-10370/CF: electron impact ionization and surface induced reactions of edge plasma constituents

    International Nuclear Information System (INIS)

    Maerk, T.D.

    1999-01-01

    In order to better understand elementary reactions which are taking place at the plasma edge of thermonuclear fusion devices, three areas of research were persuaded: I) Experimental studies about electron ionization of neutrals and ions and electron attachment to molecules, II) Theoretical studies about electron ionisation of neutrals and ions and III) Reactive interaction of molecular ions with surfaces

  10. State-of-stress in magmatic rift zones: Predicting the role of surface and subsurface topography

    Science.gov (United States)

    Oliva, S. J. C.; Ebinger, C.; Rivalta, E.; Williams, C. A.

    2017-12-01

    Continental rift zones are segmented along their length by large fault systems that form in response to extensional stresses. Volcanoes and crustal magma chambers cause fundamental changes to the density structure, load the plates, and alter the state-of-stress within the crust, which then dictates fracture orientation. In this study, we develop geodynamic models scaled to a structure, petrologic and thermodynamic studies constrain material densities, and seismicity and structural analyses constrain active and time-averaged kinematics. This area is an ideal test area because a 60º stress rotation is observed in time-averaged fault and magma intrusion, and in local seismicity, and because this was the site of a large volume dike intrusion and seismic sequence in 2007. We use physics-based 2D and 3D models (analytical and finite elements) constrained by data from active rift zones to quantify the effects of loading on state-of-stress. By modeling varying geometric arrangements, and density contrasts of topographic and subsurface loads, and with reasonable regional extensional forces, the resulting state-of-stress reveals the favored orientation for new intrusions. Although our models are generalized, they allow us to evaluate whether a magmatic system (surface and subsurface) can explain the observed stress rotation, and enable new intrusions, new faults, or fault reactivation with orientations oblique to the main border faults. Our results will improve our understanding of the different factors at play in these extensional regimes, as well as contribute to a better assessment of the hazards in the area.

  11. Surface and subsurface continuous gravimetric monitoring of groundwater recharge processes through the karst vadose zone at Rochefort Cave (Belgium)

    Science.gov (United States)

    Watlet, A.; Van Camp, M. J.; Francis, O.; Poulain, A.; Hallet, V.; Triantafyllou, A.; Delforge, D.; Quinif, Y.; Van Ruymbeke, M.; Kaufmann, O.

    2017-12-01

    Ground-based gravimetry is a non-invasive and integrated tool to characterize hydrological processes in complex environments such as karsts or volcanoes. A problem in ground-based gravity measurements however concerns the lack of sensitivity in the first meters below the topographical surface, added to limited infiltration below the gravimeter building (umbrella effect). Such limitations disappear when measuring underground. Coupling surface and subsurface gravity measurements therefore allow isolating hydrological signals occurring in the zone between the two gravimeters. We present a coupled surface/subsurface continuous gravimetric monitoring of 2 years at the Rochefort Cave Laboratory (Belgium). The gravity record includes surface measurements of a GWR superconducting gravimeter and subsurface measurements of a Micro-g LaCoste gPhone gravimeter, installed in a cave 35 m below the surface station. The recharge of karstic aquifers is extremely complex to model, mostly because karst hydrological systems are composed of strongly heterogeneous flows. Most of the problem comes from the inadequacy of conventional measuring tools to correctly sample such heterogeneous media, and particularly the existence of a duality of flow types infiltrating the vadose zone: from rapid flows via open conduits to slow seepage through porous matrix. Using the surface/subsurface gravity difference, we were able to identify a significant seasonal groundwater recharge within the karst vadose zone. Seasonal or perennial perched reservoirs have already been proven to exist in several karst areas due to the heterogeneity of the porosity and permeability gradient in karstified carbonated rocks. Our gravimetric experiment allows assessing more precisely the recharge processes of such reservoirs. The gravity variations were also compared with surface and in-cave hydrogeological monitoring (i.e. soil moisture, in-cave percolating water discharges, water levels of the saturated zone). Combined

  12. T Tank Farm Interim Surface Barrier Demonstration -- Vadose Zone Monitoring FY07 Report

    International Nuclear Information System (INIS)

    Zhang, Z. F.; Strickland, Christopher E.; Keller, Jason M.; Wittreich, Curtis D.; Sydnor, Harold A.

    2008-01-01

    CH2M HILL Hanford Group, Inc. is currently in the process of constructing a temporary surface barrier over a portion of the T Tank Farm as part of the T farm Interim Surface Barrier Demonstration Project. The surface barrier is designed to prevent the infiltration of precipitation into the contaminated soil zone created by the Tank T-106 leak and minimize movement of the contamination. As part of the demonstration effort, vadose zone moisture monitoring is being performed to assess the effectiveness of the barrier at reducing soil moisture. A solar-powered and remotely-controlled system was installed to continuously monitor soil water conditions in four instrument nests (i.e., A, B, C, and D) and the site meteorological condition. Each instrument nest was composed of a capacitance probe with multiple sensors, multiple heat-dissipation units, a neutron probe access tube and a datalogger. Nests A and B also contained a drain gauge each. The principle variables monitored for this purpose are soil-water content, soil-water pressure, and soil-water flux. In addition to these, soil temperature, precipitation, and air temperature are measured. Data from each of the dataloggers were transmitted remotely to the receiving computer. The neutron probe access tube was used to perform quarterly manual measurements of soil-water content using a neutron probe. This monitoring system was used to assess the soil water conditions in the soil outside and within the footprint of the surface barrier to be emplaced in the Hanford T Tank Farm. Data to date is baseline under the condition without the interim surface barrier in place. All the instruments except the two drain gauges were functional in FY07. The capacitance-probe measurements showed that the soil-moisture content at relatively shallow depths (e.g., 0.6 and 0.9 m) was increasing since October 2006 and reached the highest in early January 2007 followed by a slight decrease. Soil-moisture contents at the depths of 1.3 m and

  13. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

  14. Electrochemically assisted organosol method for Pt-Sn nanoparticle synthesis and in situ deposition on graphite felt support: Extended reaction zone anodes for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lycke, Derek R.; Gyenge, Elod L. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2007-03-20

    Two electrochemically assisted variants of the Boenneman organosol method were developed for Pt-Sn nanoparticle synthesis and in situ deposition on graphite felt electrodes (e.g. thickness up to 2 mm). Tetraoctylammonium triethylhydroborate N(C{sub 8}H{sub 17}){sub 4}BH(C{sub 2}H{sub 5}){sub 3} was employed as colloid stabilizer and reductant dissolved in tetrahydrofuran (THF). The role of the electric field at a low deposition current density of 1.25 mA cm{sup -2} was mainly electrophoretic causing the migration and adsorption of N(C{sub 8}H{sub 17}){sub 4}BH(C{sub 2}H{sub 5}){sub 3} on the graphite felt surface where it reduced the PtCl{sub 2}-SnCl{sub 2} mixture. Faradaic electrodeposition was detected mostly for Sn. Typical Pt-Sn loadings were between 0.4 and 0.9 mg cm{sup -2} depending on the type of pre-deposition exposure of the graphite felt: surfactant-adsorption and metal-adsorption variant, respectively. The catalyst surface area and Pt:Sn surface area ratio was determined by anodic striping of an underpotential deposited Cu monolayer. The two deposition variants gave different catalyst surfaces: total area 233 and 76 cm{sup 2} mg{sup -1}, with Pt:Sn surface area ratio of 3.5:1 and 7.7:1 for surfactant and metal adsorption, respectively. Regarding electrocatalysis of ethanol oxidation, voltammetry and chronopotentiometry studies corroborated by direct ethanol fuel cell experiments using 0.5 M H{sub 2}SO{sub 4} as electrolyte, showed that due to a combination of higher catalyst load and Pt:Sn surface ratio, the graphite felt anodes prepared by the metal-adsorption variant gave better performance. The catalyzed graphite felt provided an extended reaction zone for ethanol electrooxidation and it gave higher catalyst mass specific peak power outputs compared to literature data obtained using gas diffusion anodes with carbon black supported Pt-Sn nanoparticles. (author)

  15. Capillary zone electrophoresis-multiple reaction monitoring from 100 pg of RAW 264.7 cell lysate digest.

    Science.gov (United States)

    Sun, Liangliang; Li, Yihan; Champion, Matthew M; Zhu, Guijie; Wojcik, Roza; Dovichi, Norman J

    2013-06-07

    Capillary zone electrophoresis-multiple/single reaction monitoring (CZE-MRM/SRM), which employed an electrokinetically driven sheath-flow electrospray interface, was used for the rapid and highly sensitive detection of protein analytes in complex tryptic digests. MRM channels were developed against a commercial exponential mixture of bovine proteins. Five proteins spanning four orders of magnitude concentration range were confidently detected from only 2.5 ng of the digest mixture; the mass detection limits (S/N = 3) of two detected proteins, alpha-casein and glutamate dehydrogenase were about 600 zmol and 30 amol, respectively. This technique was then applied to a RAW 264.7 cell lysate digest. Three proteins were confidently and reproducibly detected from 100 pg of this digest. The sample amount corresponds to the approximate protein content from a single cell, which suggests that CZE-MRM may be a useful analytical tool in chemical cytometry. In addition to providing highly sensitive detection of proteins in complex mixtures, this system is highly rapid; migration time of the protein digests was less than 10 min.

  16. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Directory of Open Access Journals (Sweden)

    A. D. Elvidge

    2016-02-01

    Full Text Available Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol–Cloud Coupling And Climate Interactions in the Arctic (ACCACIA project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10 from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85  ×  10−3. CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012 tailored for sea-ice drag over the MIZ in which the two constituent components of drag – skin and form drag – are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012 scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values – especially at the higher ice fractions – than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on

  17. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2016-02-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012) tailored for sea-ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on surface roughness is recognised, and

  18. Observations of surface momentum exchange over the marginal-ice-zone and recommendations for its parameterization

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2015-10-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parameterization of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parameterization scheme (Lüpkes et al., 2012) tailored for sea ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parameterization schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement is found to hold for subsets of the data from different locations despite differences in sea ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea ice morphology and floe size on surface roughness is

  19. Influence of growth conditions and surface reaction byproducts on GaN grown via metal organic molecular beam epitaxy: Toward an understanding of surface reaction chemistry

    Science.gov (United States)

    Pritchett, David; Henderson, Walter; Burnham, Shawn D.; Doolittle, W. Alan

    2006-04-01

    The surface reaction byproducts during the growth of GaN films via metal organic molecular beam epitaxy (MOMBE) were investigated as a means to optimize material properties. Ethylene and ethane were identified as the dominant surface reaction hydrocarbon byproducts, averaging 27.63% and 7.15% of the total gas content present during growth. Intense ultraviolet (UV) photoexcitation during growth was found to significantly increase the abundance of ethylene and ethane while reducing the presence of H2 and N2. At 920°C, UV excitation was shown to enhance growth rate and crystalline quality while reducing carbon incorporation. Over a limited growth condition range, a 4.5×1019-3.4×1020 cm-3 variation in carbon incorporation was achieved at constant high vacuum. Coupled with growth rate gains, UV excitation yielded films with ˜58% less integrated carbon content. Structural material property variations are reported for various ammonia flows and growth temperatures. The results suggest that high carbon incorporation can be achieved and regulated during MOMBE growth and that in-situ optimization through hydrocarbon analysis may provide further enhancement in the allowable carbon concentration range.

  20. Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

    2017-11-02

    Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

  1. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  2. Study on reduction reactions of neptunium(V) on magnetite surface

    International Nuclear Information System (INIS)

    Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

    2004-01-01

    Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

  3. Surface photo reaction processes using synchrotron radiation; Hoshako reiki ni yoru hyomenko hanno process

    Energy Technology Data Exchange (ETDEWEB)

    Imaizumi, Y. [Tohoku University, Sendai (Japan). Institute for Materials Research; Yoshigoe, A. [Toyohashi University of Technology, Aichi (Japan); Urisu, T. [Toyohashi University of Technology, Aichi (Japan). Institute for Molecular Science

    1997-08-20

    This paper introduces the surface photo reaction processes using synchrotron radiation, and its application. A synchrotron radiation process using soft X-rays contained in electron synchrotron radiated light as an excited light source has a possibility of high-resolution processing because of its short wave length. The radiated light can excite efficiently the electronic state of a substance, and can induce a variety of photochemical reactions. In addition, it can excite inner shell electrons efficiently. In the aspect of its application, it has been found that, if radiated light is irradiated on surfaces of solids under fluorine-based reaction gas or Cl2, the surfaces can be etched. This technology is utilized practically. With regard to radiated light excited CVD process, it may be said that anything that can be deposited by the ordinary plasma CVD process can be deposited. Its application to epitaxial crystal growth may be said a nano processing application in thickness direction, such as forming an ultra-lattice structure, the application being subjected to expectation. In micromachine fabricating technologies, a possibility is searched on application of a photo reaction process of the radiated light. 5 refs., 6 figs.

  4. Small leak detection by measuring surface oscillation during sodium-water reaction in steam generator

    International Nuclear Information System (INIS)

    Nei, Hiromichi; Hori, Masao

    1977-01-01

    Small leak sodium-water reaction tests were conducted to develop various kinds of leak detectors for the sodium-heated steam generator in FBR. The super-heated steam was injected into sodium in a reaction vessel having a sodium free surface, simulating the steam generator. The level gauge in the reaction vessel generated the most reliable signal among detectors, as long as the leak rates were relatively high. The level gauge signal was estimated to be the sodium surface oscillation caused by hydrogen bubbles produced in sodium-water reaction. Experimental correlation was derived, predicting the amplitude as a function of leak rate, hydrogen dissolution ratio, bubble rise velocity and other parameters concerned, assuming that the surface oscillation is in proportion to the gas hold-up. The noise amplitude under normal operation without water leak was increased with sodium flow rate and found to be well correlated with Froud number. These two correlations predict that a water leak in a ''MONJU'' class (300 MWe) steam generator could possibly be detected by level gauges at a leak rate above 2 g/sec. (auth.)

  5. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  6. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    Science.gov (United States)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  7. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    Science.gov (United States)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  8. Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

    DEFF Research Database (Denmark)

    Olsen, Thomas; Schiøtz, Jakob

    2009-01-01

    A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such...... density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....

  9. Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

    Science.gov (United States)

    Meyer, Jörg; Reuter, Karsten

    2014-04-25

    We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Molecular resonances, fusion reactions and surface transparency of interaction between heavy ions

    International Nuclear Information System (INIS)

    Abe, Yasuhisa.

    1980-01-01

    A review of the Band Crossing Model is given, including recent results on the 16 O + 16 O system. Surface Transparency is discussed in the light of the recent development in our understanding of the fusion reaction mechanisms and by calculating the number of open channels available to direct reactions. The existence of the Molecular Resonance Region is suggested in several systems by the fact that Band Crossing Region overlaps with the Transparent Region. A systematic study predicts molecular resonances in the 14 C + 14 C and 12 C + 14 C systems as prominent as those observed in the 16 O + 16 O and 12 C + 16 O systems

  11. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  12. Surface Modification Reaction of Photocatalytic Titanium Dioxide with Triethoxysilane for Improving Dispersibility

    International Nuclear Information System (INIS)

    Lee, Myung Jin; Kim, Ji Ho; Park, Young Tae

    2010-01-01

    We have carried out the surface modification of photocatalytic TiO 2 with triethoxysilane through dehydrogenation reaction and characterized the modified photocatalyst by spectroscopic methods, such as FT-IR, solid-state 29 Si MAS NMR, XPS, and XRF, etc. We also examined photocatalytic activity of the immobilized photocatalytic titanium dioxide with triethoxysilane by decolorization reaction of dyes such as cong red and methylene blue under visible light. Dispersion test showed that the photocatalytic titanium dioxide immobilized with triethoxysilane group has kept higher dispersibility than titanium dioxide itself. No appreciable precipitation takes place even after standing for 24 h in the 4:6 mixture ratio of ethanol and water

  13. Innervation zone of the vastus medialis muscle: position and effect on surface EMG variables

    International Nuclear Information System (INIS)

    Gallina, A; Merletti, R; Gazzoni, M

    2013-01-01

    The aim of this study was to investigate the position of the innervation zone (IZ) of the vastus medialis (VM) and its effect on the electromyographic (EMG) amplitude and mean frequency estimates. Eighteen healthy subjects performed maximal isometric knee extensions at three knee angles. Surface EMG signals were collected by using a 16 × 8 electrode grid placed on the VM muscle. The position of the IZ was estimated through visual analysis, and traditional bipolar signals were obtained from channels over and away from it; amplitude and mean frequency values were extracted and compared using an analysis of variance (ANOVA) with repeated measures. The IZ is shaped as a line running from the proximal–lateral to the distal–medial aspect of the VM muscle. The presence of an IZ under the electrodes lowered the EMG amplitude (P < 0.001, F = 58.11) and increased the EMG mean frequency (P < 0.001, F = 26.47); variations of these parameters due to the knee flexion angle were less frequently observed in EMG signals collected over than away from the IZ. Electrodes placed ‘over the belly of the VM muscle’ are likely to collect EMG signals influenced by the presence of the IZ, thus hindering the detection of changes in muscle activity. (paper)

  14. Finite Element Method Analysis of An Out Flow With Free Surface In Transition Zones

    Science.gov (United States)

    Saoula, R. Iddir S.; Mokhtar, K. Ait

    The object of this work is to present this part of the fluid mechanics that relates to out-flows of the fluid to big speeds in transitions. Results usually gotten by the classic processes can only have a qualitative aspect. The method fluently used for the count of these out-flows to big speeds is the one of characteristics, this approach remains interesting so much that doesn't appear within the out-flow of intersections of shock waves, as well as of reflections of these. In the simple geometry case, the method of finite differences satisfying result, But when the complexity of this geometry imposes itself, it is the method of finite elements that is proposed to solve this type of prob- lem, in particular for problems Trans critic. The goal of our work is to analyse free surface flows in channels no prismatic has oblong transverse section in zone of tran- sition. (Convergent, divergent). The basic mathematical model of this study is Saint Venant derivatives partial equations. To solve these equations we use the finite ele- ment method, the element of reference is the triangular element with 6 nodes which are quadratic in speed and linear in height (pressure). Our results and their obtains by others are very close to experimental results.

  15. Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

    Science.gov (United States)

    Sodeau, J.; Oriordan, B.

    2003-04-01

    CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

  16. Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers

    International Nuclear Information System (INIS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

    2008-01-01

    The functionalization of surfaces and the ability to tailor their properties with desired physico-chemical functions is an important field of research with a broad spectrum of applications. These applications range from the modification of wetting properties, over the alteration of optical properties, to the fabrication of molecular electronic devices. In each of these fields, it is of specific importance to be able to control the quality of the layers with high precision. The present study demonstrates an approach that utilizes the 1,3-dipolar cycloaddition of terminal acetylenes to prepare triazole-terminated monolayers on different substrates. The characterization of the precursor monolayers, the optimization of the chemical surface reactions as well as the clicking of a fluorescent dye molecule on such azide-terminated monolayers was carried out. A coumarin 343 derivative was utilized to discuss the aspects of the functionalization approach. Based on this approach, a number of potential surface reactions, facilitated via the acetylene-substituted functional molecules, for a broad range of applications is at hand, thus leading to numerous possibilities where surface modifications are concerned. These modifications can be applied on non-structured surfaces of silicon or glass or can be used on structured surfaces. Various possibilities are discussed

  17. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-04-20

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  18. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    International Nuclear Information System (INIS)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-01-01

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  19. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

    2016-06-15

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  20. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    International Nuclear Information System (INIS)

    Nguyen, Luan; Tao, Franklin

    2016-01-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  1. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  2. CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

    Science.gov (United States)

    Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

    2002-01-01

    Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

  3. XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1996-04-01

    The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

  4. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  5. 22-year surface salinity changes in the Seasonal Ice Zone near 140°E off Antarctica

    Science.gov (United States)

    Morrow, Rosemary; Kestenare, Elodie

    2017-11-01

    Seasonal and interannual variations in sea surface salinity (SSS) are analyzed in the Sea Ice Zone south of 60°S, from a 22-year time series of observations near 140°E. In the northern sea-ice zone during the warming, melting cycle from October to March, waters warm by an average of 3.5 °C and become fresher by 0.1 to 0.25. In the southern sea-ice zone, the surface temperatures vary from - 1 to 1 °C over summer, and the maximal SSS range occurs in December, with a minimum SSS of 33.65 near the Southern Boundary of the ACC, reaching 34.4 in the shelf waters close to the coast. The main fronts, normally defined at subsurface, are shown to have more distinct seasonal characteristics in SSS than in SST. The interannual variations in SSS are more closely linked to variations in upstream sea-ice cover than surface forcing. SSS and sea-ice variations show distinct phases, with large biannual variations in the early 1990s, weaker variations in the 2000s and larger variations again from 2009 onwards. The calving of the Mertz Glacier Tongue in February 2010 leads to increased sea-ice cover and widespread freshening of the surface layers from 2011 onwards. Summer freshening in the northern sea-ice zone is 0.05-0.07 per decade, increasing to 0.08 per decade in the southern sea-ice zone, largely influenced by the Mertz Glacier calving event at the end of our time series. The summer time series of SSS on the shelf at 140°E is in phase but less variable than the SSS observed upstream in the Adélie Depression, and thus represents a spatially integrated index of the wider SSS variations.

  6. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L S; Kenny, M J; Wieczorek, L [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1994-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  7. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  8. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-04-10

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  9. Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

    International Nuclear Information System (INIS)

    Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

    2012-01-01

    The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

  10. Statistical mapping of zones of focused groundwater/surface-water exchange using fiber-optic distributed temperature sensing

    Science.gov (United States)

    Mwakanyamale, Kisa; Day-Lewis, Frederick D.; Slater, Lee D.

    2013-01-01

    Fiber-optic distributed temperature sensing (FO-DTS) increasingly is used to map zones of focused groundwater/surface-water exchange (GWSWE). Previous studies of GWSWE using FO-DTS involved identification of zones of focused GWSWE based on arbitrary cutoffs of FO-DTS time-series statistics (e.g., variance, cross-correlation between temperature and stage, or spectral power). New approaches are needed to extract more quantitative information from large, complex FO-DTS data sets while concurrently providing an assessment of uncertainty associated with mapping zones of focused GSWSE. Toward this end, we present a strategy combining discriminant analysis (DA) and spectral analysis (SA). We demonstrate the approach using field experimental data from a reach of the Columbia River adjacent to the Hanford 300 Area site. Results of the combined SA/DA approach are shown to be superior to previous results from qualitative interpretation of FO-DTS spectra alone.

  11. Evolution of surface motor activation zones in hemiplegic patients during 20 sessions of FES therapy with multi-pad electrodes

    Directory of Open Access Journals (Sweden)

    Jovana Malešević

    2016-06-01

    Full Text Available The purpose of this study was to examine surface motor activation zones for wrist, fingers and thumb extension movements and their temporal change during 20 therapy sessions using advanced multi-pad functional electrical stimulation system. Results from four hemiplegic patients indicate that certain zones have higher probability of eliciting each of the target movements. However, mutual overlap and variations of the zones are present not just between the subjects, but also on the intrasubject level, reflected through these session to session transformations of the selected virtual electrodes. The obtained results could be used as a priori knowledge for semi-automated optimization algorithm and could shorten the time required for calibration of the multi-pad electrode.

  12. Non-thermal desorption from interstellar dust grains via exothermic surface reactions

    Science.gov (United States)

    Garrod, R. T.; Wakelam, V.; Herbst, E.

    2007-06-01

    Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

  13. Understanding the mechanisms of solid-water reactions through analysis of surface topography.

    Science.gov (United States)

    Bandstra, Joel Z; Brantley, Susan L

    2015-12-01

    The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic

  14. Small water/steam leaks in sodium heated steam generators: Evaluation of the reaction zone - effects on 2 1/4 Cr 1 Mo structural material

    International Nuclear Information System (INIS)

    Dumm, K.

    1975-01-01

    On the basis of experimental data the geometry of a small leak reaction zone can be predicted for given leak sizes and steam generator operation conditions. The effects of small leaks on 2 1/4 Cr 1 Mo material have been studied and completed with test results from foreign investigators. The results have to be considered as preliminary ones which have to be further qualified by additional information. (author)

  15. Small water/steam leaks in sodium heated steam generators: Evaluation of the reaction zone - effects on 2 1/4 Cr 1 Mo structural material

    Energy Technology Data Exchange (ETDEWEB)

    Dumm, K

    1975-07-01

    On the basis of experimental data the geometry of a small leak reaction zone can be predicted for given leak sizes and steam generator operation conditions. The effects of small leaks on 2 1/4 Cr 1 Mo material have been studied and completed with test results from foreign investigators. The results have to be considered as preliminary ones which have to be further qualified by additional information. (author)

  16. Reactions of BBr(n)(+) (n = 0--2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion--surface scattering.

    Science.gov (United States)

    Wade, N; Shen, J; Koskinen, J; Cooks, R G

    2001-07-01

    Ion-surface reactions involving BBr(n)(+) (n = 0--2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B(+) ion yield BF(2)(+) at threshold energy with the simpler product ion BF(+)* appearing at higher collision energies and remaining of lower abundance than BF(2)(+) at all energies examined. In addition, the reactively sputtered ion CF(+) accompanies the formation of BF(2)(+) at low collision energies. These results stand in contrast with previous data on the ion-surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF(2)(+) being the thermodynamically favored product. The fact that the abundance of BF(2)(+) is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum--surface interface, one which involves interaction of the B(+) ion simultaneously with two fluorine atoms. By contrast with the reaction of B(+), the odd-electron species BBr(+)* reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF(+). Corresponding gas-phase ion--molecule experiments involving B(+) and BBr(+)* with C(6)F(14) also yield the products BF(+)* and BF(2)(+), but only in extremely low abundances and with no preference for double fluorine abstraction. Ion--surface reactions were also investigated for BBr(n)(+) (n = 0-2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B(+) ion and dissociative reactions of BBr(+)* result in the formation of BH(2)(+), while the thermodynamically less favorable product BH(+)* is not observed. Collisions of BBr(2)(+) with the H-SAM surface yield the dissociative ion-surface reaction products, BBrH(+) and BBrCH(3

  17. Oklo natural reactor. Study of uranium and rare earths migration on a core drilled through a reaction zone. Application to determination of the date of the nuclear reaction by measurement of fission products

    International Nuclear Information System (INIS)

    Ruffenach, J.C.

    1977-01-01

    Isotopic and chemical analysis of uranium and five rare earths: neodymium, samarium, europium, gadolinium and dysprosium were effected on fourteen samples taken in the same core drilled through a reaction zone of the Oklo uranium deposit. This study points out the general stability of uranium and fission rare earths; spatial distributions of these elements are quite analogous. Migrations have affected about 5% only of fission neodymium in the core of the reaction zone; corresponding values for samarium and gadolinium are slightly higher. These migration phenomena have carried rare earths to no more than 80 cm out of the core. By study of the europium it is shown that nuclear reactions have stayed in the ground since the time of reactions. On the other hand it is shown by analysis of the dysprosium that rare earths have not undergone an important movement. This study allow also the datation of nuclear reactions from the measurement of the quantity of fission neodymium produced. A value of 1.98x10 9 years is obtained slightly higher than the value obtained by geochronology [fr

  18. Effect of Reaction Conditions on the Surface Modification of Cellulose Nanofibrils with Aminopropyl Triethoxysilane

    Directory of Open Access Journals (Sweden)

    Eduardo Robles

    2018-04-01

    Full Text Available Nine different surface modifications of cellulose nanofibrils (CNF with 3-aminopropyl triethoxysilane (ATS by using three different solvent systems (water, ethanol, and a mixture of both were investigated. The effect of reaction conditions, such as silane to cellulose ratio and solvent type were evaluated to determine their contribution to the extent of the silane modification. Nanofibril properties were evaluated by infrared spectroscopy, powder X-ray diffraction, surface free energy, thermogravimetry, 13C and 29Si nuclear magnetic resonance, and electronic microscopy. The influence of the solvent in the solvolysis of the silane was reflected in the presence or absence of ethoxy groups in the silane. On the other hand, whereas the surface modification was increased directly proportionally to silane ratio on the reaction, the aggregation of nanofibrils was also increased, which can play a negative role in certain applications. The increment of silane modification also had substantial repercussions on the crystallinity of the nanofibrils by the addition of amorphous components to the crystalline unit; moreover, silane surface modifications enhanced the hydrophobic character of the nanofibrils.

  19. Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

    The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

  20. Study on interfacial reaction between lead-free solders and alternative surface finishes

    International Nuclear Information System (INIS)

    Siti Rabiatul Aisha; Ourdjini, A.; Saliza Osman

    2007-01-01

    This study investigates the interfacial reactions occurring during reflow soldering between Sn-Ag-Cu lead-free solder and two surface finishes: electroless nickel/ immersion gold (ENIG) and immersion silver (IAg). The study focuses on interfacial reactions evolution and growth kinetics of intermetallic compounds (IMC) formed during soldering and isothermal ageing at 150 degree Celsius for up to 2000 hours. Optical and scanning electron microscopy were used to measure IMC thickness and examine the morphology of IMC respectively, whereas the IMC phases were identified by energy dispersive X-ray analysis (EDX). The results showed that the IMC formed on ENIG finish is thinner compared to that formed on IAg finish. For IAg surface finish, Cu 6 Sn 5 IMCs with scallop morphology are formed at the solder/ surface finish interface after reflow while a second IMC, Cu 3 Sn was formed between the copper and Cu 6 Sn 5 IMC after the isothermal ageing treatment. For ENIG surface finish both (Cu,Ni) 6 Sn 5 and (Ni,Cu) 3 Sn 4 are formed after soldering. Isothermal aging of the solder joints formed on ENIG finish was found to have a significant effect on the morphology of the intermetallics by transforming to more spherical and denser morphology in addition to increase i their thickness with increased ageing time. (author)

  1. A simple method to assess unsaturated zone time lag in the travel time from ground surface to receptor.

    Science.gov (United States)

    Sousa, Marcelo R; Jones, Jon P; Frind, Emil O; Rudolph, David L

    2013-01-01

    In contaminant travel from ground surface to groundwater receptors, the time taken in travelling through the unsaturated zone is known as the unsaturated zone time lag. Depending on the situation, this time lag may or may not be significant within the context of the overall problem. A method is presented for assessing the importance of the unsaturated zone in the travel time from source to receptor in terms of estimates of both the absolute and the relative advective times. A choice of different techniques for both unsaturated and saturated travel time estimation is provided. This method may be useful for practitioners to decide whether to incorporate unsaturated processes in conceptual and numerical models and can also be used to roughly estimate the total travel time between points near ground surface and a groundwater receptor. This method was applied to a field site located in a glacial aquifer system in Ontario, Canada. Advective travel times were estimated using techniques with different levels of sophistication. The application of the proposed method indicates that the time lag in the unsaturated zone is significant at this field site and should be taken into account. For this case, sophisticated and simplified techniques lead to similar assessments when the same knowledge of the hydraulic conductivity field is assumed. When there is significant uncertainty regarding the hydraulic conductivity, simplified calculations did not lead to a conclusive decision. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. What happens when iron becomes wet? Observation of reactions at interfaces between liquid and metal surfaces

    CERN Document Server

    Kimura, M

    2003-01-01

    Synchrotron-radiation has been applied to investigation of interfaces between liquid and metal surfaces, with a special attention to corrosion. Three topics are shown: (1) nano structures of rusts formed on steel after atmospheric corrosion. Evolution of 'Fe(O, OH) sub 6 network' is the key to understand how the durable rusts prevent from formation of more rusts. (2) In situ observation of reactions at the interface has been carried out for localized corrosion of stainless steel. It is shown that change in states of Cr sup 3 sup + and Br sup - ions near the interface is deeply related with a breakout of the passivation film. (3) A structural phase transformation on a Cu sub 3 Au(001) surface was investigated. Ordering remains even at a temperature higher than the bulk-critical temperature, showing surface-induced ordering. These approaches gives us crucial information for a new steel-product. (author)

  3. Novel ion-molecular surface reaction to result in CH3 adsorbates on (111) surface of chemical vapor deposition diamond from ethane and surface anionic sites

    International Nuclear Information System (INIS)

    Komatsu, Shojiro; Okada, Katsuyuki; Shimizu, Yoshiki; Moriyoshi, Yusuke

    2001-01-01

    The existence of CH 3 adsorbates on (111) surface of chemical vapor deposited diamond, which was observed by scanning tunneling microscopy, was explained by the following S N 2 (bimolecular, substitutional, and nucleophilic) type surface reaction; C(s) - +C 2 H 6 ->C(s)-CH 3 +CH 3 - , where C(s) denotes a surface carbon atom. The activation energy was estimated to be 36.78 kcal/mol and the reaction proved to be exothermic with the enthalpy change of -9.250 kcal/mol, according to ab initio molecular orbital calculations at MP2/3-21+G * //RHF/3-21G * level; this result is consistent with typical substrate temperatures, namely about 900 degree C, for chemical vapor deposition of diamond. Charge transfer from the highest occupied molecular orbital of the surface anionic site to the lowest unoccupied molecular orbital of ethane, that is antibonding at the CH 3 - CH 3 bond, has been clearly visualized. A characteristic configuration of an ethane molecule which is associated with an anionic vacant site C(s) - on hydrogenated (111) surface of diamond was also found. [copyright] 2001 American Institute of Physics

  4. Surface area-burnoff correlation for the steam--graphite reaction

    International Nuclear Information System (INIS)

    Stark, W.A. Jr.; Malinauskas, A.P.

    1977-01-01

    The oxidation of core graphite by steam of air represents a problem area of significant concern in safety analyses for the high temperature gas cooled reactor (HTGR). Core and core-support graphite integrity and strength deteriorate with oxidation of the graphite, and oxidation furthermore could affect the rate of fission product release under upset conditions. Consequently, modeling of core response during steam or air ingress conditions requires an expression for the rate of graphite interaction with those impurities. The steam--graphite reaction in particular is a complex interaction of mass transport within the graphite with chemi-sorption and reaction on accessible surfaces; experimental results from graphite to graphite are highly variable, and the description of the reaction is not yet completely consistent. A simple etch pit model relating surface area to burnoff has been proposed and shown to provide reasonable correlation with experimental data obtained from steam oxidation studies of nuclear grade H-327 graphite. Unaccounted differences between theory and experiment arise at burnoffs exceeding 3 to 5 percent. The model, while not complete nor comprehensive, is consistent with experimental observations of graphite oxidation by O 2 (air), CO 2 , or H 2 O, and could have some utility in safety analysis

  5. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  6. Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

    Science.gov (United States)

    Beck, Rainer

    2004-03-01

    The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

  7. Arsenic transport in groundwater, surface water, and the hyporheic zone of a mine-influenced stream-aquifer system

    OpenAIRE

    Brown, Brendan

    2005-01-01

    We investigated the transport of dissolved arsenic in groundwater, surface water and the hyporheic zone in a stream-aquifer system influenced by an abandoned arsenopyrite mine. Mine tailing piles consisting of a host of arsenic-bearing minerals including arsenopyrite and scorodite remain adjacent to the stream and represent a continuous source of arsenic. Arsenic loads from the stream, springs, and groundwater were quantified at the study reach on nine dates from January to August 2005 and ...

  8. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

    KAUST Repository

    Muir, J. N.

    2012-01-01

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

  9. Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

    International Nuclear Information System (INIS)

    Amemiya, Kenta

    2015-01-01

    A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

  10. Dynamic Linkages Between the Transition Zone & Surface Plate Motions in 2D Models of Subduction

    Science.gov (United States)

    Arredondo, K.; Billen, M. I.

    2013-12-01

    While slab pull is considered the dominant force controlling plate motion and speed, its magnitude is controlled by slab behavior in the mantle, where tomographic studies show a wide range of possibilities from direct penetration to folding, or stagnation directly above the lower mantle (e.g. Fukao et al., 2009). Geodynamic studies have investigated various parameters, such as plate age and two phase transitions, to recreate observed behavior (e.g. Běhounková and Cízková, 2008). However, past geodynamic models have left out known slab characteristics that may have a large impact on slab behavior and our understanding of subduction processes. Mineral experiments and seismic observations have indicated the existence of additional phase transitions in the mantle transition zone that may produce buoyancy forces large enough to affect the descent of a subducting slab (e.g. Ricard et al., 2005). The current study systematically tests different common assumptions used in geodynamic models: kinematic versus free-slip boundary conditions, the effects of adiabatic heating, viscous dissipation and latent heat, compositional layering and a more complete suite of phase transitions. Final models have a complete energy equation, with eclogite, harzburgite and pyrolite lithosphere compositional layers, and seven composition-dependent phase transitions within the olivine, pyroxene and garnet polymorph minerals. Results show important feedback loops between different assumptions and new behavior from the most complete models. Kinematic models show slab weakening or breaking above the 660 km boundary and between compositional layers. The behavior in dynamic models with a free-moving trench and overriding plate is compared to the more commonly found kinematic models. The new behavior may have important implications for the depth distribution of deep earthquakes within the slab. Though the thermodynamic parameters of certain phase transitions may be uncertain, their presence and

  11. "Cleaning" the Surface of Hydroxyapatite Nanorods by a Reaction-Dissolution Approach.

    Science.gov (United States)

    Cao, Binrui; Yang, Mingying; Wang, Lin; Xu, Hong; Zhu, Ye; Mao, Chuanbin

    2015-10-21

    Synthetic nanoparticles are always terminated with coating molecules, which are often cytotoxic and not desired in biomedicine. Here we propose a novel reaction-dissolution approach to remove the cytotoxic coating molecules. A two-component solution is added to the nanoparticle solution; one component reacts with the coating molecules to form a salt whereas another is a solvent for dissolving and thus removing the salt. As a proof of concept, this work uses a NaOH-ethanol solution to remove the cytotoxic linoleic acid molecules coated on the hydroxyapatite nanorods (HAP-NRs). The removal of the coating molecules not only significantly improves the biocompatibility of HAP-NRs but also enables their oriented attachment into tightly-bound superstructures, which mimic the organized HAP crystals in bone and enamel and can promote the osteogenic differentiation of mesenchymal stem cells. Our reaction-dissolution approach can be extended to the surface "cleaning" of other nanomaterials.

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

    Science.gov (United States)

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

    2018-04-12

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

  13. Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

    Science.gov (United States)

    Hodgson, Murray; Wareing, Andrew

    2008-01-01

    A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.

  14. Meltwater storage in low-density near-surface bare ice in the Greenland ice sheet ablation zone

    Science.gov (United States)

    Cooper, Matthew G.; Smith, Laurence C.; Rennermalm, Asa K.; Miège, Clément; Pitcher, Lincoln H.; Ryan, Jonathan C.; Yang, Kang; Cooley, Sarah W.

    2018-03-01

    We document the density and hydrologic properties of bare, ablating ice in a mid-elevation (1215 m a.s.l.) supraglacial internally drained catchment in the Kangerlussuaq sector of the western Greenland ice sheet. We find low-density (0.43-0.91 g cm-3, μ = 0.69 g cm-3) ice to at least 1.1 m depth below the ice sheet surface. This near-surface, low-density ice consists of alternating layers of water-saturated, porous ice and clear solid ice lenses, overlain by a thin (sheet ablation zone surface. A conservative estimate for the ˜ 63 km2 supraglacial catchment yields 0.009-0.012 km3 of liquid meltwater storage in near-surface, porous ice. Further work is required to determine if these findings are representative of broader areas of the Greenland ice sheet ablation zone, and to assess the implications for sub-seasonal mass balance processes, surface lowering observations from airborne and satellite altimetry, and supraglacial runoff processes.

  15. Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

    Science.gov (United States)

    Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

    2009-06-03

    Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

  16. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.; Mudiyanselage, Kumudu; Burrell, Anthony K; Sadowski, Jerzy T.; Idriss, Hicham

    2015-01-01

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  17. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.

    2015-10-08

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  18. Competing reactions of selected atmospheric gases on Fe3O4 nanoparticles surfaces.

    Science.gov (United States)

    Eltouny, N; Ariya, Parisa A

    2014-11-14

    Heterogeneous reactions on atmospheric aerosol surfaces are increasingly considered important in understanding aerosol-cloud nucleation and climate change. To understand potential reactions in polluted atmospheres, the co-adsorption of NO2 and toluene to magnetite (Fe3O4i.e. FeO·Fe2O3) nanoparticles at ambient conditions was investigated for the first time. The surface area, size distribution, and morphology of Fe3O4 nanoparticles were characterized by BET method and high-resolution transmission electron microscopy. Adsorption isotherms, collected by gas chromatography with flame ionization detection, showed that the presence of NO2 decreased the adsorption of toluene. The analyses of the surface chemical composition of Fe3O4 by X-ray photoelectron spectroscopy (XPS) reveal that, upon the addition of NO2, the surface is oxidized and a contribution at 532.5 ± 0.4 eV in the O1s spectrum appears, showing that NO2 likely competes with toluene by dissociating on Fe(2+) sites and forming NO3(-). Different competing effects were observed for oxidized Fe3O4; oxidation occurred when exposed solely to NO2, whereas, the mixture of toluene and NO2 resulted in a reduction of the surface i.e. increased Fe(2+)/Fe(3+). Analyses by time of flight secondary ion mass spectrometry further suggest toluene reacts with Fe(3+) sites forming oxygenated organics. Our results indicate that on reduced magnetite, NO2 is more reactive and competes with toluene; in contrast, on oxidized Fe3O4, toluene is more reactive. Because magnetite can assume a range of oxidation ratios in the environment, different competing interactions between pollutants like NO2 and toluene could influence atmospheric processes, namely, the formation of Fe(2+) and the formation of atmospheric oxidants.

  19. The Effectiveness of Surface Coatings on Preventing Interfacial Reaction During Ultrasonic Welding of Aluminum to Magnesium

    Science.gov (United States)

    Panteli, Alexandria; Robson, Joseph D.; Chen, Ying-Chun; Prangnell, Philip B.

    2013-12-01

    High power ultrasonic spot welding (USW) is a solid-state joining process that is advantageous for welding difficult dissimilar material couples, like magnesium to aluminum. USW is also a useful technique for testing methods of controlling interfacial reaction in welding as the interface is not greatly displaced by the process. However, the high strain rate deformation in USW has been found to accelerate intermetallic compound (IMC) formation and a thick Al12Mg17 and Al3Mg2 reaction layer forms after relatively short welding times. In this work, we have investigated the potential of two approaches for reducing the IMC reaction rate in dissimilar Al-Mg ultrasonic welds, both involving coatings on the Mg sheet surface to (i) separate the join line from the weld interface, using a 100- μm-thick Al cold spray coating, and (ii) provide a diffusion barrier layer, using a thin manganese physical vapor deposition (PVD) coating. Both methods were found to reduce the level of reaction and increase the failure energy of the welds, but their effectiveness was limited due to issues with coating attachment and survivability during the welding cycle. The effect of the coatings on the joint's interface microstructure, and the fracture behavior have been investigated in detail. Kinetic modeling has been used to show that the benefit of the cold spray coating can be attributed to the reaction rate reverting to that expected under static conditions. This reduces the IMC growth rate by over 50 pct because at the weld line, the high strain rate dynamic deformation in USW normally enhances diffusion through the IMC layer. In comparison, the thin PVD barrier coating was found to rapidly break up early in USW and become dispersed throughout the deformation layer reducing its effectiveness.

  20. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  1. Land surface temperature as an indicator of the unsaturated zone thickness: A remote sensing approach in the Atacama Desert.

    Science.gov (United States)

    Urqueta, Harry; Jódar, Jorge; Herrera, Christian; Wilke, Hans-G; Medina, Agustín; Urrutia, Javier; Custodio, Emilio; Rodríguez, Jazna

    2018-01-15

    Land surface temperature (LST) seems to be related to the temperature of shallow aquifers and the unsaturated zone thickness (∆Z uz ). That relationship is valid when the study area fulfils certain characteristics: a) there should be no downward moisture fluxes in an unsaturated zone, b) the soil composition in terms of both, the different horizon materials and their corresponding thermal and hydraulic properties, must be as homogeneous and isotropic as possible, c) flat and regular topography, and d) steady state groundwater temperature with a spatially homogeneous temperature distribution. A night time Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) image and temperature field measurements are used to test the validity of the relationship between LST and ∆Z uz at the Pampa del Tamarugal, which is located in the Atacama Desert (Chile) and meets the above required conditions. The results indicate that there is a relation between the land surface temperature and the unsaturated zone thickness in the study area. Moreover, the field measurements of soil temperature indicate that shallow aquifers dampen both the daily and the seasonal amplitude of the temperature oscillation generated by the local climate conditions. Despite empirically observing the relationship between the LST and ∆Z uz in the study zone, such a relationship cannot be applied to directly estimate ∆Z uz using temperatures from nighttime thermal satellite images. To this end, it is necessary to consider the soil thermal properties, the soil surface roughness and the unseen water and moisture fluxes (e.g., capillarity and evaporation) that typically occur in the subsurface. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

  3. Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

    International Nuclear Information System (INIS)

    Zaera, F.; Somorhai, G.A.

    1985-01-01

    Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

  4. An ab initio potential energy surface for the reaction N+ + H2→ NH+ + H

    International Nuclear Information System (INIS)

    Gittins, M.A.; Hirst, D.M.

    1975-01-01

    Preliminary results of ab initio unrestricted Hartree-Fock calculations for the potential energy surface for the reaction N + + H 2 →NH + + H are reported. For the collinear approach of N + to H 2 , the 3 Σ - surface has no activation barrier and has a shallow well (ca.1eV). For perpendicular approach (Csub(2V)symmetry) the 3 B 2 states is of high energy, the 3 A 2 state has a shallow well but as the bond angle increases the 3 B 1 states decreases in energy to become the state of lowest energy. Neither the collinear nor the perpendicular approaches give adiabatic pathways to the deep potential well of 3 B 1 (HNH) + . (auth.)

  5. Surface Properties of Titanium dioxide and its Structural Modifications by Reactions with Transition Metals

    Science.gov (United States)

    Halpegamage, Sandamali

    Surfaces of metal oxides play a vital role in many technologically important applications. The surfaces of titanium dioxide, in particular, show quite promising properties that can be utilized in solid-state gas sensing and photocatalysis applications. In the first part of this dissertation we investigate these properties of TiO2 surfaces through a vigorous surface scientific approach. In the second part, we investigate the possibilities of modifying the TiO2 surfaces by depositing multi-component transition metal oxide monolayers so that the properties of bare TiO2 surface can be influenced in a beneficial way. For instance, via formation of new surface sites or cations that have different valance states, the chemisorption and catalytic properties can be modified. We use sophisticated experimental surface science techniques that are compatible with ultra-high vacuum technology for surface characterization. All the experimental results, except for the photocatalysis experiments, were compared to and verified by supporting DFT-based theoretical results produced by our theory collaborators. TiO2 based solid-state gas sensors have been used before for detecting trace amounts of explosives such as 2,4-dinitrololuene (DNT), a toxic decomposition product of the explosive 2,4,6-trinitrotoluene (TNT) that have very low vapor pressure. However, the adsorption, desorption and reaction mechanism were not well- understood. Here, we investigate 2,4-DNT adsorption on rutile-TiO2(110) surface in order to gain insight about these mechanisms in an atomistic level and we propose an efficient way of desorbing DNT from the surface through UV-light induced photoreactions. TiO2 exists in different polymorphs and the photocatalytic activity differs from one polymorph to another. Rutile and anatase are the most famous forms of TiO2 in photocatalysis and anatase is known to show higher activity than rutile. The photoactivity also varies depending on the surface orientation for the same

  6. Analysis of lipoproteins by capillary zone electrophoresis in microfluidic devices: Assay development and surface roughness measurements

    NARCIS (Netherlands)

    Weiller, Bruce H.; Ceriotti, Laura; Shibata, Takayuki; Rein, Dietrich; Roberts, Matthew A.; Lichtenberg, Jan; German, J. Bruce; De Rooij, Nico F.; Verpoorte, Elisabeth

    2002-01-01

    The development of a new assay for lipoproteins by capillary electrophoresis in fused-silica capillaries and in glass microdevices is described in this paper. The separation of low-density (LDL) and high-density (HDL) lipoproteins by capillary zone electrophoresis is demonstrated in fused-silica

  7. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

  8. A Monte Carlo simulation of the exchange reaction between gaseous molecules and the atoms on a heterogeneous solid surface

    International Nuclear Information System (INIS)

    Imai, Hisao

    1980-01-01

    A method of the Monte Carlo simulation of the isotopic exchange reaction between gaseous molecules and the atoms on an arbitrarily heterogeneous solid surface is described by employing hydrogen as an example. (author)

  9. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  10. Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

    Science.gov (United States)

    Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

    2016-08-01

    A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

    DEFF Research Database (Denmark)

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren

    2015-01-01

    The introduction of surface vinyl groups to PDMS microspheres broadens the latter's applicability range since the microspheres can be further functionalized or crosslinked into elastomers. Quantification of the surface vinyl concentration of PDMS microspheres is therefore essential. Here, a novel...

  12. On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

    Science.gov (United States)

    Resende, S F; Oliveira, B S; Augusti, R

    2018-06-21

    On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

  13. Effect of surface functionalisation on the interaction of iron oxide nanoparticles with polymerase chain reaction.

    Science.gov (United States)

    Aysan, Ayse Beyza; Knejzlík, Zdeněk; Ulbrich, Pavel; Šoltys, Marek; Zadražil, Aleš; Štěpánek, František

    2017-05-01

    The combination of nanoparticles with the polymerase chain reaction (PCR) can have benefits such as easier sample handling or higher sensitivity, but also drawbacks such as loss of colloidal stability or inhibition of the PCR. The present work systematically investigates the interaction of magnetic iron oxide nanoparticles (MIONs) with the PCR in terms of colloidal stability and potential PCR inhibition due to interaction between the PCR components and the nanoparticle surface. Several types of MIONs with and without surface functionalisation by sodium citrate, dextran and 3-aminopropyl-triethoxysilane (APTES) were prepared and characterised by Transmission Electron Microscopy (TEM), dynamic light scattering (DLS) and Fourier Transform Infrared (FT-IR) spectroscopy. Colloidal stability in the presence of the PCR components was investigated both at room temperature and under PCR thermo-cycling. Dextran-stabilized MIONs show the best colloidal stability in the PCR mix at both room and elevated temperatures. Citrate- and APTES-stabilised as well as uncoated MIONs show a comparable PCR inhibition near the concentration 0.1mgml -1 while the inhibition of dextran stabilized MIONs became apparent near 0.5mgml -1 . It was demonstrated that the PCR could be effectively carried out even in the presence of elevated concentration of MIONs up to 2mgml -1 by choosing the right coating approach and supplementing the reaction mix by critical components, Taq DNA polymerase and Mg 2+ ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

    Science.gov (United States)

    Favaro, Marco; Abdi, Fatwa F; Lamers, Marlene; Crumlin, Ethan J; Liu, Zhi; van de Krol, Roel; Starr, David E

    2018-01-18

    Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO 4 ) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO 4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO 4 /KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO 4 /KPi electrolyte interface.

  15. DNAPL Surface Chemistry: Its Impact on DNAPL Distribution in the Vadose Zone and its Manipulation to Enhance Remediation

    Energy Technology Data Exchange (ETDEWEB)

    Suan Power; Stefan Grimberg; Miles Denham

    2003-06-16

    The remediation of DNAPLs in subsurface environments is often limited by the heterogeneous distribution of the organic fluid. The fraction of DNAPL that is in the high conductivity regions of the subsurface can often be recovered relatively easily, although DNAPL in lower conductivity regions is much more difficult to extract, either through direct pumping or remediation measures based on interface mass transfer. The distribution of DNAPL within the vadose zone is affected by a complex interplay of heterogeneities in the porous matrix and the interfacial properties defining the interactions among all fluid and solid phases. Decreasing the interfacial tension between a DNAPL and water in the vadose zone could change the spreading of the DNAPL, thereby increase the surface area for mass transfer and the effectiveness of soil vapor extraction remediation.

  16. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  17. Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Lemming, Gitte; Manoli, Gabriele

    is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion...... is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities...... experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected reactants (donor and bacteria) are assumed to spread in horizontal injection zones of various widths, depending on the development of bioactive...

  18. Enzymatic Transesterification of Ethyl Ferulate with Fish Oil and Reaction Optimization by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Zhiyong Yang

    2012-01-01

    Full Text Available The enzymatic transesterification of ethyl ferulate (EF with fish oil from cod liver was investigated with Novozym® 435 as catalyst under solvent-free conditions. The purpose of the study is to evaluate the synthesis system for the production of feruloyl fish oil in industry. The modified HPLC method was first set up to characterise the reaction products together with liquid chromatography electrospray time-of-flight mass spectrometry (HPLC-ESI-TOF-MS. The influence of the addition of glycerol to the system on the feruloyl acylglycerol profile was investigated in terms of transesterification performance. The bioconversion rate of EF can be significantly increased with the increased formation of feruloyl fish oil products when appropriate amount of glycerol is present in the reaction. Therefore, an equivalent molar amount of glycerol was added to EF for the practical optimization of the system. The mutual effects of temperature (40 to 70 °C, reaction time (1 to 5 days, enzyme load (2 to 20 % and molar ratio of fish oil and EF in the substrate (1 to 5 were thus studied with the assistance of response surface methodology (RSM for the purpose of maximizing the formation of feruloyl fish oil. The models were well fitted and verified. The optimized conditions were found to be: temperature 70 °C, enzyme load 4.3 %, substrate ratio 4.7, and reaction time 5 days. Under these conditions, the maximum conversion of EF reached 92.4 %, and the formation of feruloyl fish oil reached 80.4 %, but the formation of by-product was minimized to 11.4 % only.

  19. Forests tend to cool the land surface in the temperate zone: An analysis of the mechanisms controlling radiometric surface temperature change in managed temperate ecosystems

    Science.gov (United States)

    Stoy, P. C.; Katul, G. G.; Juang, J.; Siqueira, M. B.; Novick, K. A.; Essery, R.; Dore, S.; Kolb, T. E.; Montes-Helu, M. C.; Scott, R. L.

    2010-12-01

    Vegetation is an important control on the surface energy balance and thereby surface temperature. Boreal forests and arctic shrubs are thought to warm the land surface by absorbing more radiation than the vegetation they replace. The surface temperatures of tropical forests tend to be cooler than deforested landscapes due to enhanced evapotranspiration. The effects of reforestation on surface temperature change in the temperate zone is less-certain, but recent modeling efforts suggest forests have a global warming effect. We quantified the mechanisms driving radiometric surface changes following landcover changes using paired ecosystem case studies from the Ameriflux database with energy balance models of varying complexity. Results confirm previous findings that deciduous and coniferous forests in the southeastern U.S. are ca. 1 °C cooler than an adjacent field on an annual basis because aerodynamic/ecophysiological cooling of 2-3 °C outweighs an albedo-related warming of stand-replacing ponderosa pine fire was ca. 1 °C warmer than unburned stands because a 1.5 °C aerodynamic warming offset a slight surface cooling due to greater albedo and soil heat flux. An ecosystem dominated by mesquite shrub encroachment was nearly 2 °C warmer than a native grassland ecosystem as aerodynamic and albedo-related warming outweighed a small cooling effect due to changes in soil heat flux. The forested ecosystems in these case studies are documented to have higher carbon uptake than the non-forested systems. Results suggest that temperate forests tend to cool the land surface and suggest that previous model-based findings that forests warm the Earth’s surface globally should be reconsidered.Changes to radiometric surface temperature (K) following changes in vegetation using paired ecosystem case studies C4 grassland and shrub ecosystem surface temperatures were adjusted for differences in air temperature across sites.

  20. Surface elevation change and susceptibility of different mangrove zones to sea-level rise on Pacific high islands of Micronesia

    Science.gov (United States)

    Krauss, K.W.; Cahoon, D.R.; Allen, J.A.; Ewel, K.C.; Lynch, J.C.; Cormier, N.

    2010-01-01

    Mangroves on Pacific high islands offer a number of important ecosystem services to both natural ecological communities and human societies. High islands are subjected to constant erosion over geologic time, which establishes an important source of terrigeneous sediment for nearby marine communities. Many of these sediments are deposited in mangrove forests and offer mangroves a potentially important means for adjusting surface elevation with rising sea level. In this study, we investigated sedimentation and elevation dynamics of mangrove forests in three hydrogeomorphic settings on the islands of Kosrae and Pohnpei, Federated States of Micronesia (FSM). Surface accretion rates ranged from 2.9 to 20.8 mm y-1, and are high for naturally occurring mangroves. Although mangrove forests in Micronesian high islands appear to have a strong capacity to offset elevation losses by way of sedimentation, elevation change over 61/2 years ranged from -3.2 to 4.1 mm y-1, depending on the location. Mangrove surface elevation change also varied by hydrogeomorphic setting and river, and suggested differential, and not uniformly bleak, susceptibilities among Pacific high island mangroves to sea-level rise. Fringe, riverine, and interior settings registered elevation changes of -1.30, 0.46, and 1.56 mm y-1, respectively, with the greatest elevation deficit (-3.2 mm y-1) from a fringe zone on Pohnpei and the highest rate of elevation gain (4.1 mm y-1) from an interior zone on Kosrae. Relative to sea-level rise estimates for FSM (0.8-1.8 mm y-1) and assuming a consistent linear trend in these estimates, soil elevations in mangroves on Kosrae and Pohnpei are experiencing between an annual deficit of 4.95 mm and an annual surplus of 3.28 mm. Although natural disturbances are important in mediating elevation gain in some situations, constant allochthonous sediment deposition probably matters most on these Pacific high islands, and is especially helpful in certain hydrogeomorphic zones

  1. Heavy metal concentrations and distribution in surface soils of the Bassa Industrial Zone 1, Douala, Cameroon

    International Nuclear Information System (INIS)

    Asaah, Victor A.; Abimbola, Akinlolu F.; Suh, Cheo E.

    2006-01-01

    Partial extraction was carried out on 33 soil samples collected from the Bassa Industrial Zone 1, Douala, Cameroon. From the samples analyzed the following metal concentrations (range) were obtained (in ppm): Ag (0-1.3), As (0-64), Cd(0-7.3), Co(0-31), Cr(34-423), Cu(12-909), Mn(55-3282), Mo(0-81.6), Ni(9-284), Pb (0-3320), Sb (0-30), Sc (0.6-7.5), V (26-110), Zn (30-3782) and Fe (in wt%) (1.50-47.31). Results obtained reveal background and anomalous populations for most of the metals except Sc and V, which have only background populations. Multi-element geochemical anomalies occur within the vicinity of industries, waste dump sites, metal workshops and mechanical workshops. R-mode factor analysis reveals three element associations and two singular elements (As, Cd) accounting for 94% of the total data variance. The three associations are: Ag-Cu-Cr-Fe-Mn-Mo-Ni-Sb; Co-Cu-Pb-Sb-Zn and Sc-V. The geoaccumulation indices show that soils in the Bassa Industrial Zone are moderately to very highly pollute. These metal-laden soils constitute a major health risk to the local population and a cause for concern. This study successfully relates the concentration and distribution of toxic metals in the soils of Bassa Industrial Zone to urban effluents generated mainly from industrial activities. (author)

  2. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  3. Library of Antifouling Surfaces Derived From Natural Amino Acids by Click Reaction.

    Science.gov (United States)

    Xu, Chen; Hu, Xin; Wang, Jie; Zhang, Ye-Min; Liu, Xiao-Jiu; Xie, Bin-Bin; Yao, Chen; Li, Yi; Li, Xin-Song

    2015-08-12

    Biofouling is of great concern in numerous applications ranging from ophthalmological implants to catheters, and from bioseparation to biosensors. In this report, a general and facile strategy to combat surface fouling is developed by grafting of amino acids onto polymer substrates to form zwitterionic structure through amino groups induced epoxy ring opening click reaction. First of all, a library of poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) hydrogels with zwitterionic surfaces were prepared, resulting in the formation of pairs of carboxyl anions and protonated secondary amino cations. The analysis of attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the successful immobilization of amino acids on the hydrogel surfaces. After that, the contact angle and equilibrium water content of the modified hydrogels showed that the hydrogels exhibited improved hydrophilicity compared with the parent hydrogel. Furthermore, the protein deposition was evaluated by bicinchoninic acid assay using bovine serum albumin (BSA) and lysozyme as models. The results indicated that the performance of the hydrogels was determined by the nature of incorporated amino acid: the hydrogels incorporated with neutral amino acids had nonspecific antiadsorption capability to both BSA and lysozyme; the hydrogels incorporated with charged amino acids showed antiadsorption behaviors against protein with same charge and enhanced adsorption to the protein with opposite charge; the optimal antiadsorption performance was observed on the hydrogels incorporated with polar amino acids with a hydroxyl residual. The improvement of antiprotein fouling of the neutral amino acids grafted hydrogels can be ascribed to the formation of zwitterionic surfaces. Finally, a couple of soft contact lenses grafted with amino acids were fabricated having improved antifouling property and hydrophilicity. The result demonstrated the success of

  4. Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

    Science.gov (United States)

    Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

    2007-01-01

    A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

  5. Laser transformation hardening effect on hardening zone features and surface hardness of tool steel AISI D2

    Directory of Open Access Journals (Sweden)

    D. Lesyk

    2017-06-01

    Full Text Available The relationship of technological input regimes of the laser transformation hardening on change the hardening depth, hardening width, and hardening angle, as well as surface hardness of the tool steel AISI D2 using multifactor experiment with elements of the analysis of variance and regression equations was determined. The laser transformation hardening process implemented by controlling the heating temperature using Nd:YAG fiber laser with scanner, pyrometer and proportional-integral-differential controller. The linear and quadratic regression models are developed, as well as response surface to determine the effect of the heating temperature and feed rate of the treated surface on the energy density of the laser beam, hardening depths, hardening width, hardening angle, and surface hardness are designed. The main effect on the energy density of the laser beam has a velocity laser treatment, on the other hand, the main effect on the geometrical parameters of the laser hardened zone and surface hardness has temperature heating are shown. The optimum magnitudes of the heating temperature (1270 °C and feed rate of the treated surface (90 mm/min for laser transformation hardening of the tool steel AISI D2 using fiber laser with scanner were defined.

  6. Effect of the roughening transition on the vicinal surface in the step droplet zone

    Science.gov (United States)

    Akutsu, Noriko

    2017-06-01

    For vicinal surfaces around the (001) surface inclined towards the 〈 111 〉 direction, the influence of roughening transitions on the surface tension and on step droplets is studied numerically. The surface tension is calculated using a restricted solid-on-solid model with a point-contact type step-step attraction (p-RSOS model) on a square lattice. To ensure the reliability of the calculations, the density matrix renormalization group method is used. The growth rate of the vicinal surface near equilibrium is also calculated by the Monte Carlo method. It is found that the roughening transition changes the morphology around the (001) surface, and the roughening transition affects the size of locally merged steps (step droplets).

  7. Distribution of 210Pb activity concentrations in marine surface sediments within East Coast Peninsula Malaysia Exclusive Economic Zone (EEZ)

    International Nuclear Information System (INIS)

    Ahmad Sanadi Abu Bakar; Zaharudin Ahmad

    2010-01-01

    A sampling expedition into the East Coast Peninsula Malaysia Exclusive Economic Zone (EEZ) was carried in June 2008. Marine surface sediment samples were taken and the activity concentrations of 210 Pb have been determined. Its distribution was plotted and the findings show that the activity concentrations decline from north to south. On the other hand, the activity concentrations are increasing from west to east right to the edge of the EEZ. The highest activity concentrations were found to be near offshore oil platforms. The 210 Pb activity concentrations were found to be in the range of 18.3 - 123.1 Bq/ kg. (author)

  8. Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce3+ phosphor

    International Nuclear Information System (INIS)

    Kumar, Vinay; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.; Mishra, Varun

    2010-01-01

    The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce 3+ nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm 2 . XPS was used to study the chemical composition of the CaS:Ce 3+ nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO 4 layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO 4 layer on the surface.

  9. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  10. Final Report Theoretical Studies of Surface Reactions on Metals and Electronic Materials

    Energy Technology Data Exchange (ETDEWEB)

    Jerry L. Whitten

    2012-04-23

    This proposal describes the proposed renewal of a theoretical research program on the structure and reactivity of molecules adsorbed on transition metal surfaces. A new direction of the work extends investigations to interfaces between solid surfaces, adsorbates and aqueous solutions and includes fundamental work on photoinduced electron transport into chemisorbed species and into solution. The goal is to discover practical ways to reduce water to hydrogen and oxygen using radiation comparable to that available in the solar spectrum. The work relates to two broad subject areas: photocatalytic processes and production of hydrogen from water. The objective is to obtain high quality solutions of the electronic structure of adsorbate-metal-surface-solution systems so as to allow activation barriers to be calculated and reaction mechanisms to be determined. An ab initio embedding formalism provides a route to the required accuracy. New theoretical methods developed during the previous grant period will be implemented in order to solve the large systems involved in this work. Included is the formulation of a correlation operator that is used to treat localized electron distributions such as ionic or regionally localized distributions. The correlation operator which is expressed as a two-particle projector is used in conjunction with configuration interaction.

  11. Reactions and Surface Transformations of a Bone-Bioactive Material in a Simulated Microgravity Environment

    Science.gov (United States)

    Radin, S.; Ducheyne, P.; Ayyaswamy, P. S.

    1999-01-01

    A comprehensive program to investigate the expeditious in vitro formation of three-dimensional bone-like tissue is currently underway at the University of Pennsylvania. The study reported here forms a part of that program. Three-dimensional bone-like tissue structures may be grown under the simulated microgravity conditions of NASA designed Rotating Wall Bioreactor Vessels (RWV's). Such tissue growth will have wide clinical applications. In addition, an understanding of the fundamental changes that occur to bone cells under simulated microgravity would yield important information that will help in preventing or minimizing astronaut bone loss, a major health issue with travel or stay in space over long periods of time. The growth of three-dimensional bone-like tissue structures in RWV's is facilitated by the use of microcarriers which provide structural support. If the microcarrier material additionally promotes bone cell growth, then it is particularly advantageous to employ such microcarriers. We have found that reactive, bone-bioactive glass (BBG) is an attractive candidate for use as microcarrier material. Specifically, it has been found that BBG containing Ca- and P- oxides upregulates osteoprogenitor cells to osteoblasts. This effect on cells is preceded by BBG reactions in solution which result in the formation of a Ca-P surface layer. This surface further transforms to a bone-like mineral (i.e., carbonated crystalline hydroxyapatite (c-HA)). At normal gravity, time-dependent, immersion-induced BBG reactions and transformations are greatly affected both by variations in the composition of the milieu in which the glass is immersed and on the immersion conditions. However, the nature of BBG reactions and phase transformations under the simulated microgravity conditions of RWV's are unknown, and must be understood in order to successfully use BBG as microcarrier material in RWV'S. In this paper, we report some of our recent findings in this regard using

  12. Surface-induced dissociation and chemical reactions of C2D4(+) on stainless steel, carbon (HOPG), and two different diamond surfaces.

    Science.gov (United States)

    Feketeová, Linda; Zabka, Jan; Zappa, Fabio; Grill, Verena; Scheier, Paul; Märk, Tilmann D; Herman, Zdenek

    2009-06-01

    Surface-induced interactions of the projectile ion C(2)D(4)(+) with room-temperature (hydrocarbon covered) stainless steel, carbon highly oriented pyrolytic graphite (HOPG), and two different types of diamond surfaces (O-terminated and H-terminated) were investigated over the range of incident energies from a few eV up to 50 eV. The relative abundance of the product ions in dependence on the incident energy of the projectile ion [collision-energy resolved mass spectra, (CERMS) curves] was determined. The product ion mass spectra contained ions resulting from direct dissociation of the projectile ions, from chemical reactions with the hydrocarbons on the surface, and (to a small extent) from sputtering of the surface material. Sputtering of the surface layer by low-energy Ar(+) ions (5-400 eV) indicated the presence of hydrocarbons on all studied surfaces. The CERMS curves of the product ions were analyzed to obtain both CERMS curves for the products of direct surface-induced dissociation of the projectile ion and CERMS curves of products of surface reactions. From the former, the fraction of energy converted in the surface collision into the internal excitation of the projectile ion was estimated as 10% of the incident energy. The internal energy of the surface-excited projectile ions was very similar for all studied surfaces. The H-terminated room-temperature diamond surface differed from the other surfaces only in the fraction of product ions formed in H-atom transfer surface reactions (45% of all product ions formed versus 70% on the other surfaces).

  13. Mapping porosity of the deep critical zone in 3D using near-surface geophysics, rock physics modeling, and drilling

    Science.gov (United States)

    Flinchum, B. A.; Holbrook, W. S.; Grana, D.; Parsekian, A.; Carr, B.; Jiao, J.

    2017-12-01

    Porosity is generated by chemical, physical and biological processes that work to transform bedrock into soil. The resulting porosity structure can provide specifics about these processes and can improve understanding groundwater storage in the deep critical zone. Near-surface geophysical methods, when combined with rock physics and drilling, can be a tool used to map porosity over large spatial scales. In this study, we estimate porosity in three-dimensions (3D) across a 58 Ha granite catchment. Observations focus on seismic refraction, downhole nuclear magnetic resonance logs, downhole sonic logs, and samples of core acquired by push coring. We use a novel petrophysical approach integrating two rock physics models, a porous medium for the saprolite and a differential effective medium for the fractured rock, that drive a Bayesian inversion to calculate porosity from seismic velocities. The inverted geophysical porosities are within about 0.05 m3/m3 of lab measured values. We extrapolate the porosity estimates below seismic refraction lines to a 3D volume using ordinary kriging to map the distribution of porosity in 3D up to depths of 80 m. This study provides a unique map of porosity on scale never-before-seen in critical zone science. Estimating porosity on these large spatial scales opens the door for improving and understanding the processes that shape the deep critical zone.

  14. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  15. Formation of porous surface layers in reaction bonded silicon nitride during processing

    Science.gov (United States)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

  16. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    Science.gov (United States)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  17. Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

    Science.gov (United States)

    Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

    2018-05-01

    Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

  18. Reaction of [3H]-taurine maleimide with platelet surface thiols

    International Nuclear Information System (INIS)

    Karl, D.W.; Mills, D.C.B.

    1986-01-01

    Taurine Maleimide (2-maleimidoethanesulfonate, TM) was synthesized from [2- 3 H]-taurine and methoxycarbonylmaleimide (MCM). The yield of a 1 μmol synthesis approached 100% (based on taurine) when MCM was used in 4-fold excess. The product (TM*) was purified by ion exchange chromatography. TM* reacted irreversibly with thiol groups on the surface of washed human platelets, leading to incorporation of radioactivity into platelet pellets. Incorporation was blocked by cysteine, mercuribenzenesulfonate (MBS), dithiobisnitrobenzoate, and N-ethylmaleimide, but not by taurine or by inhibitors of anion transport. Reaction of TM* with platelets showed the dependence on time and concentration characteristics of a bimolecular reaction. The number of reactive sites ranged from 1 to 5 x 10 5 /platelet, and the apparent rate constant from 1 to 3 x 10 3 /(M x min). TM was less effective than MBS as an inhibitor of platelet aggregation induced by several agents. TM had no effect on the uptake of serotonin, taurine, or phosphate by the platelets, processes which are sensitive to MBS. These differences, considered with the similarity in size and charge of TM and MBS, suggest that classes of thiols defined as exofacial by their accessibility to MBS can differ substantially in their reactivity with other impermeant reagents

  19. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    International Nuclear Information System (INIS)

    Shibata, T; Nishiyama, H

    2014-01-01

    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. (paper)

  20. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    Science.gov (United States)

    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.

  1. Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

    Science.gov (United States)

    He, Xin; Kim, Seong H

    2018-02-20

    Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

  2. Neural network approach to time-dependent dividing surfaces in classical reaction dynamics

    Science.gov (United States)

    Schraft, Philippe; Junginger, Andrej; Feldmaier, Matthias; Bardakcioglu, Robin; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

    2018-04-01

    In a dynamical system, the transition between reactants and products is typically mediated by an energy barrier whose properties determine the corresponding pathways and rates. The latter is the flux through a dividing surface (DS) between the two corresponding regions, and it is exact only if it is free of recrossings. For time-independent barriers, the DS can be attached to the top of the corresponding saddle point of the potential energy surface, and in time-dependent systems, the DS is a moving object. The precise determination of these direct reaction rates, e.g., using transition state theory, requires the actual construction of a DS for a given saddle geometry, which is in general a demanding methodical and computational task, especially in high-dimensional systems. In this paper, we demonstrate how such time-dependent, global, and recrossing-free DSs can be constructed using neural networks. In our approach, the neural network uses the bath coordinates and time as input, and it is trained in a way that its output provides the position of the DS along the reaction coordinate. An advantage of this procedure is that, once the neural network is trained, the complete information about the dynamical phase space separation is stored in the network's parameters, and a precise distinction between reactants and products can be made for all possible system configurations, all times, and with little computational effort. We demonstrate this general method for two- and three-dimensional systems and explain its straightforward extension to even more degrees of freedom.

  3. Effect of surface reaction layer on grindability of cast titanium alloys.

    Science.gov (United States)

    Ohkubo, Chikahiro; Hosoi, Toshio; Ford, J Phillip; Watanabe, Ikuya

    2006-03-01

    The purpose of this study was to investigate the effect of the cast surface reaction layer on the grindability of titanium alloys, including free-machining titanium alloy (DT2F), and to compare the results with the grindability of two dental casting alloys (gold and Co-Cr). All titanium specimens (pure Ti, Ti-6Al-4V and DT2F) were cast using a centrifugal casting machine in magnesia-based investment molds. Two specimen sizes were used to cast the titanium metals so that the larger castings would be the same size as the smaller gold and Co-Cr alloy specimens after removal of the surface reaction layer (alpha-case). Grindability was measured as volume loss ground from a specimen for 1 min using a handpiece engine with a SiC abrasive wheel at 0.1 kgf and four circumferential wheel speeds. For the titanium and gold alloys, grindability increased as the rotational speed increased. There was no statistical difference (p>0.05) in grindability for all titanium specimens either with or without the alpha-case. Of the titanium metals tested, Ti-6 Al-4V had the greatest grindability at higher speeds, followed by DT2F and CP Ti. The grindability of the gold alloy was similar to that of Ti-6 Al-4V, whereas the Co-Cr alloy had the lowest grindability. The results of this study indicated that the alpha-case did not significantly affect the grindability of the titanium alloys. The free-machining titanium alloy had improved grindability compared to CP Ti.

  4. Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

    Energy Technology Data Exchange (ETDEWEB)

    Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang [Univ. Da Coruna (Spain)

    2003-12-01

    The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

  5. Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

    International Nuclear Information System (INIS)

    Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang

    2003-12-01

    The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

  6. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

    Science.gov (United States)

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  7. Near-surface structure of the Carpathian Foredeep marginal zone in the Roztocze Hills area

    Science.gov (United States)

    Majdański, M.; Grzyb, J.; Owoc, B.; Krogulec, T.; Wysocka, A.

    2018-03-01

    Shallow seismic survey was made along 1280 m profile in the marginal zone of the Carpathian Foredeep. Measurements performed with standalone wireless stations and especially designed accelerated weight drop system resulted in high fold (up to 60), long offset seismic data. The acquisition has been designed to gather both high-resolution reflection and wide-angle refraction data at long offsets. Seismic processing has been realised separately in two paths with focus on the shallow and deep structures. Data processing for the shallow part combines the travel time tomography and the wide angle reflection imaging. This difficult analysis shows that a careful manual front mute combined with correct statics leads to detailed recognition of structures between 30 and 200 m. For those depths, we recognised several SW dipping tectonic displacements and a main fault zone that probably is the main fault limiting the Roztocze Hills area, and at the same time constitutes the border of the Carpathian Forebulge. The deep interpretation clearly shows a NE dipping evaporate layer at a depth of about 500-700 m. We also show limitations of our survey that leads to unclear recognition of the first 30 m, concluding with the need of joint interpretation with other geophysical methods.

  8. Chemical composition of aerosol in the atmospheric surface layer of the East Antarctica coastal zone

    Directory of Open Access Journals (Sweden)

    L. P. Golobokova

    2016-01-01

    Full Text Available Chemical composition of aerosol in the ground layer of the coastal zone in East Antarctica is analyzed in the article. The aerosol samples were taken in 2006–2015 during seasonal works of the Russian Antarctic Expeditions (RAE, namely, these were 52nd–53rd, 55th, and 58th–60th expeditions. Samples were taken in the 200‑km band of the sea-shore zone along routes of the research vessels (REV «Akademik Fedorov» and «Akademik Treshnikov» as well as on territories of the Russian stations Molodezhnaya and Mirny. Although the results obtained did show the wide range of the aerosol concentrations and a certain variability of their chemical composition, some common features of the variability were revealed. Thus, during the period from 2006 to 2014 a decrease of average values of the sums were noted. Spatially, a tendency of decreasing of the ion concentrations was found in the direction from the station Novolazarevskaya to the Molodezhnaya one, but the concentrations increased from the Molodezhnaya to the station Mirny. The sum of ions of the aerosol in the above mentioned coastal zone was, on the average, equal to 2.44 μg/m3, and it was larger than that on the territory of the Antarctic stations Molodezhnaya (0,29 μg/m3 and Mirny (0,50 ág / m3. The main part to the sum of the aerosol ions on the Antarctic stations was contributed by Na+, Ca2+, Cl−, SO4 2−. The main ions in aerosol composition in the coastal zone are ions Na+ and Cl−. The dominant contribution of the sea salt and SO4 2− can be traced in not only the composition of atmospheric aerosols, but also in the chemical composition of the fresh snow in the coastal areas of East Antarctica: at the Indian station Maitri, on the Larsemann Hills, and in a boring located in 55.3 km from the station Progress (K = 1.4÷6.1. It was noted that values of the coefficient of enrichment K of these ions decreases as someone moves from a shore to inland. Estimation of

  9. Zone separator for multiple zone vessels

    Science.gov (United States)

    Jones, John B.

    1983-02-01

    A solids-gas contact vessel, having two vertically disposed distinct reaction zones, includes a dynamic seal passing solids from an upper to a lower zone and maintaining a gas seal against the transfer of the separate treating gases from one zone to the other, and including a stream of sealing fluid at the seal.

  10. Radioactivity in the Exclusive Economic Zone of east coast Peninsular Malaysia. Distribution trends of 137Cs in surface seawater

    International Nuclear Information System (INIS)

    Zaharudin Ahmad; Zal U'yun Wan Mahmood; Hidayah Shahar; Mei Wo Yii; Ahmad Sanadi Abu Bakar

    2011-01-01

    Large volumes of surface seawater samples were collected from thirty locations in the Exclusive Economic Zone (EEZ) of the east coast Peninsular Malaysia on June 2008 to study the activity concentrations of 137 Cs. The results will serve as additional information to the existing baseline data and is very useful for monitoring fresh input of anthropogenic radionuclide into Malaysian marine environment. In this study, the activity concentrations of 137 Cs were determined using co-precipitation technique, followed by Gamma Spectrometry measurement. The mean activity concentration of 137 Cs ranged between 3.40 and 5.89 Bq/m 3 . Higher activity concentrations were observed at the coastal and towards the south of Peninsular Malaysia and were aligned with the high turbidity. These may due to the rapid diffusion of 137 Cs from suspended particulates and fine sediments into surface seawater. The activity concentrations of 137 Cs observed in this study were slightly higher than the concentrations reported in seawater at the Straits of Malacca, Vietnam and Philippines. This might be because the study area received more input of 137 Cs that originated from global fallout and then deposited on land which later being transported subsequently into the coastal zone due to siltation and erosion processes. It could also be attributed to the intrusion of river waters containing higher concentrations of 137 Cs. (author)

  11. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  12. Influence of inhomogeneous surface heat capacity on the estimation of radiative response coefficients in a two-zone energy balance model

    Science.gov (United States)

    Park, Jungmin; Choi, Yong-Sang

    2018-04-01

    Observationally constrained values of the global radiative response coefficient are pivotal to assess the reliability of modeled climate feedbacks. A widely used approach is to measure transient global radiative imbalance related to surface temperature changes. However, in this approach, a potential error in the estimate of radiative response coefficients may arise from surface inhomogeneity in the climate system. We examined this issue theoretically using a simple two-zone energy balance model. Here, we dealt with the potential error by subtracting the prescribed radiative response coefficient from those calculated within the two-zone framework. Each zone was characterized by the different magnitude of the radiative response coefficient and the surface heat capacity, and the dynamical heat transport in the atmosphere between the zones was parameterized as a linear function of the temperature difference between the zones. Then, the model system was forced by randomly generated monthly varying forcing mimicking time-varying forcing like an observation. The repeated simulations showed that inhomogeneous surface heat capacity causes considerable miscalculation (down to -1.4 W m-2 K-1 equivalent to 31.3% of the prescribed value) in the global radiative response coefficient. Also, the dynamical heat transport reduced this miscalculation driven by inhomogeneity of surface heat capacity. Therefore, the estimation of radiative response coefficients using the surface temperature-radiation relation is appropriate for homogeneous surface areas least affected by the exterior.

  13. Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

    Science.gov (United States)

    Lynch, Gillian C.; Halvick, Philippe; Zhao, Meishan; Truhlar, Donald G.; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.

    1991-01-01

    Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

  14. A theoretical study on the use of microwaves in reducing energy consumption for an endothermic reaction: Role of metal coated bounding surface

    International Nuclear Information System (INIS)

    Bhattacharya, Madhuchhanda; Basak, Tanmay

    2013-01-01

    This work presents a theoretical analysis on savings of energy during an endothermic reaction under microwave heating compared to conventional heating and shows the use of metal coated bounding surface to enhance the energy savings in otherwise low saving zones. Main thrust of this work is the quantification of energy savings for various probable microwave heating scenarios that may arise either due to varying reactor dimension (2L) over thin, intermediate and thick regimes or due to varying dielectric properties of the reactor. The analysis considers detailed transport equations in conjunction with Helmholtz equation for microwave propagation within a semiinfinite batch reactor. Simulations show that use of microwave can significantly save energy (as high as 60%) depending on reactor configuration. Simulations also show efficient use of metal coated bounding surface to enhance energy savings for reactors with 2L/λ eff = 0.5n−0.25, where n = 1, 2, 3… and λ eff is wavelength of microwave within the reactor. The enhancement is found to be 2 and 1.5 times at 2L/λ eff = 0.25 and 0.75, respectively. Various regions of efficient use of metal coated bounding surface for different microwave heating scenarios have been identified in a series of master curves. - Highlights: • This work simulates chemical reaction under microwave radiation using detailed model. • Simulations are presented in presence or absence of metal coated bounding surface. • Savings of energy under microwave have been analyzed for various probable scenarios. • Simulations show significant savings of energy under microwave heating. • Simulations show the potential of metal coated bounding surface to further enhance energy savings

  15. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

    Science.gov (United States)

    Arenillas, Ana; Rubiera, Fernando; Pis, José J

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

  16. Surface-enhanced Raman scattering active gold nanostructure fabricated by photochemical reaction of synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Akinobu, E-mail: yamaguti@lasti.u-hyogo.ac.jp [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Matsumoto, Takeshi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Okada, Ikuo; Sakurai, Ikuya [Synchrotoron Radiation Research Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Utsumi, Yuichi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan)

    2015-06-15

    The deposition of gold nanoparticles in an electroplating solution containing gold (I) trisodium disulphite under synchrotron X-ray radiation was investigated. The nanoparticles grew and aggregated into clusters with increasing radiation time. This behavior is explained by evaluating the effect of Derjaguin-Landau-Verweyand-Overbeek (DLVO) interactions combining repulsive electrostatic and attractive van der Waals forces on the particle deposition process. The surface-enhanced Raman scattering (SERS) of 4,4′ -bipyridine (4bpy) in aqueous solution was measured using gold nanoparticles immobilized on silicon substrates under systematically-varied X-ray exposure. The substrates provided an in situ SERS spectrum for 1 nM 4bpy. This demonstration creates new opportunities for chemical and environmental analyses through simple SERS measurements. - Highlights: • Gold nanoparticles were produced by photochemical reaction of synchrotron radiation. • The gold nanoparticles grew and aggregated into the higher-order nanostructure. • The behavior is qualitatively explained by analytical estimation. • The surface-enhanced Raman spectroscopy of 4,4′-bipyridine (4bpy) was demonstrated. • The substrate fabricated in a suitable condition provides in situ SERS for 1 nM 4bpy.

  17. Surface modification of highly oriented pyrolytic graphite by reaction with atomic nitrogen at high temperatures

    International Nuclear Information System (INIS)

    Zhang Luning; Pejakovic, Dusan A.; Geng Baisong; Marschall, Jochen

    2011-01-01

    Dry etching of {0 0 0 1} basal planes of highly oriented pyrolytic graphite (HOPG) using active nitridation by nitrogen atoms was investigated at low pressures and high temperatures. The etching process produces channels at grain boundaries and pits whose shapes depend on the reaction temperature. For temperatures below 600 deg. C, the majority of pits are nearly circular, with a small fraction of hexagonal pits with rounded edges. For temperatures above 600 deg. C, the pits are almost exclusively hexagonal with straight edges. The Raman spectra of samples etched at 1000 deg. C show the D mode near 1360 cm -1 , which is absent in pristine HOPG. For deep hexagonal pits that penetrate many graphene layers, neither the surface number density of pits nor the width of pit size distribution changes substantially with the nitridation time, suggesting that these pits are initiated at a fixed number of extended defects intersecting {0 0 0 1} planes. Shallow pits that penetrate 1-2 graphene layers have a wide size distribution, which suggests that these pits are initiated on pristine graphene surfaces from lattice vacancies continually formed by N atoms. A similar wide size distribution of shallow hexagonal pits is observed in an n-layer graphene sample after N-atom etching.

  18. Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time.

    Science.gov (United States)

    Thompson, Katherine C; Rennie, Adrian R; King, Martin D; Hardman, Samantha J O; Lucas, Claire O M; Pfrang, Christian; Hughes, Brian R; Hughes, Arwel V

    2010-11-16

    The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

  19. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Evora, M.C., E-mail: cecilia@ieav.cta.br [Institute for Advanced Studies-IEAV/DCTA, Av. Cel Jose Alberto Albano do Amarante, 1-Putim, 12228-001 São Jose dos Campos, SP (Brazil); Araujo, J.R., E-mail: jraraujo@inmetro.gov.br [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Ferreira, E.H.M. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Strohmeier, B.R. [Thermo Fisher Scientific, 5225 Verona Road, Madison, WI 53711 (United States); Silva, L.G.A., E-mail: lgasilva@ipen.br [Institute for Nuclear and Energy Research- IPEN, Av. Prof lineu Prestes, 2242- Cidade Universitaria, 05508-000 SP (Brazil); Achete, C.A. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil)

    2015-04-30

    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp{sup 2} structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO{sub 4}·7H{sub 2}O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful.

  20. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    International Nuclear Information System (INIS)

    Evora, M.C.; Araujo, J.R.; Ferreira, E.H.M.; Strohmeier, B.R.; Silva, L.G.A.; Achete, C.A.

    2015-01-01

    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp 2 structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO 4 ·7H 2 O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful

  1. In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

    International Nuclear Information System (INIS)

    Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

    2012-01-01

    Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

  2. Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

    Science.gov (United States)

    Banks, Simon T; Clary, David C

    2009-01-14

    We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

  3. Denitrifiers in the surface zone are primarily responsible for the nitrous oxide emission of dairy manure compost

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, Koki, E-mail: k_maeda@affrc.go.jp [Dairy Research Division, National Agricultural Research Center for Hokkaido Region, National Agricultural and Food Research Organization, 1 Hitsujigaoka, Sapporo 062-8555 (Japan); Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Toyoda, Sakae [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Hanajima, Dai [Dairy Research Division, National Agricultural Research Center for Hokkaido Region, National Agricultural and Food Research Organization, 1 Hitsujigaoka, Sapporo 062-8555 (Japan); Yoshida, Naohiro [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2013-03-15

    Highlights: ► Nitrous oxide (N{sub 2}O) productions of each compost zones were compared. ► The pile surface emitted significant fluxes of N{sub 2}O. ► The isotopic signature of N{sub 2}O from surface and NO{sub 2}{sup −} amended core were different. ► The denitrifying gene abundance was significantly higher in pile surface than the pile core. -- Abstract: During the dairy manure composting process, significant nitrous oxide (N{sub 2}O) emissions occur just after the pile turnings. To understand the characteristics of this N{sub 2}O emission, samples were taken from the compost surface and core independently, and the N{sub 2}O production was monitored in laboratory incubation experiments. Equal amounts of surface and core samples were mixed to simulate the turning, and the {sup 15}N isotope ratios within the molecules of produced N{sub 2}O were analyzed by isotopomer analysis. The results showed that the surface samples emitted significant levels of N{sub 2}O, and these emissions were correlated with NO{sub x}{sup −}-N accumulation. Moreover, the surface samples and surface-core mixed samples incubated at 30 °C produced N{sub 2}O with a low site preference (SP) value (−0.9 to 7.0‰) that was close to bacteria denitrification (0‰), indicating that denitrifiers in the surface samples are responsible for this N{sub 2}O production. On the other hand, N{sub 2}O produced by NO{sub 2}{sup −}-amended core samples and surface samples incubated at 60 °C showed unrecognized isotopic signatures (SP = 11.4–20.3‰). From these results, it was revealed that the N{sub 2}O production occurring just after the turnings was mainly derived from bacterial denitrification (including nitrifier denitrification) of NO{sub x}{sup −}-N under mesophilic conditions, and surface denitrifying bacteria appeared to be the main contributor to this process.

  4. Proton magnetic spectroscopy agreed better with magnetic resonance image to lateralization of epileptogenic zone than with surface electroencephalography

    Directory of Open Access Journals (Sweden)

    Ricardo Andre Amorim Leite

    2013-09-01

    Full Text Available Objective To analyze the agreement rate of proton magnetic spectroscopy with magnetic resonance image (MRI and surface electroence-phalography (EEG in extratemporal neocortical epilepsies. Methods A cross-sectional study, type series of cases included 33 patients, age range 13–59 years old, of both gender, presenting structural alteration identified by MRI (75.8% or by neurophysiologic techniques (72.7%. The variables were alterations of N-acetyl-aspartate/choline, N-acetyl-aspartate/creatine, choline/creatine, and N-acetyl-aspartate/cho-line+creatine coefficient of asymmetry. Results Agreement rates of lateralization by coefficient of asymmetry of NAA/Cho, NAA/Cr, Co/Cr, and NAA/Cho+Cr with MRI, independent of alteration of surface EEG, were equal to 93.3, 57.9, 15.4, and 93.3%, respectively, modifying to 100, 33.3, 0, and 100%, in 16 patients, with lateralization agreement of MRI and surface EEG. Conclusion Proton magnetic spectroscopy agreed better with MRI to lateralization of epileptogenic zone than with surface EEG.

  5. Surface displacements and energy release rates for constant stress drop slip zones in joined elastic quarter spaces

    Science.gov (United States)

    Rodgers, Michael J.; Wen, Shengmin; Keer, Leon M.

    2000-08-01

    A three-dimensional quasi-static model of faulting in an elastic half-space with a horizontal change of material properties (i.e., joined elastic quarter spaces) is considered. A boundary element method is used with a stress drop slip zone approach so that the fault surface relative displacements as well as the free surface displacements are approximated in elements over their respective domains. Stress intensity factors and free surface displacements are calculated for a variety of cases to show the phenomenological behavior of faulting in such a medium. These calculations showed that the behavior could be distinguished from a uniform half-space. Slip in a stiffer material increases, while slip in a softer material decreases the energy release rate and the free surface displacements. Also, the 1989 Kalapana earthquake was located on the basis of a series of forward searches using this method and leveling data. The located depth is 8 km, which is the closer to the seismically inferred depth than that determined from other models. Finally, the energy release rate, which can be used as a fracture criterion for fracture at this depth, is calculated to be 11.1×106 J m-2.

  6. Near Surface Geophysical Investigations of Potential Direct Recharge Zones in the Biscayne Aquifer within Everglades National Park, Florida.

    Science.gov (United States)

    Mount, G.; Comas, X.

    2017-12-01

    The karstic Miami Limestone of the Biscayne aquifer is characterized as having water flow that is controlled by the presence of dissolution enhanced porosity and mega-porous features. The dissolution features and other high porosity areas create horizontal preferential flow paths and high rates of ground water velocity, which may not be accurately conceptualized in groundwater flow models. In addition, recent research suggests the presence of numerous vertical dissolution features across Everglades National Park at Long Pine Key Trail, that may act as areas of direct recharge to the aquifer. These vertical features have been identified through ground penetrating radar (GPR) surveys as areas of velocity pull-down which have been modeled to have porosity values higher than the surrounding Miami Limestone. As climate change may induce larger and longer temporal variability between wet and dry times in the Everglades, a more comprehensive understanding of preferential flow pathways from the surface to the aquifer would be a great benefit to modelers and planners. This research utilizes near surface geophysical techniques, such as GPR, to identify these vertical dissolution features and then estimate the spatial variability of porosity using petrophysical models. GPR transects that were collected for several kilometers along the Long Pine Key Trail, show numerous pull down areas that correspond to dissolution enhanced porosity zones within the Miami Limestone. Additional 3D GPR surveys have attempted to delineate the boundaries of these features to elucidate their geometry for future modelling studies. We demonstrate the ability of near surface geophysics and petrophysical models to identify dissolution enhanced porosity in shallow karstic limestones to better understand areas that may act as zones of direct recharge into the Biscayne Aquifer.

  7. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  8. Applications of computer simulation, nuclear reactions and elastic scattering to surface analysis of materials

    Directory of Open Access Journals (Sweden)

    Pacheco de Carvalho, J. A.

    2008-08-01

    Full Text Available This article involves computer simulation and surface analysis by nuclear techniques, which are non-destructive. Both the “energy method of analysis” for nuclear reactions and elastic scattering are used. Energy spectra are computer simulated and compared with experimental data, giving target composition and concentration profile information. The method is successfully applied to thick flat targets of graphite, quartz and sapphire and targets containing thin films of aluminium oxide. Depth profiles of 12C and 16O nuclei are determined using (d,p and (d,α deuteron induced reactions. Rutherford and resonance elastic scattering of (4He+ ions are also used.

    Este artículo trata de simulación por ordenador y del análisis de superficies mediante técnicas nucleares, que son no destructivas. Se usa el “método de análisis en energia” para reacciones nucleares, así como el de difusión elástica. Se simulan en ordenador espectros en energía que se comparan com datos experimentales, de lo que resulta la obención de información sobre la composición y los perfiles de concentración de la muestra. Este método se aplica con éxito em muestras espesas y planas de grafito, cuarzo y zafiro y muestras conteniendo películas finas de óxido de aluminio. Se calculan perfiles en profundidad de núcleos de 12C y de 16O a través de reacciones (d,p y (d,α inducidas por deuterones. Se utiliza también la difusión elástica de iones (4He+, tanto a Rutherford como resonante.

  9. Rate of Isotope Exchange Reaction Between Tritiated Water in a Gas Phase and Water on the Surface of Piping Materials

    International Nuclear Information System (INIS)

    Nakashio, Nobuyuki; Yamaguchi, Junya; Kobayashi, Ryusuke; Nishikawa, Masabumi

    2001-01-01

    The system effect of tritium arises from the interaction of tritium in the gas phase with water on the surface of piping materials. It has been reported that the system effect can be quantified by applying the serial reactor model to the piping system and that adsorption and isotope exchange reactions play the main roles in the trapping of tritium. The isotope exchange reaction that occurs when the chemical form of tritium in the gas phase is in the molecular form, i.e., HT or T 2 , has been named isotope exchange reaction 1, and that which occurs when tritium in the gas phase is in water form, i.e., HTO or T 2 O, has been named isotope exchange reaction 2.The rate of isotope exchange reaction 2 is experimentally quantified, and the rate is observed to be about one-third of the rate of adsorption. The trapping and release behavior of tritium from the piping surface due to isotope exchange reaction 2 is also discussed. It is certified that swamping of water vapor to process gas is effective to release tritium from the surface contaminated with tritium

  10. Soil-gas helium and surface-waves detection of fault zones in ...

    Indian Academy of Sciences (India)

    a thin regolith. Based on satellite imagery and geologic mapping, three sites were selected for ... were also obtained using the multichannel analysis of surface waves. The study ... Fracture and fault networks form an important ... for a small-scale watershed development in a ... ing plain regions, where they may exist beneath.

  11. Defining and measuring the mean residence time of lateral surface transient storage zones in small streams

    Science.gov (United States)

    T.R. Jackson; R. Haggerty; S.V. Apte; A. Coleman; K.J. Drost

    2012-01-01

    Surface transient storage (STS) has functional significance in stream ecosystems because it increases solute interaction with sediments. After volume, mean residence time is the most important metric of STS, but it is unclear how this can be measured accurately or related to other timescales and field-measureable parameters. We studied mean residence time of lateral...

  12. WEAR OF THE FRICTION SURFACES PARTS IN THE PRESENSE OF SOLID PARTICLES CONTACTING ZONE

    Directory of Open Access Journals (Sweden)

    B. M. Musaibov

    2015-01-01

    Full Text Available The problems of intensity of wear of details of the cars working in the oil polluted by abrasive particles, depending on mechanical properties of material of details and abrasive particles, their sizes, a form and concentration, loading, temperature of a surface of friction, speed of sliding, quality of lubricant are considered. 

  13. Air, surfaces and copper halos, interstitial microbial zones. Has it been measured; can it be predicted?

    CSIR Research Space (South Africa)

    Nice, Jaco A

    2014-07-01

    Full Text Available microbial modelling, inhibition of microbial contamination and microbial ‘fall out’. However the literature implicitly addresses mechanism of inhibition by ionisation and contact, methods for model development and for airborne and surface microbial ‘fall out...

  14. The influence of the fault zone width on land surface vibrations after the high-energy tremor in the "Rydułtowy-Anna" hard coal mine

    Science.gov (United States)

    Pilecka, Elżbieta; Szwarkowski, Dariusz

    2018-04-01

    In the article, a numerical analysis of the impact of the width of the fault zone on land surface tremors on the area of the "Rydułtowy - Anna" hard coal mine was performed. The analysis covered the dynamic impact of the actual seismic wave after the high-energy tremor of 7 June 2013. Vibrations on the land surface are a measure of the mining damage risk. It is particularly the horizontal components of land vibrations that are dangerous to buildings which is reflected in the Mining Scales of Intensity (GSI) of vibrations. The run of a seismic wave in the rock mass from the hypocenter to the area's surface depends on the lithology of the area and the presence of fault zones. The rock mass network cut by faults of various widths influences the amplitude of tremor reaching the area's surface. The analysis of the impact of the width of the fault zone was done for three alternatives.

  15. Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

    Science.gov (United States)

    Rissmann, C.; Christenson, B.; Werner, C.; Leybourne, M.; Cole, J.; Gravley, D.

    2012-01-01

    Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20a of production (116MW e). Soil CO2 degassing was quantified with 2663 CO2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (Wm -2) using published soil temperature heat flow functions. Both CO2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20a of production, current CO2 emissions equated to 111??6.7T/d. Observed heat flow was 70??6.4MW, compared with a pre-production value of 122MW. This 52MW reduction in surface heat flow is due to production-induced drying up of all alkali-Cl outflows (61.5MW) and steam-heated pools (8.6MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali-Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18MW (from 25MW to 43.3??5MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20a of production, with an observed heat flow of 26.7??3MW and a CO 2 emission rate of 39??3T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali-Cl outflows once contributed significantly to the natural surface heat flow (~50%) they contributed little (99% of the original CO 2

  16. Surface wave tomography across the Sorgenfrei-Tornquist Zone, SW Scandinavia, using ambient noise and earthquake data

    Science.gov (United States)

    Köhler, Andreas; Maupin, Valérie; Balling, Niels

    2015-10-01

    We produce a S-wave velocity model of the crust and upper mantle around the Sorgenfrei-Tornquist Zone, southern Scandinavia, by analysing ambient seismic noise and earthquake recordings on temporary and permanent regional network stations. In a first step, we perform tomographical inversion of surface wave dispersion data from seismic noise to obtain Rayleigh and Love wave phase-velocity maps from 3 to about 30 s period. Local dispersion curves are then combined with regionally averaged surface wave velocities from earthquake data measured between 15 and about 100 s period. Dispersion curves are jointly inverted for a 3-D model of the S-wave velocity and radial velocity anisotropy by using a combined Monte Carlo and linearized inversion approach. Results reveal significant crustal as well as uppermost mantle velocity variations at all depth levels. Upper crustal structural variations are mainly controlled by the thick sedimentary Danish Basin with both low S-wave velocities and high anisotropy. Despite of the known limited capability of surface wave inversion to constrain interface depths and model parameter trade-offs, obtained Moho depths are in good agreement with previous studies in the region. Marked crustal thinning is clearly revealed beneath the Danish Basin with a narrow transition to the thicker crust in Swedish shield areas. Despite very different crustal and morphological structures, Denmark and southern Norway both have similar well-defined upper-mantle low-velocity zones, interpreted as asthenosphere, starting a depth of about 100 km. Compared with southern Sweden, showing high upper-mantle velocities, characteristic for shields, velocities are reduced by 0.30-0.40 km s-1 (6-8 per cent) at the depth levels of 140-200 km and radial anisotropy of 2-4 per cent is observed. Our study confirms the importance of the Sorgenfrei-Tornquist Zone, as a very deep structural boundary, separating old, thick, cratonic Baltica lithosphere in southern Sweden from

  17. Hoof accelerations and ground reaction forces of Thoroughbred racehorses measured on dirt, synthetic, and turf track surfaces.

    Science.gov (United States)

    Setterbo, Jacob J; Garcia, Tanya C; Campbell, Ian P; Reese, Jennifer L; Morgan, Jessica M; Kim, Sun Y; Hubbard, Mont; Stover, Susan M

    2009-10-01

    To compare hoof acceleration and ground reaction force (GRF) data among dirt, synthetic, and turf surfaces in Thoroughbred racehorses. 3 healthy Thoroughbred racehorses. Forelimb hoof accelerations and GRFs were measured with an accelerometer and a dynamometric horseshoe during trot and canter on dirt, synthetic, and turf track surfaces at a racecourse. Maxima, minima, temporal components, and a measure of vibration were extracted from the data. Acceleration and GRF variables were compared statistically among surfaces. The synthetic surface often had the lowest peak accelerations, mean vibration, and peak GRFs. Peak acceleration during hoof landing was significantly smaller for the synthetic surface (mean + or - SE, 28.5g + or - 2.9g) than for the turf surface (42.9g + or - 3.8g). Hoof vibrations during hoof landing for the synthetic surface were dirt and turf surfaces. Peak GRF for the synthetic surface (11.5 + or - 0.4 N/kg) was 83% and 71% of those for the dirt (13.8 + or - 0.3 N/kg) and turf surfaces (16.1 + or - 0.7 N/kg), respectively. The relatively low hoof accelerations, vibrations, and peak GRFs associated with the synthetic surface evaluated in the present study indicated that synthetic surfaces have potential for injury reduction in Thoroughbred racehorses. However, because of the unique material properties and different nature of individual dirt, synthetic, and turf racetrack surfaces, extending the results of this study to encompass all track surfaces should be done with caution.

  18. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  19. Surface analytical investigations of the thermal behaviour of passivated Zircaloy-4 surfaces and of the reaction behaviour of iodine with Zircaloy-4 surfaces

    International Nuclear Information System (INIS)

    Kaufmann, R.

    1988-07-01

    In the first part of the present work the thermal behaviour of atmospherically oxidized Zircaloy-4 samples was investigated at various temperatures. In a next step the amount of iodine adsorbed at the metallic surface was determined as well at room temperature with varying iodine exposures as for constant exposure but varying temperatures. Furthermore, the zirconium iodide species resulting from the interaction of iodine with the Zircaloy-4 and desorbed at higher temperatures were identified by means of residual gas analysis. During these studies it was found that the oxidic overlayer of the passivated Zircaloy-4 samples is decomposed at temperatures above 200 0 C. The iodine uptake at metallic surfaces (cleaned by Ar-ion sputtering) at room temperature slows markedly down after formation of a closed zirconium-iodide overlayer and consequently the further reaction proceeds diffusion-controlled. At 200 0 C ZrI 4 is formed being the thermodynamically most stable Zr-iodide. During desorption experiments using iodine exposed Zircaloy-4 samples the release of ZrI 4 was proved. The results obtained from the various experiments are finally discussed with respect to the iodine-induced stress corrosion cracking process and the underlying basic mechanisms and a transport mechanism for the SCC in nuclear fuel rods is proposed. (orig./RB) [de

  20. Local Effects of Ice Floes on Skin Sea Surface Temperature in the Marginal Ice Zone from UAVs

    Science.gov (United States)

    Zappa, C. J.; Brown, S.; Emery, W. J.; Adler, J.; Wick, G. A.; Steele, M.; Palo, S. E.; Walker, G.; Maslanik, J. A.

    2013-12-01

    Recent years have seen extreme changes in the Arctic. Particularly striking are changes within the Pacific sector of the Arctic Ocean, and especially in the seas north of the Alaskan coast. These areas have experienced record warming, reduced sea ice extent, and loss of ice in areas that had been ice-covered throughout human memory. Even the oldest and thickest ice types have failed to survive through the summer melt period in areas such as the Beaufort Sea and Canada Basin, and fundamental changes in ocean conditions such as earlier phytoplankton blooms may be underway. Marginal ice zones (MIZ), or areas where the "ice-albedo feedback" driven by solar warming is highest and ice melt is extensive, may provide insights into the extent of these changes. Airborne remote sensing, in particular InfraRed (IR), offers a unique opportunity to observe physical processes at sea-ice margins. It permits monitoring the ice extent and coverage, as well as the ice and ocean temperature variability. It can also be used for derivation of surface flow field allowing investigation of turbulence and mixing at the ice-ocean interface. Here, we present measurements of visible and IR imagery of melting ice floes in the marginal ice zone north of Oliktok Point AK in the Beaufort Sea made during the Marginal Ice Zone Ocean and Ice Observations and Processes EXperiment (MIZOPEX) in July-August 2013. The visible and IR imagery were taken from the unmanned airborne vehicle (UAV) ScanEagle. The visible imagery clearly defines the scale of the ice floes. The IR imagery show distinct cooling of the skin sea surface temperature (SST) as well as a intricate circulation and mixing pattern that depends on the surface current, wind speed, and near-surface vertical temperature/salinity structure. Individual ice floes develop turbulent wakes as they drift and cause transient mixing of an influx of colder surface (fresh) melt water. The upstream side of the ice floe shows the coldest skin SST, and

  1. Processing yttrium-barium-copper oxide superconductor zero gravity using a double float zone surface

    International Nuclear Information System (INIS)

    Pettit, D.R.; Peterson, D.E.; Kubat-Martin, K.A.; Petrovic, J.J.; Sheinberg, H.; Coulter, Y.; Day, D.E.

    1997-04-01

    The effects of processing YBa 2 Cu 3 O x (Y123) superconductor in the near-zero gravity (0g) environment provided by the NASA KC-135 airplane flying on parabolic trajectories were studied. A new sheet float zone furnace, designed for this study, enabled fast temperature ramps. Up to an 18-gram sample was processed with each parabola. Samples of Y123 were processed as bulk sheets, composites containing Ag and Pd, and films deposited on single crystal Si and MgO substrates. The 0g-processed samples were multi-phase yet retained a localized Y123 stoichiometry where a single ground-based (1g) oxygen anneal at temperatures of 800 C recovered nearly 100-volume percent superconducting Y123. The 1g processed control samples remained multi-phase after the same ground-based anneal with less than 45 volume percent as superconducting Y123. The superconducting transition temperature was 91 K for both 0g and 1g processed samples. A 29 wt.% Ag/Y123 composite had a transition temperature of 93 K. Melt texturing of bulk Y123 in 0g produced aligned grains about a factor of three larger than in analogous 1g samples. Transport critical current densities were at or below 18 A/cm 2 , due to the formation of cracks caused by the rapid heating rates required by the short time at 0g. Y123 deposited on single crystal Si and MgO in 0g was 30 vol.% y123 without an anneal. A weak superconducting transition at 80 K on MgO showed that substrate interactions occurred

  2. The application of white radiation to residual stress analysis in the intermediate zone between surface and volume

    CERN Document Server

    Genzel, C; Wallis, B; Reimers, W

    2001-01-01

    Mechanical surface processing is known to give rise to complex residual stress fields in the near surface region of polycrystalline materials. Consequently, their analysis by means of non-destructive X-ray and neutron diffraction methods has become an important topic in materials science. However, there remains a gap with respect to the accessible near surface zone, which concerns a range between about 10 mu m and 1 mm, where the conventional X-ray methods are no longer and the neutron methods are not yet sensitive. In order to achieve the necessary penetration depth tau to perform residual stress analysis (RSA) in this region, advantageous use can be made of energy dispersive X-ray diffraction of synchrotron radiation (15-60 keV) in the reflection mode. Besides an example concerning the adaptation of methods applied so far in the angle dispersive RSA to the energy dispersive case, the concept of a new materials science beamline at BESSY II for residual stress and texture analysis is presented.

  3. The application of white radiation to residual stress analysis in the intermediate zone between surface and volume

    International Nuclear Information System (INIS)

    Genzel, Ch.; Stock, C.; Wallis, B.; Reimers, W.

    2001-01-01

    Mechanical surface processing is known to give rise to complex residual stress fields in the near surface region of polycrystalline materials. Consequently, their analysis by means of non-destructive X-ray and neutron diffraction methods has become an important topic in materials science. However, there remains a gap with respect to the accessible near surface zone, which concerns a range between about 10 μm and 1 mm, where the conventional X-ray methods are no longer and the neutron methods are not yet sensitive. In order to achieve the necessary penetration depth τ to perform residual stress analysis (RSA) in this region, advantageous use can be made of energy dispersive X-ray diffraction of synchrotron radiation (15-60 keV) in the reflection mode. Besides an example concerning the adaptation of methods applied so far in the angle dispersive RSA to the energy dispersive case, the concept of a new materials science beamline at BESSY II for residual stress and texture analysis is presented

  4. Buried and Surface Polymetallic Nodule Distribution in the Eastern CLARION-CLIPPERTON Zone: Main Distinctions and Similarities

    Science.gov (United States)

    Kotlinski, R.; Stoyanova, V.

    The distribution pattern, abundance variations, morphology, chemical and mineralogical composition of buried polymetallic nodules in the eastern Clarion-Clipperton Zone (CCZ) are presented. Our observations are based on data collected from 59 boxcore stations, which comprise about 22.6% of all sampled stations in the Interoceanmetal exploration area site B2 in the eastern CCZ, with recorded buried and surface polymetallic nodules. The majority of stations with buried nodules (>90%) is below 4300 m water depth and is associated mainly with seafloor hills and slopes of ridges and depressions. Buried nodules lie completely beneath the active sediment-water boundary layer (with thickness range from 0 to 15 cm), and they are vertically recorded down to the 45 cm in sediment cores. Abundance of buried nodules varies from 0.2 to 22.1 kg/m2, averaging 3.2 kg/m2. By comparison, surface nodules are more abundant, varying from 0 to 20.2 kg/m2, averaging 10.3 kg/m2. As a general rule the size of buried nodules is larger than surface nodules, and >27% of recovered buried nodules exceed 10 cm in diameter. It is assumed that more than 90% of analyzed buried nodules have a diagenetic origin; however, the identification of factors and conditions responsible for their formation still remains unknown.

  5. Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

    Science.gov (United States)

    Chambon, J.; Lemming, G.; Manoli, G.; Broholm, M. M.; Bjerg, P.; Binning, P. J.

    2011-12-01

    Enhanced Reductive Dechlorination (ERD) has been successfully used in high permeability media, such as sand aquifers, and is considered to be a promising technology for low permeability settings. Pilot and full-scale applications of ERD at several sites in Denmark have shown that the main challenge is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion transport processes, and this affects the timeframes for the remediation. Due to the limited ERD applications and the complex transport and reactive processes occurring in low-permeability media, design guidelines are currently not available for ERD in such settings, and remediation performance assessments are limited. The objective of this study is to combine existing knowledge from several sites with numerical modeling to assess the effect of the injection interval, development of bioactive zones and reaction kinetics on the remediation efficiency for ERD in diffusion-dominated media. A numerical model is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities and hydraulic parameters, which are relevant for clay till sites in general. The numerical model couples flow and transport in the fracture network and low-permeability matrix. Sequential degradation of TCE to ethene is modeled using Monod kinetics, and the kinetic parameters are obtained from laboratory experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected

  6. Effects of a laser surface processing induced heat-affected zone on the fatigue behavior of AISI 4340 steel

    International Nuclear Information System (INIS)

    McDaniels, R.L.; White, S.A.; Liaw, K.; Chen, L.; McCay, M.H.; Liaw, P.K.

    2008-01-01

    The effects of the heat-affected zone (HAZ) in AISI 4340 steel created by laser-surface alloying (LSA) on high-cycle fatigue behavior have been investigated. This research was performed by producing several lots of laser-processed AISI 4340 steel using different laser processing parameters, and then subjecting the samples to high-cycle fatigue and Knoop microindentation hardness studies. Samples of tested material from each lot were examined using scanning-electron microscopy (SEM) in order to establish the effects of laser processing on the microstructure of the fatigue-tested AISI 4340 steel. When these three techniques, microindentation hardness testing, high-cycle fatigue testing, and SEM, are combined, a mechanistic understanding of the effect of the HAZ on the fatigue behavior of this alloy might be gained. It was found that the HAZ did not appear to have an adverse effect on the high-cycle fatigue behavior of LSA-processed AISI 4340 steel

  7. Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

    Science.gov (United States)

    Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

    2018-05-22

    Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

  8. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Science.gov (United States)

    Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

    Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

  9. Transforming growth factor β-induced superficial zone protein accumulation in the surface zone of articular cartilage is dependent on the cytoskeleton.

    Science.gov (United States)

    McNary, Sean M; Athanasiou, Kyriacos A; Reddi, A Hari

    2014-03-01

    The phenotype of articular chondrocytes is dependent on the cytoskeleton, specifically the actin microfilament architecture. Articular chondrocytes in monolayer culture undergo dedifferentiation and assume a fibroblastic phenotype. This process can be reversed by altering the actin cytoskeleton by treatment with cytochalasin. Whereas dedifferentiation has been studied on chondrocytes isolated from the whole cartilage, the effects of cytoskeletal alteration on specific zones of cells such as superficial zone chondrocytes are not known. Chondrocytes from the superficial zone secrete superficial zone protein (SZP), a lubricating proteoglycan that reduces the coefficient of friction of articular cartilage. A better understanding of this phenomenon may be useful in elucidating chondrocyte dedifferentiation in monolayer and accumulation of the cartilage lubricant SZP, with an eye toward tissue engineering functional articular cartilage. In this investigation, the effects of cytoskeletal modulation on the ability of superficial zone chondrocytes to secrete SZP were examined. Primary superficial zone chondrocytes were cultured in monolayer and treated with a combination of cytoskeleton modifying reagents and transforming growth factor β (TGFβ) 1, a critical regulator of SZP production. Whereas cytochalasin D maintains the articular chondrocyte phenotype, the hallmark of the superficial zone chondrocyte, SZP, was inhibited in the presence of TGFβ1. A decrease in TGFβ1-induced SZP accumulation was also observed when the microtubule cytoskeleton was modified using paclitaxel. These effects of actin and microtubule alteration were confirmed through the application of jasplakinolide and colchicine, respectively. As Rho GTPases regulate actin organization and microtubule polymerization, we hypothesized that the cytoskeleton is critical for TGFβ-induced SZP accumulation. TGFβ-mediated SZP accumulation was inhibited by small molecule inhibitors ML141 (Cdc42), NSC23766 (Rac1

  10. Structure of the 1906 near-surface rupture zone of the San Andreas Fault, San Francisco Peninsula segment, near Woodside, California

    Science.gov (United States)

    Rosa, C.M.; Catchings, R.D.; Rymer, M.J.; Grove, Karen; Goldman, M.R.

    2016-07-08

    High-resolution seismic-reflection and refraction images of the 1906 surface rupture zone of the San Andreas Fault near Woodside, California reveal evidence for one or more additional near-surface (within about 3 meters [m] depth) fault strands within about 25 m of the 1906 surface rupture. The 1906 surface rupture above the groundwater table (vadose zone) has been observed in paleoseismic trenches that coincide with our seismic profile and is seismically characterized by a discrete zone of low P-wave velocities (Vp), low S-wave velocities (Vs), high Vp/Vs ratios, and high Poisson’s ratios. A second near-surface fault strand, located about 17 m to the southwest of the 1906 surface rupture, is inferred by similar seismic anomalies. Between these two near-surface fault strands and below 5 m depth, we observed a near-vertical fault strand characterized by a zone of high Vp, low Vs, high Vp/Vs ratios, and high Poisson’s ratios on refraction tomography images and near-vertical diffractions on seismic-reflection images. This prominent subsurface zone of seismic anomalies is laterally offset from the 1906 surface rupture by about 8 m and likely represents the active main (long-term) strand of the San Andreas Fault at 5 to 10 m depth. Geometries of the near-surface and subsurface (about 5 to 10 m depth) fault zone suggest that the 1906 surface rupture dips southwestward to join the main strand of the San Andreas Fault at about 5 to 10 m below the surface. The 1906 surface rupture forms a prominent groundwater barrier in the upper 3 to 5 m, but our interpreted secondary near-surface fault strand to the southwest forms a weaker barrier, suggesting that there has been less or less-recent near-surface slip on that strand. At about 6 m depth, the main strand of the San Andreas Fault consists of water-saturated blue clay (collected from a hand-augered borehole), which is similar to deeply weathered serpentinite observed within the main strand of the San Andreas Fault at

  11. Final Report: Molecular Basis for Microbial Adhesion and Geochemical Surface Reactions: A Study Across Scales

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-06-27

    Computational chemistry was used to help provide a molecular level description of the interactions of Gram-negative microbial membranes with subsurface materials. The goal is to develop a better understanding of the molecular processes involved in microbial metal binding, microbial attachment to mineral surfaces, and, eventually, oxidation/reduction reactions (electron transfer) that can occur at these surfaces and are mediated by the bacterial exterior surface. The project focused on the interaction of the outer microbial membrane, which is dominated by an exterior lipopolysaccharide (LPS) portion, of Pseudomonas aeruginosa with the mineral goethite and with solvated ions in the environment. This was originally a collaborative project with T.P. Straatsma and B. Lowery of the Pacific Northwest National Laboratory. The University of Alabama effort used electronic structure calculations to predict the molecular behavior of ions in solution and the behavior of the sugars which form a critical part of the LPS. The interactions of the sugars with metal ions are expected to dominate much of the microscopic structure and transport phenomena in the LPS. This work, in combination with the molecular dynamics simulations of Straatsma and the experimental electrochemistry and microscopy measurements of Lowry, both at PNNL, is providing new insights into the detailed molecular behavior of these membranes in geochemical environments. The effort at The University of Alabama has three components: solvation energies and structures of ions in solution, prediction of the acidity of the critical groups in the sugars in the LPS, and binding of metal ions to the sugar anions. An important aspect of the structure of the LPS membrane as well as ion transport in the LPS is the ability of the sugar side groups such as the carboxylic acids and the phosphates to bind positively charged ions. We are studying the acidity of the acidic side groups in order to better understand the ability of

  12. Hydrocarbons in surface sediments from the Sfax coastal zone, (Tunisia) Mediterranean Sea.

    Science.gov (United States)

    Zaghden, Hatem; Kallel, Monem; Louati, Afifa; Elleuch, Boubaker; Oudot, Jean; Saliot, Alain

    2005-11-01

    The Semi-enclosed Mediterranean Sea records various signals of high anthropic pressures from surrounding countries and the industrialized European countries. This is particularly true for oil pollution. Although accounting for 1% of the world's ocean surface, it receives about 25% of the petroleum inputs to the ocean. To achieve a global budget we need to collect information from different parts of the Mediterranean. Particularly, we focus in this paper on the Southern Mediterranean, where data are presently very scarce. In this context, the University of Sfax has undertaken an estimation of hydrocarbon pollution along the coasts of Sfax and Gabès Gulf. Non-aromatic hydrocarbons were analysed in 8 surface sediments by FT/IR and GC/MS. Non-aromatic hydrocarbon concentrations vary in the range 310-1406 microg g(-1) sediments dry weight, which is high, compared to other Mediterranean sites. GC/MS data indicate a large group of unresolved compounds suggesting a petroleum contamination, confirmed by the identification of hopanes with predominant C29 and C30alpha,beta compounds and steranes with predominance of C27 over C28) and C29 compounds.

  13. Influences of Dam Operations in Groundwater-Surface Water Mixing Zones: Towards Multiscale Understanding

    Science.gov (United States)

    Stegen, J.; Scheibe, T. D.; Chen, X.; Huang, M.; Arntzen, E.; Garayburu-Caruso, V. A.; Graham, E.; Johnson, T. C.; Strickland, C. E.

    2017-12-01

    The installation and operation of dams have myriad influences on ecosystems, from direct effects on hydrographs to indirect effects on marine biogeochemistry and terrestrial food webs. With > 50000 existing and > 3700 planned large dams world-wide there is a pressing need for holistic understanding of dam impacts. Such understanding is likely to reveal unrecognized opportunities to modify dam operations towards beneficial outcomes. One of the most dramatic influences of daily dam operations is the creation of `artificial intertidal zones' that emerge from short-term increases and decreases in discharge due to hydroelectric power demands; known as hydropeaking. There is a long history of studying the influences of hydropeaking on macrofauna such as fish and invertebrates, but only recently has significant attention been paid to the hydrobiogeochemical effects of hydropeaking. Our aim here is to develop an integrated conceptual model of the hydrobiogeochemical influences of hydropeaking. To do so we reviewed available literature focusing on hydrologic and/or biogeochemical influences of hydropeaking. Results from these studies were collated into a single conceptual model that integrates key physical (e.g., sediment transport, hydromorphology) and biological (e.g., timescale of microbiome response) processes. This conceptual model highlights non-intuitive impacts of hydropeaking, the presence of critical thresholds, and strong interactions among processes. When examined individually these features suggest context dependency, but when viewed through an integrated conceptual model, common themes emerge. We will further discuss a critical next step, which is the local to regional to global evaluation of this conceptual model, to enable multiscale understanding. We specifically propose a global `hydropeaking network' of researchers using common methods, data standards, and analysis techniques to quantify the hydrobiogeochemical effects of hydropeaking across biomes. We

  14. Evolution of Diurnal Asymmetry of Surface Temperature over Different Climatic Zones

    Science.gov (United States)

    Rajendran, V.; C T, D.; Chakravorty, A.; AghaKouchak, A.

    2016-12-01

    that the DTR changes are influenced by both, local and global factors working in tandem, since a warmed up ocean produces contradictory DTR trends in different climatic zones. It can be inferred from this study that the impact of a global change in a region will depend on the regional climate.

  15. Prediction and characterization of heat-affected zone formation due to neighboring nickel-aluminum multilayer foil reaction

    Energy Technology Data Exchange (ETDEWEB)

    Adams, David P. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Hirschfeld, Deidre A. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Hooper, Ryan J. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Manuel, Michelle V. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. Much of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To enhance the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical model for the purpose of evaluating new foil-substrate combinations for screening and optimization. The model is experimentally validated using a commercially available Ni-Al multilayer foils and different alloys.

  16. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  17. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  18. Quantifying Organic Matter in Surface Waters of the United States and Delivery to the Coastal Zone

    Science.gov (United States)

    Boyer, E. W.; Alexander, R. B.; Smith, R. A.; Shih, J.

    2012-12-01

    Organic carbon (OC) is a critical water quality characteristic in surface waters. It is an important component of the energy balance and food chains in freshwater and estuarine aquatic ecosystems, is significant in the mobilization and transport of contaminants along flow paths, and is associated with the formation of known carcinogens in drinking water supplies. The importance of OC dynamics on water quality has been recognized, but challenges remain in quantitatively addressing processes controlling OC fluxes over broad spatial scales in a hydrological context, and considering upstream-downstream linkages along flow paths. Here, we: 1) quantified lateral OC fluxes in rivers, streams, and reservoirs across the nation from headwaters to the coasts; 2) partitioned how much organic carbon that is stored in lakes, rivers and streams comes from allochthonous sources (produced in the terrestrial landscape) versus autochthonous sources (produced in-stream by primary production); 3) estimated the delivery of dissolved and total forms of organic carbon to coastal estuaries and embayments; and 4) considered seasonal factors affecting the temporal variation in OC responses. To accomplish this, we developed national-scale models of organic carbon in U.S. surface waters using the spatially referenced regression on watersheds (SPARROW) technique. The modeling approach uses mechanistic formulations, imposes mass balance constraints, and provides a formal parameter estimation structure to statistically estimate sources and fate of OC in terrestrial and aquatic ecosystems. We calibrated and evaluated the model with statistical estimates of OC loads that were observed at a network of monitoring stations across the nation, and further explored factors controlling seasonal dynamics of OC based on these long term monitoring data. Our results illustrate spatial patterns and magnitudes OC loadings in rivers, highlighting hot spots and suggesting origins of the OC to each location

  19. Characterizing multiple sources and interaction in the critical zone through Sr-isotope tracing of surface and groundwater

    Science.gov (United States)

    Negrel, Philippe; Pauwels, Hélène

    2017-04-01

    The Critical Zone (CZ) is the lithosphere-atmosphere boundary where complex physical, chemical and biological processes occurs and control the transfer and storage of water and chemical elements. This is the place where life-sustaining resources are, where nutrients are being released from the rocks. Because it is the place where we are living, this is a fragile zone, a critical zone as a perturbed natural ecosystem. Water resources in hard-rocks commonly involve different hydrogeological compartments such as overlying sediments, weathered rock, the weathered-fissured zone, and fractured bedrock. Streams, lakes and wetlands that drain such environments can drain groundwater, recharge groundwater, or do both. Groundwater resources in many countries are increasingly threatened by growing demand, wasteful use, and contamination. Surface water and shallow groundwater are particularly vulnerable to pollution, while deeper resources are more protected from contamination. Here, we first report on Sr isotope data as well as major ions, from shallow and deep groundwater in several granite and schist areas over France with intensive agriculture covering large parts of these catchments. In three granite and Brioverian 'schist' areas of the Armorican Massif, the range in Sr contents in groundwater from different catchments agrees with previous work on groundwater sampled from granites in France. The Sr content is well correlated with Mg and both are partly related to agricultural practices and water rock interaction. The relationship between Sr- isotope and Mg/Sr ratios allow defining the different end-members, mainly rain, agricultural practice and water-rock interaction. The data from the Armorican Massif and other surface and groundwater for catchment draining silicate bedrocks (300-450Ma) like the Hérault, Seine, Moselle, Garonne, Morvan, Margeride, Cantal, Pyrénées and Vosges are scattered between at least three geochemical signatures. These include fertilizer and

  20. Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

    2014-01-01

    Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

  1. Bone reactions adjacent to titanium implants with different surface characteristics subjected to static load. A study in the dog (II)

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2001-01-01

    The purpose of the present study was to compare bone reactions adjacent to titanium implants with either a titanium plasma-sprayed (TPS) or a machined surface subjected to lateral static loading induced by an expansion force. In 3 labrador dogs, the 2nd, 3rd and 4th mandibular premolars were...

  2. Radionuclide transport from near-surface repository for radioactive waste - The unsaturated zone approach

    Energy Technology Data Exchange (ETDEWEB)

    Jakimaviciute-Maseliene, V. [Vilnius University (Lithuania); Mazeika, J. [Nature Research Centre (Lithuania); Motiejunas, S. [Radioactive Waste Management Agency (Lithuania)

    2014-07-01

    About 100 000 m{sup 3} of solid conditioned Low and Intermediate Level Waste (LILW), generated during operation and decommissioning of the Ignalina nuclear power plant (INPP), are to be disposed of in a near-surface repository (NSR) - a 'hill'-type repository with reinforced concrete vaults and with engineered and natural barriers. The northeastern Lithuania and the environment of the INPP in particular were recognized as the areas most suitable for a near-surface repository (Stabatiske Site). The engineered barriers of the repository consist of concrete cells surrounded by clay-based material of low permeability with about the same isolating capacity in all directions. The clay materials must be effectively compactable so that required hydraulic conductivity is reached. The Lithuanian Triassic clay turned out to be sufficiently rich in smectites and was proposed as main candidate for sealing of the repository. When the concrete vaults are filled, the repository cover will be constructed. The surface of the mound will be planted with grass. In this study a computer code FEFLOW 5.0 was applied for simulating the transport of the most mobile radionuclides ({sup 3}H, {sup 14}C, {sup 59}Ni and {sup 94}Nb) with moisture through an unsaturated vault of the near-surface repository in Stabatiske Site. The HYDRUS-1D analysis was used to assess the radionuclide transport in the repository and to estimate initial activity concentrations of radionuclides transported from the cemented waste matrix. Radionuclide release from the vault in the unsaturated conditions after closure of the repository and consequent contaminant plume transport has been assessed taking into account site-specific natural and engineering conditions and based on a normal evolution scenario. The highest peak radionuclide activity concentrations were estimated applying the FEFLOW code. The highest value of {sup 14}C activity concentration(about 1.3x10{sup 8} Bq/m{sup 3}) at the groundwater table

  3. Mixing and overshooting in surface convection zones of DA white dwarfs: first results from ANTARES

    Science.gov (United States)

    Kupka, F.; Zaussinger, F.; Montgomery, M. H.

    2018-03-01

    We present results of a large, high-resolution 3D hydrodynamical simulation of the surface layers of a DA white dwarf (WD) with Teff = 11 800 K and log (g) = 8 using the ANTARES code, the widest and deepest such simulation to date. Our simulations are in good agreement with previous calculations in the Schwarzschild-unstable region and in the overshooting region immediately beneath it. Farther below, in the wave-dominated region, we find that the rms horizontal velocities decay with depth more rapidly than the vertical ones. Since mixing requires both vertical and horizontal displacements, this could have consequences for the size of the region that is well mixed by convection, if this trend is found to hold for deeper layers. We discuss how the size of the mixed region affects the calculated settling times and inferred steady-state accretion rates for WDs with metals observed in their atmospheres.

  4. Coastal zone color scanner pigment concentrations in the southern ocean and relationships to geophysical surface features

    Science.gov (United States)

    Comiso, J. C.; Mcclain, C. R.; Sullivan, C. W.; Ryan, J. P.; Leonard, C. L.

    1993-01-01

    Climatological data on the distribution of surface pigment fields in the entire southern ocean over a seasonal cycle are examined. The occurrence of intense phytoplankton blooms during austral summer months and during other seasons in different regions is identified and analyzed. The highest pigment concentrations are observed at high latitudes and over regions with water depths usually less than 600 m. Basin-scale pigment distribution shows a slightly asymmetric pattern of enhanced pigment concentrations about Antarctica, with enhanced concentrations extending to lower latitudes in the Atlantic and Indian sectors than in the Pacific sector. A general increase in pigment concentrations is evident from the low latitudes toward the Antarctic circumpolar region. Spatial relationships between pigment and archived geophysical data reveal significant correlation between pigment distributions and both bathymetry and wind stress, while general hemispheric scale patterns of pigment distributions are most coherent with the geostrophic flow of the Antarctic Circumpolar Current.

  5. DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

    Science.gov (United States)

    Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

    2017-09-24

    We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

  6. Effects of Turbulent Reynolds Number on the Displacement Speed Statistics in the Thin Reaction Zones Regime of Turbulent Premixed Combustion

    Directory of Open Access Journals (Sweden)

    Nilanjan Chakraborty

    2011-01-01

    nature of the correlations remains unaffected. The dependence of displacement speed on strain rate and curvature is found to weaken with increasing turbulent Reynolds number when either Damköhler or Karlovitz number is held constant, but the qualitative nature of the correlation remains unaltered. The implications of turbulent Reynolds number effects in the context of Flame Surface Density (FSD modelling have also been addressed, with emphasis on the influence of displacement speed on the curvature and propagation terms in the FSD balance equation.

  7. Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Shengnan [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Liu, Xinhui, E-mail: xhliu@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Cheng, Dengmiao [Institute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing 100081 (China); Liu, Guannan [MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, CAGS, Beijing 100037 (China); Liang, Baocui; Cui, Baoshan; Bai, Junhong [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China)

    2016-11-01

    As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L{sup −} {sup 1} and 40.97–207.44 ng·g{sup −} {sup 1}, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using

  8. Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

    International Nuclear Information System (INIS)

    Zhao, Shengnan; Liu, Xinhui; Cheng, Dengmiao; Liu, Guannan; Liang, Baocui; Cui, Baoshan; Bai, Junhong

    2016-01-01

    As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L"− "1 and 40.97–207.44 ng·g"− "1, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using the physicochemical

  9. Physico-chemical state of mercury, cadmium, and zinc in surface waters of arid zone of the USSR

    International Nuclear Information System (INIS)

    Kulmatov, R.A.; Rakhmatov, U.; Kist, A.A.; Savenko, V.S.

    1983-01-01

    Experimental study was made on physico-chemical state of high-toxic heavy metals (Zn, Cd, and Hg) in waters of the Aral Sea and the Syr Darya and the Amu Darya rivers, representing the basic resrevoirs of surface waters of the Middle Asia. The complex of high-sensitive and selective radioanalytical techniques was developed for solution of the problem. The complex uncludes ultrafiltration, centrifugation, electrodialysis, sorption on sorbents of different nature, as well as neutron activation analysis. It was established that the major part of Hg, Cd and Zn can migrate in surface waters of the Middle Asia in the form of real and colloidal solutions. Zn and Cd are characterized by the prevalence of cationic really dissolved forms and Hg-anionic neutral and colloidal forms. The presence of the major mass of the given elements in the form of real and the finest colloids which are rather stable forms and can be transfered to long distances points to the promising character of applying hydrochemical methods of prospecting in arid zone of the USSR, because dispersion aureoles must be sufficiently wide. Possibility of formation of large aureoles of natural water contamination in the regions of mining and metallurgical enterprises must be considered as well

  10. The effect of ochre applied to buffer zones on soluble phosphorus retention during combined surface and subsurface flow conditions

    Science.gov (United States)

    Habibiandehkordi, R.; Quinton, J.; Surridge, B.

    2012-12-01

    Despite invention of a wide range of mitigating measures, diffuse phosphorus (P) pollution from agricultural lands still remains a major threat to the water resources. Thus, reducing P inputs along with improving the effectiveness of current best management practices (BMPs) is necessary to avoid eutrophication. Buffer zones are considered to be among the BMPs to control diffuse P pollution. However, these features are less effective in controlling soluble P loss with a retention range of -71 to +95% which is generally governed by the process of infiltration. Moreover, the soil in buffer strip system can be saturated over a course of time thereby enriching surface and subsurface runoff with soluble P. The aim of this study is to evaluate effectiveness of ochre applied to buffer strips in reducing the loss of soluble P during coupled surface and subsurface flow conditions. Batch experiments showed a maximum P retention capacity of 17.2 g kg-1 for ochre collected from a mine water treatment plant in Capehouse, UK without any risk of P desorption or releasing trace elements to the environment. The preliminarily results of flume experiments confirms the suitability of ochre to be used as a soil amendment in conjunction with buffer strips for tackling soluble P loss.

  11. Mass effect of redox reactions: A novel mode for surface plasmon resonance-based bioanalysis.

    Science.gov (United States)

    Yuan, Pei-Xin; Deng, Sheng-Yuan; Xin, Peng; Ji, Xu-Bo; Shan, Dan; Cosnier, Serge

    2015-12-15

    The pursuit of more specific and sensitive response is a perpetual goal for modern bioassays. This work proposed a novel label-free strategy about redox-related mass effect based on the surface plasmon resonance (SPR) technique for ultrasensitive determination of DNA. The protocol starts with the modification of SPR gilded disk with the capture DNA (cDNA). After the conjugation of immobilized cDNA with the target DNA (tDNA), the hybridization chain reaction was triggered by the introduction of mutual partial complementary primers to elongate the terminal into a nanoscale duplex. As it is reported that porphyrin could intercalate into the grooves of the double-stranded DNA (dsDNA) scaffold, multiple positive-charged Fe(III)meso-tetra(N-methyl-4-pyridyl) porphine (FeTMPyP) with symmetric structure were uptaken for in situ formation of porphyrin-dsDNA complex. Given FeTMPyP a highly efficient catalysis for the peroxide reduction, its presence as a biomimetic cofactor was validated via circular dichroism and UV-vis spectroscopy, demonstrating a tight binding as well as high catalytic activity and stability. Using 4-chloro-1-naphthol as a proton donor, the catalytic reduction of H2O2 would oxidize it into insoluble benzo-4-chloro-hexadienone, which simultaneously deposited on the heterogeneous interface, leading to a significant amplification in both SPR response and topological height profile. The signal increment was proportional to the concentration of tDNA, thus an ultrasensitive SPR-based DNA assay was developed with a linear range over four orders of magnitudes and a sub-femtomolar detection limit of 0.73 fM. The developed methodology exemplifies a different way of thinking about mass-sensing modes, extending conventional SPR-based DNA analysis to relevant biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

    Energy Technology Data Exchange (ETDEWEB)

    Tan Zuxian [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Yang Yifu [Department of Chemistry, Wuhan University, Wuhan 430072 (China)]. E-mail: yang-y-f1@vip.sina.com; Jiang Fengshan [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Shao Huixia [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2006-10-05

    A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I {sub tip}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I {sub sub}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected.

  13. Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Zuxian; Yang, Yifu; Jiang, Fengshan; Shao, Huixia [Wuhan University, Wuhan (China). Department of Chemistry

    2006-10-05

    A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I{sub tip}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I{sub sub}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected. (author)

  14. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method

    International Nuclear Information System (INIS)

    Chen, Jun; Sun, Zhigang; Zhang, Dong H.

    2015-01-01

    A three dimensional potential energy surface for the F + H 2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2) Q ] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H 2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface

  15. Critical Zone Co-dynamics: Quantifying Interactions between Subsurface, Land Surface, and Vegetation Properties Using UAV and Geophysical Approaches

    Science.gov (United States)

    Dafflon, B.; Leger, E.; Peterson, J.; Falco, N.; Wainwright, H. M.; Wu, Y.; Tran, A. P.; Brodie, E.; Williams, K. H.; Versteeg, R.; Hubbard, S. S.

    2017-12-01

    Improving understanding and modelling of terrestrial systems requires advances in measuring and quantifying interactions among subsurface, land surface and vegetation processes over relevant spatiotemporal scales. Such advances are important to quantify natural and managed ecosystem behaviors, as well as to predict how watershed systems respond to increasingly frequent hydrological perturbations, such as droughts, floods and early snowmelt. Our study focuses on the joint use of UAV-based multi-spectral aerial imaging, ground-based geophysical tomographic monitoring (incl., electrical and electromagnetic imaging) and point-scale sensing (soil moisture sensors and soil sampling) to quantify interactions between above and below ground compartments of the East River Watershed in the Upper Colorado River Basin. We evaluate linkages between physical properties (incl. soil composition, soil electrical conductivity, soil water content), metrics extracted from digital surface and terrain elevation models (incl., slope, wetness index) and vegetation properties (incl., greenness, plant type) in a 500 x 500 m hillslope-floodplain subsystem of the watershed. Data integration and analysis is supported by numerical approaches that simulate the control of soil and geomorphic characteristic on hydrological processes. Results provide an unprecedented window into critical zone interactions, revealing significant below- and above-ground co-dynamics. Baseline geophysical datasets provide lithological structure along the hillslope, which includes a surface soil horizon, underlain by a saprolite layer and the fractured Mancos shale. Time-lapse geophysical data show very different moisture dynamics in various compartments and locations during the winter and growing season. Integration with aerial imaging reveals a significant linkage between plant growth and the subsurface wetness, soil characteristics and the topographic gradient. The obtained information about the organization and

  16. Prevalence of pathogenic bacteria in surface and groundwater of urban and rural zones of El-Gaza generative, Egypt

    International Nuclear Information System (INIS)

    Abo-State, M.A.M.; El-Khatat, A.M.R.; El-Shahat, M.F.

    2005-01-01

    Thirty three water and soil samples, from the urban and rural zones of El-Giza, Egypt, were used to evaluate the microbiological quality of soil, surface and groundwater samples. Total aerobic bacterial count of groundwater ranged from 2 x10 4 to 1. 2 x 10 7 CFU/ml, which were B. cereus (1 x10 2 - 1 x10 4 CFU/ml), Enterobacteriacea (1 x 10 2 - 2 x 10 6 CFU/ml), E.Coli (0 - 9 x 10 4 CFU/ml), Pseudomonas (9 x 10 2 - 3 x 10 6 CFU/ml), total Staph. (0 - 5.6 x 10 3 CFU/ml) and Staph. aureus (0 - 5 x10 3 CFU/ml). Meanwhile, surface water contained total aerobic bacterial count in the range of 1 x 10 5 -9 x 10 6 CFU/ml, which where l x10 2 - 4 x 10 3 CFU/ml B. cereus, 3.9 x 10''3 -1.6 x 10 6 CFU/ml Enterobacteriacea, 1 x 10 2 - 2.9 x 10 4 CFU/ml Ent. faecalis, 5 x 10 2 - 1.1 x 10 5 CFU/ml E. coli, 4.9 x 10 4 - 1.1 x 10 4 CFU/ml Pseudomonas, 3 x 10 2 - 4 x 10 4 CFU/ml total Staph. and 1 x 10 -1 x 10 4 CFU/ml Staph. aureus. Salmonella was detected in almost all surface water samples except in one sample. No Ent. faecalis, total Staph. and Staph. aureus or Salmonella had been detected in soil samples except in one sample, which recorded 4 x10 3 CFU/ml Ent. faecalis. Inactivation of pathogenic bacteria by heat treatment revealed that heating of water for 5 minutes at 100 degree C (boiling) got rid completely of pathogens except the spore forming Bacilli which still persisted

  17. Soil Moisture Active Passive (SMAP) Mission Level 4 Surface and Root Zone Soil Moisture (L4_SM) Product Specification Document

    Science.gov (United States)

    Reichle, Rolf H.; Ardizzone, Joseph V.; Kim, Gi-Kong; Lucchesi, Robert A.; Smith, Edmond B.; Weiss, Barry H.

    2015-01-01

    This is the Product Specification Document (PSD) for Level 4 Surface and Root Zone Soil Moisture (L4_SM) data for the Science Data System (SDS) of the Soil Moisture Active Passive (SMAP) project. The L4_SM data product provides estimates of land surface conditions based on the assimilation of SMAP observations into a customized version of the NASA Goddard Earth Observing System, Version 5 (GEOS-5) land data assimilation system (LDAS). This document applies to any standard L4_SM data product generated by the SMAP Project. The Soil Moisture Active Passive (SMAP) mission will enhance the accuracy and the resolution of space-based measurements of terrestrial soil moisture and freeze-thaw state. SMAP data products will have a noteworthy impact on multiple relevant and current Earth Science endeavors. These include: Understanding of the processes that link the terrestrial water, the energy and the carbon cycles, Estimations of global water and energy fluxes over the land surfaces, Quantification of the net carbon flux in boreal landscapes Forecast skill of both weather and climate, Predictions and monitoring of natural disasters including floods, landslides and droughts, and Predictions of agricultural productivity. To provide these data, the SMAP mission will deploy a satellite observatory in a near polar, sun synchronous orbit. The observatory will house an L-band radiometer that operates at 1.40 GHz and an L-band radar that operates at 1.26 GHz. The instruments will share a rotating reflector antenna with a 6 meter aperture that scans over a 1000 km swath.

  18. Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

    Science.gov (United States)

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2009-12-02

    Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

  19. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  20. Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

    Science.gov (United States)

    Liu, Xuyang; Ray, Jessica R; Neil, Chelsea W; Li, Qingyun; Jun, Young-Shin

    2015-05-05

    Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

  1. Oxygen 18 concentration profile measurements near the surface by 18O(p,α)15N resonance reaction

    International Nuclear Information System (INIS)

    Amsel, G.; David, D.

    1975-01-01

    The method of spectrum reduction in nuclear reaction microanalysis does not allow to obtain depth resolutions better than the order of 2000A. Resolutions of the order of 200A may be obtained by using the narrow resonance technique, when applied to thin films. The latter technique was extended to thick targets, with deep concentration profiles presenting a sharp gradient near the surface. This method is presented and illustrated by the study of 18 O profiles in oxygen diffusion measurements in growing ZrO 2 , using the 629keV resonance of the reaction 18 O(p,α) 15 N [fr

  2. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  3. AES study of the reaction between a thin Fe-film and β-SiC (100) surface

    International Nuclear Information System (INIS)

    Mizokawa, Yusuke; Nakanishi, Shigemitsu; Miyase, Sunao

    1989-01-01

    The solid state reaction between thin Fe-films and β-SiC(100) in UHV has been studied using AES. Even at room temperature, the reaction between the thin Fe-film and SiC occurred and formed Fe-silicide and graphite with a minor product of Fe-carbide (Fe 3 C). The reaction proceeded with an increase of Fe-coverage to some extent. With annealing of 15 A-Fe-film/SiC below 540degC, the Fe-silicide formation was accelerated, but because the amount of available Fe was small, the dissolved carbon atoms were forced to form not the Fe-carbide but the graphite phase. Above 640degC, the Fe-silicide started to decompose and the carbon atoms diffused to the surface and formed surface graphite layers. With annealing at 1080degC, the free-Si segregats at the surface and formed Si-Si bonds, as well as the Si-C bonds consuming the surface graphite phase. (author)

  4. Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

    International Nuclear Information System (INIS)

    Rissmann, Clinton; Christenson, Bruce; Werner, Cynthia; Leybourne, Matthew; Cole, Jim; Gravley, Darren

    2012-01-01

    Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW e ). Soil CO 2 degassing was quantified with 2663 CO 2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m −2 ) using published soil temperature heat flow functions. Both CO 2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO 2 emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO 2 emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they

  5. The seasonal cycle and interannual variability of surface energy balance and melt in the ablation zone of the west Greenland ice sheet

    NARCIS (Netherlands)

    van den Broeke, M.R.; Smeets, C.J.P.P.; van de Wal, R.S.W.

    2011-01-01

    We present the seasonal cycle and interannual variability of the surface energy balance (SEB) in the ablation zone of the west Greenland ice sheet, using seven years (September 2003–August 2010) of hourly observations from three automatic weather stations (AWS). The AWS are situated along the 67◦ N

  6. Modifying surface resistivity and liquid moisture management property of keratin fibers through thiol-ene click reactions.

    Science.gov (United States)

    Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

    2014-01-22

    This paper reports on a new method for improving the antistatic and liquid moisture management properties of keratinous materials. The method involves the generation of thiols by controlled reduction of cystine disulfide bonds in keratin with tris(2-carboxyethyl) phosphine hydrochloride and subsequent grafting of hydrophilic groups onto the reduced keratin by reaction with an acrylate sulfonate or acrylamide sulfonate through thiol-ene click chemistry. The modified substrates were characterized with Raman spectroscopy and scanning electron microscopy and evaluated for their performance changes in liquid moisture management, surface resistivity, and wet burst strength. The results have revealed that the thiol-acrylate reaction is more efficient than the thiol-acrylamide reaction, and the keratinous substrate modified with an acrylate sulfonate salt exhibits significantly improved antistatic and liquid moisture management properties.

  7. ZOOPLANKTON COMMUNITY STRUCTURE OF THE SEA SURFACE MICROLAYER NEAR NUCLEAR POWER PLANTS AND MARINE FISH CULTURE ZONES IN DAYA BAY

    Institute of Scientific and Technical Information of China (English)

    杨宇峰; 王肇鼎; 潘明祥; 焦念志

    2002-01-01

    The authors' surveys in May-June 1999 (two cruises) at six sampling stations near nuclear power plants (NPP) and marine fish culture zones in Daya Bay, Guangdong, revealed species composition, densities and body-size of thesea surface microlayer (SM) zooplankton (>35 μm). Results showed that protozoans and copepod nauplii were the predominant components, accounting for 65.40% to95.56% of total zooplankton in abundance. The size-frequency distributions showed that the frequency of micro-zooplankton (0.02-0.2 mm) reached 0.8235. The SM zooplankton community structure revealed in the present study was quite different from that revealed by investigations in the 1980s in Daya Bay. Difference of sampling method has important influence on the obtained zooplankton community structure. SM zooplankton consisted of micro- and mesozooplankton (0.2-2.0 mm), with micro-zooplankton being predominant. Some possible cause-effect relations between the zooplankton community structure and mariculture, nuclear power plants cooling systems and sampling method are discussed.``

  8. Photoreactive polymer brushes for high-density patterned surface derivatization using a Diels-Alder photoclick reaction.

    Science.gov (United States)

    Arumugam, Selvanathan; Orski, Sara V; Locklin, Jason; Popik, Vladimir V

    2012-01-11

    Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities. © 2011 American Chemical Society

  9. The adsorption and reactions of the amino acid proline on rutile TiO 2(1 1 0) surfaces

    Science.gov (United States)

    Fleming, G. J.; Adib, K.; Rodriguez, J. A.; Barteau, M. A.; White, J. M.; Idriss, H.

    2008-06-01

    The reaction of the amino acid DL-proline is studied over stoichiometric and Ar-ions sputtered (reduced) TiO 2(1 1 0) single crystal surfaces by synchrotron High Resolution X-ray Photoelectron Spectroscopy (HRXPS). On the stoichiometric surface proline gives two different species at 300 K: dissociated and zwitterionic. Upon heating the zwitterionic structure is removed first from the surface followed by the dissociated form. The C1s signal for the COO function is found close to 288.5 eV for both forms while the N 1s for the dissociated form is found at 400.0 eV and that of the zwitterionic from close to 401.8 eV. From the attenuation of the Ti 2p signal the surface coverage was estimated less than ½ (about 0.35). This smaller coverage than dissociatively adsorbed carboxylic acids on this surface (usually close to ½), is attributed to lateral repulsion caused by the ring of adjacent proline molecules adsorbed on five-fold coordinated Ti cations along the [0 0 1] direction. On the reduced surface the amount of zwitterion structure is found two times higher than that on the stoichiometric surface, at 300 K, most likely due to the considerable decrease of the amount of surface oxygen available. The stability of the zwitterionic structure on this surface is however found similar to that found on the stoichiometric surface. In addition, evidence of oxidation of reduced Ti cations upon adsorption at 300 K is noticed and explained as breaking of the carbon-oxygen bond of a fraction of adsorbed proline. Variable temperature HRXPS has been collected and results indicated that proline is more stable on the reduced surface compared to the stoichiometric surface.

  10. Adsorption of cadmium ions on nickel surface skeleton catalysts and its effect on reaction of cathodic hydrogen evolution

    International Nuclear Information System (INIS)

    Korovin, N.V.; Udris, E.Ya.; Savel'eva, O.N.

    1986-01-01

    Cadmium adsorption from different concentration CdSO 4 solutions on nickel surface skeleton catalysts (Ni ssc ) is studied by recording of polarization and potentiodynamic curves using electron microscopy and X-ray spectrometry. Main regularities of cadmium adsorption on Ni ssc are shown to be similar to those on smooth and skeleton nickel. A conclusion is drawn that increase of catalytic activity in reaction of cathodic hydrogen evolution from alkali solutions of Ni ssc base electrodes after their treatment in solutions containing Cd 2+ ions is due to irreversible desorption of strongly and averagely bound hydrogen from electrode surface at cadmium adsorption on them

  11. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  12. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  13. Joint inversion of ambient noise surface wave and gravity data to image the upper crustal structure of the Tanlu fault zone to the southeast of Hefei, China

    Science.gov (United States)

    Wang, K.; Gu, N.; Zhang, H.; Zhou, G.

    2017-12-01

    The Tanlu fault is a major fault located in the eastern China, which stretches 2400 km long from Tancheng in the north to Lujiang in the south. It is generally believed that the Tanlu fault zone was formed in Proterozoic era and underwent a series of complicated processes since then. To understand the upper crustal structure around the southern segment of the Tanlu fault zone, in 2017 we deployed 53 short period seismic stations around the fault zone to the southeast of Hefei, capital city of Anhui province. The temporary array continuously recorded the data for about one month from 17 March to 26 April 2017. The seismic array spans an area of about 30km x 30Km with an average station spacing of about 5-6km. The vertical component data were used for extracting Rayleigh wave phase and group velocity dispersion data for the period of 0.2 to 5 seconds. To improve imaging the upper crustal structure of the fault zone, we jointly inverted the surface wave dispersion data and the gravity data because they have complementary strengths. To combine surface wave dispersion data and gravity observations into a single inversion framework, we used an empirical relationship between seismic velocity and density of Maceira and Ammon (2009). By finding the optimal relative weighting between two data types, we are able to find a shear wave velocity (Vs) model that fits both data types. The joint inversion can resolve the upper crustal fault zone structure down to about 7 km in depth. The Vs model shows that in this region the Tanlu fault is associated with high velocity anomalies, corresponding well to the Feidong complex seen on the surface. This indicates that the Tanlu fault zone may provide a channel for the intrusion of hot materials.

  14. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2007-05-15

    Pressed graphite felt (thickness {proportional_to}350 {mu}m) with electrodeposited PtRu (43 g m{sup -2}, 1.4:1 atomic ratio) or PtRuMo (52 g m{sup -2}, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m{sup -2} with PtRuMo at 5500 A m{sup -2} and 353 K while under the same conditions PtRu yielded 1925 W m{sup -2}. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation. (author)

  15. Mechanism of formation of a zone without vacancy pores along a surface under electron irradiation of a metal in the high-volt electron microscope

    International Nuclear Information System (INIS)

    Golubov, S.I.; Konobeev, Yu.V.; Ryabov, V.A.

    1981-01-01

    Formation mechanism of zones free of vacancy pores near the vacant surface of a metal preliminary irradiated at a high neutron dose when irradiating with electrons in a high-voltage electron microscope has been suggested. It was assumed to explain experimentally observed values of width and time of such zone formation that interstitial atoms are reflected from foil surface while boundary serves as an ideal sink for the vacancies. The carried out calculation of stationary equations of vacancy and interstitial diffusion with the mentioned boundary condition has shown that determination of a stable zone width is possible only in assumption on a variable in a depth of dislocation density. Theoretical evaluations of a zone width being in good agreement with an experiment and with the results of numerical calculations have been obtained in negligence of recombination of point defects as well as for the case of total reflection of interstitials. Discussed are different mechanisms of weak capture of proper interstitial atoms diffusing to it with the metal surface [ru

  16. IDENTIFICATION OF DANGER ZONES FOR SURFACE WATER USING GIS (SIP – MAPINFO SYSTEM ON AN EXAMPLE OF UPPER NAREW RIVER CATCHMENT

    Directory of Open Access Journals (Sweden)

    Mirosław Skorbiłowicz

    2016-07-01

    Full Text Available Creating the buffer zones is a function intended to designate an area in particular, of a constant distance around the spatial objects. The aim of the study was to create maps as thematic layers, which served to identify areas of existing and potential contamination of surface water and other environmental elements. Among others, it made possible to localize the areas potentially affected by the surface water pollution due to transport; localize the areas potentially affected by the surface water pollution due to the discharge of sewage from human settlements; localize the zones with mitigated impact of communication emissions due to the natural protection of forests taking the form of so-called geochemical barriers. The spatial analyzes allowed to generate model-zones of the existing and potential threat of water pollution in the Narew river catchment. Designated danger zones can be verified by studies as well as they can be very helpful in determining the monitoring network and for water quality modeling process.

  17. Use of deuteron-induced nuclear reactions for quantitative surface analysis

    International Nuclear Information System (INIS)

    Simpson, J.C.B.; Earwaker, L.G.

    1986-01-01

    A summary of the basic features of nuclear reaction analysis is given; particular emphasis is placed on quantitative light element determination using (d,p) and (d,α) reactions. The experimental apparatus is also described, with reference to the 3MV Dynamitron accelerator at the University of Birmingham Radiation Centre. Finally, a set of standard (d, p) spectra for the elements Z=3 to Z=17, using 2 MeV incident deuterons, is included together with examples of the more useful of the (d,α) spectra. (orig.)

  18. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    Science.gov (United States)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  19. Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations.

    Science.gov (United States)

    Peretz-Soroka, Hagit; Pevzner, Alexander; Davidi, Guy; Naddaka, Vladimir; Kwiat, Moria; Huppert, Dan; Patolsky, Fernando

    2015-07-08

    Significant research efforts have been dedicated to the integration of biological species with electronic elements to yield smart bioelectronic devices. The integration of DNA, proteins, and whole living cells and tissues with electronic devices has been developed into numerous intriguing applications. In particular, the quantitative detection of biological species and monitoring of biological processes are both critical to numerous areas of medical and life sciences. Nevertheless, most current approaches merely focus on the "monitoring" of chemical processes taking place on the sensing surfaces, and little efforts have been invested in the conception of sensitive devices that can simultaneously "control" and "monitor" chemical and biological reactions by the application of on-surface reversible stimuli. Here, we demonstrate the light-controlled fine modulation of surface pH by the use of photoactive molecularly modified nanomaterials. Through the use of nanowire-based FET devices, we showed the capability of modulating the on-surface pH, by intensity-controlled light stimulus. This allowed us simultaneously and locally to control and monitor pH-sensitive biological reactions on the nanodevices surfaces, such as the local activation and inhibition of proteolytic enzymatic processes, as well as dissociation of antigen-antibody binding interactions. The demonstrated capability of locally modulating the on-surface effective pH, by a light stimuli, may be further applied in the local control of on-surface DNA hybridization/dehybridization processes, activation or inhibition of living cells processes, local switching of cellular function, local photoactivation of neuronal networks with single cell resolution and so forth.

  20. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    2008-07-01

    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  1. Colour and surface fluorescence development and their relationship with Maillard reaction markers as influenced by structural changes during cornflakes production.

    Science.gov (United States)

    Farroni, Abel; Buera, María Del Pilar

    2012-12-01

    The aim of this work was to study colour and surface fluorescence development in relation to the chemical markers for the Maillard reaction at the cooking, flaking and toasting stages of cornflake production process. Colour was measured by a calibrated computer vision system. Surface fluorescence was measured on compressed samples. Aqueous extracted Maillard reaction markers (hydroxymethylfurfural, carboxymethyl-lysine, absorbance at 420nm and total fluorescence) were measured on protease hydrolyzed samples. Sample microstructure was observed by scanning electron microscopy. During cooking the colour coordinates L(∗) and b(∗) decreased and a(∗) increased. After flaking, the samples appeared lighter, while the pigment concentration, fluorescence and hydroxymethylfurfural did not change. Toasting generated bubbles in the matrix and L(∗) apparently increased, although brown pigment concentration increased. Pigment concentration did not correlate with surface colour due to the destruction or generation of interfaces. Surface and microstructure effects can be avoided by milling and compressing the samples. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Silver mirror reaction as an approach to construct a durable, robust superhydrophobic surface of bamboo timber with high conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Chunde; Li, Jingpeng [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Key Laboratory of Wood Science and Technology, Zhejiang Province (China); Han, Shenjie; Wang, Jin; Yao, Qiufang [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Sun, Qingfeng, E-mail: zafuqfsun@163.com [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Key Laboratory of Wood Science and Technology, Zhejiang Province (China)

    2015-06-25

    Highlights: • Ag NPs were deposited onto the surface of bamboo timber by silver mirror reaction. • The Ag NPs made the intrinsic insulating bamboo timber have a high conductivity. • The modified surfaces displayed superhydrophobicity even for corrosive solutions. - Abstract: Silver nanoparticles (Ag NPs) were successfully in situ deposited onto the surface of the bamboo timber through a simple silver mirror reaction. Scanning electron microscopy (SEM) images showed that the surface of the bamboo timber was densely covered with the uniform Ag NPs, which made the intrinsic insulating bamboo timber conductive. With further modification by fluoroalkylsilane (FAS), the Ag NPs-covered bamboo timber showed superhydrophobicity with the water contact angle (WCA) of 155°. Simultaneously, the modified bamboo timber displayed a durable and robust superhydrophobic property even under corrosive solutions including acidic, alkali and NaCl solutions with different molar concentrations. Especially in harsh conditions of boiling water or intense water stirring, the modified bamboo timber remained superhydrophobicity and high conductivity.

  3. Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy

    NARCIS (Netherlands)

    Kessels, W.M.M.; Knoops, H.C.M.; Dielissen, S.A.F.; Mackus, A.J.M.; Sanden, van de M.C.M.

    2009-01-01

    Infrared spectroscopy was used to obtain absolute number information on the reaction products during atomic layer deposition of Pt from (methylcyclopentadienyl)trimethylplatinum [(MeCp)PtMe3] and O2. From the detection of CO2 and H2O it was established that the precursor ligands are oxidatively

  4. Fast surface modification by microwave assisted click reactions on silicon substrates

    NARCIS (Netherlands)

    Haensch, C.; Erdmenger, T.; Fijten, M.W.M.; Höppener, S.; Schubert, U.S.

    2009-01-01

    Microwave irradiation has been used for the chemical modification of functional monolayers on silicon surfaces. The thermal and chemical stability of these layers was tested under microwave irradiation to investigate the possibility to use this alternative heating process for the surface

  5. Ab Initio and DFT Potential Energy Surfaces for Cyanuric Chloride Reactions

    National Research Council Canada - National Science Library

    Pai, Sharmila

    1998-01-01

    ... on the potential energy surface were calculated using the 6-31G and 6-311 +Gbasis sets. DFT(B3LYP) geometry optimizations and zero-point corrections for critical points on the potential energy surface were calculated with the 6-31G, 6-311...

  6. In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

    International Nuclear Information System (INIS)

    Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

    2017-01-01

    Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ . In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage. (topical review)

  7. Pollution status of polycyclic aromatic hydrocarbons in surface sediments from the Yangtze River Estuary and its adjacent coastal zone.

    Science.gov (United States)

    Wang, Chenglong; Zou, Xinqing; Gao, Jianhua; Zhao, Yifei; Yu, Wenwen; Li, Yali; Song, Qiaochu

    2016-11-01

    Polycyclic aromatic hydrocarbons (PAHs) are mainly produced by incomplete combustion and are used as indicators of anthropogenic activities on the environment. This study analyses the PAHs level in the Yangtze River Estuary (YRE), an important component of Yangtze River and a developed and populated region in China. Surface sediments were collected from 77 sites at the YRE and its adjacent coastal zone (IACZ) for a comprehensive study of PAHs. Kriging interpolation technology and Positive matrix factorization (PMF) model were applied to explore the spatial distribution and sources of PAHs. Concentrations of 16 PAHs (ΣPAHs) varied from 27.2 ng g(-1) to 621.6 ng g(-1) dry weight, with an average value of 158.2 ng g(-1). Spatially, ΣPAHs exhibited wide fluctuation and exhibited an increasing tendency from north to south. In addition, ΣPAHs exhibited a decreasing trend with increasing distance between the estuary and IACZ. The deposition flux of PAHs indicated that more than 107.8 t a(-1) PAHs was deposited in the study area annually. The results of the PMF model revealed that anthropogenic activities were the main sources of PAHs in the study area. Vehicle emissions and marine engines were the most important sources and accounted for 40.9% of the pollution. Coal combustion, petrogenic sources, and wood combustion were other sources that contributed 23.9%, 23.6%, and 11.5%, respectively. The distribution patterns of PAHs in the YRE and IACZ were influenced by many complicated factors such as sediment grain size, hydrodynamics and so on. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Interfacial separation of a mature biofilm from a glass surface - A combined experimental and cohesive zone modelling approach.

    Science.gov (United States)

    Safari, Ashkan; Tukovic, Zeljko; Cardiff, Philip; Walter, Maik; Casey, Eoin; Ivankovic, Alojz

    2016-02-01

    A good understanding of the mechanical stability of biofilms is essential for biofouling management, particularly when mechanical forces are used. Previous biofilm studies lack a damage-based theoretical model to describe the biofilm separation from a surface. The purpose of the current study was to investigate the interfacial separation of a mature biofilm from a rigid glass substrate using a combined experimental and numerical modelling approach. In the current work, the biofilm-glass interfacial separation process was investigated under tensile and shear stresses at the macroscale level, known as modes I and II failure mechanisms respectively. The numerical simulations were performed using a Finite Volume (FV)-based simulation package (OpenFOAM®) to predict the separation initiation using the cohesive zone model (CZM). Atomic force microscopy (AFM)-based retraction curve was used to obtain the separation properties between the biofilm and glass colloid at microscale level, where the CZM parameters were estimated using the Johnson-Kendall-Roberts (JKR) model. In this study CZM is introduced as a reliable method for the investigation of interfacial separation between a biofilm and rigid substrate, in which a high local stress at the interface edge acts as an ultimate stress at the crack tip.This study demonstrated that the total interfacial failure energy measured at the macroscale, was significantly higher than the pure interfacial separation energy obtained by AFM at the microscale, indicating a highly ductile deformation behaviour within the bulk biofilm matrix. The results of this study can significantly contribute to the understanding of biofilm detachments. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer

    Science.gov (United States)

    Ma, Yan; Diao, Yiwei; Zhang, Bingjie; Wang, Weiwei; Ren, Xinrong; Yang, Dongsen; Wang, Ming; Shi, Xiaowen; Zheng, Jun

    2016-12-01

    A proton transfer reaction ion-drift chemical ionization mass spectrometer (PTR-ID-CIMS) equipped with a hydronium (H3+O) ion source was developed and deployed near an industrial zone in the Yangtze River Delta (YRD) region of China in spring 2015 to investigate industry-related emissions of volatile organic compounds (VOCs). Air pollutants including formaldehyde (HCHO), aromatics, and other trace gases (O3 and CO) were simultaneously measured. Humidity effects on the sensitivity of the PTR-ID-CIMS for HCHO detection were investigated and quantified. The performances of the PTR-ID-CIMS were also validated by intercomparing with offline HCHO measurement technique using 2,4-dinitrophenylhydrazone (DNPH) cartridges and the results showed fairly good agreement (slope = 0.81, R2 = 0.80). The PTR-ID-CIMS detection limit of HCHO (10 s, three-duty-cycle averages) was determined to be 0.9-2.4 (RH = 1-81.5 %) parts per billion by volume (ppbv) based on 3 times the standard deviations of the background signals. During the field study, observed HCHO concentrations ranged between 1.8 and 12.8 ppbv with a campaign average of 4.1 ± 1.6 ppbv, which was comparable with previous HCHO observations in other similar locations of China. However, HCHO diurnal profiles showed few features of secondary formation. In addition, time series of both HCHO and aromatic VOCs indicated strong influence from local emissions. Using a multiple linear regression fit model, on average the observed HCHO can be attributed to secondary formation (13.8 %), background level (27.0 %), and industry-related emissions, i.e., combustion sources (43.2 %) and chemical productions (16.0 %). Moreover, within the plumes the industry-related emissions can account for up to 69.2 % of the observed HCHO. This work has provided direct evidence of strong primary emissions of HCHO from industry-related activities. These primary HCHO sources can potentially have a strong impact on local and regional air pollution formation

  10. Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

    Science.gov (United States)

    Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

    2016-03-29

    Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

  11. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  12. Photocatalysis of irradiated semiconductor surfaces: Its application to water splitting and some organic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sakata, T

    1985-05-01

    Hydrogen production from organic compounds and water was investigated using powdered semiconductor photocatalysts. The complete decomposition observed for several organic compounds demonstrated that water is involved in the reactions as an oxidizing agent. Photocatalyses of dyes and semiconductors were found to be applicable to amino acid synthesis. The quantum yields of photocatalytic amino acid synthesis using visible light are about 20%-40% in the absence of a metal catalyst such as platinum. Moreover the reactions are highly selective and depend strongly on the type of semiconductor. This method was applied to the asymmetric synthesis of amino acids using asymmetric catalysts. Rather high optical yields of 50% were achieved for the synthesis of L-phenylalanine.

  13. Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

    International Nuclear Information System (INIS)

    Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

    1994-01-01

    CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

  14. Shaping surface of palladium nanospheres through the control of reaction parameters

    International Nuclear Information System (INIS)

    Wang Lianmeng; Tan Enzhong; Guo Lin; Wang Lihua; Han Xiaodong

    2011-01-01

    Solid, cracked, and flower-shaped surfaces of palladium nanospheres with high yields and good uniformity were successfully prepared by a wet chemical method. On the basis of the experimental data, the same size of palladium nanosphere with different surface morphologies can be regulated only by changing the amount of ammonium hydroxide and reductant in one experimental system. The as-prepared products were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and x-ray diffraction (XRD). In addition, surface-enhanced Raman scattering (SERS) spectra on the as-prepared different surface of palladium nanospheres exhibit high activity towards p-aminothiophenol (PATP) detection, and the result further reveals that the predominance of the a1 vibration mode in the SERS spectra via an electromagnetic (EM) mechanism is significant.

  15. Characterisation and surface reactions of iron oxides and fluorapatite in aqueous suspensions

    OpenAIRE

    Jarlbring, Mathias

    2004-01-01

    The final objective of this study is to produce chemical models of flotation- like systems, including oxidation products of magnetite (maghemite and hematite) together with apatite. This is started by investigating the acid base properties, surface complexation and surface characteristics of the systems hematite-H+ and maghemite-H+ (paper I), fluorapatite-OH- (paper II) and a mixed system of maghemite-fluorapatite-OH- (paper III). Synthetic minerals were prepared and characterised with BET, S...

  16. Defining context-specific scenarios to design vegetated buffer zones that limit pesticide transfer via surface runoff.

    Science.gov (United States)

    Carluer, N; Lauvernet, C; Noll, D; Munoz-Carpena, R

    2017-01-01

    When used in addition to environmentally friendly cultural practices, buffer zones can limit the water transfer of pollutants, in particular pesticides, towards water resources. The choice of the buffer zones' type and positioning, considering water pathways and flow components, is crucial. When this choice has been performed, buffer zones dimensions must still be optimized, according to the environment characteristics, which strongly influence their effectiveness. This article presents a method and its associated tools, including VFSMOD model, which aim at optimizing vegetative buffer zones (VFS) sizes, by simulating their transfer mitigation effectiveness. A first application of this methodology is illustrated on a small agricultural watershed in Brittany. A second application, based on the simulation of a large number of scenarios, leads to the elaboration of nomograms. They allow optimizing VFS size in a simpler way from the user's point of view. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  18. An integrated high temperature environmental cell for atom probe tomography studies of gas-surface reactions: Instrumentation and results

    International Nuclear Information System (INIS)

    Dumpala, S.; Broderick, S.R.; Bagot, P.A.J.; Rajan, K.

    2014-01-01

    An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument. - Highlights: • Designed and built atom probe environmental cell for in situ reactions. • Investigated Al oxidation, and demonstrated improvement with new cell. • in situ APT analysis of Pt-alloys showed surface segregation of Rh and Ir

  19. Corrosion of ferritic steels by molten lithium: Influence of competing thermal gradient mass transfer and surface product reactions

    International Nuclear Information System (INIS)

    Tortorelli, P.F.

    1987-10-01

    An Fe-12Cr-1MoVW steel was exposed to thermally convective lithium for 6962 h. Results showed that the weight change profile of Fe-12Cr-1MoVW steel changed substantially as the maximum loop temperature was raised from 500 to 600 0 C. Furthermore, for a particular loop experiment, changes in the structure and composition of the exposed surfaces did not reflect typical thermal gradient mass transfer effects for all elements: the surface concentration of chromium was often a maximum at intermediate temperatures, while nickel (present at low concentrations in the starting material) tended to be transported to the coldest part of the loop. Such data were interpreted in terms of a qualitative model in which there are different dominant reactions or the various constituents of the ferritic steels (surface product formation involving nitrogen and/or carbon and solubility-driven elemental transport). This competition among different reactions is important in evaluating overall corrosion behavior and the effects of temperature. The overall corrosion rate of the 12Cr-1MoVW steel was relatively low when compared to that for austenitic stainless steel exposed under similar conditions

  20. Assessment Of Surface-Catalyzed Reaction Products From High Temperature Materials In Plasmas

    Science.gov (United States)

    Allen, Luke Daniel

    Current simulations of atmospheric entry into both Mars and Earth atmospheres for the design of thermal protections systems (TPS) typically invoke conservative assumptions regarding surface-catalyzed recombination and the amount of energy deposited on the surface. The need to invoke such assumptions derives in part from lack of adequate experimental data on gas-surface interactions at trajectory relevant conditions. Addressing this issue, the University of Vermont's Plasma Test and Diagnostics Laboratory has done extensive work to measure atomic specie consumption by measuring the concentration gradient over various material surfaces. This thesis extends this work by attempting to directly diagnose molecular species production in air plasmas. A series of spectral models for the A-X and B-X systems of nitric oxide (NO), and the B-X system of boron monoxide (BO) have been developed. These models aim to predict line positions and strengths for the respective molecules in a way that is best suited for the diagnostic needs of the UVM facility. From the NO models, laser induced fluorescence strategies have been adapted with the intent of characterizing the relative quantity and thermodynamic state of NO produced bysurface-catalyzed recombination, while the BO model adds a diagnostic tool for the testing of diboride-based TPS materials. Boundary layer surveys of atomic nitrogen and NO have been carried out over water-cooled copper and nickel surfaces in air/argon plasmas. Translation temperatures and relative number densities throughout the boundary layer are reported. Additional tests were also conducted over a water-cooled copper surface to detect evidence of highly non-equilibrium effects in the form of excess population in elevated vibrational levels of the A-X system of NO. The tests showed that near the sample surface there is a much greater population in the upsilon'' = 1ground state than is predicted by a Boltzmann distribution.

  1. The effect of coadsorbed oxygen on the reaction of methanol on Rh(111) and on a rhodium/vanadium surface alloy

    International Nuclear Information System (INIS)

    Schennach, R.; Krenn, G.; Rendulic, K.D.

    2002-01-01

    Full text: Molecular adsorption of methanol can be observed on all transition metal surfaces at low temperatures. Methanol is adsorbed on Rh (111) at 98 K. With increasing methanol exposure first a mono-layer and then multi-layers of methanol are formed at this surface temperature. During heating, desorption of the methanol from physisorbed multi-layers is detected at about 120 K, followed by desorption of methanol from a chemisorbed mono-layer at 170 K. About 50 % of the adsorbed methanol undergoes a dehydrogenation reaction to form hydrogen and carbon monoxide adsorbed on the surface. These reaction products desorb at 300 K and 480 K, respectively. Less than 0.05 monolayers of coadsorbed oxygen increases the amount of methanol that reacts on the surface to about 80 %. Experiments using a Rh/V surface alloy were performed, in order to distinguish between steric and electronic effects in the adsorption and reaction processes. Deposition of 0.3 monolayers of V on the Rh (111) surface leads to the formation of a subsurface alloy, with V atoms in the second atomic layer only. The initial reaction probability was measured as a function of surface temperature and molecular beam energy. A marked difference was found between the two surfaces. On the clean surface methanol adsorption and reaction stops above 198 K, whereas on the alloy surface adsorption and subsequent reaction occurs up to 473 K. The effects of coadsorbed oxygen are similar on both surfaces. The results are discussed in terms of the possible reactions of the adsorbed methanol on the surface. (author)

  2. The speciation of Si and other alloying elements in the oxide surface film of galvanically corroded weld fusion zone of laser welded AA6061 aluminium alloy

    Energy Technology Data Exchange (ETDEWEB)

    Mujibur Rahman, A.B.M.; Kumar, Sunil [Ian Wark Research Institute, University of South Australia, Mawson Lakes Campus, Mawson Lakes, South Australia 5095 (Australia); Gerson, Andrea R. [Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes Campus, Mawson Lakes, South Australia 5095 (Australia)], E-mail: Andrea.Gerson@unisa.edu.au

    2008-05-15

    It has recently been proposed that on galvanic corrosion of laser weldments of AA6061 aluminium alloy the temporal increase in galvanic corrosion resulted from either the build up of intermetallic phases in the surface oxide layer and/or a significant increase in the surface area of the cathodic weld fusion zone due to the porous nature of the surface layer. This proposition has motivated a comprehensive surface analytical study of the incorporation of alloying elements into the oxide surface film, which is composed predominately of alumina. Si is found to be present as silicate and silicides. The Gibbs free energy of formation, per cation, of silicate is more negative than that for alumina and hence silicate formation is thermodynamically, relatively, favourable. In contrast the Gibbs free energy for oxide formation, per cation, for the other alloying elements is less negative and hence relatively unfavourable compared to the formation of alumina. We propose therefore that Fe, Cu and Cr are present in the metallic form, possibly as silicides, within the oxide surface layer. Magnesium is found to be depleted relative to the weld fusion zone presumably due to dissolution within the electrolyte.

  3. The speciation of Si and other alloying elements in the oxide surface film of galvanically corroded weld fusion zone of laser welded AA6061 aluminium alloy

    International Nuclear Information System (INIS)

    Mujibur Rahman, A.B.M.; Kumar, Sunil; Gerson, Andrea R.

    2008-01-01

    It has recently been proposed that on galvanic corrosion of laser weldments of AA6061 aluminium alloy the temporal increase in galvanic corrosion resulted from either the build up of intermetallic phases in the surface oxide layer and/or a significant increase in the surface area of the cathodic weld fusion zone due to the porous nature of the surface layer. This proposition has motivated a comprehensive surface analytical study of the incorporation of alloying elements into the oxide surface film, which is composed predominately of alumina. Si is found to be present as silicate and silicides. The Gibbs free energy of formation, per cation, of silicate is more negative than that for alumina and hence silicate formation is thermodynamically, relatively, favourable. In contrast the Gibbs free energy for oxide formation, per cation, for the other alloying elements is less negative and hence relatively unfavourable compared to the formation of alumina. We propose therefore that Fe, Cu and Cr are present in the metallic form, possibly as silicides, within the oxide surface layer. Magnesium is found to be depleted relative to the weld fusion zone presumably due to dissolution within the electrolyte

  4. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Wei Yuchen; Liu Chenwei; Chang Weijung; Wang Kuanwen

    2011-01-01

    Research highlights: → Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. → O 2 treatment results in obvious Ru segregation and formation of RuO 2 . → Catalysts treated in H 2 have the excellent CO de-poisoning ability. → N 2 treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O 2 treatment results in obvious Ru segregation and formation of RuO 2 . Catalysts treated in H 2 have the highest I f /I b value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N 2 treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion (∼60% Pt on the surface), make the components stable and hence promote the MOR significantly.

  5. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wei Yuchen; Liu Chenwei; Chang Weijung [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China); Wang Kuanwen, E-mail: kuanwen.wang@gmail.com [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China)

    2011-01-12

    Research highlights: > Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. > O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. > Catalysts treated in H{sub 2} have the excellent CO de-poisoning ability. > N{sub 2} treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. Catalysts treated in H{sub 2} have the highest I{sub f}/I{sub b} value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N{sub 2} treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion ({approx}60% Pt on the surface), make the components stable and hence promote the MOR significantly.

  6. Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

    Science.gov (United States)

    Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

    2017-03-01

    The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

  7. Mass Spectral Investigation of Laboratory Made Tholins and Their Reaction Products: Implications to Tholin Surface Chemistry on Titan

    Science.gov (United States)

    Somogyi, Arpad; Smith, M. A.

    2006-09-01

    The success of the Huygens mission does not overshadow the importance of laboratory simulations of gas-phase and surface reactions that might occur in Titan's atmosphere and surface, respectively. We present here our latest results on chemical reactions (hydrolysis, peroxidation and hydrogenation) of laboratory made tholins obtained by FT-ICR mass spectrometry. The laboratory synthesis of tholins has been described in our earlier papers [1,2]. Overall, we conclude that our laboratory tholins are reactive materials that undergo fast hydrolysis, oxidation and reduction. Thus, if the tholin on Titan's surface resemble our laboratory made tholins, it can be considered as a potential starting material for several synthetic processes that can provide organic compounds of pre-biotic interest. Hydrolysis reactions occur with rate constants of 2-10 hour-1 at room temperature. Formal water addition to several species of CxHyNz has been observed by detecting the formation of CxHy+2NzO species. MS/MS fragmentation of the oxygen containing ions leads to the loss of water, ammonia, HCN, acetonitrile, etc. This suggests that tholin hydrolysis may occur in temporary melted ponds of water/ammonia ice on Titan. Peroxidation, which can be considered as a very harsh oxidation, leads to mono-, and multiple oxygenated compounds within a few minutes. The MS/MS fragmentation of these compounds suggests the presence of organic amides and, presumably, amino acid like compounds. Hydrogenation leads to compounds in which the originally present carbon-carbon or carbon-nitrogen double and triple bonds are saturated. H/D exchange experiments show different kinetics depending on the degree of unsaturation/saturation and the number of N atoms. [1] Sarker, N.; Somogyi, A.; Lunine, J. I.; Smith, M. A. Astrobiology, 2003, 3, 719-726. [2] Somogyi, A.; Oh, C-H.; Lunine, J. I.; Smith, M. A. J. Am. Soc. Mass Spectrom. 2005, 16, 850-859.

  8. Coastal Zone Color Scanner (CZCS): Imagery of near-surface phytoplankton pigment concentrations from the first coastal ocean dynamics experiment (CODE-1), March - July 1981

    Science.gov (United States)

    Abbott, M. R.; Zion, P. M.

    1984-01-01

    As part of the first Coastal Ocean Dynamics Experiment, images of ocean color were collected from late March until late July, 1981, by the Coastal Zone Color Scanner aboard Nimbus-7. Images that had sufficient cloud-free area to be of interest were processed to yield near-surface phytoplankton pigment concentrations. These images were then remapped to a fixed equal-area grid. This report contains photographs of the digital images and a brief description of the processing methods.

  9. Spatio-temporal Root Zone Soil Moisture Estimation for Indo - Gangetic Basin from Satellite Derived (AMSR-2 and SMOS) Surface Soil Moisture

    Science.gov (United States)

    Sure, A.; Dikshit, O.

    2017-12-01

    Root zone soil moisture (RZSM) is an important element in hydrology and agriculture. The estimation of RZSM provides insight in selecting the appropriate crops for specific soil conditions (soil type, bulk density, etc.). RZSM governs various vadose zone phenomena and subsequently affects the groundwater processes. With various satellite sensors dedicated to estimating surface soil moisture at different spatial and temporal resolutions, estimation of soil moisture at root zone level for Indo - Gangetic basin which inherits complex heterogeneous environment, is quite challenging. This study aims at estimating RZSM and understand its variation at the level of Indo - Gangetic basin with changing land use/land cover, topography, crop cycles, soil properties, temperature and precipitation patterns using two satellite derived soil moisture datasets operating at distinct frequencies with different principles of acquisition. Two surface soil moisture datasets are derived from AMSR-2 (6.9 GHz - `C' Band) and SMOS (1.4 GHz - `L' band) passive microwave sensors with coarse spatial resolution. The Soil Water Index (SWI), accounting for soil moisture from the surface, is derived by considering a theoretical two-layered water balance model and contributes in ascertaining soil moisture at the vadose zone. This index is evaluated against the widely used modelled soil moisture dataset of GLDAS - NOAH, version 2.1. This research enhances the domain of utilising the modelled soil moisture dataset, wherever the ground dataset is unavailable. The coupling between the surface soil moisture and RZSM is analysed for two years (2015-16), by defining a parameter T, the characteristic time length. The study demonstrates that deriving an optimal value of T for estimating SWI at a certain location is a function of various factors such as land, meteorological, and agricultural characteristics.

  10. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    Science.gov (United States)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  11. Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks

    Energy Technology Data Exchange (ETDEWEB)

    Kolb, Brian [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Zhao, Bin; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Li, Jun [School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331 (China); Jiang, Bin [Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2016-06-14

    The applicability and accuracy of the Behler-Parrinello atomistic neural network method for fitting reactive potential energy surfaces is critically examined in three systems, H + H{sub 2} → H{sub 2} + H, H + H{sub 2}O → H{sub 2} + OH, and H + CH{sub 4} → H{sub 2} + CH{sub 3}. A pragmatic Monte Carlo method is proposed to make efficient choice of the atom-centered mapping functions. The accuracy of the potential energy surfaces is not only tested by fitting errors but also validated by direct comparison in dynamically important regions and by quantum scattering calculations. Our results suggest this method is both accurate and efficient in representing multidimensional potential energy surfaces even when dissociation continua are involved.

  12. Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks

    International Nuclear Information System (INIS)

    Kolb, Brian; Zhao, Bin; Guo, Hua; Li, Jun; Jiang, Bin

    2016-01-01

    The applicability and accuracy of the Behler-Parrinello atomistic neural network method for fitting reactive potential energy surfaces is critically examined in three systems, H + H 2 → H 2 + H, H + H 2 O → H 2 + OH, and H + CH 4 → H 2 + CH 3 . A pragmatic Monte Carlo method is proposed to make efficient choice of the atom-centered mapping functions. The accuracy of the potential energy surfaces is not only tested by fitting errors but also validated by direct comparison in dynamically important regions and by quantum scattering calculations. Our results suggest this method is both accurate and efficient in representing multidimensional potential energy surfaces even when dissociation continua are involved.

  13. Investigation of silicate surface chemistry and reaction mechanisms associated with mass transport in geologic media

    International Nuclear Information System (INIS)

    White, A.F.; Perry, D.L.

    1982-01-01

    The concentration and rate of transport of radionuclides through geologic media can be strongly influenced by the extent of sorption on aquifer surfaces. Over time intervals relevant to such transport processes, rock and mineral surfaces cannot be considered as inert, unreactive substrates but rather as groundwater/solidphase interfaces which are commonly in a state of natural or artificially induced disequilibrium. The goal of the present research is to define experimentally the type of water/rock interactions that will influence surface chemistry and hence sorption characteristics and capacities of natural aquifers. As wide a range of silicate minerals as possible was selected for study to represent rock-forming minerals in basalt, tuff, and granite. The minerals include K-feldspar, plagioclase feldspar, olivine, hornblende, biotite, and volcanic glass

  14. Reaction paths of alane dissociation on the Si(0 0 1) surface

    Science.gov (United States)

    Smith, Richard; Bowler, David R.

    2018-03-01

    Building on our earlier study, we examine the kinetic barriers to decomposition of alane, AlH3, on the Si(0 0 1) surface, using the nudged elastic band approach within density functional theory. We find that the initial decomposition to AlH with two H atoms on the surface proceeds without a significant barrier. There are several pathways available to lose the final hydrogen, though these present barriers of up to 1 eV. Incorporation is more challenging, with the initial structures less stable in several cases than the starting structures, just as was found for phosphorus. We identify a stable route for Al incorporation following selective surface hydrogen desorption (e.g. by scanning tunneling microscope tip). The overall process parallels PH3, and indicates that atomically precise acceptor doping should be possible.

  15. X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

    International Nuclear Information System (INIS)

    Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

    1999-10-01

    The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

  16. Radiation-induced reactions in D, L-α-alanine adsorbed in solid surfaces

    International Nuclear Information System (INIS)

    Aguilar, E; Negrón-Mendoza, A.; Camargo, C.

    2013-01-01

    The aim of this work is to study the behavior under irradiation of D, L and D-L α-alanine adsorbed in solid surfaces, as possible phase in the chemical evolution that may have occurred on the primitive Earth or in extraterrestrial environments and to evaluate the contribution of solids (a clay mineral) as shields for the adsorbed amino acids against a external energy source. The results show that α-alanine is adsorbed in the surfaces as function of pH and its yield of decomposition in mineral suspension is lower than the system without the solid surface. These results show the importance of nuclear techniques in these types of studies. (author)

  17. [The reaction of human surface and inside body temperature to extreme hypothermia].

    Science.gov (United States)

    Panchenko, O A; Onishchenko, V O; Liakh, Iu Ie

    2011-01-01

    The dynamics of changes in the parameters of the surface and core body temperature under the systematic impact of ultra-low temperature is described in this article. As a source of ultra-low temperature was used (Cryo Therapy Chamber) Zimmer Medizin Systeme firm Zimmer Electromedizin (Germany) (-110 degrees C). Surface and internal body temperature was measured by infrared thermometer immediately before visiting cryochamber and immediately after exiting. In the study conducted 47,464 measurements of body temperature. It was established that the internal temperature of the human body under the influence of ultra-low temperatures in the proposed mode of exposure remains constant, and the surface temperature of the body reduces by an average of 11.57 degrees C. The time frame stabilization of adaptive processes of thermoregulation under the systematic impact of ultra-low temperature was defined in the study.

  18. Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

    Science.gov (United States)

    Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

    1987-01-01

    The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

  19. A numerical model for chemical reaction on slag layer surface and slag layer behavior in entrained-flow gasifier

    Directory of Open Access Journals (Sweden)

    Liu Sheng

    2013-01-01

    Full Text Available The paper concerns with slag layer accumulation, chemical reaction on slag layer surface, and slag layer flow, heat and mass transfer on the wall of entrained-flow coal gasifier. A slag layer model is developed to simulate slag layer behaviors in the coal gasifier. This 3-D model can predict temperature, slag particle disposition rate, disposition particle composition, and syngas distribution in the gasifier hearth. The model is used to evaluate the effects of O2/coal ratio on slag layer behaviors.

  20. Core-shell Si/Cu nanocomposites synthesized by self-limiting surface reaction as anodes for lithium ion batteries

    Science.gov (United States)

    Xu, Kaiqi; Zhang, Zhizhen; Su, Wei; Huang, Xuejie

    Core-shell Si/Cu nanocomposites were synthesized via a flexible self-limiting surface reaction without extra reductant for the first time. The nano Si was uniformly coated with Cu nanoparticles with a diameter of 5-10nm, which can enhance the electronic conductivity of the nanocomposites and buffer the huge volume change during charge/discharge owing to its high ductility. Benefited from the unique structure, the Si/Cu nanocomposites exhibited a good electrochemical performance as anodes for lithium ion batteries, which exhibited a capacity retention of 656mAh/g after 50 cycles and a coulombic efficiency of more than 99%.

  1. Light-induced heterogeneous reactions of NO2 on indoor surfaces: How they affect the balance of nitrous acid

    Science.gov (United States)

    Gomez Alvarez, E.; Soergel, M.; Bassil, S.; Zetzsch, C.; Gligorovski, S.; Wortham, H.

    2011-12-01

    Nitrous acid (HONO) is an important indoor pollutant. The adverse health effects due to the formation of nitrosamines are well known. HONO acts as a nitrosating agent after wall reactions of HONO with nicotine [Sleiman et al., 2010]. Indoor air can be surprisingly rich in HONO (homes with fireplaces, stoves, gas heating and cooking) and also surfaces are abundant. High HONO concentrations have been measured in indoor environments, from the direct emissions and heterogeneous reactions of NO2 in darkness. However, the measured HONO concentrations do not correspond to the HONO levels determined by the models [Carslaw, 2007]. We have tested in a flow tube reactor on-line coupled to a NOx analyzer and a sensitive Long Path Absorption Photometry instrument, the behaviour of various indoor surfaces towards NO2 under simulated solar light irradiation (λ= 300-700 nm). Our study has allowed us to obtain a deeper knowledge on the mechanisms of heterogeneous formation of HONO, quantifying the dependence of HONO formation on behalf of NO2 concentration and relative humidity and the enhancement of HONO formation in the presence of light. Pyrex, acidic detergent, alkaline detergent, paint and lacquer were tested on behalf of their heterogeneous reactivity towards NO2 in the absence and in presence of light. The results obtained demonstrated that indoor surfaces are photo-chemically active under atmospherically relevant conditions. The strongly alkaline surfaces (such as certain types of detergent) show a strong long-term uptake capacity. However, other surfaces such as detergents with a more acidic character released HONO. In some cases such as paint and varnish, a strong HONO release with light was detected, which was significantly higher than that obtained over clean glass surfaces. Certain organics present on their composition could exert a photo-sensitizing effect that may explain their increased reactivity. Unfortunately, the final balance points towards an important net

  2. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2012-06-01

    Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  3. Contributions of electron microscopy to the understanding of reactions on compound semiconductor surfaces

    International Nuclear Information System (INIS)

    Sands, T.

    1986-01-01

    Reacted films on compound semiconductor substrates present challenging materials characterization problems which often require the application of transmission electron microscopy (TEM) techniques. In this paper, both the problem - solving potential of the TEM techniques and the limits imposed by preparation of thin film/compound semiconductor TEM specimens are discussed. Studies of the Ni/GaAs, CuCl/aq)/CdS and Pd/GaAs reactions exemplify the role of TEM in identifying and determining the spatial distribution of interface - stabilized polymorphs and new ternary phases (e.g. tetragonal Cu/sub 2/S, Ni/sub 3/GaAs and Pd/sub x/GaAs). These examples also serve to clarify the relationship between TEM and complementary analysis techniques such as Rutherford backscattering spectrometry, Auger electron spectroscopy and glancing-angle x-ray diffraction. In particular, it is argued that a combination of (1) high-spatial-resolution information obtained by TEM and (2) an indication of the ''average'' behavior provided by data from a complementary characterization technique provide the minimum quality and quantity of data necessary to understand most reactions on compound semiconductor substrates

  4. Crustal thickness variations in the Zagros continental collision zone (Iran) from joint inversion of receiver functions and surface wave dispersion

    Science.gov (United States)

    Tatar, M.; Nasrabadi, A.

    2013-10-01

    Variations in crustal thickness in the Zagros determined by joint inversion of P wave receiver functions (RFs) and Rayleigh wave group and phase velocity dispersion. The time domain iterative deconvolution procedure was employed to compute RFs from teleseismic recordings at seven broadband stations of INSN network. Rayleigh wave phase velocity dispersion curves were estimated employing two-station method. Fundamental mode Rayleigh wave group velocities for each station is taken from a regional scale surface wave tomographic imaging. The main variations in crustal thickness that we observe are between stations located in the Zagros fold and thrust belt with those located in the Sanandaj-Sirjan zone (SSZ) and Urumieh-Dokhtar magmatic assemblage (UDMA). Our results indicate that the average crustal thickness beneath the Zagros Mountain Range varies from ˜46 km in Western and Central Zagros beneath SHGR and GHIR up to ˜50 km beneath BNDS located in easternmost of the Zagros. Toward NE, we observe an increase in Moho depth where it reaches ˜58 km beneath SNGE located in the SSZ. Average crustal thickness also varies beneath the UDMA from ˜50 km in western parts below ASAO to ˜58 in central parts below NASN. The observed variation along the SSZ and UDMA may be associated to ongoing slab steepening or break off in the NW Zagros, comparing under thrusting of the Arabian plate beneath Central Zagros. The results show that in Central Iran, the crustal thickness decrease again to ˜47 km below KRBR. There is not a significant crustal thickness difference along the Zagros fold and thrust belt. We found the same crystalline crust of ˜34 km thick beneath the different parts of the Zagros fold and thrust belt. The similarity of crustal structure suggests that the crust of the Zagros fold and thrust belt was uniform before subsidence and deposition of the sediments. Our results confirm that the shortening of the western and eastern parts of the Zagros basement is small and

  5. Surface analytical investigations of the release behaviour of volatile fission products during simulated core meltdown accidents and of the reaction behaviour of iodine with silver surfaces

    International Nuclear Information System (INIS)

    Moers, H.

    1986-07-01

    The report presents the results of the analysis of aerosol particles formed in simulated laboratory scale core meltdown experiments. In addition the interaction of silver surfaces with gaseous molecular iodine and with iodide and molecular iodine in aqueous solution was investigated. The composition of the aerosol samples and the progress of the reactions mentioned were determined by use of surface analytical techniques (X-ray photoelectron spectroscopy, Auger electron spectroscopy, secondary ion mass spectroscopy). The major information can be evaluated from X-ray photoelectron spectra which exhibit chemical shifts of the photoelectron lines which allowing a discrimination between different chemical species of the same element. The analyses showed that iodine is present in the aerosol particles mainly as caesium iodide and, to a smaller fraction, as silver iodide. During the adsorption of gaseous molecular iodine at metallic silver surfaces a closed silver iodide overlayer is formed. In aqueous iodide solutions one observes chemisorption of the iodide anions up to a coverage of the metallic silver surface of about half a monolayer. Molecular iodine in aqueous solution is completely converted to silver iodide which covers the substrate irregularly. (orig./HP) [de

  6. Effects of polishing on surface roughness, gloss and color of surface reaction type pre-reacted glass-ionomer filled resin composite.

    Science.gov (United States)

    Hosoya, Yumiko; Shiraishi, Takanobu; Odatsu, Tetsuro; Miyazaki, Masashi; García-Godoy, Franklin

    2011-06-01

    To evaluate the effects of polishing on surface roughness, gloss and color of different shades of surface reaction type pre-reacted glass-ionomer (S-PRG) filled nano-hybrid resin composite. Resin disks of 15 mm diameter and 2 mm thickness and final polish with 1000-grit SiC paper, super fine cut diamond (FG) point, silicon (MFR) point and Super-Snap mini-disk red (SNAP) were made with Beautifil II shades: A2, A20, Inc). One week after curing, the surface roughness, gloss and color were measured. Data was analyzed with ANOVA and Fisher's PLSD with alpha= 0.05 For all shades, the order of roughness (Ra) ranked according to groups of 1000-grit SiC > FG > MFR > SNAP with significant differences among all groups. For all shades, the order of gloss ranked according to groups of SNAP > MFR > FG > 1000-grit SiC with significant differences among the groups except for between MFR and FG without significant difference. The influence of the surface roughness on color differed among the polishing groups and shades. However, the values of the color differences (deltaE*ab) between the polishing groups of all shades were imperceptible to the naked eye.

  7. Modification of the glass surface induced by redox reactions and internal diffusion processes

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

    In this paper we report a novel way to modify the glass surface in favor of some physical performances. The main step is to perform iso-thermal treatments on the selected silicate glasses containing transition metal at temperatures near the glass transition temperature for various durations under...

  8. Production of specific structured lipids by enzymatic interesterification: optimization of the reaction by response surface design

    DEFF Research Database (Denmark)

    Xu, Xuebing; Skands, Anja Rebecca Havegaard; Adler-Nissen, Jens

    1998-01-01

    Rapeseed oil and capric acid were interesterified in solvent-free media catalyzed by Lipozyme IM (Rhizomucor miehei) to produce specific-structured lipids (SSLs). The process was optimized by response surface design concerning the effects of acyl migration and the by-products of diacylglycerols...

  9. Reaction of Tri-methylaluminum on Si (001) Surface for Initial Aluminum Oxide Thin-Film Growth

    International Nuclear Information System (INIS)

    Kim, Dae Hee; Kim, Dae Hyun; Jeong, Yong Chan; Seo, Hwa Il; Kim, Yeong Cheol

    2010-01-01

    We studied the reaction of tri-methylaluminum (TMA) on hydroxyl (OH)-terminated Si (001) surfaces for the initial growth of aluminum oxide thin-films using density functional theory. TMA was adsorbed on the oxygen atom of OH due to the oxygen atom's lone pair electrons. The adsorbed TMA reacted with the hydrogen atom of OH to produce a di-methylaluminum group (DMA) and methane with an energy barrier of 0.50 eV. Low energy barriers in the range of 0 - 0.11 eV were required for DMA migration to the inter-dimer, intra-dimer, and inter-row sites on the surface. A unimethylaluminum group (UMA) was generated at each site with low energy barriers in the range of 0.21 - 0.25 eV. Among the three sites, the inter-dimer site was the most probable for UMA formation

  10. Noctis Landing: A Proposed Landing Site/Exploration Zone for Human Missions to the Surface of Mars

    Science.gov (United States)

    Lee, Pascal; Acedillo, Shannen; Braham, Stephen; Brown, Adrian; Elphic, Richard; Fong, Terry; Glass, Brian; Hoftun, Christopher; Johansen, Brage W.; Lorber, Kira; hide

    2015-01-01

    The proposed Noctis Landing Site/Exploration Zone (LS/EZ) is shown in Figure 1. Our preliminary study suggests that the proposed site meets all key Science and Resources (incl. Civil Engineering) requirements. The site is of significant interest, as the EZ not only offers a large number and wide range of regions of interest (ROIs) for short-term exploration, it is also located strategically at the crossroads between Tharsis and Valles Marineris, which are key for long-term exploration. The proposed site contains Regions of Interest (ROIs) that meet the following Science requirements: -­- Access to (1) deposits with a high preservation potential for evidence of past habitability and fossil biosignatures and (2) sites that are promising for present habitability. The site presents a wide variety of ROIs qith likely aqueous features and deposits, including sinous channels and valleys, slope gullies, lobate debris aprons, impact craters with lobate ejecta flows, and "bathtub ring" deposits. Neutron spectrometry also suggests hydrogen is present within the topmost 0.3 m or so of 4 to 10 wt% WEH (Water Equivalent Hydrogen). -­- Noachian and/or Hesperian rocks in a stratigraphic context that have a high likelihood of containing trapped atmospheric gases. Collapsed canyon rim material with preserved stratigraphy is abundantly present and accessible. -­- Exposures of at least two crustal units that have regional or global extents, that are suitable for radiometric dating, and that have relative ages that sample a significant range of martian geological time. Canyons floors in Ius Chasma, Tithonium Chasma, and plateau tops on Tharsis and in Sinai Planum offer access to distinct crustal units of regional extent. -­- Access to outcrops with linked morphological and/or geochemical signatures indicative of aqueous or groundwater/ mineral interactions. Iron and sulfur-bearing deposits on canyon floors in Noctis Labyrinthus, and in Ius Chasma (IC) and Tithonium Chasma (TC

  11. Improving Density Functional Tight Binding Predictions of Free Energy Surfaces for Slow Chemical Reactions in Solution

    Science.gov (United States)

    Kroonblawd, Matthew; Goldman, Nir

    2017-06-01

    First principles molecular dynamics using highly accurate density functional theory (DFT) is a common tool for predicting chemistry, but the accessible time and space scales are often orders of magnitude beyond the resolution of experiments. Semi-empirical methods such as density functional tight binding (DFTB) offer up to a thousand-fold reduction in required CPU hours and can approach experimental scales. However, standard DFTB parameter sets lack good transferability and calibration for a particular system is usually necessary. Force matching the pairwise repulsive energy term in DFTB to short DFT trajectories can improve the former's accuracy for reactions that are fast relative to DFT simulation times (Contract DE-AC52-07NA27344.

  12. Chemical reaction effect on MHD free convective surface over a moving vertical plate through porous medium

    Directory of Open Access Journals (Sweden)

    R.S. Tripathy

    2015-09-01

    Full Text Available An attempt has been made to study the heat and mass transfer effect in a boundary layer flow of an electrically conducting viscous fluid subject to transverse magnetic field past over a moving vertical plate through porous medium in the presence of heat source and chemical reaction. The governing non-linear partial differential equations have been transformed into a two-point boundary value problem using similarity variables and then solved numerically by fourth order Runge–Kutta fourth order method with shooting technique. Graphical results are discussed for non-dimensional velocity, temperature and concentration profiles while numerical values of the skin friction, Nusselt number and Sherwood number are presented in tabular form for various values of parameters controlling the flow system.

  13. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Kexin; Han, Yu

    2013-01-01

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized

  14. Probing the rate-determining region of the potential energy surface for a prototypical ion-molecule reaction.

    Science.gov (United States)

    Xie, Changjian; Liu, Xinguo; Sweeny, Brendan C; Miller, Thomas M; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

    2018-03-13

    We report a joint experimental-theoretical study of the F -  + HCl → HF + Cl - reaction kinetics. The experimental measurement of the rate coefficient at several temperatures was made using the selected ion flow tube method. Theoretical rate coefficients are calculated using the quasi-classical trajectory method on a newly developed global potential energy surface, obtained by fitting a large number of high-level ab initio points with augmentation of long-range electrostatic terms. In addition to good agreement between experiment and theory, analyses suggest that the ion-molecule reaction rate is significantly affected by shorter-range interactions, in addition to the traditionally recognized ion-dipole and ion-induced dipole terms. Furthermore, the statistical nature of the reaction is assessed by comparing the measured and calculated HF product vibrational state distributions to that predicted by the phase space theory.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  15. Optimization of Maillard reaction with ribose for enhancing anti-allergy effect of fish protein hydrolysates using response surface methodology.

    Science.gov (United States)

    Yang, Sung-Yong; Kim, Se-Wook; Kim, Yoonsook; Lee, Sang-Hoon; Jeon, Hyeonjin; Lee, Kwang-Won

    2015-06-01

    Halibut is served on sushi and as sliced raw fish fillets. We investigated the optimal conditions of the Maillard reaction (MR) with ribose using response surface methodology to reduce the allergenicity of its protein. A 3-factored and 5-leveled central composite design was used, where the independent variables were substrate (ribose) concentration (X1, %), reaction time (X2, min), and pH (X3), while the dependent variables were browning index (Y1, absorbance at 420nm), DPPH scavenging (Y2, EC50 mg/mL), FRAP (Y3, mM FeSO4/mg extract) and β-hexosaminidase release (Y4, %). The optimal conditions were obtained as follows: X1, 28.36%; X2, 38.09min; X3, 8.26. Maillard reaction products of fish protein hydrolysate (MFPH) reduced the amount of nitric oxide synthesis compared to the untreated FPH, and had a significant anti-allergy effect on β-hexosaminidase and histamine release, compared with that of the FPH control. We concluded that MFPH, which had better antioxidant and anti-allergy activities than untreated FPH, can be used as an improved dietary source. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Berman, A D; Krylov, O V

    1978-01-01

    This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

  17. Radiation-induced reactions of amino acids adsorbed on solid surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Esquivel Kranksith, L.; Negron-Mendoza, A. [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, UNAM. Cd. Universitaria, A.P. 70-543, 04510 Mexico D.F. (Mexico); Mosqueira, F.G. [Direcion General de Divulgacion de la Ciencia, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, AP. 70-487 Mexico D.F. (Mexico); Ramos-Bernal, Sergio, E-mail: ramos@nucleares.unam.m [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, UNAM. Cd. Universitaria, A.P. 70-543, 04510 Mexico D.F. (Mexico)

    2010-07-21

    The purpose of this work is to study the adsorption of compounds such as amino acids on clays and carbon nanotubes (CNTs) as a possible phase in the chemical evolution that may have occurred on the primitive Earth or in extraterrestrial environments. We further study the behavior of amino acids adsorbed on these solid surfaces at different conditions of pH and levels of irradiation, simulating a high-radiation field at early Earth conditions. The relevance of this work is to explain the possible contribution of solids (clays and CNTs) as promoters of polymerization and as shields for the adsorbed organic compounds against external sources of energy. To this end, tryptophan, aspartic acid, and glutamic acid were adsorbed on fixed amounts of solid surfaces and were irradiated by a {sup 60}Co source for different periods of time at fixed dose rates. After irradiation, the amino acids were extracted from the solid and analyzed with UV and IR spectroscopes and high-performance liquid chromatography. The most efficient surface for adsorption of amino acids was clay, followed by CNTs. Studies of the gamma irradiation of amino acids adsorbed on clay (in the solid phase) show a low yield of recovery of the amino acid.

  18. Distribution of Cr atoms in the surface zone of Fe-rich Fe–Cr alloys quenched into various media: Mössbauer spectroscopic study

    International Nuclear Information System (INIS)

    Dubiel, Stanisław M.; Cieślak, Jakub; Żukrowski, Jan

    2015-01-01

    Graphical abstract: Chromium depletion, Δx = x_k − x, in Fe_1_0_0_−_xCr_x (x = 2.2, 3.9, 6.4, 8.5, 10.25, 10.75, 14.9, 15.15) alloys quenched into LN (left panel) and those quenched onto brass (right panel) as found from CEMS (pre surface zone) and TRANS (bulk) Mössbauer spectra (x_k – Cr content in the pre surface or bulk as estimated from the average hyperfine field found for the quenched samples). - Highlights: • Effect of quenching media on Cr atom distribution in Fe–Cr alloys was determined. • Significant differences between bulk and pre surface zone were revealed. • Quenching into water and LH resulted in surface oxidation of samples. • Samples quenched onto a block of brass were not oxidized. - Abstract: Effect of a quenching medium (water, liquid nitrogen and block of brass) on a distribution of Cr atoms in the surface zone of Fe_1_0_0_−_xCr_x (x ≤ 19) alloys was studied with the Mössbauer spectroscopy. The distribution of Cr atoms was expressed in terms of the Cowley–Warren short-range order (SRO) parameters: 〈α_1〉 for the first neighbor-shell, 〈α_2〉 for the second neighbor-shell and 〈α_1_2〉 for both neighbor-shells. It was revealed that none of the quenching media resulted in a random distribution of atoms, yet the degree of randomness was the highest for the samples quenched onto the block of brass. The quenching into water and liquid nitrogen caused a partial oxidation of samples’ surface accompanied by a chromium depletion of the bulk. Quantitative analysis of various phases in the studied samples both in their bulk as well as in pre surface zones was carried out.

  19. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    Science.gov (United States)

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-10-01

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

  20. Correlation of Growth and Surface Properties of Poly(\\(p\\-xylylenes to  Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Andreas Reichel

    2015-05-01

    Full Text Available Parylene, a non-critical, non-toxic layer material, which is not only a candidate for low-\\(K\\ dielectrics, but also well suited for long-term applications in the human body, has been deposited by (plasma-enhanced chemical vapor deposition of the monomeric species. To that end, a specially-designed reactor exhibiting a cracker tube at its entrance, which serves as the upstream control, and a cooling trap in front of the downstream control has been applied. The process of polymerization has been traced and is explained by evaporating the dimeric species followed by dissociation in the cracker at elevated temperatures and, eventually, to the coating of the polymeric film in terms of thermodynamics. Alternatively, the process of dissociation has been accomplished applying a microwave plasma. In both cases, the monomerization is controlled by mass spectrometry. The window for surface polymerization could be clearly defined in terms of a factor of dilution by an inert gas for the chemical vapor deposition (CVD case and in the case of plasma-enhanced chemical vapor deposition (PECVD, additionally by the power density. The characterization of the layer parameters has been carried out by several analytical tools: scanning electron microscopy and atomic force microscopy to determine the surface roughness and density and depth of voids in the film, which influence the layer capacitance and deteriorate the breakdown voltage, a bulk property. The main issue is the conduct against liquids between the two borders' hydrophilic and hydrophobic conduct, but also the super-hydrophobic character, which is the condition for the Lotus effect. The surface tension has been evaluated by contact angle measurements. Fourier-transform infrared spectroscopy has proven the conservation of all of the functional groups during polymerization.

  1. Reaction probability of molecular deuterium with a disordered InSb (110) surface

    International Nuclear Information System (INIS)

    Wolf, B.; Zehe, A.

    1987-01-01

    A detailed experimental analysis of the interaction of molecular deuterium with sputter-damaged InSb surfaces by the aid of SIMS is given. The sticking probability of D 2 and its transformation to a chemisorbed state resulting in InD + signals in SIMS measurements can be determined by adsorption experimens both with and without a hot tungsten filament. The calculated sticking probability of D 2 = 2 x 10 -4 is at least three orders of magnitude higher than the known-value for a cleavage plane of InSb

  2. Groundwater monitoring and modelling of the “Vector” site for near-surface radioactive waste disposal in the Chornobyl exclusion zone

    Directory of Open Access Journals (Sweden)

    D. Bugai

    2017-12-01

    Full Text Available Results of purposeful groundwater monitoring and modelling studies are presented, which were carried out in order to better understand groundwater flow patterns from the “Vector” site for near-surface radioactive waste disposal and storage in the Chornobyl exclusion zone towards river network. Both data of observations at local-scale monitoring well network at “Vector” site carried out in 2015 - 2016 and modelling analyses using the regional groundwater flow model of Chornobyl exclusion zone suggest that the groundwater discharge contour for water originating from “Vector” site is Sakhan River, which is the tributary to Pripyat River. The respective groundwater travel time is estimated at 210 - 340 years. The travel times in subsurface for 90Sr, 137Cs, and transuranium radionuclides (Pu isotopes, 241Am are estimated respectively at thousands, tenths of thousands, hundreds of thousands – million of years. These results, as well as presented data of analyses of lithological properties of the geological deposits of the unsaturated zone at “Vector” site, provide evidence for good protection of surface water resources from radioactivity sources (e.g., radioactive wastes to be disposed in the near-sursface facilities at “Vector” site.

  3. The Modification of Cellulosic Surface with Fatty Acids via Plasma Mediated Reactions

    Science.gov (United States)

    Nada, Ahmed Ali Ahmed

    Much attention has been paid recently to understand the healing process made by the human body, in order to develop new approaches for promoting healing. The wound healing process includes four main phases, namely, hemostatic, inflammatory, proliferation, and remodeling, which take place successively. The human body can provide all the requirements of the healing process in normal wounds, unless there is a kind of deficiency of the skin function or massive fluid losses of vast wounds. Therefore, wound care of non-healing wounds has recently been the growing concern of many applications. The goal of this work is to explore the development of a new cellulose-based wound dressing composite that contain or release wound healing agents attained via dry textile chemical finishing techniques (thermal curing-plasma treatment). The synthesis of different wound healing agents derived from fatty acids and attached chemically to cellulose or even delivered through cyclodextrine modified cellulose are reported in this work. First, free fatty acids, which are obtained from commercial vegetable oils, were identified as wound healing agents. Many of these free acids are known to bind with and deactivate the proteases associated with inflammation at a wound site. Linoleic acid is extracted from commercial products of safflower seed oil while ricinoleic acid is obtained from castor oil. Conjugated linoleic acid was synthesized. Un-conjugated linoleic acid was used to prepare two derivatives namely linoleic azide and allylic ketone of linoleic acid. Different cellulose derivatives such as cellulose peroxide, iododeoxycellulose and cellulose diazonium salt in different degree of substitutions were synthesized in order to facilitate the free radical reaction with the fatty acid derivatives. New modified cellulosic products were synthesized by reacting the cellulosic and the linoleic acid derivatives via thermal or plasma technique and characterized by FT-IR ATR, the wettability test

  4. A critical assessment of theoretical methods for finding reaction pathways and transition states of surface processes

    International Nuclear Information System (INIS)

    Klimes, JirI; Michaelides, Angelos; Bowler, David R

    2010-01-01

    The performance of a variety of techniques for locating transition states on potential energy surfaces is evaluated within the density functional theory framework. Diffusion of a water molecule across NaCl(001) and HCl bond breaking on the same surface are treated as general test cases; the former is an example of a low barrier diffusion process and the latter an example of a relatively high barrier covalent bond rupture event. The methods considered include the nudged elastic band (NEB), Dewar, Healy and Stewart (DHS), dimer, constrained optimization (CO), activation-relaxation technique (ART) and one-side growing string (OGS) as well as novel combinations of the DHS with growing string (DHS + GS) and DHS plus climbing image (CI-DHS). A key conclusion to come from this study is that the NEB method is relatively fast, especially when just a single (climbing) image is used. Indeed, using more images represents an unnecessary computational burden for our set of processes. The dimer method exhibits variable performance; being poor for the water diffusion processes, which have small activation energies, but much more efficient for the HCl bond breaking process which has a higher barrier. When only a poor initial guess of the transition state geometry is available, the CI-DHS scheme is one of the most efficient techniques considered. And as a means to quickly establish an approximate minimum energy pathway the DHS + GS scheme offers some potential.

  5. Spectroscopic studies on surface reactions between minerals and reagents in flotation systems

    International Nuclear Information System (INIS)

    Giesekke, E.W.

    1981-01-01

    A study of the adsorbed species at the interface between the minerals and the aqueous solution is reported in the hope that it will contribute to a better understanding of selective mineral flotation by various reagents. The results of infrared spectroscopic studies are cited from the author's investigation on the fluorite-sodium oleate and fluorite-linoleate systems. Electron-spectroscopic techniques, e.g., electron spectroscopy for chemical analysis (ESCA) have also been useful in the identification of adsorbed species on mineral surfaces. Some experimental data from the literature are discussed. These studies have the disadvantage that they are not in situ investigations of the interface between the mineral and the aqueous solution. The potential use of other spectroscopic techniques are discussed, photo-acoustic, Raman, and electron-spin-resonance spectroscopy being considered as possible alternatives. It is suggested that the relatively small surface areas of minerals used in flotation (i.e. smaller than 2m 2 .g- 1 ) impose severe restrictions on the use of such techniques

  6. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Rubiera, F.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with on-line battery of analyzers. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behaviour in other combustion equipments, i.e. fluidized bed combustors. It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor. 27 refs., 6 figs., 1 tab.

  7. Mapping of upper electronic reaction surfaces by tuned laser photolysis and by absorption and emission spectroscopies

    International Nuclear Information System (INIS)

    Morgan, M.A.

    1989-07-01

    Potential energy surfaces for photorotamerization of two intramolecularly hydrogen-bonded molecules, o-hydroxybenzaldehyde (OHBA) and methyl salicylate (MS), isolated in cryogenic matrices have been spectroscopically mapped. In addition, the external heavy atom effect of krypton and xenon matrices on the coupling between the S 1 and T 1 surfaces of 4-(dimethylamino)benzonitrile has been examined. Heavy atom matrices are known to increase rates of spin-forbidden processes. The phosphorescence intensity of DMABN increases in krypton and xenon matrices, while the fluorescence intensity, and phosphorescence and fluorescence lifetimes, decrease. These effects are interpreted in terms of a model in which the phosphorescence rate constant increases 300-fold in xenon compared to argon, while the rate constants for intersystem crossing and nonradiative relaxation from the triplet state increase by factors of less than 5. Lifetime measurements in argon matrices doped with heavy atoms indicate that even one heavy atom neighbor has a significant effect on both singlet and triplet lifetimes. 78 refs., 35 figs., 15 tabs

  8. On the methane paradox: Transport from shallow water zones rather than in situ methanogenesis is the major source of CH4 in the open surface water of lakes

    Science.gov (United States)

    Encinas Fernández, Jorge; Peeters, Frank; Hofmann, Hilmar

    2016-10-01

    Estimates of global methane (CH4) emissions from lakes and the contributions of different pathways are currently under debate. In situ methanogenesis linked to algae growth was recently suggested to be the major source of CH4 fluxes from aquatic systems. However, based on our very large data set on CH4 distributions within lakes, we demonstrate here that methane-enriched water from shallow water zones is the most likely source of the basin-wide mean CH4 concentrations in the surface water of lakes. Consistently, the mean surface CH4 concentrations are significantly correlated with the ratio between the surface area of the shallow water zone and the entire lake, fA,s/t, but not with the total surface area. The categorization of CH4 fluxes according to fA,s/t may therefore improve global estimates of CH4 emissions from lakes. Furthermore, CH4 concentrations increase substantially with water temperature, indicating that seasonally resolved data are required to accurately estimate annual CH4 emissions.

  9. Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

    Science.gov (United States)

    Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

    2018-05-01

    Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

  10. Formation of poorly crystalline iron monosulfides: Surface redox reactions on high purity iron, spectroelectrochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Hansson, E.B. [Geological Institute, University of Copenhagen, Oster Voldgade 10, Copenhagen K, DK-1350 (Denmark); Odziemkowski, M.S. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)]. E-mail: marek@sciborg.uwaterloo.ca; Gillham, R.W. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)

    2006-11-15

    In the use of iron for reductive dehalogenation of chlorinated solvents in ground water, due to presence of sulfate-reducing bacteria the formation of hydrogen sulfide is expected. To simulate those processes the interface between 99.99% pure iron and 0.1 M NaHCO{sub 3} deoxygenated solution with 3.1 x 10{sup -5}-7.8 x 10{sup -3} M Na{sub 2}S . 9H{sub 2}O added was studied. The surface processes were characterised by the in situ normal Raman spectroscopy (NRS) and ex situ techniques; X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The open circuit potential (OCP) was monitored during in situ NRS measurements, and potentiodynamic anodic polarization measurements were carried out to reveal electrochemical behaviour of iron electrode. Open circuit potential-time transients indicated that the native oxide is unstable in deaerated bicarbonate solution and undergoes reductive dissolution (i.e. autoreduction) leaving the metallic Fe covered by Fe(OH){sub 2}, adsorbed OH{sup -}, and patches of 'magnetite-like' oxide. Immediately upon injection of the Na{sub 2}S-solution the iron interface undergoes complex redox surface processes and a poorly crystalline FeS film forms. Potentiodynamic anodic polarization measurements indicated a mechanical breakdown of the FeS film. The origin and initiation of this breakdown process is not clear but is probably a result of internal stress developed during film growth. Based on surface studies supported by electrochemical measurements, a conceptual model for the complex redox processes occurring at the iron interface is proposed. This model describes the structural development of a poorly crystalline FeS, which breaks down, allowing further dissolution of the Fe and formation of FeOOH at the interface. Simultaneously and despite the existence of thick layer of FeS the entrance of hydrogen was evident as the typical hydrogen cracks in bulk of the

  11. Surface reactions during low-k etching using H2/N2 plasma

    International Nuclear Information System (INIS)

    Fukasawa, Masanaga; Tatsumi, Tetsuya; Oshima, Keiji; Nagahata, Kazunori; Uchida, Saburo; Takashima, Seigo; Hori, Masaru; Kamide, Yukihiro

    2008-01-01

    We investigated the relationship between the hard mask faceting that occurs during organic low-k etching and the ion energy distribution function of a capacitively coupled plasma reactor. We minimized the hard mask faceting by precisely controlling the ion energy. This precise control was obtained by selecting the optimum bottom frequency and bias power. We measured the amount of damage done to a SiOCH film exposed to H 2 /N 2 plasma in order to find the H 2 /N 2 ratio at which the plasma caused the least damage. The amount of moisture uptake by the damaged SiOCH film is the dominant factor controlling the dielectric constant increase (Δk). To suppress Δk, the incident ion species and ion energies have to be precisely controlled. This reduces the number of adsorption sites in the bulk SiOCH and maintains the hydrophobic surface that suppresses water permeation during air exposure

  12. Two-Dimensional Free Energy Surfaces for Electron Transfer Reactions in Solution

    Directory of Open Access Journals (Sweden)

    Shigeo Murata

    2008-01-01

    Full Text Available Change in intermolecular distance between electron donor (D and acceptor (A can induce intermolecular electron transfer (ET even in nonpolar solvent, where solvent orientational polarization is absent. This was shown by making simple calculations of the energies of the initial and final states of ET. In the case of polar solvent, the free energies are functions of both D-A distance and solvent orientational polarization. On the basis of 2-dimensional free energy surfaces, the relation of Marcus ET and exciplex formation is discussed. The transient effect in fluorescence quenching was measured for several D-A pairs in a nonpolar solvent. The results were analyzed by assuming a distance dependence of the ET rate that is consistent with the above model.

  13. The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

    Science.gov (United States)

    Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

    2018-03-01

    The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies

  14. A Microfluidic Chip Based on Localized Surface Plasmon Resonance for Real-Time Monitoring of Antigen-Antibody Reactions

    Science.gov (United States)

    Hiep, Ha Minh; Nakayama, Tsuyoshi; Saito, Masato; Yamamura, Shohei; Takamura, Yuzuru; Tamiya, Eiichi

    2008-02-01

    Localized surface plasmon resonance (LSPR) connecting to noble metal nanoparticles is an important issue for many analytical and biological applications. Therefore, the development of microfluidic LSPR chip that allows studying biomolecular interactions becomes an essential requirement for micro total analysis systems (µTAS) integration. However, miniaturized process of the conventional surface plasmon resonance system has been faced with some limitations, especially with the usage of Kretschmann configuration in total internal reflection mode. In this study, we have tried to solve this problem by proposing a novel microfluidic LSPR chip operated with a simple collinear optical system. The poly(dimethylsiloxane) (PDMS) based microfluidic chip was fabricated by soft-lithography technique and enables to interrogate specific insulin and anti-insulin antibody reaction in real-time after immobilizing antibody on its surface. Moreover, the sensing ability of microfluidic LSPR chip was also evaluated with various glucose concentrations. The kinetic constant of insulin and anti-insulin antibody was determined and the detection limit of 100 ng/mL insulin was archived.

  15. Fabrication of hydrophobic surface of titanium dioxide films by successive ionic layer adsorption and reaction (SILAR) method

    International Nuclear Information System (INIS)

    More, A.M.; Gunjakar, J.L.; Lokhande, C.D.; Joo, Oh Shim

    2009-01-01

    Titanium dioxide (TiO 2 ) films were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using successive ionic layer adsorption and reaction (SILAR) method. The X-ray diffraction, scanning electron microscopy, transmission electron microscopy, optical absorption and contact angle measurement were applied to study the structural, surface morphological, optical and surface wettability properties of the as-deposited and annealed TiO 2 films. The X-ray diffraction studies revealed both as-deposited and annealed TiO 2 films are amorphous. Irregular shaped spherical grains of random size and well covered to the fluorine doped tin oxide coated glass substrates were observed from SEM studies with some cracks after annealing. The optical band gap values of virgin TiO 2, annealed, methyl violet and rose bengal sensitized TiO 2 were found to be 3.6, 3.5, 2.87 and 2.95 eV, respectively. Surface wettability studied in contact with liquid interface, showed hydrophobic nature as water contact angles were greater than 90 deg. The adsorption of dyes, as confirmed by the photographs, is one of the prime requirements for dye sensitized solar cells (DSSC).

  16. HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

    International Nuclear Information System (INIS)

    Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

    2004-01-01

    We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

  17. Application of atomic mutations included in nuclear reactions, 40Ar(γ, p)39Cl(β decay)39Ar, to surface study

    International Nuclear Information System (INIS)

    Ohkuma, Juzo

    1987-01-01

    It has been found that the nuclear transformation processes which are initiated by photonuclear reactions can be used for studying the adsorption and chemical reactions taking place on solid surfaces. Chemically reactive 39 Cl was produced by irradiating 40 Ar with high-energy bremsstrahlung, and its blow was directed onto several material surfaces. The amount of chlorine adsorption was ascertained by detecting its radioactivity. Desorption without heating the adsorber samples inevitably occurred owing to the nuclear decay of 39 Cl. The adsorption and desorption rates were compared for several elements. A fast growth of oxide islands on sample surfaces was observed during the adsorption-desorption process. (author)

  18. MHD Convective Flow of Jeffrey Fluid Due to a Curved Stretching Surface with Homogeneous-Heterogeneous Reactions.

    Directory of Open Access Journals (Sweden)

    Maria Imtiaz

    Full Text Available This paper looks at the flow of Jeffrey fluid due to a curved stretching sheet. Effect of homogeneous-heterogeneous reactions is considered. An electrically conducting fluid in the presence of applied magnetic field is considered. Convective boundary conditions model the heat transfer analysis. Transformation method reduces the governing nonlinear partial differential equations into the ordinary differential equations. Convergence of the obtained series solutions is explicitly discussed. Characteristics of sundry parameters on the velocity, temperature and concentration profiles are analyzed by plotting graphs. Computations for pressure, skin friction coefficient and surface heat transfer rate are presented and examined. It is noted that fluid velocity and temperature through curvature parameter are enhanced. Increasing values of Biot number correspond to the enhancement in temperature and Nusselt number.

  19. Organic photochemical reactions on solid surfaces: Enrichment and separation of isotopes. Final report. SBIR-1988, Phase 2

    International Nuclear Information System (INIS)

    Ruderman, W.; Fehlner, J.; Spencer, J.

    1988-01-01

    The objectives of the Phase II program were to: (1) investigate organic photochemical reactions on solid porous silica surfaces, (2) utilize the magnetic isotope effect to develop a (13)C enrichment process using a fluidized bed reactor, and (3) investigate the possibility of enrichment of heavier isotopes having a nuclear spin. Although researchers were able to demonstrate a continuous fluidized bed (13)C enrichment process, analysis showed that the process could not compete with low temperature distillation of CO because of the high cost of the starting material, dibenzylketone (DBK), and the difficulty of converting the photochemical decomposition products back to DBK. However, the process shows promise for the separation of heavier isotopes such as (29)Si. The photochemical studies led to the discovery that the selectivity for terminal chlorination of alkanes can be increased more than 25 fold by sorbing the alkanes on ZSM-5 zeolites in a fluidized bed. The selectivity is ascribed to the presence of interfaces within the crystals

  20. From near-surface to root-zone soil moisture using an exponential filter: an assessment of the method based on in-situ observations and model simulations

    Directory of Open Access Journals (Sweden)

    C. Albergel

    2008-12-01

    Full Text Available A long term data acquisition effort of profile soil moisture is under way in southwestern France at 13 automated weather stations. This ground network was developed in order to validate remote sensing and model soil moisture estimates. In this paper, both those in situ observations and a synthetic data set covering continental France are used to test a simple method to retrieve root zone soil moisture from a time series of surface soil moisture information. A recursive exponential filter equation using a time constant, T, is used to compute a soil water index. The Nash and Sutcliff coefficient is used as a criterion to optimise the T parameter for each ground station and for each model pixel of the synthetic data set. In general, the soil water indices derived from the surface soil moisture observations and simulations agree well with the reference root-zone soil moisture. Overall, the results show the potential of the exponential filter equation and of its recursive formulation to derive a soil water index from surface soil moisture estimates. This paper further investigates the correlation of the time scale parameter T with soil properties and climate conditions. While no significant relationship could be determined between T and the main soil properties (clay and sand fractions, bulk density and organic matter content, the modelled spatial variability and the observed inter-annual variability of T suggest that a weak climate effect may exist.

  1. Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

    2003-01-01

    Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

  2. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Directory of Open Access Journals (Sweden)

    G. Li

    2016-08-01

    Full Text Available Gaseous formaldehyde (HCHO is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs. Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of  ∼  10 to 40 ppbv. For the determination of uptake coefficients (γ, we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity  =  0 %, an initial γ of (1.1 ± 0.05  ×  10−4 is determined, which gradually drops to (5.5 ± 0.4  ×  10−5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition at the atmosphere–soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  3. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Science.gov (United States)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  4. Optimization of Al-CVD process based on elementary reaction simulation and experimental verification: From the growth rate to the surface morphology

    International Nuclear Information System (INIS)

    Sugiyama, Masakazu; Iino, Tomohisa; Nakajima, Tohru; Tanaka, Takeshi; Egashira, Yasuyuki; Yamashita, Kohichi; Komiyama, Hiroshi; Shimogaki, Yukihiro

    2006-01-01

    We propose a method to reduce the surface roughness of Al film in the chemical vapor deposition (CVD) using dimethyl-aluminum-hydride (DMAH) as the precursor. An elementary reaction simulation was executed not only to predict the deposition rate but also to predict the coverage of the film by surface adsorbates. It was assumed that high surface coverage is essential in order to deposit smooth films because the adsorbates protect the surface from oxidation which causes discontinuous growth of crystal grains. According to this principle, the condition, that realizes both high surface coverage and high deposition rate at the same time by using the elementary reaction simulation, was sought. A nozzle inlet was used instead of a conventional showerhead. This drastically improved the surface morphology, showing the effectiveness of this theoretical optimization procedure

  5. Developments for the ultrasonic in-service inspection of the inner near surface zone of circular welds in the vessel of the fast breeder-reactor SNR 300

    International Nuclear Information System (INIS)

    Salzburger, H.J.; Huebschen, G.; Neuschwander, R.; Kleffner, G.; Wessels, J.

    1990-01-01

    For in-service, ultrasonic inspection of the inner near-surface zone of the welds 1 and 6 of the vessel of the SNR-300, an automated system has been developed for scanning, manipulation and evaluation tasks. The scanning system which currently is tested and qualified as a prototype system uses heat-resistant EMUS probes which do not require coupling agents, and which have been optimized for three different testing tasks. The required electronic equipment has also been developed to prototype stage, and both have been incorporated into the automated manipulation, data acquisition and evaluation system. (orig.) [de

  6. The Effect of Simulated Microgravity Environment of RWV Bioreactors on Surface Reactions and Adsorption of Serum Proteins on Bone-bioactive Microcarriers

    Science.gov (United States)

    Radin, Shula; Ducheyne, P.; Ayyaswamy, P. S.

    2003-01-01

    Biomimetically modified bioactive materials with bone-like surface properties are attractive candidates for use as microcarriers for 3-D bone-like tissue engineering under simulated microgravity conditions of NASA designed rotating wall vessel (RWV) bioreactors. The simulated microgravity environment is attainable under suitable parametric conditions of the RWV bioreactors. Ca-P containing bioactive glass (BG), whose stimulatory effect on bone cell function had been previously demonstrated, was used in the present study. BG surface modification via reactions in solution, resulting formation of bone-like minerals at the surface and adsorption of serum proteins is critical for obtaining the stimulatory effect. In this paper, we report on the major effects of simulated microgravity conditions of the RWV on the BG reactions surface reactions and protein adsorption in physiological solutions. Control tests at normal gravity were conducted at static and dynamic conditions. The study revealed that simulated microgravity remarkably enhanced reactions involved in the BG surface modification, including BG dissolution, formation of bone-like minerals at the surface and adsorption of serum proteins. Simultaneously, numerical models were developed to simulate the mass transport of chemical species to and from the BG surface under normal gravity and simulated microgravity conditions. The numerical results showed an excellent agreement with the experimental data at both testing conditions.

  7. Welding-induced local maximum residual stress in heat affected zone of low-carbon austenitic stainless steel with machined surface layer and its influential factors

    International Nuclear Information System (INIS)

    Okano, Shigetaka; Ihara, Ryohei; Kanamaru, Daisuke; Mochizuki, Masahito

    2015-01-01

    In this study, the effects of work-hardening and pre-existing stress in the machined surface layer of low-carbon austenitic stainless steel on the welding-induced residual stress were experimentally investigated through the use of weld specimens with three different surface layers; as-cutout, mechanically-polished and electrolytically-polished. The high tensile and compressive stresses exist in the work-hardened surface layer of the as-cutout and mechanically-polished specimens, respectively. Meanwhile, no stress and work-hardened surface layer exist in the electrolytically-polished specimen. TIG bead-on-plate welding under the same welding heat input conditions was performed to introduce the residual stress into these specimens. Using these welded specimens, the distributions of welding-induced residual stress were measured by the X-ray diffraction method. Similarly, the distributions of hardness in welds were estimated by the Vickers hardness test. And then, these distributions were compared with one another. Based on the results, the residual stress in the weld metal (WM) is completely unaffected by the machined surface layer because the work-hardened surface layer disappears through the processes of melting and solidification during welding. The local maximum longitudinal tensile residual stress in the heat affected zone (HAZ) depends on the work-hardening but not on the existing stress, regardless of whether tensile or compressive, in the machined surface layer before welding. At the base metal far from WM and HAZ, the residual stress is formed by the addition of the welding-induced residual stress to the pre-existing stress in the machined surface layer before welding. The features of the welding-induced residual stress in low-carbon austenitic stainless steel with the machined surface layer and their influential factors were thus clarified. (author)

  8. User's Guide: Database of literature pertaining to the unsaturated zone and surface water-ground water interactions at the Idaho National Engineering Laboratory

    International Nuclear Information System (INIS)

    Hall, L.F.

    1993-05-01

    Since its beginnings in 1949, hydrogeologic investigations at the Idaho National Engineering Laboratory (INEL) have resulted in an extensive collection of technical publications providing information concerning ground water hydraulics and contaminant transport within the unsaturated zone. Funding has been provided by the Department of Energy through the Department of Energy Idaho Field Office in a grant to compile an INEL-wide summary of unsaturated zone studies based on a literature search. University of Idaho researchers are conducting a review of technical documents produced at or pertaining to the INEL, which present or discuss processes in the unsaturated zone and surface water-ground water interactions. Results of this review are being compiled as an electronic database. Fields are available in this database for document title and associated identification number, author, source, abstract, and summary of information (including types of data and parameters). AskSam reg-sign, a text-based database system, was chosen. WordPerfect 5.1 copyright is being used as a text-editor to input data records into askSam

  9. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  10. A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

    Science.gov (United States)

    Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

    2017-04-05

    The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

  11. Surface tectonics of nanoporous networks of melamine-capped molecular building blocks formed through interface Schiff-base reactions.

    Science.gov (United States)

    Liu, Xuan-He; Wang, Dong; Wan, Li-Jun

    2013-10-01

    Control over the assembly of molecules on a surface is of great importance for the fabrication of molecule-based miniature devices. Melamine (MA) and molecules with terminal MA units are promising candidates for supramolecular interfacial packing patterning, owing to their multiple hydrogen-bonding sites. Herein, we report the formation of self-assembled structures of MA-capped molecules through a simple on-surface synthetic route. MA terminal groups were successfully fabricated onto rigid molecular cores with 2-fold and 3-fold symmetry through interfacial Schiff-base reactions between MA and aldehyde groups. Sub-molecular scanning tunneling microscopy (STM) imaging of the resultant adlayer revealed the formation of nanoporous networks. Detailed structural analysis indicated that strong hydrogen-bonding interactions between the MA groups persistently drove the formation of nanoporous networks. Herein, we demonstrate that functional groups with strong hydrogen-bond-formation ability are promising building blocks for the guided assembly of nanoporous networks and other hierarchical 2D assemblies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces.

    Science.gov (United States)

    Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R; Sakai, Naomi; Matile, Stefan

    2016-03-18

    To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. VT Data - Zoning 20070306, Marlboro

    Data.gov (United States)

    Vermont Center for Geographic Information — Zoning districts, Marlboro, Vermont. Surface water buffer overlay is in a separate shapefile. Data were originally created by WRC in 2005. Marlboro's zoning bylaw...

  14. A Novel Application of the Multichannel Analysis of Surface Waves (MASW) Method for Estimating the Critical Zone Thicknes

    Science.gov (United States)

    Nelson, S.; Yaede, J.; McBride, J. H.; Park, C.; Turnbull, S. J.; Tingey, D. G.

    2014-12-01

    MASW approaches are suitable for the accurate measurement of variably thick weathering profiles by producing shear-wave (Vs) profiles. The critical zone (CZ) base is usually a transitional boundary, which is captured by MASW but not by conventional seismic reflection techniques. Modified MASW methods were used in Hawaii, USA to extend the investigative depth of saprolite (kaolin clays, Fe-oxides) thickness calibrated against wells with geologic logs. Active-source ± passive dispersion curves produced improved low-frequency fundamental modes by combining records with varying source-receiver offsets, enabling the generation of Vs profiles to >50 m depth. The top of unaltered bedrock occurs at a Vs of >~500 m/s. Intra-saprolite high Vs zones probably represent aa flow interiors with fewer primary discontinuities (vesicles and fractures), therefore imparting higher secondary stiffness than altered pahoehoe and pyroclastic material. The MASW approach permits measuring CZ thicknesses at discrete locations rapidly, inexpensively, and without drilling. For example, employed on slopes of the Koolau Volcano (neither aggrading nor degrading), the downward rate of advance of the weathering front of the CZ varies from 0.02 to 0.03 mm/yr in wet and ~0.01 mm/yr in dry areas. This compares well with recent work based on solute mass fluxes averaged over large areas. MASW can be deployed in a variety of settings where rapid estimation of the CZ thickness at particular locations is desired.

  15. State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface.

    Science.gov (United States)

    Li, Anyang; Guo, Hua; Sun, Zhigang; Kłos, Jacek; Alexander, Millard H

    2013-10-07

    The state-to-state reaction dynamics of the title reaction is investigated on the ground electronic state potential energy surface using two quantum dynamical methods. The results obtained using the Chebyshev real wave packet method are in excellent agreement with those obtained using the time-independent method, except at low translational energies. It is shown that this exothermic hydrogen abstraction reaction is direct, resulting in a strong back-scattered bias in the product angular distribution. The HF product is highly excited internally. Agreement with available experimental data is only qualitative. We discuss several possible causes of disagreement with experiment.

  16. Organic contamination of surface sediments in the metropolitan coastal zone of Athens, Greece: sources, degree, and ecological risk.

    Science.gov (United States)

    Kapsimalis, V; Panagiotopoulos, I P; Talagani, P; Hatzianestis, I; Kaberi, H; Rousakis, G; Kanellopoulos, T D; Hatiris, G A

    2014-03-15

    Bottom sediments represent a crucial component of the marine environment, since they constitute a habitat, a trophic resource, and a spawning place for various organisms. Unfortunately, the sediments of urban coastal areas are deeply impacted by anthropogenic activities that degrade their quality. In the Drapetsona-Keratsini metropolitan coastal zone of Athens, current industrial and shipping activities together with the effluents from a sewage outfall, which was in operation in the past, have resulted in one of the most contaminated sedimentary environments, in terms of organic compound loads, in Mediterranean. Exceptionally high concentrations of aliphatic hydrocarbons (up to 4457 μg g⁻¹), carcinogenic PAHs (up to 7284 ng g⁻¹), and organochlorines (up to 544 ng g⁻¹ for PCBs; up to 208 ng g⁻¹ for DDTs) constitute a major threat to the marine life of the associated Saronikos Gulf. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.

    Science.gov (United States)

    Gao, Erping; Wang, Wenzhong

    2013-11-21

    Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2˙(-) anions as the major oxidation species instead of ˙OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25.

  18. A global model for SF6 plasmas coupling reaction kinetics in the gas phase and on the surface of the reactor walls

    International Nuclear Information System (INIS)

    Kokkoris, George; Panagiotopoulos, Apostolos; Gogolides, Evangelos; Goodyear, Andy; Cooke, Mike

    2009-01-01

    Gas phase and reactor wall-surface kinetics are coupled in a global model for SF 6 plasmas. A complete set of gas phase and surface reactions is formulated. The rate coefficients of the electron impact reactions are based on pertinent cross section data from the literature, which are integrated over a Druyvesteyn electron energy distribution function. The rate coefficients of the surface reactions are adjustable parameters and are calculated by fitting the model to experimental data from an inductively coupled plasma reactor, i.e. F atom density and pressure change after the ignition of the discharge. The model predicts that SF 6 , F, F 2 and SF 4 are the dominant neutral species while SF 5 + and F - are the dominant ions. The fit sheds light on the interaction between the gas phase and the reactor walls. A loss mechanism for SF x radicals by deposition of a fluoro-sulfur film on the reactor walls is needed to predict the experimental data. It is found that there is a net production of SF 5 , F 2 and SF 6 , and a net consumption of F, SF 3 and SF 4 on the reactor walls. Surface reactions as well as reactions between neutral species in the gas phase are found to be important sources and sinks of the neutral species.

  19. Critical Zone structure inferred from multiscale near surface geophysical and hydrological data across hillslopes at the Eel River CZO

    Science.gov (United States)

    Lee, S. S.; Rempe, D. M.; Holbrook, W. S.; Schmidt, L.; Hahm, W. J.; Dietrich, W. E.

    2017-12-01

    Except for boreholes and road cut, landslide, and quarry exposures, the subsurface structure of the critical zone (CZ) of weathered bedrock is relatively invisible and unmapped, yet this structure controls the short and long term fluxes of water and solutes. Non-invasive geophysical methods such as seismic refraction are widely applied to image the structure of the CZ at the hillslope scale. However, interpretations of such data are often limited due to heterogeneity and anisotropy contributed from fracturing, moisture content, and mineralogy on the seismic signal. We develop a quantitative framework for using seismic refraction tomography from intersecting geophysical surveys and hydrologic data obtained at the Eel River Critical Zone Observatory (ERCZO) in Northern California to help quantify the nature of subsurface structure across multiple hillslopes of varying topography in the area. To enhance our understanding of modeled velocity gradients and boundaries in relation to lithological properties, we compare refraction tomography results with borehole logs of nuclear magnetic resonance (NMR), gamma and neutron density, standard penetration testing, and observation drilling logs. We also incorporate laboratory scale rock characterization including mineralogical and elemental analyses as well as porosity and density measurements made via pycnometry, helium and mercury porosimetry, and laboratory scale NMR. We evaluate the sensitivity of seismically inferred saprolite-weathered bedrock and weathered-unweathered bedrock boundaries to various velocity and inversion parameters in relation with other macro scale processes such as gravitational and tectonic forces in influencing weathered bedrock velocities. Together, our sensitivity analyses and multi-method data comparison provide insight into the interpretation of seismic refraction tomography for the quantification of CZ structure and hydrologic dynamics.

  20. How deep can surface signals be traced in the critical zone? Merging biodiversity with biogeochemistry research in a central German Muschelkalk landscape

    Directory of Open Access Journals (Sweden)

    Kirsten eKüsel

    2016-04-01

    Full Text Available The Earth’s Critical Zone (CZ is a thin living layer connecting atmosphere and geosphere, including aquifers. Humans live in the CZ and benefit from the vital supporting services it provides. However, the CZ is increasingly impacted by human activities including land and resource use, pollution and climate change. Recent interest in uniting the many disciplines studying this complex domain has initiated an international network of research infrastructure platforms that allow access to the CZ in a range of geologic settings. In this paper a new such infrastructure platform associated with the Collaborative Research Center AquaDiva is described, that uniquely seeks to combine CZ research with detailed investigation of the functional biodiversity of the subsurface. Overall, AquaDiva aims to test hypotheses about how water connects surface conditions set by land cover and land management to the biota and biogeochemical functions in the subsurface. With long-term and continuous observations, hypotheses about how seasonal variations and extreme events at the surface impact subsurface processes, community structure and function, are tested. AquaDiva has established the Hainich Critical Zone Exploratory (CZE in central Germany in an alkaline geological setting of German Triassic Muschelkalk formations. The Hainich CZE includes specialized monitoring wells to access the vadose zone and two main groundwater complexes in limestone and marlstone parent materials along a ~6 km transect spanning forest, pasture and agricultural land uses. Initial results demonstrate fundamental differences in the biota and biogeochemistry of the two aquifer complexes that trace back to the land uses in their respective recharge areas. They also show the importance of antecedent conditions on the impact of precipitation events on responses in terms of groundwater dynamics, chemistry and ecology. Thus we find signals of surface land use and events can be detected in the

  1. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  2. Limitations on Inferring 3D Architecture and Dynamics From Surface Velocities in the India-Eurasia Collision Zone

    Science.gov (United States)

    Flesch, L.; Bendick, R.; Bischoff, S.

    2018-02-01

    Surface velocities derived from Global Positioning System observations and Quaternary fault slip rates measured throughout an extended region of high topography in South Asia vary smoothly over thousands of kilometers and are broadly symmetrical, with components of both north-south shortening and east-west extension relative to stable Eurasia. The observed velocity field does not contain discontinuities or steep gradients attributable to along-strike differences in collision architecture, despite the well-documented presence of a lithospheric slab beneath the Pamir but not the Tibetan Plateau. We use a modified Akaike information criterion (AICc) to show that surface velocities do not efficiently constrain 3D rheology, geometry, or force balance. Therefore, although other geophysical and geological observations may indicate the presence of mechanical or dynamic heterogeneities within the Indian-Asian collision, the surface Global Positioning System velocities contain little or no usable information about them.

  3. Application of the response surface and desirability design to the Lambda-cyhalothrin degradation using photo-Fenton reaction.

    Science.gov (United States)

    Colombo, Renata; Ferreira, Tanare C R; Alves, Suellen A; Carneiro, Renato L; Lanza, Marcos R V

    2013-03-30

    Lambda-cyhalothrin is a potent pyrethroid insecticide used widely in pest management. Detectable levels of the pyrethroid in agricultural watersheds are potentially toxic to aquatic organisms. There is little information in the scientific literature about degradation in aqueous media of the Lambda-cyhalothrin by Advanced Oxidative Process. A mathematical approach for the degradation of this compound has not yet been fully explored… The Central composite design (CCD) and response surface method (RSM) were applied to evaluate and optimize the interactive effects of two operating variables. The initial dosages of H2O2 and Fe(2+) on photo-Fenton degradation of an aqueous solution of Lambda-cyhalothrin in a recirculation flow-through UV photoreactor were used. The remaining concentration of Lambda-cyhalothrin (y1) and the percentage removal of total organic carbon (y2) were the monitored factors since they are dependent parameters of y1 and y2. According to analysis of variances (ANOVA) results, two proposed models can be used to navigate the design space with regression coefficient R(2) - 0.834 and 0.843 for y1 and y2, respectively. A multi-response optimization procedure, based on the global desirability of the factors, was performed to establish the best concentrations of hydrogen peroxide and ferrous sulfate that would allow the most efficient degradation of Lambda-cyhalothrin concomitant with a maximal removal of total organic carbon. The global desirability surface revealed that 0.295 mmol L(-1) of ferrous sulfate and 3.85 mmol L(-1) of hydrogen peroxide were close to the optimum conditions to satisfy both factors simultaneously using minimal amounts of reagents. These photo-Fenton conditions promoted 100% of Lambda-cyhalothrin degradation and 79.83% TOC removal (mineralization) in 120 min of reaction time. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Direct characterization of phase transformations and morphologies in moving reaction zones in Al/Ni nanolaminates using dynamic transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, J.S., E-mail: judy.kim@materials.ox.ac.uk [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); LaGrange, T.; Reed, B.W. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Knepper, R.; Weihs, T.P. [Department of Materials Science and Engineering, Johns Hopkins University, 3400 N. Charles St., Baltimore, MD 21218 (United States); Browning, N.D. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); Campbell, G.H. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States)

    2011-05-15

    Highlights: > Fast phase transformations are examined in Al/Ni reactive nanolaminates. > Results visible only by dynamic transmission electron microscopy at ns resolution. > NiAl forms under 15 ns after reaction front in all three stoichiometries studied. > DTEM imaging reveals a transient cellular morphology in nonequiatomic films. - Abstract: Phase transformations and transient morphologies are examined as exothermic formation reactions self-propagate across Al/Ni nanolaminate films. The rapid evolution of these phases and sub-micrometer morphological features requires nanoscale temporal and spatial resolution that is not available with traditional in situ electron microscopy. This work uses dynamic transmission electron microscopy to identify intermetallic products and phase morphologies, as exothermic formation reactions self-propagate in nanolaminate films grown with 3:2, 2:3 and 1:1 Al/Ni atomic ratios. Single-shot diffraction patterns with 15 ns temporal resolution reveal that the NiAl intermetallic forms within {approx}15 ns of the reaction front's arrival in all three types of films and is the only intermetallic phase to form, as the reactions self-propagate and quench very rapidly. Time-resolved imaging reveals a transient cellular morphology in the Al-rich and Ni-rich foils, but not in the equiatomic films. The cellular features in the Al-rich and Ni-rich films are attributed to a cooling trajectory through a two-phase field of liquid + NiAl.

  5. Mechanisms for surface contamination of soils and bottom sediments in the Shagan River zone within former Semipalatinsk Nuclear Test Site.

    Science.gov (United States)

    Aidarkhanov, A O; Lukashenko, S N; Lyakhova, O N; Subbotin, S B; Yakovenko, Yu Yu; Genova, S V; Aidarkhanova, A K

    2013-10-01

    The Shagan River is the only surface watercourse within the former Semipalatinsk Test Site (STS). Research in the valley of the Shagan River was carried out to study the possible migration of artificial radionuclides with surface waters over considerable distances, with the possibility these radionuclides may have entered the Irtysh River. The investigations revealed that radioactive contamination of soil was primarily caused by the first underground nuclear test with soil outburst conducted at the "Balapan" site in Borehole 1004. The surface nuclear tests carried out at the "Experimental Field" site and global fallout made insignificant contributions to contamination. The most polluted is the area in the immediate vicinity of the "Atomic" Lake crater. Contamination at the site is spatial. The total area of contamination is limited to 10-12 km from the crater piles. The ratio of plutonium isotopes was useful to determine the source of soil contamination. There was virtual absence of artificial radionuclide migration with surface waters, and possible cross-border transfer of radionuclides with the waters of Shagan and Irtysh rivers was not confirmed. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Surface energy balance in the ablation zone of Langfjordjøkelen, an arctic, maritime glacier in northern Norway

    NARCIS (Netherlands)

    Giesen, Rianne H.; Andreassen, Liss M.; Oerlemans, Johannes; van den Broeke, Michiel R.

    2014-01-01

    Glaciers in northern and southern Norway are subject to different daily and seasonal cycles of incoming solar radiation, which is presumably reflected in the importance of net solar radiation in their surface energy balance. We present a 3 year continuous record from an automatic weather station in

  7. ECO Update / Groundwater Foum Issue Paper: Evaluating Ground-Water/Surface-Water Transition Zones in Ecological Risk Assessments

    Science.gov (United States)

    This ECO Update builds on the standard approach to ERA (U.S. EPA 1997), by providing a framework for incorporating groundwater/surface-water (GW/SW) interactions into existing ERAs (see U.S. EPA 1997 and 2001a for an introduction to ecological risk....

  8. Molecular dynamics simulation of sodium aluminosilicate glass structures and glass surface-water reactions using the reactive force field (ReaxFF)

    Science.gov (United States)

    Dongol, R.; Wang, L.; Cormack, A. N.; Sundaram, S. K.

    2018-05-01

    Reactive potentials are increasingly used to study the properties of glasses and glass water reactions in a reactive molecular dynamics (MD) framework. In this study, we have simulated a ternary sodium aluminosilicate glass and investigated the initial stages of the glass surface-water reactions at 300 K using reactive force field (ReaxFF). On comparison of the simulated glass structures generated using ReaxFF and classical Buckingham potentials, our results show that the atomic density profiles calculated for the surface glass structures indicate a bond-angle distribution dependency. The atomic density profiles also show higher concentrations of non-bridging oxygens (NBOs) and sodium ions at the glass surface. Additionally, we present our results of formation of silanol species and the diffusion of water molecules at the glass surface using ReaxFF.

  9. Effects of Thermal Radiation and Chemical Reaction on MHD Free Convection Flow past a Flat Plate with Heat Source and Convective Surface Boundary Condition

    OpenAIRE

    E.Hemalatha; N. Bhaskar Reddy

    2015-01-01

    This paper analyzes the radiation and chemical reaction effects on MHD steady two-dimensional laminar viscous incompressible radiating boundary layer flow over a flat plate in the presence of internal heat generation and convective boundary condition. It is assumed that lower surface of the plate is in contact with a hot fluid while a stream of cold fluid flows steadily over the upper surface with a heat source that decays exponentially. The Rosseland approximation is used to desc...

  10. Effects of the innervation zone on the time and frequency domain parameters of the surface electromyographic signal.

    Science.gov (United States)

    Smith, Cory M; Housh, Terry J; Herda, Trent J; Zuniga, Jorge M; Ryan, Eric D; Camic, Clayton L; Bergstrom, Haley C; Smith, Doug B; Weir, Joseph P; Cramer, Joel T; Hill, Ethan C; Cochrane, Kristen C; Jenkins, Nathaniel D M; Schmidt, Richard J; Johnson, Glen O

    2015-08-01

    The purposes of the present study were to examine the effects of electrode placements over, proximal, and distal to the innervation zone (IZ) on electromyographic (EMG) amplitude (RMS) and frequency (MPF) responses during: (1) a maximal voluntary isometric contraction (MVIC), and; (2) a sustained, submaximal isometric muscle action. A linear array was used to record EMG signals from the vastus lateralis over the IZ, 30mm proximal, and 30mm distal to the IZ during an MVIC and a sustained isometric muscle action of the leg extensors at 50% MVIC. During the MVIC, lower EMG RMS (p>0.05) and greater EMG MPF (ptime relationships over, proximal, and distal to the IZ occurred. Thus, the results of the present study indicated that during an MVIC, EMG RMS and MPF values recorded over the IZ are not comparable to those away from the IZ. However, the rates of fatigue-induced changes in EMG RMS and MPF during sustained, submaximal isometric muscle actions of the leg extensors were the same regardless of the electrode placement locations relative to the IZ. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Study of the Reactions Controlling the Mobility of Uranium in Ground and Surface Water Systems in Contact with Apatite

    International Nuclear Information System (INIS)

    Taffet, M

    2004-01-01

    The objective of this project was to define the mechanisms, equilibria, kinetics, and extent of sorption of aqueous uranium onto hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)) for a range of pH, ionic strength, aqueous uranium concentration, dissolved carbon/air CO 2 , and mineral surface area. We conducted chemical modeling, batch and flow-through experiments, chemical analysis, x-ray absorption and diffraction measurement, and electron microscopy. Our motivation was the need to immobilize U in water and soil to prevent it's entry into water supplies and ultimately, biological systems. Applying hydroxyapatite to in-situ treatment of uranium-bearing ground water could be an effective, low cost technology. We found that hydroxyapatite quickly, effectively, and reversibly sorbed uranium at a high capacity by inner-sphere complexation over a wide range of conditions. Our results indicate that at aqueous uranium concentrations below 10-20 ppb: (1) equilibrium sorption of uranium to hydroxyapatite occurs in hours, regardless of pH; (2) in ambient and CO 2 -free atmospheres, over 98% of initial uranium is sorbed to hydroxyapatite, (3) in waters in equilibrium with higher air CO 2 concentrations, sorption removed over 97% of aqueous uranium, except above pH 9, where aqueous uranium concentrations were reduced by less than 40%, and (4) at near-neutral pH, bicarbonate alkalinities in excess of 500 slightly retarded sorption of uranium to hydroxyapatite, relative to lower alkalinities. Uranium sorption and precipitation are reversible and are not appreciably affected by ionic strength. The reversibility of these reactions requires that in situ treatment be carefully monitored to avoid breakthrough and de-sorption of uranium unto ground water. At typical surface conditions, sorption is the only mode of uranium sequestration below 20-50 ppb U - above this range, precipitation of uranium phosphate minerals begins to dominate sequestration processes. We verified that one m 2 of

  12. Continuous Estimates of Surface Density and Annual Snow Accumulation with Multi-Channel Snow/Firn Penetrating Radar in the Percolation Zone, Western Greenland Ice Sheet

    Science.gov (United States)

    Meehan, T.; Marshall, H. P.; Bradford, J.; Hawley, R. L.; Osterberg, E. C.; McCarthy, F.; Lewis, G.; Graeter, K.

    2017-12-01

    A priority of ice sheet surface mass balance (SMB) prediction is ascertaining the surface density and annual snow accumulation. These forcing data can be supplied into firn compaction models and used to tune Regional Climate Models (RCM). RCMs do not accurately capture subtle changes in the snow accumulation gradient. Additionally, leading RCMs disagree among each other and with accumulation studies in regions of the Greenland Ice Sheet (GrIS) over large distances and temporal scales. RCMs tend to yield inconsistencies over GrIS because of sparse and outdated validation data in the reanalysis pool. Greenland Traverse for Accumulation and Climate Studies (GreenTrACS) implemented multi-channel 500 MHz Radar in multi-offset configuration throughout two traverse campaigns totaling greater than 3500 km along the western percolation zone of GrIS. The multi-channel radar has the capability of continuously estimating snow depth, average density, and annual snow accumulation, expressed at 95% confidence (+-) 0.15 m, (+-) 17 kgm-3, (+-) 0.04 m w.e. respectively, by examination of the primary reflection return from the previous year's summer surface.

  13. Surface Runoff and Snowmelt Infiltration into the Soil on Plowlands in the Forest-Steppe and Steppe Zones of the East European Plain

    Science.gov (United States)

    Barabanov, A. T.; Dolgov, S. V.; Koronkevich, N. I.; Panov, V. I.; Petel'ko, A. I.

    2018-01-01

    Long-term series of observations over the spring water balance elements on fields with hydrologically contrasting agricultural backgrounds―a loose soil after fall moldboard plowing and a plowland compacted by 12-16% compared to the former soil (perennial grasses, winter crops, stubble)―have been analyzed. The values of surface