WorldWideScience

Sample records for surface reaction channels

  1. Surface channeling

    International Nuclear Information System (INIS)

    Sizmann, R.; Varelas, C.

    1976-01-01

    There is experimental evidence that swift light ions incident at small angles towards single crystalline surfaces can lose an appreciable fraction of their kinetic energy during reflection. It is shown that these projectiles penetrate into the bulk surface region of the crystal. They can travel as channeled particles along long paths through the solid (surface channeling). The angular distribution and the depth history of the re-emerged projectiles are investigated by computer simulations. A considerable fraction of the penetrating projectiles re-emerges from the crystal with constant transverse energy if the angle of incidence is smaller than the critical angle for axial channeling. Analytical formulae are derived based on a diffusion model for surface channeling. A comparison with experimental data exhibits the relevance of the analytical solutions. (Auth.)

  2. 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.

  3. 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.

  4. Competing reaction channels in IR-laser-induced unimolecular reactions

    International Nuclear Information System (INIS)

    Berman, M.R.

    1981-01-01

    The competing reaction channels in the unimolecular decomposition of two molecules, formaldehyde and tetralin were studied. A TEA CO 2 laser was used as the excitation source in all experiments. The dissociation of D 2 CO was studied by infrared multiphoton dissociation (MPD) and the small-molecule nature of formaldehyde with regard to MPD was explored. The effect of collisions in MPD were probed by the pressure dependence of the MPD yield and ir fluorescence from multiphoton excited D 2 CO. MPD yield shows a near cubic dependence in pure D 2 CO which is reduced to a 1.7 power dependence when 15 torr of NO is added. The peak amplitude of 5 μm ir fluorescence from D 2 CO is proportional to the square of the D 2 CO pressure in pure D 2 CO or in the presence of 50 torr of Ar. Results are explained in terms of bottlenecks to excitation at the v = 1 level which are overcome by a combination of vibrational energy transfer and rotational relaxation. The radical/molecule branching ratio in D 2 CO MPD was 0.10 +- 0.02 at a fluence of 125 J/cm 2 at 946.0 cm -1 . The barrier height to molecular dissociation was calculated to be 3.6 +- 2.0 kcal/mole below the radical threshold or 85.0 +- 3.0 kcal/mole above the ground state of D 2 CO. In H 2 CO, this corresponds to 2.5 +- 2.0 kcal/mole below the radical threshold or 83.8 +- 3.0 kcal/mole above the ground state. Comparison with uv data indicate that RRKM theory is an acceptable description of formaldehyde dissociation in the 5 to 10 torr pressure range. The unimolecular decomposition of tetralin was studied by MPD and SiF 4 - sensitized pyrolysis. Both techniques induce decomposition without the interference of catalytic surfaces. Ethylene loss is identified as the lowest energy reaction channel. Dehydrogenation is found to result from step-wise H atom loss. Isomerization via disproportionation is also identified as a primary reaction channel

  5. Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bin; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2013-12-14

    Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

  6. Multi-reaction-channel fitting calculations in a coupled-channel model : Photoinduced strangeness production

    NARCIS (Netherlands)

    Scholten, O.; Usov, A.

    To describe photo- and meson-induced reactions on the nucleon, one is faced with a rather extensive coupled-channel problem Ignoring the effects of channel coupling, as one would do in describing a certain reaction at the tree level; invariably creates a large inconsistency between the different

  7. Channeling regimes in ion surface scattering

    NARCIS (Netherlands)

    Robin, A; Heiland, W

    We report on surface channeling experiments of singly charged ions on single crystal surfaces of Pt(1 1 0) and Pd(1 1 0). Using a time-of-flight system installed in forward direction we analyze the energy distribution of the scattered projectiles. By variation of the primary energy and the angle of

  8. Radiation reaction in a continuous focusing channel

    International Nuclear Information System (INIS)

    Huang, Z.; Chen, P.; Ruth, R.D.

    1995-01-01

    We show that the radiation damping rate of the transverse action of a particle in a straight, continuous focusing system is independent of the particle energy, and that no quantum excitation is induced. This absolute damping effect leads to the existence of a transverse ground state to which the particle inevitably decays and yields the minimum beam emittance that one can ever attain, γε min =ℎ/2mc, limited only by the uncertainty principle. Because of adiabatic invariance, the particle can be accelerated along the focusing channel in its ground state without any radiation energy loss

  9. Effects of reaction channels in subbarrier fusion reactions

    International Nuclear Information System (INIS)

    Dasso, C.H.

    1984-01-01

    In this lecture we consider some aspects of fusion reactions between heavy ions at bombarding energies which are below or close to that of the Coulomb barrier. This problem has been traditionally confronted with simple barrier penetration calculations. So we start with a very brief review of what we can call the ''conventional'' procedure. (orig.)

  10. Homogeneous-heterogeneous reactions in curved channel with porous medium

    Science.gov (United States)

    Hayat, T.; Ayub, Sadia; Alsaedi, A.

    2018-06-01

    Purpose of the present investigation is to examine the peristaltic flow through porous medium in a curved conduit. Problem is modeled for incompressible electrically conducting Ellis fluid. Influence of porous medium is tackled via modified Darcy's law. The considered model utilizes homogeneous-heterogeneous reactions with equal diffusivities for reactant and autocatalysis. Constitutive equations are formulated in the presence of viscous dissipation. Channel walls are compliant in nature. Governing equations are modeled and simplified under the assumptions of small Reynolds number and large wavelength. Graphical results for velocity, temperature, heat transfer coefficient and homogeneous-heterogeneous reaction parameters are examined for the emerging parameters entering into the problem. Results reveal an activation in both homogenous-heterogenous reaction effect and heat transfer rate with increasing curvature of the channel.

  11. 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

  12. 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).

  13. 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)

  14. Study of elastic scattering between heavy ions. Reaction channel influence

    International Nuclear Information System (INIS)

    Doubre, Hubert.

    1978-01-01

    The role of absorption on the behavior of heavy ion angular distributions and excitaton functions has been investigated on light and medium mass systems. Comparison between 20 Ne+ 12 C and 16 O+ 16 O systems which lead to the same compound nucleus, shows that it originates from the direct channels strongly coupled to the entrance channel. Structures in the excitation functions occur for almost all the light systems and it is shown that the damping observed for heavier systems such as 40 Ca+ 40 Ca, essentially results on the predominance of Coulomb effects which hide the nuclear structure effects. Thus no valuable information on the details of S-matrix can be extracted for such an heavy system. A coherent description of the elastic scattering, based on a splitting of the scattering amplitude into two components, the modulus of each component varying smoothly as a function of energy and angle. The interference between these sub-amplitudes give rise to interference effects in angular distributions and excitation functions. The study of the main reaction channels of the 40 Ca+ 40 Ca system - i.e. deep inelastic reactions and fusion - also shows that the closed-shell nature of the interacting nuclei does not play any role in these processes due to the excitation processes in the first stage of the reactions which destroy the specific structure of the nuclei [fr

  15. 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.

  16. 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

  17. Soil bioengineering methods for abandoned mine land surface drainage channels

    Energy Technology Data Exchange (ETDEWEB)

    Sotir, R.B.; Simms, A.P.; Sweigard, R.J.; Hammer, P.; Graves, D.H.; Adkins, M. [Robbin B. Sotir & Associates, Marietta, GA (USA)

    1999-07-01

    Research to determine the suitability of soil bioengineering for slope stabilization at abandoned surface mining sites is described. The technology uses live woody plant material as a structural component, in this case live fascine with coir erosion control fabric made from coconut. A large water collection pond draining to nine channels on the slope below was constructed as a test site. The pond has drainage channels for testing at low, intermediate, and steep slope grades. Each group of three channels is composed of one riprap rock channel, one gabion channel, and one soil bioengineering channel. The channels will be tested summer 1999. 11 refs., 5 figs., 2 tabs., 8 photos.

  18. 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)

  19. 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.

  20. DFT studies on the multi-channel reaction of CH3S+NO2

    Science.gov (United States)

    Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

    The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero-point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6-311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO.

  1. Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-01-01

    Full Text Available Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p SCRF=(PCM, solvent = 1,2-ethanediol optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H2N–NH2 and (H2O8. A ready reaction channel of acetone → acetone hydrazine (Me2C=N–NH2 was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimine intermediate (Me2C(H–N=N–H. Two base-catalyzed reactions were investigated by models of the ketone, H2N–NH2 and OH−(H2O7. Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N2 extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenylethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.

  2. 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.

  3. Rare events via multiple reaction channels sampled by path replica exchange

    NARCIS (Netherlands)

    Bolhuis, P.G.

    2008-01-01

    Transition path sampling (TPS) was developed for studying activated processes in complex systems with unknown reaction coordinate. Transition interface sampling (TIS) allows efficient evaluation of the rate constants. However, when the transition can occur via more than one reaction channel

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. Reaction channels of 6,7Li+28Si at near-barrier energies

    International Nuclear Information System (INIS)

    Pakou, A; Rusek, K; Nicolis, N G; Alamanos, N; Doukelis, G; Gillibert, A; Kalyva, G; Kokkoris, M; Lagoyannis, A; Musumarra, A; Papachristodoulou, C; Perdikakis, G; Pierroutsakou, D; Pollacco, E C; Spyrou, A; Zarkadas, Ch

    2005-01-01

    The production of α-particles in the reactions 6,7 Li+ 28 Si was studied as a means to disentangle the various reaction channels at near-barrier energies. The competition between compound and direct reactions was determined by using the shape of angular distributions and statistical model calculations. DWBA calculations were also performed to probe the various direct channels. It was found that, approaching barrier, transfer channels are the most dominant for both reactions. For 7 Li+ 28 Si d-transfer is one of the contributing channels without excluding t-transfer, while for 6 Li+ 28 Si, n-transfer and p-transfer have substantial contribution but without excluding d-transfer

  9. 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

  10. Entrance channel excitations in the 28Si + 28Si reaction

    International Nuclear Information System (INIS)

    Decowski, P.; Gierlik, E.; Box, P.F.; Kamermans, R.; Nieuwenhuizen, G.J. van; Meijer, R.J.; Griffioen, K.A.; Wilschut, H.W.; Giorni, A.; Morand, C.; Demeyer, A.; Guinet, D.

    1991-01-01

    Velocity spectra of heavy ions produced in the 28 Si + 28 Si reaction at bombarding energies of 19.7 and 30 MeV/nucleon were measured and interpreted within the Q-optimum model extended by the inclusion of particle evaporation from excited fragments. Regions of forward angle spectra corresponding to the mutual excitation of the reaction partners with net mass transfer zero projected onto the Q-value variable show an enhancement at Q-values of -60 - -80 MeV (excitation energies of the reaction partners equal to 30 - 40 MeV). This energy range coincides with the region of 2ℎω - 3ℎω excitations characteristic for giant osciallations. This selective excitation, which occurs at a very early stage of the reaction (the cross section is the largest at very forward angles), provides an important doorway to other dissipative processes

  11. 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

  12. Channel surface plasmons in a continuous and flat graphene sheet

    Science.gov (United States)

    Chaves, A. J.; Peres, N. M. R.; da Costa, D. R.; Farias, G. A.

    2018-05-01

    We derive an integral equation describing surface-plasmon polaritons in graphene deposited on a substrate with a planar surface and a dielectric protrusion in the opposite surface of the dielectric slab. We show that the problem is mathematically equivalent to the solution of a Fredholm equation, which we solve exactly. In addition, we show that the dispersion relation of the channel surface plasmons is determined by the geometric parameters of the protrusion alone. We also show that such a system supports both even and odd modes. We give the electrostatic potential and the intensity plot of the electrostatic field, which clearly show the transverse localized nature of the surface plasmons in a continuous and flat graphene sheet.

  13. 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

  14. 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.

  15. Water Transport and Removal in PEMFC Gas Flow Channel with Various Water Droplet Locations and Channel Surface Wettability

    Directory of Open Access Journals (Sweden)

    Yanzhou Qin

    2018-04-01

    Full Text Available Water transport and removal in the proton exchange membrane fuel cell (PEMFC is critically important to fuel cell performance, stability, and durability. Water emerging locations on the membrane-electrode assembly (MEA surface and the channel surface wettability significantly influence the water transport and removal in PEMFC. In most simulations of water transport and removal in the PEMFC flow channel, liquid water is usually introduced at the center of the MEA surface, which is fortuitous, since water droplet can emerge randomly on the MEA surface in PEMFC. In addition, the commonly used no-slip wall boundary condition greatly confines the water sliding features on hydrophobic MEA/channel surfaces, degrading the simulation accuracy. In this study, water droplet is introduced with various locations along the channel width direction on the MEA surface, and water transport and removal is investigated numerically using an improved model incorporating the sliding flow property by using the shear wall boundary condition. It is found that the water droplet can be driven to the channel sidewall by aerodynamics when the initial water location deviates from the MEA center to a certain amount, forming the water corner flow in the flow channel. The channel surface wettability on the water transport is also studied and is shown to have a significant impact on the water corner flow in the flow channel.

  16. 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)

  17. Search for entrance channel effects in fusion reactions via neutron evaporation

    International Nuclear Information System (INIS)

    Ajay Kumar; Kaur, J.; Kumar, A.; Singh, G.; Govil, I.M.; Rakesh Kumar; Datta, S.K.; Chatterjee, M.B.; Yogi, B.K.

    2001-01-01

    It is generally expected that the compound nuclei formed at the given excitation energies and the angular momenta follow a statistical decay pattern independent of a particular reaction that led to fusion. In order to search the entrance channel effects in the decay of compound nucleus, the reaction 16 O + 64 Zn at oxygen beam energy of 91 MeV and 95 MeV are investigated

  18. THEORETICAL RESEARCH ON THE MULTI-CHANNEL REACTION MECHANISM AND KINETICS OF HNCS WITH OH-

    Directory of Open Access Journals (Sweden)

    Li-Jie Hou

    Full Text Available We presented a theoretical study on the detailed reaction mechanism and kinetics of the HNCS molecule with the OH-. The barrierless minimum energy path and the most favorable entrance channel have been determined by study the thermodynamic and kinetic characters of the channel with low energy barrier. The B3LYP/6-311++G** method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the G3 energies was employed for further energy refinements. In addition, the analysis of the combining interaction between hydroxide ion and HNCS was performed by natural bond orbitals (NBO analysis. The calculation results indicated that the reaction of OH- with HNCS had four channels, and the channel of H-atom in HNCS direct extraction to OH- (OH-+HNCS→IM1→TS3→IM4→P2(SCN- +H2O in singlet state was the main channel with the low potential energy and high equilibrium constant and reaction rate constant. SCN- and H2O were main products.

  19. Numerical Simulations of Competitive-Consecutive Reactions in Turbulent Channel Flow

    NARCIS (Netherlands)

    Vrieling, A.J.

    2003-01-01

    This thesis deals with mixing of passive scalars in a turbulent flow. The passive scalars are released in a turbulent plane channel flow and interpreted as either non-reactive components or reactive components that are involved in a competitive-consecutive reaction system. The evolution of these

  20. 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

  1. 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

  2. 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.

  3. Enhancement of Friction against a Rough Surface by a Ridge-Channel Surface Microstructure.

    Science.gov (United States)

    Bai, Ying; Hui, Chung-Yuen; Levrard, Benjamin; Jagota, Anand

    2015-07-14

    We report on a study of the sliding friction of elastomeric surfaces patterned with ridges and channels (and unstructured flat controls), against both smooth and roughened spherical indenters. Against the smooth spherical indenter, all of the structured surfaces have highly reduced sliding friction due to the reduction in actual area of contact. Against roughened spherical indenters, however, the sliding force for structured samples can be up to 50% greater than that of an unstructured flat control. The mechanism of enhanced friction against a rough surface is due to a combination of increased actual area of contact, interlocking between roughness and the surface structure, and attendant dynamic instabilities that dissipate energy.

  4. 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.

  5. 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

  6. 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.

  7. Multi-channel Analysis of Passive Surface Waves (MAPS)

    Science.gov (United States)

    Xia, J.; Cheng, F. Mr; Xu, Z.; Wang, L.; Shen, C.; Liu, R.; Pan, Y.; Mi, B.; Hu, Y.

    2017-12-01

    Urbanization is an inevitable trend in modernization of human society. In the end of 2013 the Chinese Central Government launched a national urbanization plan—"Three 100 Million People", which aggressively and steadily pushes forward urbanization. Based on the plan, by 2020, approximately 100 million people from rural areas will permanently settle in towns, dwelling conditions of about 100 million people in towns and villages will be improved, and about 100 million people in the central and western China will permanently settle in towns. China's urbanization process will run at the highest speed in the urbanization history of China. Environmentally friendly, non-destructive and non-invasive geophysical assessment method has played an important role in the urbanization process in China. Because human noise and electromagnetic field due to industrial life, geophysical methods already used in urban environments (gravity, magnetics, electricity, seismic) face great challenges. But humanity activity provides an effective source of passive seismic methods. Claerbout pointed out that wavefileds that are received at one point with excitation at the other point can be reconstructed by calculating the cross-correlation of noise records at two surface points. Based on this idea (cross-correlation of two noise records) and the virtual source method, we proposed Multi-channel Analysis of Passive Surface Waves (MAPS). MAPS mainly uses traffic noise recorded with a linear receiver array. Because Multi-channel Analysis of Surface Waves can produces a shear (S) wave velocity model with high resolution in shallow part of the model, MPAS combines acquisition and processing of active source and passive source data in a same flow, which does not require to distinguish them. MAPS is also of ability of real-time quality control of noise recording that is important for near-surface applications in urban environment. The numerical and real-world examples demonstrated that MAPS can be

  8. Thermodynamic Simulation of Equilibrium Composition of Reaction Products at Dehydration of a Technological Channel in a Uranium-Graphite Reactor

    Science.gov (United States)

    Pavliuk, A. O.; Zagumennov, V. S.; Kotlyarevskiy, S. G.; Bespala, E. V.

    2018-01-01

    The problems of accumulation of nuclear fuel spills in the graphite stack in the course of operation of uranium-graphite nuclear reactors are considered. The results of thermodynamic analysis of the processes in the graphite stack at dehydration of a technological channel, fuel element shell unsealing and migration of fission products, and activation of stable nuclides in structural elements of the reactor and actinides inside the graphite moderator are given. The main chemical reactions and compounds that are produced in these modes in the reactor channel during its operation and that may be hazardous after its shutdown and decommissioning are presented. Thermodynamic simulation of the equilibrium composition is performed using the specialized code TERRA. The results of thermodynamic simulation of the equilibrium composition in different cases of technological channel dehydration in the course of the reactor operation show that, if the temperature inside the active core of the nuclear reactor increases to the melting temperature of the fuel element, oxides and carbides of nuclear fuel are produced. The mathematical model of the nonstationary heat transfer in a graphite stack of a uranium-graphite reactor in the case of the technological channel dehydration is presented. The results of calculated temperature evolution at the center of the fuel element, the replaceable graphite element, the air gap, and in the surface layer of the block graphite are given. The numerical results show that, in the case of dehydration of the technological channel in the uranium-graphite reactor with metallic uranium, the main reaction product is uranium dioxide UO2 in the condensed phase. Low probability of production of pyrophoric uranium compounds (UH3) in the graphite stack is proven, which allows one to disassemble the graphite stack without the risk of spontaneous graphite ignition in the course of decommissioning of the uranium-graphite nuclear reactor.

  9. Silicide/Silicon Heterointerfaces, Reaction Kinetics and Ultra-short Channel Devices

    Science.gov (United States)

    Tang, Wei

    , and that limits transport parameter extraction from SB-FETs using the conventional field-effect transconductance measurements. In addition to application of silicide in Si NW devices, the fundamental materials science of Ni-Si reaction is also of interest, and in-situ TEM has been shown to be a useful tool in obtaining dynamical phase transformation information and therefore providing insights into the new phase formation process. By using in-situ TEM techniques, a new gold catalyzed solid-liquid-solid (SLS) silicide phase growth mechanism in Si NWs is observed for the first time, which shows the liquid mediating growth can be also used in synthesis of metallic silicide nanowires. SLS is analogous to the VLS in both being liquid-mediated, but is fundamentally different in terms of nucleation and mass transport. In our SLS growth at 700 ºC, the Ni atoms are supplied from remote Ni particles by interstitial diffusion through Si NW into the pre-existing Au particle at the tip. Upon supersaturation of both Ni and Si in Au, octahedral shape of Ni disilicide phase nucleates in the middle of the Au liquid alloy, which thereafter sweeps through the Si NW and transform Si into NiSi2. Dissolution of Si by Au(Si,Ni) liquid mediating layer and growth of NiSi2 are shown to proceed in different manners. Using in-situ TEM technique, we also have the chance to present direct evidence that Si (111) twin boundaries and Si grain boundaries on Si NW surface can be efficient heterogeneous nucleation site for the silicide growth. By analyzing the nucleation site favorability, unlike other typical FCC materials like Cu or Si, we infer (111) twin defects in NiSi2 may have high interfacial energy. These results may provide valuable insights into the MOSFET source/drain (S/D) contact silicide formation process when defects are either unintentionally formed during the process or intentionally introduced to engineering the strain along the channel.

  10. Effect of the Pauli principle and channel coupling on the nuclear reactions, 2

    International Nuclear Information System (INIS)

    Kanada, Hiroyuki; Kaneko, Tsuneo; Nomoto, Morikazu

    1976-01-01

    The effect of the Pauli principle on nuclear reactions of a six-nucleon system is investigated in the presence of a breakup channel, by using the resonating group method (RGM). The microscopic treatment with full exchange effects for the t( 3 He, d) 4 He reaction is examined together with the 3 He-t and d- 4 He elastic scattering. It is shown that the exchange effects (especially owing to the Pauli principle) play an important role in the differential cross section in the backward region. The t( 3 He, d) 4 He reaction is examined by decomposing the reaction processes into three terms, that is, proton stripping, neutron pick-up and residual processes. The asymmetry of the angular distribution for the t( 3 He, d) 4 He reaction is also discussed. (auth.)

  11. Novel CLCNKB mutations causing Bartter syndrome affect channel surface expression.

    Science.gov (United States)

    Keck, Mathilde; Andrini, Olga; Lahuna, Olivier; Burgos, Johanna; Cid, L Pablo; Sepúlveda, Francisco V; L'hoste, Sébastien; Blanchard, Anne; Vargas-Poussou, Rosa; Lourdel, Stéphane; Teulon, Jacques

    2013-09-01

    Mutations in the CLCNKB gene encoding the ClC-Kb Cl(-) channel cause Bartter syndrome, which is a salt-losing renal tubulopathy. Here, we investigate the functional consequences of seven mutations. When expressed in Xenopus laevis oocytes, four mutants carried no current (c.736G>C, p.Gly246Arg; c.1271G>A, p.Gly424Glu; c.1313G>A, p.Arg438His; c.1316T>C, p.Leu439Pro), whereas others displayed a 30%-60% reduction in conductance as compared with wild-type ClC-Kb (c.242T>C, p.Leu81Pro; c.274C>T, p.Arg92Trp; c.1052G>C, p.Arg351Pro). Anion selectivity and sensitivity to external Ca(2+) and H(+), typical of the ClC-Kb channel, were not modified in the partially active mutants. In oocytes, we found that all the mutations reduced surface expression with a profile similar to that observed for currents. In HEK293 cells, the currents in the mutants had similar profiles to those obtained in oocytes, except for p.Leu81Pro, which produced no current. Furthermore, p.Arg92Trp and p.Arg351Pro mutations did not modify the unit-conductance of closely related ClC-K1. Western blot analysis in HEK293 cells showed that ClC-Kb protein abundance was lower for the nonconducting mutants but similar to wild-type for other mutants. Overall, two classes of mutants can be distinguished: nonconducting mutants associated with low total protein expression, and partially conducting mutants with unaltered channel properties and ClC-Kb protein abundance. © 2013 WILEY PERIODICALS, INC.

  12. Ion channel activity of membrane vesicles released from sea urchin sperm during the acrosome reaction

    International Nuclear Information System (INIS)

    Schulz, Joseph R.; Vega-Beltran, Jose L. de la; Beltran, Carmen; Vacquier, Victor D.; Darszon, Alberto

    2004-01-01

    The sperm acrosome reaction (AR) involves ion channel activation. In sea urchin sperm, the AR requires Ca 2+ and Na + influx and K + and H + efflux. During the AR, the plasma membrane fuses with the acrosomal vesicle membrane forming hybrid membrane vesicles that are released from sperm into the medium. This paper reports the isolation and preliminary characterization of these acrosome reaction vesicles (ARVs), using synaptosome-associated protein of 25 kDa (SNAP-25) as a marker. Isolated ARVs have a unique protein composition. The exocytosis regulatory proteins vesicle-associated membrane protein and SNAP-25 are inside ARVs, as judged by protease protection experiments, and membrane associated based on Triton X-114 partitioning. ARVs fused with planar bilayers display three main types of single channel activity. The most frequently recorded channel is cationic, weakly voltage dependent and has a low open probability that increases with negative potentials. This channel is activated by cAMP, blocked by Ba 2+ , and has a PK + /PNa + selectivity of 4.5. ARVs represent a novel membrane preparation suitable to deepen our understanding of ion channel activity in the AR and during fertilization

  13. 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.

  14. 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...

  15. Turbine component having surface cooling channels and method of forming same

    Science.gov (United States)

    Miranda, Carlos Miguel; Trimmer, Andrew Lee; Kottilingam, Srikanth Chandrudu

    2017-09-05

    A component for a turbine engine includes a substrate that includes a first surface, and an insert coupled to the substrate proximate the substrate first surface. The component also includes a channel. The channel is defined by a first channel wall formed in the substrate and a second channel wall formed by at least one coating disposed on the substrate first surface. The component further includes an inlet opening defined in flow communication with the channel. The inlet opening is defined by a first inlet wall formed in the substrate and a second inlet wall defined by the insert.

  16. 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.

  17. 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

  18. Channel Storage change: a new remote sensed surface water measurement

    Science.gov (United States)

    Coss, S. P.; Durand, M. T.; Yi, Y.; Guo, Q.; Shum, C. K.; Allen, G. H.; Pavelsky, T.

    2017-12-01

    Here we present river channel storage change (CSC) measurements for 17 major world rivers from 2002-2016. We combined interpolated daily 1 km resolution Global River Radar Altimeter Time Series (GRRATS) river surface elevation data with static widths from the global river Global River Widths from Landsat (GRWL) dataset, to generate preliminary channel storage measurements. CSC is a previously unmeasured component of the terrestrial water balance It is a fundamental Earth science quantity with global bearing on floodplains, ecology, and geochemistry. CSC calculations require only remote sensed data, making them an ideal tool for studying remote regions where hydrological data is not easily accessible. CSC is uniquely suited to determine the role of hydrologic and hydraulic controls in basins with strong seasonal cycles (freeze-up and break-up). The cumulative CSC anomaly can impart spatial details that discharge measurements cannot. With this new measurement, we may be able to determine critical hydrological and hydraulic controls on rapidly changing systems like Arctic rivers. Results for Mississippi River indicate that peak CSC anomaly was the highest in 2011 (12.6 km3) and minimum CSC anomaly was in 2012 (-12.2 km3). Peak CSC has most frequently occurs in May (5 years), but has come as late in the year as July, and as early as January. Results for the Yukon River indicate that peak CSC anomaly was the highest in 2013 (13.9 km3) and minimum CSC anomaly was in 2010 (-14.2 km3). Peak CSC has most frequently come in early to mid-June (4-18), but has occurred in May (19-31) four years in the study period (three of the last 6 years) and once on April 30th.

  19. 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)

  20. 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.)

  1. 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...

  2. 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

  3. 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.

  4. 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

  5. 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

  6. Distribution of small channels on the Martian surface

    Science.gov (United States)

    Pieri, D.

    1976-01-01

    The distribution of small channels on Mars has been mapped from Mariner 9 images at the 1:5,000,000 scale. The small channels referred to here are small valleys ranging in width from the resolution limit of the Mariner 9 wide-angle images (about 1 km) to about 10 km. The greatest density of small channels occurs in dark cratered terrain. This dark zone forms a broad subequatorial band around the planet. The observed distribution may be the result of decreased small-channel visibility in bright areas due to obscuration by a high albedo dust or sediment mantle. Crater densities within two small-channel segments show crater size-frequency distributions consistent with those of the oldest of the heavily cratered plains units. Such crater densities coupled with the almost exclusive occurrence of small channels in old cratered terrain and the generally degraded appearance of small channels in the high-resolution images (about 100 m) imply a major episode of small-channel formation early in Martian geologic history.

  7. Surface dynamics of voltage-gated ion channels

    Science.gov (United States)

    Heine, Martin; Ciuraszkiewicz, Anna; Voigt, Andreas; Heck, Jennifer; Bikbaev, Arthur

    2016-01-01

    ABSTRACT Neurons encode information in fast changes of the membrane potential, and thus electrical membrane properties are critically important for the integration and processing of synaptic inputs by a neuron. These electrical properties are largely determined by ion channels embedded in the membrane. The distribution of most ion channels in the membrane is not spatially uniform: they undergo activity-driven changes in the range of minutes to days. Even in the range of milliseconds, the composition and topology of ion channels are not static but engage in highly dynamic processes including stochastic or activity-dependent transient association of the pore-forming and auxiliary subunits, lateral diffusion, as well as clustering of different channels. In this review we briefly discuss the potential impact of mobile sodium, calcium and potassium ion channels and the functional significance of this for individual neurons and neuronal networks. PMID:26891382

  8. Determination of optimum "multi-channel surface wave method" field parameters.

    Science.gov (United States)

    2012-12-01

    Multi-channel surface wave methods (especially the multi-channel analyses of surface wave method; MASW) are routinely used to : determine the shear-wave velocity of the subsurface to depths of 100 feet for site classification purposes. Users are awar...

  9. One-Channel Surface Electromyography Decomposition for Muscle Force Estimation

    Directory of Open Access Journals (Sweden)

    Wentao Sun

    2018-05-01

    Full Text Available Estimating muscle force by surface electromyography (sEMG is a non-invasive and flexible way to diagnose biomechanical diseases and control assistive devices such as prosthetic hands. To estimate muscle force using sEMG, a supervised method is commonly adopted. This requires simultaneous recording of sEMG signals and muscle force measured by additional devices to tune the variables involved. However, recording the muscle force of the lost limb of an amputee is challenging, and the supervised method has limitations in this regard. Although the unsupervised method does not require muscle force recording, it suffers from low accuracy due to a lack of reference data. To achieve accurate and easy estimation of muscle force by the unsupervised method, we propose a decomposition of one-channel sEMG signals into constituent motor unit action potentials (MUAPs in two steps: (1 learning an orthogonal basis of sEMG signals through reconstruction independent component analysis; (2 extracting spike-like MUAPs from the basis vectors. Nine healthy subjects were recruited to evaluate the accuracy of the proposed approach in estimating muscle force of the biceps brachii. The results demonstrated that the proposed approach based on decomposed MUAPs explains more than 80% of the muscle force variability recorded at an arbitrary force level, while the conventional amplitude-based approach explains only 62.3% of this variability. With the proposed approach, we were also able to achieve grip force control of a prosthetic hand, which is one of the most important clinical applications of the unsupervised method. Experiments on two trans-radial amputees indicated that the proposed approach improves the performance of the prosthetic hand in grasping everyday objects.

  10. Consistent analysis of peripheral reaction channels and fusion for the 16,18O+58Ni systems

    International Nuclear Information System (INIS)

    Alves, J.J.S.; Gomes, P.R.S.; Lubian, J.; Chamon, L.C.; Pereira, D.; Anjos, R.M.; Rossi, E.S.; Silva, C.P.; Alvarez, M.A.G.; Nobre, G.P.A.; Gasques, L.R.

    2005-01-01

    We have measured elastic scattering and peripheral reaction channel cross sections for the 16,18 O+ 58 Ni systems at ELab=46 MeV. The data were analyzed through extensive coupled-channel calculations. It was investigated the consistency of the present analysis with a previous one at sub-barrier energies. Experimental fusion cross sections for these systems are also compared with the corresponding predictions of the coupled-channel calculations

  11. 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.

  12. Study of Internal Channel Surface Roughnesses Manufactured by Selective Laser Melting in Aluminum and Titanium Alloys

    Science.gov (United States)

    Pakkanen, Jukka; Calignano, Flaviana; Trevisan, Francesco; Lorusso, Massimo; Ambrosio, Elisa Paola; Manfredi, Diego; Fino, Paolo

    2016-08-01

    Interest in additive manufacturing (AM) has gained considerable impetus over the past decade. One of the driving factors for AM success is the ability to create unique designs with intrinsic characteristics as, e.g., internal channels used for hydraulic components, cooling channels, and heat exchangers. However, a couple of the main problems in internal channels manufactured by AM technologies are the high surface roughness obtained and the distortion of the channel shape. There is still much to understand in these design aspects. In this study, a cylindrical geometry for internal channels to be built with different angles with respect to the building plane in AlSi10Mg and Ti6Al4V alloys by selective laser melting was considered. The internal surfaces of the channels produced in both materials were analyzed by means of a surface roughness tester and by optical and electron microscopy to evaluate the effects of the material and design choices.

  13. From Surface Down To Bulk X-Ray Channeling

    International Nuclear Information System (INIS)

    Dabagov, Sultan B.

    2003-01-01

    The basic point to be considered in this report is that X-ray capillary optics relies on the ability of a tapered and/or bent capillary channel to act as an X-ray waveguide. Recently several coherent phenomena associated with propagation of X-rays in capillary optical elements have been observed. In order to describe coherent phenomena of radiation propagation a quantum-wave theory of X-ray channeling was developed. Simple estimations speak on possibility of X-ray channeling in nano-scale capillaries, but with a significant change in character of channeling. In this connection, discovery of carbon nanotubes opens new opportunities to apply capillary waveguide optics. X-ray propagation in capillary micro- and nanostructures within the frame of wave approach will be discussed

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. Simulation of an Underwater Acoustic Communication Channel Characterized by Wind-Generated Surface Waves and Bubbles

    NARCIS (Netherlands)

    Dol, H.S.; Colin, M.E.G.D.; Ainslie, M.A.; Walree, P.A. van; Janmaat, J.

    2012-01-01

    Sea surface scattering by wind-generated waves and bubbles is regarded to be the main non-platform related cause of the time variability of shallow acoustic communication channels. Simulations for predicting the quality of acoustic communication links in such channels thus require adequate modeling

  19. Effects of free-surface on design charts for open channels

    African Journals Online (AJOL)

    2011-12-14

    Dec 14, 2011 ... Normal depth is an important parameter for the design of channels and canals. For rectangular, trapezoidal, and circular channel sections it is possible to express normal depth by a trial-and-error procedure or analytically. However, the effects of free-surface on the design charts for determination of the ...

  20. Coupled-channels analyses for 9,11Li + 208Pb fusion reactions with multi-neutron transfer couplings

    Science.gov (United States)

    Choi, Ki-Seok; Cheoun, Myung-Ki; So, W. Y.; Hagino, K.; Kim, K. S.

    2018-05-01

    We discuss the role of two-neutron transfer processes in the fusion reaction of the 9,11Li + 208Pb systems. We first analyze the 9Li + 208Pb reaction by taking into account the coupling to the 7Li + 210Pb channel. To this end, we assume that two neutrons are directly transferred to a single effective channel in 210Pb and solve the coupled-channels equations with the two channels. By adjusting the coupling strength and the effective Q-value, we successfully reproduce the experimental fusion cross sections for this system. We then analyze the 11Li + 208Pb reaction in a similar manner, that is, by taking into account three effective channels with 11Li + 208Pb, 9Li + 210Pb, and 7Li + 212Pb partitions. In order to take into account the halo structure of the 11Li nucleus, we construct the potential between 11Li and 208Pb with a double folding procedure, while we employ a Woods-Saxon type potential with the global Akyüz-Winther parameters for the other channels. Our calculation indicates that the multiple two-neutron transfer process plays a crucial role in the 11Li + 208Pb fusion reaction at energies around the Coulomb barrier.

  1. The influence of the entrance channel mass asymmetry on the reaction mechanism

    International Nuclear Information System (INIS)

    Agarwal, S.; Galin, J.; Gatty, B.; Guerreau, D.; Lefort, M.; Tarrago, X.; Babinet, R.; Girard, J.

    1980-01-01

    We have tried to investigate the influence of the entrance channel mass asymmetry on the reaction mechanisms associated with heavy ion collisions. Two systems, one very much asymmetric (O + Mo) and the other one almost symmetric (Cr + Fe), were studied in detail by measuring evaporation residues, deep inelastic collision products and fission fragments. An important fraction of the fragments observed in the Cr + Fe system exhibits all the characteristics of fission fragments. The analysis of these data seems to indicate that these fission like products are most likely emitted by a long lived composite system having not reached full statistical equilibrium for all the degrees of freedom. As a consequence, the fusion cross section for this symmetric system is too low as compared to predictions based on a critical distance approach for fusion, whereas the asymmetric system (O + Mo) is well understood in terms of the same model. (orig.)

  2. Effect of surface bilayer charges on the magnetic field around ionic channels

    Energy Technology Data Exchange (ETDEWEB)

    Gomes Soares, Marília Amável [Post-graduation in Computational Sciences, Rio de Janeiro State University (Brazil); Cortez, Celia Martins, E-mail: ccortezs@ime.uerj.br [Post-graduation in Computational Sciences, Rio de Janeiro State University (Brazil); Department of Applied Mathematics, Rio de Janeiro State University (Brazil); Oliveira Cruz, Frederico Alan de [Post-graduation in Computational Sciences, Rio de Janeiro State University (Brazil); Department of Physics, Rural Federal University of Rio de Janeiro (Brazil); Silva, Dilson [Post-graduation in Computational Sciences, Rio de Janeiro State University (Brazil); Department of Applied Mathematics, Rio de Janeiro State University (Brazil)

    2017-01-01

    In this work, we present a physic-mathematical model for representing the ion transport through membrane channels, in special Na{sup +} and K{sup +}-channels, and discuss the influence of surface bilayer charges on the magnetic field behavior around the ionic current. The model was composed of a set of equations, including: a nonlinear differential Poisson-Boltzmann equation which usually allows to estimate the surface potentials and electric potential profile across membrane; equations for the ionic flux through channel and the ionic current density based on Armstrong's model for Na{sup +} and K{sup +} permeability and other Physics concepts; and a magnetic field expression derived from the classical Ampère equation. Results from computational simulations using the finite element method suggest that the ionic permeability is strongly dependent of surface bilayer charges, the current density through a K{sup +}-channel is very less sensible to temperature changes than the current density through a Na{sup +}- channel, active Na{sup +}-channels do not directly interfere with the K{sup +}-channels around, and vice-versa, since the magnetic perturbation generated by an active channel is of short-range.

  3. Tarantula toxins use common surfaces for interacting with Kv and ASIC ion channels.

    Science.gov (United States)

    Gupta, Kanchan; Zamanian, Maryam; Bae, Chanhyung; Milescu, Mirela; Krepkiy, Dmitriy; Tilley, Drew C; Sack, Jon T; Yarov-Yarovoy, Vladimir; Kim, Jae Il; Swartz, Kenton J

    2015-05-07

    Tarantula toxins that bind to voltage-sensing domains of voltage-activated ion channels are thought to partition into the membrane and bind to the channel within the bilayer. While no structures of a voltage-sensor toxin bound to a channel have been solved, a structural homolog, psalmotoxin (PcTx1), was recently crystalized in complex with the extracellular domain of an acid sensing ion channel (ASIC). In the present study we use spectroscopic, biophysical and computational approaches to compare membrane interaction properties and channel binding surfaces of PcTx1 with the voltage-sensor toxin guangxitoxin (GxTx-1E). Our results show that both types of tarantula toxins interact with membranes, but that voltage-sensor toxins partition deeper into the bilayer. In addition, our results suggest that tarantula toxins have evolved a similar concave surface for clamping onto α-helices that is effective in aqueous or lipidic physical environments.

  4. 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

  5. Spatial distribution of spin polarization in a channel on the surface of a topological insulator

    International Nuclear Information System (INIS)

    Zhou Xiaoying; Shao Huaihua; Liu Yiman; Tang Dongsheng; Zhou Guanghui

    2012-01-01

    We study the spatial distribution of electron spin polarization for a gate-controlled T-shaped channel on the surface of a three-dimensional topological insulator (3D TI). We demonstrate that an energy gap depending on channel geometry parameters is definitely opened due to the spatial confinement. Spin surface locking in momentum space for a uniform wide channel with Hamiltonian linearity in the wavevector is still kept, but it is broken with Hamiltonian nonlinearity in the wavevector, like that for two-dimensional surface states widely studied in the literature. However, the spin surface locking for a T-shaped channel is broken even with Hamiltonian linearity in the wavevector. Interestingly, the magnitude and direction of the in-plane spin polarization are spatially dependent in all regions due to the breaking of translational symmetry of the T-shaped channel system. These interesting findings for an electrically controlled nanostructure based on the 3D TI surface may be testable with the present experimental technique, and may provide further understanding the nature of 3D TI surface states. (paper)

  6. Turbulent oscillating channel flow subjected to a free-surface stress.

    NARCIS (Netherlands)

    Kramer, W.; Clercx, H.J.H.; Armenio, V.

    2010-01-01

    The channel flow subjected to a wind stress at the free surface and an oscillating pressure gradient is investigated using large-eddy simulations. The orientation of the surface stress is parallel with the oscillating pressure gradient and a purely pulsating mean flow develops. The Reynolds number

  7. 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.

  8. Environmental impact of by pass channel of surface waters

    International Nuclear Information System (INIS)

    Vismara, R.; Renoldi, M.; Torretta, V.

    1996-01-01

    In this paper are analyzed the impacts generated by surface waters drawing on river course. This impacts are generated also by reduction of water flow. This effect is most important for the presence of biological community: algae, fiches, micro invertebrates. Are also reported regional laws, water master plan of Lombardia region

  9. Channeling effect in electronic spectra produced by grazing impact of fast protons on insulator surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Archubi, C D; Gravielle, M S, E-mail: archubi@iafe.uba.a, E-mail: msilvia@iafe.uba.a [Instituto de Astronomia y Fisica del Espacio, Casilla de Correo 67, Sucursal 28, 1428, Buenos Aires (Argentina)

    2009-11-01

    Electron emission due to grazing scattering of fast protons from LiF and KCl surfaces is studied under axial incidence conditions. The differential emission probability is calculated within a distorted-wave formalism, taking into account axial channeled trajectories. For different emission angles, electronic spectra for proton incidence along the two principal crystal axes ([100] and [110]) are compared with those corresponding to an impact velocity in a random direction, finding effects associated with the channeling conditions.

  10. 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...

  11. Coupled-reaction-channel analysis of the (d,6Li) reaction on 24Mg and 26Mg to low-lying states

    International Nuclear Information System (INIS)

    Oelert, W.

    1986-01-01

    Experimental spectroscopic factors of the alpha-transfer reaction on nuclei of the sd-shell show rather strong inconsistencies and scatter much more strongly than explainable by the quoted errors. The poorer the quality of agreement between experimental and theoretical angular distribution shapes, the more inconsistent the comparison of spectroscopic factors either between different experiments or between theory and experiment. In view of the strong deformation of nuclei in the lower part of the sd-shell, higher-order reaction mechanisms are expected. A coupled-reaction-channel analysis for the transitions to the 0 + , 2 + , and 4 + states of the ground-state bands in 20 Ne and 22 Ne excited via the (d, 6 Li) reaction yields good agreement between experimental and theoretical angular distribution shapes as well as spectroscopic information. (orig.)

  12. Resonance amplification of the nuclear reaction X(a,b)Y near the a+X channel threshold

    International Nuclear Information System (INIS)

    Melezhik, V.S.

    1991-01-01

    Deviation of the cross section for the nuclear reaction X(a,b)Y from the Gamow formula due to an interaction additional to the Coulomb one in the entrance channel has been analyzed. It is shown that the reaction cross section has an oscillating structure at low energies. If the maximum of the first oscillation is close to the threshold of the channel a+X, it has a resonance behaviour. The peculiarity of the cross sections leads to the resonance amplification of the rate for a muon-catalyzed fusion reaction ('in flight' fusion) tμ+d→ 4 He+n+μ at the energy =76 eV and may influence the μ-capture rate in a dense mixture of hydrogen isotopes. 26 refs.; 4 figs

  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. Coevolution of bed surface patchiness and channel morphology: 2. Numerical experiments

    Science.gov (United States)

    Nelson, Peter A.; McDonald, Richard R.; Nelson, Jonathan M.; Dietrich, William E.

    2015-01-01

    In gravel bed rivers, bed topography and the bed surface grain size distribution evolve simultaneously, but it is not clear how feedbacks between topography and grain sorting affect channel morphology. In this, the second of a pair of papers examining interactions between bed topography and bed surface sorting in gravel bed rivers, we use a two-dimensional morphodynamic model to perform numerical experiments designed to explore the coevolution of both free and forced bars and bed surface patches. Model runs were carried out on a computational grid simulating a 200 m long, 2.75 m wide, straight, rectangular channel, with an initially flat bed at a slope of 0.0137. Over five numerical experiments, we varied (a) whether an obstruction was present, (b) whether the sediment was a gravel mixture or a single size, and (c) whether the bed surface grain size feeds back on the hydraulic roughness field. Experiments with channel obstructions developed a train of alternate bars that became stationary and were connected to the obstruction. Freely migrating alternate bars formed in the experiments without channel obstructions. Simulations incorporating roughness feedbacks between the bed surface and flow field produced flatter, broader, and longer bars than simulations using constant roughness or uniform sediment. Our findings suggest that patches are not simply a by-product of bed topography, but they interact with the evolving bed and influence morphologic evolution.

  16. Subcooled flow boiling heat transfer from microporous surfaces in a small channel

    International Nuclear Information System (INIS)

    Yan, Sun; Li, Zhang; Hong, Xu; Xiaocheng, Zhong

    2011-01-01

    The continuously increasing requirement for high heat transfer rate in a compact space can be met by combining the small channel/microchannel and heat transfer enhancement methods during fluid subcooled flow boiling. In this paper, the sintered microporous coating, as an efficient means of enhancing nucleate boiling, was applied to a horizontal, rectangular small channel. Water flow boiling heat transfer characteristics from the small channel with/without the microporous coating were experimentally investigated. The small channel, even without the coating, presented flow boiling heat transfer enhancement at low vapor quality due to size effects of the channel. This enhancement was also verified by under-predictions from macro-scale correlations. In addition to the enhancement from the channel size, all six microporous coatings with various structural parameters were found to further enhance nucleate boiling significantly. Effects of the coating structural parameters, fluid mass flux and inlet subcooling were also investigated to identify the optimum condition for heat transfer enhancement. Under the optimum condition, the microporous coating could produce the heat transfer coefficients 2.7 times the smooth surface value in subcooled flow boiling and 3 times in saturated flow boiling. The combination of the microporous coating and small channel led to excellent heat transfer performance, and therefore was deemed to have promising application prospects in many areas such as air conditioning, chip cooling, refrigeration systems, and many others involving compact heat exchangers. (authors)

  17. Phi-value analysis of a linear, sequential reaction mechanism: theory and application to ion channel gating.

    Science.gov (United States)

    Zhou, Yu; Pearson, John E; Auerbach, Anthony

    2005-12-01

    We derive the analytical form of a rate-equilibrium free-energy relationship (with slope Phi) for a bounded, linear chain of coupled reactions having arbitrary connecting rate constants. The results confirm previous simulation studies showing that Phi-values reflect the position of the perturbed reaction within the chain, with reactions occurring earlier in the sequence producing higher Phi-values than those occurring later in the sequence. The derivation includes an expression for the transmission coefficients of the overall reaction based on the rate constants of an arbitrary, discrete, finite Markov chain. The results indicate that experimental Phi-values can be used to calculate the relative heights of the energy barriers between intermediate states of the chain but provide no information about the energies of the wells along the reaction path. Application of the equations to the case of diliganded acetylcholine receptor channel gating suggests that the transition-state ensemble for this reaction is nearly flat. Although this mechanism accounts for many of the basic features of diliganded and unliganded acetylcholine receptor channel gating, the experimental rate-equilibrium free-energy relationships appear to be more linear than those predicted by the theory.

  18. Method of relative comparison of the thermohydraulic efficiency of heat exchange intensification in channels of heat-exchange surfaces

    International Nuclear Information System (INIS)

    Dubrovskij, E.V.; Vasil'ev, V.Ya.

    2002-01-01

    One introduces a technique to compare relatively thermohydraulic efficiency of heat transfer intensification in channels of heat exchange surfaces of any design types. It is shown that one should compare thermohydraulic efficiency of heat exchange intensification as to the thermal power of heat exchangers and pressure losses in channels with turbulators and in polished channels of heat exchange surfaces on the basis of dimensions of heat exchangers, their heat exchange surfaces and at similar (as to Re numbers) modes of coolant flow [ru

  19. Investigation of reordered (001) Au surfaces by positive ion channeling spectroscopy, LEED and AES

    International Nuclear Information System (INIS)

    Appleton, B.R.; Noggle, T.S.; Miller, J.W.; Schow, O.E. III; Zehner, D.M.; Jenkins, L.H.; Barrett, J.H.

    1974-01-01

    As a consequence of the channeling phenomenon of positive ions in single crystals, the yield of ions Rutherford scattered from an oriented single crystal surface is dependent on the density of surface atoms exposed to the incident ion beam. Thus, the positive ion channeling spectroscopy (PICS) technique should provide a useful tool for studying reordered surfaces. This possibility was explored by examining the surfaces of epitaxially grown thin Au single crystals with the combined techniques of LEED-AES and PICS. The LEED and AES investigations showed that when the (001) surface was sputter cleaned in ultra-high vacuum, the normal (1 x 1) symmetry of the (001) surfaces reordered into a structure which gave a complex (5 x 20) LEED pattern. The yield and energy distributions of 1 MeV He ions scattered from the Au surfaces were used to determine the number of effective monolayers contributing to the normal and reordered surfaces. These combined measurements were used to characterize the nature of the reordered surface. The general applicability of the PICS technique for investigations of surface and near surface regions is discussed

  20. 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.

  1. A computer simulation of the surface channeling of MeV heavy charged particles

    International Nuclear Information System (INIS)

    Morita, K.

    1980-01-01

    The surface channeling of 1.5 MeV N + ions incident near the [011] direction on the (100) surface and near the [001] direction on the (110) surface of Ge crystals has been studied using computer simulation. The trajectories of ions incident at angles near the critical angle for axial channeling were traced. The energy spectra, the angular distributions and the reflection-depth distributions of scattered ions were obtained. The calculated energy spectra for both directions are found to be composed of a surface peak and a broad peak, the latter being at the low energy side of the surface peak. The height of the surface peak and the energy position of the broad peak are found to depend on the azimuthal component and the tilt component of the incident angle, respectively. This result is explained to be due to the focusing effect of channeled ions deflected by the atomic rows at the surface. It is shown that the calculated angular distributions of scattered ions form a half-ring pattern and clear dips appear in the scattering intensity curve along the half-ring. The dips are found to be caused by the blocking for scattered ions by the atomic rows arrayed in the major planar directions. (author)

  2. Numerical Modeling of Surface and Volumetric Cooling using Optimal T- and Y-shaped Flow Channels

    Science.gov (United States)

    Kosaraju, Srinivas

    2017-11-01

    The layout of T- and V-shaped flow channel networks on a surface can be optimized for minimum pressure drop and pumping power. The results of the optimization are in the form of geometric parameters such as length and diameter ratios of the stem and branch sections. While these flow channels are optimized for minimum pressure drop, they can also be used for surface and volumetric cooling applications such as heat exchangers, air conditioning and electronics cooling. In this paper, an effort has been made to study the heat transfer characteristics of multiple T- and Y-shaped flow channel configurations using numerical simulations. All configurations are subjected to same input parameters and heat generation constraints. Comparisons are made with similar results published in literature.

  3. Use of Large Surface MicroChannel Plates for the Tagging of Intermediate Energy Exotic Beams

    Energy Technology Data Exchange (ETDEWEB)

    Lombardo, I., E-mail: ilombardo@lns.infn.it [Dipartimento di Fisica, Universita di Catania, Catania (Italy); INFN Laboratori Nazionali del Sud, Catania (Italy); Amorini, F. [INFN Laboratori Nazionali del Sud, Catania (Italy); Cardella, G. [INFN, Sezione di Catania, Catania (Italy); Cavallaro, S. [Dipartimento di Fisica, Universita di Catania, Catania (Italy); INFN Laboratori Nazionali del Sud, Catania (Italy); De Filippo, E. [INFN, Sezione di Catania, Catania (Italy); Geraci, E.; Grassi, L. [Dipartimento di Fisica, Universita di Catania, Catania (Italy); INFN, Sezione di Catania, Catania (Italy); La Guidara, E. [INFN, Sezione di Catania, Catania (Italy); Centro Siciliano di Fisica Nucleare e Struttura della Materia, Catania (Italy); Lanzalone, G. [INFN Laboratori Nazionali del Sud, Catania (Italy); Libera Universita Kore, Enna (Italy); Pagano, A.; Papa, M.; Pirrone, S. [INFN, Sezione di Catania, Catania (Italy); Politi, G. [Dipartimento di Fisica, Universita di Catania, Catania (Italy); INFN, Sezione di Catania, Catania (Italy); Porto, F.; Rizzo, F.; Russotto, P. [Dipartimento di Fisica, Universita di Catania, Catania (Italy); INFN Laboratori Nazionali del Sud, Catania (Italy); Verde, G. [INFN, Sezione di Catania, Catania (Italy); Vigilante, M. [INFN, Sezione di Napoli and Dipartimento di Fisica, Universita Federico II di Napoli (Italy)

    2011-06-15

    We show the properties of the tagging system for exotic beams coupled to the CHIMERA detector. In particular, the characteristics of a newly developed large surface MicroChannel Plate will be discussed. Timing and efficiency of this instrument have been investigated. Preliminary results of tests performed with radioactive beams and alpha sources are presented.

  4. DNS of Turbulent Flow and Heat Transfer in a Channel with Surface Mounted Cubes

    NARCIS (Netherlands)

    Verstappen, R.W.C.P.; Velde, R.M. van der; Veldman, A.E.P.

    2000-01-01

    The turbulent flow and heat transfer in a channel with surface mounted cubical obstacles forms a generic example of a problem that occurs in many engineering applications, for instance in the design of cooling devices. We have performed a numerical simulation of it without using any turbulence

  5. DNS of turbulent flow and heat transfer in a channel with surface mounted cubes

    NARCIS (Netherlands)

    Verstappen, R.W.C.P.; Velde, R.M. van der; Veldman, A.E.P.

    2000-01-01

    The turbulent flow and heat transfer in a channel with surface mounted cubical obstacles forms a generic example of a problem that occurs in many engineering applications, for instance in the design of cooling devices. We have performed a numerical simulation of it without using any turbulence

  6. Influence of the entrance channel in the fusion reaction 318 MeV 74Ge+74Ge

    International Nuclear Information System (INIS)

    Zhu, L.H.; Cinausero, M.; Angelis, G. de; De Poli, M.; Fioretto, E.; Gadea, A.; Napoli, D.R.; Prete, G.; Lucarelli, F.

    1998-01-01

    Entrance channel effects in the fusion of heavy ions have been studied by using the 74 Ge+ 74 Ge reaction at 318 MeV. The population of the yrast superdeformed band in 144 Gd shows an increase when compared with the results obtained in the more asymmetric 48 Ti+ 100 Mo reaction at 215 MeV. The relative yields of the different evaporation residues produced in the 74 Ge+ 74 Ge and in the 48 Ti+ 100 Mo reactions are very similar, with the exception of the 145,144 Gd residual nuclei (3n and 4n decay channels) which are populated with a larger yield in the symmetric reaction. Statistical model calculations reproduce qualitatively such effect if a fission delay is explicitly taken into account. Effects related to fusion barrier fluctuations seem to be important in determining the spin distributions of the compound nucleus. The spectra of the high energy γ-rays emitted in the 74 Ge+ 74 Ge reaction have been measured as a function of the γ-ray multiplicity as well as in coincidence with selected evaporation residues. They are reproduced by standard statistical model calculations with GDR parameters taken from systematics, demonstrating that, in agreement with dynamical model prediction, the emission of γ-rays from the dinucleus formed in the earlier stage of the collision is unimportant. (orig.)

  7. 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.

  8. Synergistic Malaria Parasite Killing by Two Types of Plasmodial Surface Anion Channel Inhibitors.

    Directory of Open Access Journals (Sweden)

    Margaret Pain

    Full Text Available Malaria parasites increase their host erythrocyte's permeability to a broad range of ions and organic solutes. The plasmodial surface anion channel (PSAC mediates this uptake and is an established drug target. Development of therapies targeting this channel is limited by several problems including interactions between known inhibitors and permeating solutes that lead to incomplete channel block. Here, we designed and executed a high-throughput screen to identify a novel class of PSAC inhibitors that overcome this solute-inhibitor interaction. These new inhibitors differ from existing blockers and have distinct effects on channel-mediated transport, supporting a model of two separate routes for solute permeation though PSAC. Combinations of inhibitors specific for the two routes had strong synergistic action against in vitro parasite propagation, whereas combinations acting on a single route produced only additive effects. The magnitude of synergism depended on external nutrient concentrations, consistent with an essential role of the channel in parasite nutrient acquisition. The identified inhibitors will enable a better understanding of the channel's structure-function and may be starting points for novel combination therapies that produce synergistic parasite killing.

  9. N-linked glycans are required on epithelial Na+ channel subunits for maturation and surface expression.

    Science.gov (United States)

    Kashlan, Ossama B; Kinlough, Carol L; Myerburg, Michael M; Shi, Shujie; Chen, Jingxin; Blobner, Brandon M; Buck, Teresa M; Brodsky, Jeffrey L; Hughey, Rebecca P; Kleyman, Thomas R

    2018-03-01

    Epithelial Na + channel (ENaC) subunits undergo N-linked glycosylation in the endoplasmic reticulum where they assemble into an αβγ complex. Six, 13, and 5 consensus sites (Asn-X-Ser/Thr) for N-glycosylation reside in the extracellular domains of the mouse α-, β-, and γ-subunits, respectively. Because the importance of ENaC N-linked glycans has not been fully addressed, we examined the effect of preventing N-glycosylation of specific subunits on channel function, expression, maturation, and folding. Heterologous expression in Xenopus oocytes or Fischer rat thyroid cells with αβγ-ENaC lacking N-linked glycans on a single subunit reduced ENaC activity as well as the inhibitory response to extracellular Na + . The lack of N-linked glycans on the β-subunit also precluded channel activation by trypsin. However, channel activation by shear stress was N-linked glycan independent, regardless of which subunit was modified. We also discovered that the lack of N-linked glycans on any one subunit reduced the total and surface levels of cognate subunits. The lack of N-linked glycans on the β-subunit had the largest effect on total levels, with the lack of N-linked glycans on the γ- and α-subunits having intermediate and modest effects, respectively. Finally, channels with wild-type β-subunits were more sensitive to limited trypsin proteolysis than channels lacking N-linked glycans on the β-subunit. Our results indicate that N-linked glycans on each subunit are required for proper folding, maturation, surface expression, and function of the channel.

  10. Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

    Science.gov (United States)

    Gurnev, Philip A; Bezrukov, Sergey M

    2012-11-13

    We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

  11. 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)

  12. Direct numerical simulation of turbulent channel flow over a liquid-infused micro-grooved surface

    Science.gov (United States)

    Chang, Jaehee; Jung, Taeyong; Choi, Haecheon; Kim, John

    2016-11-01

    Recently a superhydrophobic surface has drawn much attention as a passive device to achieve high drag reduction. Despite the high performance promised at ideal conditions, maintaining the interface in real flow conditions is an intractable problem. A non-wetting surface, known as the slippery liquid-infused porous surface (SLIPS) or the lubricant-impregnated surface (LIS), has shown a potential for drag reduction, as the working fluid slips at the interface but cannot penetrate into the lubricant layer. In the present study, we perform direct numerical simulation of turbulent channel flow over a liquid-infused micro-grooved surface to investigate the effects of this surface on the interfacial slip and drag reduction. The flow rate of water is maintained constant corresponding to Reτ 180 in a fully developed turbulent channel flow, and the lubricant layer is shear-driven by the turbulent water flow. The lubricant layer is also simulated with the assumption that the interface is flat (i.e. the surface tension effect is neglected). The solid substrate in which the lubricant is infused is modelled as straight ridges using an immersed boundary method. DNS results show that drag reduction by the liquid-infused surface is highly dependent on the viscosity of the lubricant.

  13. 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...

  14. 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....

  15. Effect of surface radiation on natural convection in an asymmetrically heated channel-chimney system

    Science.gov (United States)

    Nasri, Zied; Derouich, Youssef; Laatar, Ali Hatem; Balti, Jalloul

    2018-05-01

    In this paper, a more realistic numerical approach that takes into account the effect of surface radiation on the laminar air flow induced by natural convection in a channel-chimney system asymmetrically heated at uniform heat flux is used. The aim is to enrich the results given in Nasri et al. (Int J Therm Sci 90:122-134, 2015) by varying all the geometric parameters of the system and by taking into account the effect of surface radiation on the flows. The numerical results are first validated against experimental and numerical data available in the literature. The computations have allowed the determination of optimal configurations that maximize the mass flow rate and the convective heat transfer and minimize the heated wall temperatures. The analysis of the temperature fields with the streamlines and the pressure fields has helped to explain the effects of surface radiation and of the different thermo-geometrical parameters on the system performances to improve the mass flow rate and the heat transfer with respect to the simple channel. It is shown that the thermal performance of the channel-chimney system in terms of lower heated wall temperatures is little affected by the surface radiation. At the end, simple correlation equations have been proposed for quickly and easily predict the optimal configurations as well as the corresponding enhancement rates of the induced mass flow rate and the convective heat transfer.

  16. Elucidating distinct ion channel populations on the surface of hippocampal neurons via single-particle tracking recurrence analysis

    Science.gov (United States)

    Sikora, Grzegorz; Wyłomańska, Agnieszka; Gajda, Janusz; Solé, Laura; Akin, Elizabeth J.; Tamkun, Michael M.; Krapf, Diego

    2017-12-01

    Protein and lipid nanodomains are prevalent on the surface of mammalian cells. In particular, it has been recently recognized that ion channels assemble into surface nanoclusters in the soma of cultured neurons. However, the interactions of these molecules with surface nanodomains display a considerable degree of heterogeneity. Here, we investigate this heterogeneity and develop statistical tools based on the recurrence of individual trajectories to identify subpopulations within ion channels in the neuronal surface. We specifically study the dynamics of the K+ channel Kv1.4 and the Na+ channel Nav1.6 on the surface of cultured hippocampal neurons at the single-molecule level. We find that both these molecules are expressed in two different forms with distinct kinetics with regards to surface interactions, emphasizing the complex proteomic landscape of the neuronal surface. Further, the tools presented in this work provide new methods for the analysis of membrane nanodomains, transient confinement, and identification of populations within single-particle trajectories.

  17. 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.

  18. Quantitative Determination of Nicotine in a PDMS Microfluidic Channel Using Surface Enhanced Raman Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Jae Hyun; Choo, Jae Bum [Hanyang University, Ansan (Korea, Republic of); Kim, Duck Joong [Dankook University, Cheonan (Korea, Republic of); Lee, Sang Hoon [Korea University, Seoul (Korea, Republic of)

    2006-02-15

    Rapid and highly sensitive determination of nicotine in a PDMS microfluidic channel was investigated using surface enhanced Raman spectroscopy (SERS). A three-dimensional PDMS microfluidic channel was fabricated for this purpose. This channel shows a high mixing efficiency because the transverse and vertical dispersions of the fluid occur simultaneously through the upper and lower zig zag-type blocks. A higher efficiency of mixing could also be obtained by splitting each of the confluent streams into two sub-streams that then joined and recombined. The SERS signal was measured after nicotine molecules were effectively adsorbed onto silver nanoparticles by passing through the three-dimensional channel. A quantitative analysis of nicotine was performed based on the measured peak area at 1030 cm{sup -1}. The detection limit was estimated to be below 0.1 ppm. In this work, the SERS detection, in combination with a PDMS microfluidic channel, has been applied to the quantitative analysis of nicotine in aqueous solution. Compared to the other conventional analytical methods, the detection sensitivity was enhanced up to several orders of magnitude.

  19. Air-side performance of a micro-channel heat exchanger in wet surface conditions

    Directory of Open Access Journals (Sweden)

    Srisomba Raviwat

    2017-01-01

    Full Text Available The effects of operating conditions on the air-side heat transfer, and pressure drop of a micro-channel heat exchanger under wet surface conditions were studied experimentally. The test section was an aluminum micro-channel heat exchanger, consisting of a multi-louvered fin and multi-port mini-channels. Experiments were conducted to study the effects of inlet relative humidity, air frontal velocity, air inlet temperature, and refrigerant temperature on air-side performance. The experimental data were analyzed using the mean enthalpy difference method. The test run was performed at relative air humidities ranging between 45% and 80%; air inlet temperature ranges of 27, 30, and 33°C; refrigerant-saturated temperatures ranging from 18 to 22°C; and Reynolds numbers between 128 and 166. The results show that the inlet relative humidity, air inlet temperature, and the refrigerant temperature had significant effects on heat transfer performance and air-side pressure drop. The heat transfer coefficient and pressure drop for the micro-channel heat exchanger under wet surface conditions are proposed in terms of the Colburn j factor and Fanning f factor.

  20. 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 ...

  1. Effect of nano-scale morphology on micro-channel wall surface and electrical characterization in lead silicate glass micro-channel plate

    Science.gov (United States)

    Cai, Hua; Li, Fangjun; Xu, Yanglei; Bo, Tiezhu; Zhou, Dongzhan; Lian, Jiao; Li, Qing; Cao, Zhenbo; Xu, Tao; Wang, Caili; Liu, Hui; Li, Guoen; Jia, Jinsheng

    2017-10-01

    Micro-channel plate (MCP) is a two dimensional arrays of microscopic channel charge particle multiplier. Silicate composition and hydrogen reduction are keys to determine surface morphology of micro-channel wall in MCP. In this paper, lead silicate glass micro-channel plates in two different cesium contents (0at%, 0.5at%) and two different hydrogen reduction temperatures (400°C,450°C) were present. The nano-scale morphology, elements content and chemical states of microporous wall surface treated under different alkaline compositions and reduction conditions was investigated by Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), respectively. Meanwhile, the electrical characterizations of MCP, including the bulk resistance, electron gain and the density of dark current, were measured in a Vacuum Photoelectron Imaging Test Facility (VPIT).The results indicated that the granular phase occurred on the surface of microporous wall and diffuses in bulk glass is an aggregate of Pb atom derived from the reduction of Pb2+. In micro-channel plate, the electron gain and bulk resistance were mainly correlated to particle size and distribution, the density of dark current (DDC) went up with the increasing root-mean-square roughness (RMS) on the microporous wall surface. Adding cesiums improved the size of Pb atomic aggregation, lowered the relative concentration of [Pb] reduced from Pb2+ and decreased the total roughness of micro-channel wall surface, leading a higher bulk resistance, a lower electron gain and a less dark current. Increasing hydrogen reduction temperature also improved the size of Pb atomic aggregation, but enhanced the relative concentration of [Pb] and enlarged the total roughness of micro-channel wall surface, leading a higher bulk resistance, a lower electron gain and a larger dark current. The reasons for the difference of electrical characteristics were discussed.

  2. 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.

  3. Preliminary Plugging tests in Narrow Sodium Channels by Sodium and Carbon Dioxide reaction

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sun Hee; Wi, Myung-Hwan; Min, Jae Hong [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    This report is on the investigation of the physical/chemical phenomena that a slow loss of CO{sub 2} inventory into sodium after the sodium-CO{sub 2} boundary failure in PCHEs in realistic operating conditions. The first phenomenon is potential channel plugging inside the narrow PCHE channel. Unlike a conventional shell and- tube type HXs, failures in a PCHE are expected to be small cracks. If the faulted channel is blocked, it may have a positive function for plant safety because the pressure boundary would automatically recover due to this self-plugging. The other one is damage propagation on pressure boundary, which is referred to as potential wastage with combined corrosion/erosion effect. Physical/chemical phenomena that a slow loss of CO{sub 2} inventory into sodium after the sodium-CO{sub 2} boundary failure in printed circuit heat exchangers (PCHEs) were investigated. Our preliminary experimental results of plugging show that sodium flow immediately stopped as CO{sub 2} was injected through the nozzle at 300-400 .deg. C in 3 mm sodium channels, whereas sodium flow stopped about 60 min after CO{sub 2} injection in 5 mm sodium channels.

  4. 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)

  5. Numerical Simulation of Turbulent Half-corrugated Channel Flow by Hydrophilic and Hydrophobic Surfaces

    Directory of Open Access Journals (Sweden)

    M. R. Rastan

    2018-03-01

    Full Text Available In the first part of the present study, a two dimensional half-corrugated channel flow is simulated at Reynolds number of 104, in no-slip condition (hydrophilic surfaces( using various low Reynolds turbulence models as well as standard k-ε model; and an appropriate turbulence model (k-ω 1998 model( is proposed. Then, in order to evaluate the proposed solution method in simulation of flow adjacent to hydrophobic surfaces, turbulent flow is simulated in simple channel and the results are compared with the literature. Finally, two dimensional half-corrugated channel flow at Reynolds number of 104 is simulated again in vicinity of hydrophobic surfaces for varoius slip lengths. The results show that this method is capable of drag reduction in such a way that an increase of 200 μm in slip length leads to a massive drag reduction up to 38%. In addition, to access a significant drag reduction in turbulent flows, the non-dimensionalized slip length should be larger than the minimum.

  6. Visualization of pre-set vortices in boundary layer flow over wavy surface in rectangular channel

    KAUST Repository

    Budiman, Alexander Christantho

    2014-12-04

    Abstract: Smoke-wire flow visualization is used to study the development of pre-set counter-rotating streamwise vortices in boundary layer flow over a wavy surface in a rectangular channel. The formation of the vortices is indicated by the vortical structures on the cross-sectional plane normal to the wavy surface. To obtain uniform spanwise vortex wavelength which will result in uniform vortex size, two types of spanwise disturbances were used: a series of perturbation wires placed prior and normal to the leading edge of the wavy surface, and a jagged pattern in the form of uniform triangles cut at the leading edge. These perturbation wires and jagged pattern induce low-velocity streaks that result in the formation of counter-rotating streamwise vortices that evolve downstream to form the mushroom-like structures on the cross-sectional plane of the flow. The evolution of the most amplified disturbances can be attributed to the formation of these mushroom-like structures. It is also shown that the size of the mushroom-like structures depends on the channel entrance geometry, Reynolds number, and the channel gap.Graphical Abstract: [Figure not available: see fulltext.

  7. Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O+232Th reaction

    Directory of Open Access Journals (Sweden)

    R. Léguillon

    2016-10-01

    Full Text Available It is shown that the multinucleon transfer reactions is a powerful tool to study fission of exotic neutron-rich actinide nuclei, which cannot be accessed by particle-capture or heavy-ion fusion reactions. In this work, multinucleon transfer channels of the 18O+232Th reaction are used to study fission of fourteen nuclei 231,232,233,234Th, 232,233,234,235,236Pa, and 234,235,236,237,238U. Identification of fissioning nuclei and of their excitation energy is performed on an event-by-event basis, through the measurement of outgoing ejectile particle in coincidence with fission fragments. Fission fragment mass distributions are measured for each transfer channel, in selected bins of excitation energy. In particular, the mass distributions of 231,234Th and 234,235,236Pa are measured for the first time. Predominantly asymmetric fission is observed at low excitation energies for all studied cases, with a gradual increase of the symmetric mode towards higher excitation energy. The experimental distributions are found to be in general agreement with predictions of the fluctuation–dissipation model.

  8. 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....

  9. CONCENTRATION DEPENDENCE OF STERN LAYER CAPACITANCES AND SURFACE EQUILIBRIUM CONSTANTS IN SILICA-BASED NANOFLUIDIC CHANNELS

    DEFF Research Database (Denmark)

    Andersen, Mathias Bækbo; Frey, J.; Bruus, Henrik

    2010-01-01

    Fundamental understanding of the unique physics at the solid-liquid interface in nanofluidic channels is essential for the advancement of basic scientific knowledge and the development of novel applications for pharmaceuticals, environmental health and safety, energy harvesting and biometrics [1......]. The current models used to describe surface phenomena in nanofluidics can differ by orders of magnitude from experimentally measured values [2]. To mitigate the discrepancies, we hypothesize that the Stern-layer capacitance Cs and the surface equilibrium constants pKa, vary with the composition of the solid...

  10. 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.

  11. pH-sensitive diamond field-effect transistors (FETs) with directly aminated channel surface

    International Nuclear Information System (INIS)

    Song, Kwang-Soup; Nakamura, Yusuke; Sasaki, Yuichi; Degawa, Munenori; Yang, Jung-Hoon; Kawarada, Hiroshi

    2006-01-01

    We have introduced pH sensors fabricated on diamond thin films through modification of the surface-terminated atom. We directly modified the diamond surface from hydrogen to amine or oxygen with ultraviolet (UV) irradiation under ammonia gas. The quantified amine site based on the spectra obtained by X-ray photoelectron spectroscopy (XPS) is 26% (2.6 x 10 14 cm -2 ) with UV irradiation for 8 h and its coverage is dependent on the UV irradiation time. This directly aminated diamond surface is stable with long-term exposure in air and electrolyte solution. We fabricated diamond solution-gate field-effect transistors (SGFETs) without insulating layers on the channel surface. These diamond SGFETs with amine modified by direct amination are sensitive to pH (45 mV/pH) over a wide range from pH 2 to 12 and their sensitivity is dependent on the density of binding sites corresponding to UV irradiation time on the channel surface

  12. /sup 16/O(/sup 16/O, /sup 12/C)/sup 20/Ne reaction in the framework of the coupled channel formalism

    Energy Technology Data Exchange (ETDEWEB)

    Krause, O; Scheid, W; Greiner, W [Frankfurt Univ. (Germany, F.R.). Inst. fuer Theoretische Physik

    1974-01-01

    The transfer reaction /sup 16/O(/sup 16/O, /sup 12/C)/sup 20/Ne is treated in the coupled channel formalism. The influence of the transfer channels on the intermediate structure in the elastic excitation function is discussed. The /sup 16/O and /sup 20/Ne-nuclei are described in an ..cap alpha..-cluster model.

  13. Amphotericin B channels in phospholipid membrane-coated nanoporous silicon surfaces: implications for photovoltaic driving of ions across membranes.

    Science.gov (United States)

    Yilma, Solomon; Liu, Nangou; Samoylov, Alexander; Lo, Ting; Brinker, C Jeffrey; Vodyanoy, Vitaly

    2007-03-15

    The antimycotic agent amphotericin B (AmB) functions by forming complexes with sterols to form ion channels that cause membrane leakage. When AmB and cholesterol mixed at 2:1 ratio were incorporated into phospholipid bilayer membranes formed on the tip of patch pipettes, ion channel current fluctuations with characteristic open and closed states were observed. These channels were also functional in phospholipid membranes formed on nanoporous silicon surfaces. Electrophysiological studies of AmB-cholesterol mixtures that were incorporated into phospholipid membranes formed on the surface of nanoporous (6.5 nm pore diameter) silicon plates revealed large conductance ion channels ( approximately 300 pS) with distinct open and closed states. Currents through the AmB-cholesterol channels on nanoporous silicon surfaces can be driven by voltage applied via conventional electrical circuits or by photovoltaic electrical potential entirely generated when the nanoporous silicon surface is illuminated with a narrow laser beam. Electrical recordings made during laser illumination of AmB-cholesterol containing membrane-coated nanoporous silicon surfaces revealed very large conductance ion channels with distinct open and closed states. Our findings indicate that nanoporous silicon surfaces can serve as mediums for ion-channel-based biosensors. The photovoltaic properties of nanoporous silicon surfaces show great promise for making such biosensors addressable via optical technologies.

  14. Study of incomplete fusion reaction dynamics in 13C +165 Ho system and its dependence on various entrance channel parameters

    Science.gov (United States)

    Tali, Suhail A.; Kumar, Harish; Ansari, M. Afzal; Ali, Asif; Singh, D.; Ali, Rahbar; Giri, Pankaj K.; Linda, Sneha B.; Parashari, Siddharth; Kumar, R.; Singh, R. P.; Muralithar, S.

    2018-02-01

    The excitation functions for the evaporation residues populated in the interaction of 13C +165 Ho system have been measured at projectile energies ≈ 4-7 MeV/nucleon. Stacked foil activation technique followed by off-line γ-ray spectroscopy have been employed in the present work. The experimentally measured cross-sections are analyzed in the frame work of statistical model code PACE4, which takes into account only the complete fusion reaction cross-sections. The evaporation residues populated via xn and pxn channels were found to be in good agreement with the PACE4 predictions, while a significant enhancement in the measured cross-sections over PACE4 predictions is observed in case of α-emitting channels, which may be attributed to the incomplete fusion process. For the better understanding of incomplete fusion dynamics, the incomplete fusion fraction has also been deduced and its sensitivity with various entrance channel parameters like: projectile energy, mass-asymmetry, projectile structure in terms of Qα-value and Coulomb effect has been studied in the present work. The incomplete fusion fraction is found to increase with increasing the projectile energy and a strong projectile structure dependent mass-asymmetry systematic is also observed. The incomplete fusion fraction is also found to be small for more negative Qα-value projectile (13C) induced reactions as compared to less negative Qα-value projectiles (12C, 16O and 20Ne) induced reactions with the same target nucleus 165Ho. An interesting trend is obtained on further investigation of incomplete fusion dependence on Coulomb effect (ZPZT).

  15. Pool Boiling Characteristics on the Microstructure surfaces with Both Rectangular Cavities and Channels

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong Eok; Myung, Byung-Soo [Kyungpook Nat’l Univ., Daegu (Korea, Republic of); Park, Su Cheong; Yu, Dong In [POSTECH, Pohang (Korea, Republic of); Kim, Moo Hwan [Korea Institute of Nuclear Safety (KINS), Daejeon (Korea, Republic of); Ahn, Ho Seon [Incheon Nat’l Univ., Incheon (Korea, Republic of)

    2016-06-15

    Based on a surface design with rectangular cavities and channels, we investigated the effects of gravity and capillary pressure on pool-boiling Critical Heat Flux (CHF). The microcavity structures could prevent liquid flow by the capillary pressure effect. In addition, the microchannel structures contributed to induce one-dimensional liquid flow on the boiling surface. The relationship between the CHF and capillary flow was clearly established. The driving potentials for the liquid supply into a boiling surface can be generated by the gravitational head and capillary pressure. Through an analysis of pool boiling and visualization data, we reveal that the liquid supplement to maintain the nucleate boiling condition on a boiling surface is closely related to the gravitational pressure head and capillary pressure effect.

  16. Interatomic potentials from rainbow scattering of keV noble gas atoms under axial surface channeling

    International Nuclear Information System (INIS)

    Schueller, A.; Wethekam, S.; Mertens, A.; Maass, K.; Winter, H.; Gaertner, K.

    2005-01-01

    For grazing scattering of keV Ne and Ar atoms from a Ag(1 1 1) and a Cu(1 1 1) surface under axial surface channeling conditions we observe well defined peaks in the angular distributions for scattered projectiles. These peaks can be attributed to 'rainbow-scattering' and are closely related to the geometry of potential energy surfaces which can be approximated by the superposition of continuum potentials along strings of atoms in the surface plane. The dependence of rainbow angles on the scattering geometry provides stringent tests on the scattering potentials. From classical trajectory calculations based on universal (ZBL), adjusted Moliere (O'Connor and Biersack), and individual interatomic potentials we obtain corresponding rainbow angles for comparison with the experimental data. We find good overall agreement with the experiments for a description of trajectories based on adjusted Moliere and individual potentials, whereas the agreement is poorer for potentials with ZBL screening

  17. 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.

  18. 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.

  19. 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.

  20. Free Convection Heat and Mass Transfer MHD Flow in a Vertical Channel in the Presence of Chemical Reaction

    Directory of Open Access Journals (Sweden)

    R. N. Barik

    2013-09-01

    Full Text Available An analysis is made to study the effects of diffusion-thermo and chemical reaction on fully developed laminar MHD flow of electrically conducting viscous incompressible fluid in a vertical channel formed by two vertical parallel plates was taken into consideration with uniform temperature and concentration. The analytical solution by Laplace transform technique of partial differential equations is used to obtain the expressions for the velocity, temperature and concentration. It is interesting to note that during the course of computation, the transient solution at large time coincides with steady state solution derived separately and the diffusion-thermo effect creates an anomalous situation in temperature and velocity profiles for small Prandtl numbers. The study is restricted to only destructive reaction and non-conducting case cannot be derived as a particular case still it is quite interesting and more realistic than the earlier one.

  1. A Low-Cost and Portable Dual-Channel Fiber Optic Surface Plasmon Resonance System.

    Science.gov (United States)

    Liu, Qiang; Liu, Yun; Chen, Shimeng; Wang, Fang; Peng, Wei

    2017-12-04

    A miniaturization and integration dual-channel fiber optic surface plasmon resonance (SPR) system was proposed and demonstrated in this paper. We used a yellow light-emitting diode (LED, peak wavelength 595 nm) and built-in web camera as a light source and detector, respectively. Except for the detection channel, one of the sensors was used as a reference channel to compensate nonspecific binding and physical absorption. We packaged the LED and surface plasmon resonance (SPR) sensors together, which are flexible enough to be applied to mobile devices as a compact and portable system. Experimental results show that the normalized intensity shift and refractive index (RI) of the sample have a good linear relationship in the RI range from 1.328 to 1.348. We used this sensor to monitor the reversible, specific interaction between lectin concanavalin A (Con A) and glycoprotein ribonuclease B (RNase B), which demonstrate its capabilities of specific identification and biochemical samples concentration detection. This sensor system has potential applications in various fields, such as medical diagnosis, public health, food safety, and environment monitoring.

  2. Evidence of two-channel distortion effects in positronium formation reactions

    International Nuclear Information System (INIS)

    Macri, P A; Miraglia, J E; Hanssen, J; Fojon, O A; Rivarola, R D

    2004-01-01

    The formation of ground-state positronium in collisions of positrons on hydrogen-like atoms is considered. In previous theoretical works, two-centre distorted wavefunctions were employed to approximate either the initial or the final channel. Here we report results obtained by means of the eikonal final state continuum distorted wave approximation for which asymptotically correct distorted wavefunctions are used for both the initial and final states of the scattering system. Comparison of the present theoretical total cross sections with experimental data reveals that distortion effects become important in both channels as the impact energy decreases. This work also shows that distorted-wave theories may be extended from their usual domain of high impact energies to lower ones. (letter to the editor)

  3. Evidence of two-channel distortion effects in positronium formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macri, P A [Instituto de AstronomIa y FIsica del Espacio, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad de Buenos Aires, Casilla de Correo 67, Suc. 28, 1428 Buenos Aires (Argentina); Miraglia, J E [Instituto de AstronomIa y FIsica del Espacio, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad de Buenos Aires, Casilla de Correo 67, Suc. 28, 1428 Buenos Aires (Argentina); Hanssen, J [Laboratoire de Physique Moleculaire et des Collisions, Institute de Physique Rue Arago, Tecnopole 2000, Metz (France); Fojon, O A [Instituto de FIsica de Rosario, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad Nacional de Rosario, Av. Pellegrini 250, 2000 Rosario (Argentina); Rivarola, R D [Instituto de FIsica de Rosario, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad Nacional de Rosario, Av. Pellegrini 250, 2000 Rosario (Argentina)

    2004-03-28

    The formation of ground-state positronium in collisions of positrons on hydrogen-like atoms is considered. In previous theoretical works, two-centre distorted wavefunctions were employed to approximate either the initial or the final channel. Here we report results obtained by means of the eikonal final state continuum distorted wave approximation for which asymptotically correct distorted wavefunctions are used for both the initial and final states of the scattering system. Comparison of the present theoretical total cross sections with experimental data reveals that distortion effects become important in both channels as the impact energy decreases. This work also shows that distorted-wave theories may be extended from their usual domain of high impact energies to lower ones. (letter to the editor)

  4. 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

  5. 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

  6. 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...

  7. 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

  8. 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 ...

  9. 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....

  10. Heat transport and surface heat transfer with helium in rotating channels

    International Nuclear Information System (INIS)

    Schnapper, C.

    1978-06-01

    Heat transport and surface heat transfer with helium in rotating radially arranged channels were experimentally studied with regard to cooling of large turbogenerators with superconducting windings. Measurements with thermosiphon and thermosiphon loops of different channel diameters were performed, and results are presented. The thermodynamic state of the helium in a rotating thermosiphon and the mass flow rate in a thermosiphon loop is characterized by formulas. Heat transport by directed convection in thermosiphon loops is found to be more efficient 12 cm internal convection in thermosiphons. Steady state is reached sooner in thermosiphon loops than in thermosiphons, when heat load suddenly changes. In a very large centrifugal field single-phase heat transfer with natural and forced convection is described by similar formulas which are also applicable 10 thermosiphons in gravitation field or to heat transfer to non-rotating helium. (orig.) [de

  11. Dai Omega, a large solid angle axial focusing superconducting surface muon channel

    International Nuclear Information System (INIS)

    Miyadera, H.; Nagamine, K.; Shimomura, K.; Nishiyama, K.; Tanaka, H.; Fukuchi, K.; Makimura, S.; Ishida, K.

    2003-01-01

    An axial focusing surface muon channel, Dai Omega, was installed at KEK-MSL in the summer of 2001. Large aperture superconducting coils are utilized instead of quadrupole magnets. Dai Omega adopts an axial focusing beam path using symmetric magnetic fields from four coils. Computer simulations were performed on constructing Dai Omega, and the calculated solid angle acceptance of Dai Omega was larger than 1 sr at the optimum momentum. The momentum acceptance of Dai Omega was 6% FWHM. Dai Omega improved the solid angle acceptance by almost 20 times, in comparison with conventional muon channels. Beam tuning tests of Dai Omega have been carried out, and a beam intensity of 10 6 μ + /s was achieved at KEK-NML (500 MeV, 5 μA), which was almost comparable with that of RAL (800 MeV, 200 μA)

  12. Binding modes and functional surface of anti-mammalian scorpion α-toxins to sodium channels.

    Science.gov (United States)

    Chen, Rong; Chung, Shin-Ho

    2012-10-02

    Scorpion α-toxins bind to the voltage-sensing domains of voltage-gated sodium (Na(V)) channels and interfere with the inactivation mechanisms. The functional surface of α-toxins has been shown to contain an NC-domain consisting of the five-residue turn (positions 8-12) and the C-terminus (positions 56-64) and a core-domain centered on the residue 18. The NC- and core-domains are interconnected by the linker-domain (positions 8-18). Here with atomistic molecular dynamics simulations, we examine the binding modes between two α-toxins, the anti-mammalian AahII and the anti-insect LqhαIT, and the voltage-sensing domain of rat Na(V)1.2, a subtype of Na(V) channels expressed in nerve cells. Both toxins are docked to the extracellular side of the voltage-sensing domain of Na(V)1.2 using molecular dynamics simulations, with the linker-domain assumed to wedge into the binding pocket. Several salt bridges and hydrophobic clusters are observed to form between the NC- and core-domains of the toxins and Na(V)1.2 and stabilize the toxin-channel complexes. The binding modes predicted are consistent with available mutagenesis data and can readily explain the relative affinities of AahII and LqhαIT for Na(V)1.2. The dissociation constants for the two toxin-channel complexes are derived, which compare favorably with experiment. Our models demonstrate that the functional surface of anti-mammalian scorpion α-toxins is centered on the linker-domain, similar to that of β-toxins.

  13. Interannual Variations of Surface Currents and Transports in the Sicily Channel Derived From Coastal Altimetry

    Science.gov (United States)

    Jebri, Fatma; Zakardjian, Bruno; Birol, Florence; Bouffard, Jérôme; Jullion, Loïc.; Sammari, Cherif

    2017-11-01

    A 20 year coastal altimetry data set (X-TRACK) is used, for the first time, to gain insight into the long-term interannual variations of the surface circulation in the Sicily Channel. First, a spectral along with a time/space diagram analysis are applied to the monthly means. They reveal a regionally coherent current patterns from track to track with a marked interannual variability that is unequally shared between the Atlantic Tunisian Current and Atlantic Ionian Stream inflows in the Sicily Channel and the Bifurcation Tyrrhenian Current outflow northeast of Sicily. Second, an empirical altimetry-based transport-like technique is proposed to quantify volume budgets inside the closed boxes formed by the crossing of the altimetry tracks and coastlines over the study area. A set of hydrographic measurements is used to validate the method. The inferred altimetry transports give a well-balanced mean eastward Atlantic Waters baroclinic flow of 0.4 Sv and standard deviations of 0.2 Sv on a yearly basis throughout the Sicily Channel and toward the Ionian Sea, which is fairly coherent with those found in the literature. Furthermore, the analysis allows to quantify the intrusions of Atlantic Waters over the Tunisian Shelf (0.12 ± 0.1 Sv) and highlights two main modes of variability of the main surface waters path over the Sicily Channel through the Bifurcation Atlantic Tunisian Current and Atlantic Ionian Stream systems. Some physical mechanisms are finally discussed with regards to changes in the observed currents and transports.

  14. Four-channel surface coil array for sequential CW-EPR image acquisition

    Science.gov (United States)

    Enomoto, Ayano; Emoto, Miho; Fujii, Hirotada; Hirata, Hiroshi

    2013-09-01

    This article describes a four-channel surface coil array to increase the area of visualization for continuous-wave electron paramagnetic resonance (CW-EPR) imaging. A 776-MHz surface coil array was constructed with four independent surface coil resonators and three kinds of switches. Control circuits for switching the resonators were also built to sequentially perform EPR image acquisition for each resonator. The resonance frequencies of the resonators were shifted using PIN diode switches to decouple the inductively coupled coils. To investigate the area of visualization with the surface coil array, three-dimensional EPR imaging was performed using a glass cell phantom filled with a solution of nitroxyl radicals. The area of visualization obtained with the surface coil array was increased approximately 3.5-fold in comparison to that with a single surface coil resonator. Furthermore, to demonstrate the applicability of this surface coil array to animal imaging, three-dimensional EPR imaging was performed in a living mouse with an exogenously injected nitroxyl radical imaging agent.

  15. Pore channel surface modification for enhancing anti-fouling membrane distillation

    Science.gov (United States)

    Qiu, Haoran; Peng, Yuelian; Ge, Lei; Villacorta Hernandez, Byron; Zhu, Zhonghua

    2018-06-01

    Membrane surface modification by forming a functional layer is an effective way to improve the anti-fouling properties of membranes; however, the additional layer and the potential blockage of bulk pores may increase the mass transfer resistance and reduce the permeability. In this study, we applied a novel method of preparing anti-fouling membranes for membrane distillation by dispersing graphene oxide (GO) on the channel surface of polyvinylidene fluoride membranes. The surface morphology and properties were characterized by scanning electron microscopy, atomic force microscope, and Fourier transform infrared spectrometry. Compared to the membrane surface modification by nanoparticles (e.g. SiO2), GO was mainly located on the pore surface of the membrane bulk, rather than being formed as an individual layer onto the membrane surface. The performance was evaluated via a direct-contact membrane distillation process with anionic and cationic surfactants as the foulants, separately. Compared to the pristine PVDF membrane, the anti-fouling behavior and distillate flux of the GO-modified membranes were improved, especially when using the anionic surfactant as the foulant. The enhanced anti-fouling performance can be attributed to the oxygen containing functional groups in GO and the healing of the membrane pore defects. This method may provide an effective route to manipulate membrane pore surface properties for anti-fouling separation without increasing mass transfer resistance.

  16. Experimental and numerical study on heat transfer and pressure drop performance of Cross-Wavy primary surface channel

    International Nuclear Information System (INIS)

    Ma, Ting; Du, Lin-xiu; Sun, Ning; Zeng, Min; Sundén, Bengt; Wang, Qiu-wang

    2016-01-01

    Highlights: • Naphthalene sublimation experiments were performed for Cross-Wavy channels. • Entrance region has a small effect on unit-averaged heat transfer coefficient of Cross-Wavy channels. • Correlations of Nusselt number and friction factor in Cross-Wavy channel were obtained. • Similar Cross-Wavy channels have similar thermal hydraulic performance. - Abstract: The Cross-Wavy primary surface heat exchanger is one of the most promising candidates for microturbine recuperators. In this paper, naphthalene sublimation experiments are performed for Cross-Wavy channels in a wind tunnel. The experimental results indicate that the entrance region has a small effect on the unit-averaged heat transfer coefficient of whole Cross-Wavy channels. Correlations of Nusselt number and friction factor in the Cross-Wavy channel are obtained. However, only the Cross-Wavy channel with a large equivalent diameter is tested because the actual Cross-Wavy channels are very complicated and small. Therefore, based on the similarity rules, five Cross-Wavy channels with similar structures but different equivalent diameters are further investigated by numerical simulations. The numerical results indicate that the Cross-Wavy channels with similar structures but different equivalent diameters have similar thermal-hydraulic performance in the studied Reynolds number range.

  17. 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.

  18. 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.

  19. 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.

  20. Large-eddy simulation of open channel flow with surface cooling

    International Nuclear Information System (INIS)

    Walker, R.; Tejada-Martínez, A.E.; Martinat, G.; Grosch, C.E.

    2014-01-01

    Highlights: • Open channel flow comparable to a shallow tidal ocean flow is simulated using LES. • Unstable stratification is imposed by a constant surface cooling flux. • Full-depth, convection-driven, rotating supercells develop when cooling is applied. • Strengthening of cells occurs corresponding to an increasing of the Rayleigh number. - Abstract: Results are presented from large-eddy simulations of an unstably stratified open channel flow, driven by a uniform pressure gradient and with zero surface shear stress and a no-slip lower boundary. The unstable stratification is applied by a constant cooling flux at the surface and an adiabatic bottom wall, with a constant source term present to ensure the temperature reaches a statistically steady state. The structure of the turbulence and the turbulence statistics are analyzed with respect to the Rayleigh number (Ra τ ) representative of the surface buoyancy relative to shear. The impact of the surface cooling-induced buoyancy on mean and root mean square of velocity and temperature, budgets of turbulent kinetic energy (and components), Reynolds shear stress and vertical turbulent heat flux will be investigated. Additionally, colormaps of velocity fluctuations will aid the visualization of turbulent structures on both vertical and horizontal planes in the flow. Under neutrally stratified conditions the flow is characterized by weak, full-depth, streamwise cells similar to but less coherent than Couette cells in plane Couette flow. Increased Ra τ and thus increased buoyancy effects due to surface cooling lead to full-depth convection cells of significantly greater spanwise size and coherence, thus termed convective supercells. Full-depth convective cell structures of this magnitude are seen for the first time in this open channel domain, and may have important implications for turbulence analysis in a comparable tidally-driven ocean boundary layer. As such, these results motivate further study of the

  1. The interaction between fluid flow and ultra-hydrophobic surface in mini channel

    Directory of Open Access Journals (Sweden)

    Jasikova Darina

    2017-01-01

    Full Text Available Interaction of liquid with ultra-hydrophobic surface is accompanied by creation of layer of air. The effect of the air film has a potential of use in industry in many applications. The quality of the surface is influenced by matrix roughness, the character of physical or chemical cover. There was developed a method for analysis of the liquid flow and the air film using the lighting in volume, visualization with CCD camera and long distance microscope, and optical filters. There were prepared four stainless steel samples of inner channel of dimensions (80 × 8 × 8 mm and initial surface roughness Ra 0.33, Ra 1.0, Ra 2.0, and Ra 2.2. The inner channel was treated with plasma and commercial hydrophobic coating Greblon (WEILBURGER Coatings GmbH. There was realized study focused on the liquid flow velocity profile close to the air film. There are present results for laminar, transient and turbulent flows. The study also estimated the air film thickness depending on the Re number. The knowledge of the air film behaviour helps applied suitable degree of processing and cover for the target application.

  2. Hyperon production in photonuclear reactions on protons and deuterons : The Kappa(0)Sigma(+) channel

    NARCIS (Netherlands)

    Lohner, H; Bacelar, J; Castelijns, R; Messchendorp, J; Shende, S; Maeda, K; Tamura, H; Nakamura, SN; Hashimoto, O

    2004-01-01

    With the combined setup of the Crystal Barrel and TAPS photonspectrometers at ELSA in Bonn we have studied photonuclear reactions on protons and deuterons. From the series of experiments on single and multiple neutral meson emission we concentrate here on the hyperon production off protons and

  3. FT-IR spectroscopic imaging of reactions in multiphase flow in microfluidic channels.

    Science.gov (United States)

    Chan, K L Andrew; Kazarian, Sergei G

    2012-05-01

    Rapid, in situ, and label-free chemical analysis in microfluidic devices is highly desirable. FT-IR spectroscopic imaging has previously been shown to be a powerful tool to visualize the distribution of different chemicals in flows in a microfluidic device at near video rate imaging speed without tracers or dyes. This paper demonstrates the possibility of using this imaging technology to capture the chemical information of all reactants and products at different points in time and space in a two-phase system. Differences in the rates of chemical reactions in laminar flow and segmented flow systems are also compared. Neutralization of benzoic acid in decanol with disodium phosphate in water has been used as the model reaction. Quantitative information, such as concentration profiles of reactant and products, can be extracted from the imaging data. The same feed flow rate was used in both the laminar flow and segmented flow systems. The laminar flow pattern was achieved using a plain wide T-junction, whereas the segmented flow was achieved by introducing a narrowed section and a nozzle at the T-junction. The results show that the reaction rate is limited by diffusion and is much slower with the laminar flow pattern, whereas the reaction is completed more quickly in the segmented flow due to better mixing.

  4. Coupled channel theory of pion--deuteron reaction applied to threshold scattering

    International Nuclear Information System (INIS)

    Mizutani, T.; Koltun, D.S.

    1977-01-01

    Scattering and absorption of pions by a nuclear target are treated together in a coupled channel theory. The theory is developed explicitly for the problem of pion scattering and absorption by a deuteron. The equations are presented in terms of the integral equations of three-body scattering theory. The method is then applied in an approximate from to calculate the contribution of pion absorption to the scattering length for pion--deuteron scattering. The sensitivity of the calculated results to the model assumptions and approximations is investigated

  5. Reaction channel coupling effects for nucleons on 16O: Induced undularity and proton-neutron potential differences

    Science.gov (United States)

    Keeley, N.; Mackintosh, R. S.

    2018-01-01

    Background: Precise fitting of scattering observables suggests that the nucleon-nucleus interaction is l dependent. Such l dependence has been shown to be S -matrix equivalent to an undulatory l -independent potential. The undulations include radial regions where the imaginary term is emissive. Purpose: To study the dynamical polarization potential (DPP) generated in proton-16O and neutron-16O interaction potentials by coupling to pickup channels. Undulatory features occurring in these DPPs can be compared with corresponding features of empirical optical model potentials (OMPs). Furthermore, the additional inclusion of coupling to vibrational states of the target will provide evidence for dynamically generated nonlocality. Methods: The fresco code provides the elastic channel S -matrix Sl j for chosen channel couplings. Inversion, Sl j→V (r ) +l .s VSO(r ) , followed by subtraction of the bare potential, yields an l -independent and local representation of the DPP due to the chosen couplings. Results: The DPPs have strongly undulatory features, including radial regions of emissivity. Certain features of empirical DPPs appear, e.g., the full inverted potential has emissive regions. The DPPs for different collective states are additive except near the nuclear center, whereas the collective and reaction channel DPPs are distinctly nonadditive over a considerable radial range, indicating dynamical nonlocality. Substantial differences between the DPPs due to pickup coupling for protons and neutrons occur; these imply a greater difference between proton and neutron OMPs than the standard phenomenological prescription. Conclusions: The onus is on those who object to undularity in the local and l -independent representation of nucleon elastic scattering to show why such undulations do not occur. This work suggests that it is not legitimate to halt model-independent fits to high-quality data at the appearance of undularity.

  6. 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

  7. Structure and morphology of surface of silicon crystals to be applied for channeling at relativistic energies

    International Nuclear Information System (INIS)

    Vomiero, Alberto; Restello, Silvio; Scian, Carlo; Marchi, Enrico Boscolo; Mea, Gianantonio Della; Guidi, Vincenzo; Milan, Emiliano; Baricordi, Stefano; Martinelli, Giuliano; Carnera, Alberto; Sambo, Andrea

    2006-01-01

    Bent crystals can be successfully applied for extraction/collimation of relativistic particles. A crucial feature to obtain high extraction efficiencies is the treatment of the surfaces being encountered by the beam, since mechanical operations induce considerable lattice imperfections. In order to remove the superficial damaged layer a planar etching can be applied on the surface exposed to the beam. This work presents a systematic study of the morphology and the crystalline perfection of the surface of the samples that have been used in accelerators with high efficiency. Crystals with different surface treatments have been investigated. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were applied on the characterisation of surface morphology. Low energy backscattering channeling of 2-MeV α particles or protons was used as a probe for the crystalline structure. The presence of a superficial damaged layer in the samples just after mechanical treatment was unveiled, while, in contrast, chemical etching leaves a surface with high crystalline perfection that can be related to the record efficiency

  8. 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.

  9. 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

  10. Hand Motion Classification Using a Multi-Channel Surface Electromyography Sensor

    Directory of Open Access Journals (Sweden)

    Dong Sun

    2012-01-01

    Full Text Available The human hand has multiple degrees of freedom (DOF for achieving high-dexterity motions. Identifying and replicating human hand motions are necessary to perform precise and delicate operations in many applications, such as haptic applications. Surface electromyography (sEMG sensors are a low-cost method for identifying hand motions, in addition to the conventional methods that use data gloves and vision detection. The identification of multiple hand motions is challenging because the error rate typically increases significantly with the addition of more hand motions. Thus, the current study proposes two new methods for feature extraction to solve the problem above. The first method is the extraction of the energy ratio features in the time-domain, which are robust and invariant to motion forces and speeds for the same gesture. The second method is the extraction of the concordance correlation features that describe the relationship between every two channels of the multi-channel sEMG sensor system. The concordance correlation features of a multi-channel sEMG sensor system were shown to provide a vast amount of useful information for identification. Furthermore, a new cascaded-structure classifier is also proposed, in which 11 types of hand gestures can be identified accurately using the newly defined features. Experimental results show that the success rate for the identification of the 11 gestures is significantly high.

  11. Hand motion classification using a multi-channel surface electromyography sensor.

    Science.gov (United States)

    Tang, Xueyan; Liu, Yunhui; Lv, Congyi; Sun, Dong

    2012-01-01

    The human hand has multiple degrees of freedom (DOF) for achieving high-dexterity motions. Identifying and replicating human hand motions are necessary to perform precise and delicate operations in many applications, such as haptic applications. Surface electromyography (sEMG) sensors are a low-cost method for identifying hand motions, in addition to the conventional methods that use data gloves and vision detection. The identification of multiple hand motions is challenging because the error rate typically increases significantly with the addition of more hand motions. Thus, the current study proposes two new methods for feature extraction to solve the problem above. The first method is the extraction of the energy ratio features in the time-domain, which are robust and invariant to motion forces and speeds for the same gesture. The second method is the extraction of the concordance correlation features that describe the relationship between every two channels of the multi-channel sEMG sensor system. The concordance correlation features of a multi-channel sEMG sensor system were shown to provide a vast amount of useful information for identification. Furthermore, a new cascaded-structure classifier is also proposed, in which 11 types of hand gestures can be identified accurately using the newly defined features. Experimental results show that the success rate for the identification of the 11 gestures is significantly high.

  12. High Guanidinium Permeability Reveals Dehydration-Dependent Ion Selectivity in the Plasmodial Surface Anion Channel

    Directory of Open Access Journals (Sweden)

    Abdullah A. B. Bokhari

    2014-01-01

    Full Text Available Malaria parasites grow within vertebrate erythrocytes and increase host cell permeability to access nutrients from plasma. This increase is mediated by the plasmodial surface anion channel (PSAC, an unusual ion channel linked to the conserved clag gene family. Although PSAC recognizes and transports a broad range of uncharged and charged solutes, it must efficiently exclude the small Na+ ion to maintain infected cell osmotic stability. Here, we examine possible mechanisms for this remarkable solute selectivity. We identify guanidinium as an organic cation with high permeability into human erythrocytes infected with Plasmodium falciparum, but negligible uptake by uninfected cells. Transport characteristics and pharmacology indicate that this uptake is specifically mediated by PSAC. The rank order of organic and inorganic cation permeabilities suggests cation dehydration as the rate-limiting step in transport through the channel. The high guanidinium permeability of infected cells also allows rapid and stringent synchronization of parasite cultures, as required for molecular and cellular studies of this pathogen. These studies provide important insights into how nutrients and ions are transported via PSAC, an established target for antimalarial drug development.

  13. Independence Between Two Channels of Surface Electromyogram Signal to Measure the Loss of Motor Units

    Directory of Open Access Journals (Sweden)

    Arjunan Sridhar P.

    2015-06-01

    Full Text Available This study has investigated the relationship in the connectivity of motor units in surface electromyogram (sEMG of biceps brachii muscle. It is hypothesized that with ageing, there is reduction/loss in number of motor units, leading to reduction in the independence between the channels of the recorded muscle activity. Two channels of sEMG were recorded during three levels of isometric muscle contraction: 50 %, 75 % and 100 % maximal voluntary contraction (MVC. 73 subjects (age range 20-70 participated in the experiments. The independence in channel index (ICI between the two sEMG recording locations was computed using the independent components and Frobenius norm. ANOVA Statistical analysis was performed to test the effect of age (loss of motor units and level of contraction on ICI. The results show that the ICI among the older cohort was significantly lower compared with the younger adults. This research study has shown that the reduction in number of motor units is reflected by the reduction in the ICI of the sEMG signal.

  14. A theoretical study of the atmospherically important radical-radical reaction BrO + HO2; the product channel O2(a1Δg) + HOBr is formed with the highest rate.

    Science.gov (United States)

    Chow, Ronald; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2016-11-09

    A theoretical study has been made of the BrO + HO 2 reaction, a radical-radical reaction which contributes to ozone depletion in the atmosphere via production of HOBr. Reaction enthalpies, activation energies and mechanisms have been determined for five reaction channels. Also rate coefficients have been calculated, in the atmospherically important temperature range 200-400 K, for the two channels with the lowest activation energies, both of which produce HOBr: (R1a) HOBr(X 1 A') + O 2 (X 3 Σ) and (R1b) HOBr(X 1 A') + O 2 (a 1 Δ g ). The other channels considered are: (R2) BrO + HO 2 → HBr + O 3 , (R3) BrO + HO 2 → OBrO + OH and (R4) BrO + HO 2 → BrOO + OH. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/AVDZ level, while relative energies of the stationary points on the reaction surface were improved at a higher level (BD(TQ)/CBS or CCSD(T)/CBS). The computed standard reaction enthalpies (ΔH) for channels (R1a), (R1b), (R2), (R3) and (R4) are -47.5, -25.0, -4.3, 14.9 and 5.9 kcal mol -1 , and the corresponding computed activation energies (ΔE) are 2.53, -3.07, 11.83, 35.0 and 37.81 kcal mol -1 . These values differ significantly from those obtained in earlier work by Kaltsoyannis and Rowley (Phys. Chem. Chem. Phys., 2002, 4, 419-427), particularly for channel (R1b), and reasons for this are discussed. In particular, the importance of obtaining an open-shell singlet wavefunction, rather than a closed-shell singlet wavefunction, for the transition state of this channel is emphasized. Rate coefficient calculations from computed potential energy surfaces were made for BrO + HO 2 for the first time. Although channel (R1a) is the most exothermic, channel (R1b) has the lowest barrier height, which is negative (at -3.07 kcal mol -1 ). Most rate coefficient calculations were therefore made for (R1b). A two transition state model has been used, involving an outer and an inner transition state. The inner transition

  15. Polarized axonal surface expression of neuronal KCNQ potassium channels is regulated by calmodulin interaction with KCNQ2 subunit.

    Directory of Open Access Journals (Sweden)

    John P Cavaretta

    Full Text Available KCNQ potassium channels composed of KCNQ2 and KCNQ3 subunits give rise to the M-current, a slow-activating and non-inactivating voltage-dependent potassium current that limits repetitive firing of action potentials. KCNQ channels are enriched at the surface of axons and axonal initial segments, the sites for action potential generation and modulation. Their enrichment at the axonal surface is impaired by mutations in KCNQ2 carboxy-terminal tail that cause benign familial neonatal convulsion and myokymia, suggesting that their correct surface distribution and density at the axon is crucial for control of neuronal excitability. However, the molecular mechanisms responsible for regulating enrichment of KCNQ channels at the neuronal axon remain elusive. Here, we show that enrichment of KCNQ channels at the axonal surface of dissociated rat hippocampal cultured neurons is regulated by ubiquitous calcium sensor calmodulin. Using immunocytochemistry and the cluster of differentiation 4 (CD4 membrane protein as a trafficking reporter, we demonstrate that fusion of KCNQ2 carboxy-terminal tail is sufficient to target CD4 protein to the axonal surface whereas inhibition of calmodulin binding to KCNQ2 abolishes axonal surface expression of CD4 fusion proteins by retaining them in the endoplasmic reticulum. Disruption of calmodulin binding to KCNQ2 also impairs enrichment of heteromeric KCNQ2/KCNQ3 channels at the axonal surface by blocking their trafficking from the endoplasmic reticulum to the axon. Consistently, hippocampal neuronal excitability is dampened by transient expression of wild-type KCNQ2 but not mutant KCNQ2 deficient in calmodulin binding. Furthermore, coexpression of mutant calmodulin, which can interact with KCNQ2/KCNQ3 channels but not calcium, reduces but does not abolish their enrichment at the axonal surface, suggesting that apo calmodulin but not calcium-bound calmodulin is necessary for their preferential targeting to the axonal

  16. 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

  17. Unsteady Bioconvection Squeezing Flow in a Horizontal Channel with Chemical Reaction and Magnetic Field Effects

    Directory of Open Access Journals (Sweden)

    Qingkai Zhao

    2017-01-01

    Full Text Available The time-dependent mixed bioconvection flow of an electrically conducting fluid between two infinite parallel plates in the presence of a magnetic field and a first-order chemical reaction is investigated. The fully coupled nonlinear systems describing the total mass, momentum, thermal energy, mass diffusion, and microorganisms equations are reduced to a set of ordinary differential equations via a set of new similarity transformations. The detailed analysis illustrating the influences of various physical parameters such as the magnetic, squeezing, and chemical reaction parameters and the Schmidt and Prandtl numbers on the distributions of temperature and microorganisms as well as the skin friction and the Nusselt number is presented. The conclusion is drawn that the flow field, temperature, and chemical reaction profiles are significantly influenced by magnetic parameter, heat generation/absorption parameter, and chemical parameter. Some examples of potential applications of such bioconvection could be found in pharmaceutical industry, microfluidic devices, microbial enhanced oil recovery, modeling oil, and gas-bearing sedimentary basins.

  18. 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.

  19. Effects of irregular two-dimensional and three-dimensional surface roughness in turbulent channel flows

    International Nuclear Information System (INIS)

    De Marchis, M.; Napoli, E.

    2012-01-01

    Highlights: ► 3D irregular rough surfaces produce higher effects than those observed over 2D. ► Effective slope is a geometrical parameter representative of the roughness effects. ► 3D rough surfaces enhance the turbulence isotropization. ► 2D and 3D irregular roughness partially support the wall similarity. ► Irregular rough surfaces shear some features with regular rough walls. - Abstract: Wall-resolved Large Eddy Simulation of fully developed turbulent channel flows over two different rough surfaces is performed to investigate on the effects of irregular 2D and 3D roughness on the turbulence. The two geometries are obtained through the superimposition of sinusoidal functions having random amplitudes and different wave lengths. In the 2D configuration the irregular shape in the longitudinal direction is replicated in the transverse one, while in the 3D case the sinusoidal functions are generated both in streamwise and spanwise directions. Both channel walls are roughened in such a way as to obtain surfaces with statistically equivalent roughness height, but different shapes. In order to compare the turbulence properties over the two rough walls and to analyse the differences with a smooth wall, the simulations are performed at the same Reynolds number Re τ = 395. The same mean roughness height h = 0.05δ (δ the half channel height) is used for the rough walls. The roughness function obtained with the 3D roughness is larger than in the 2D case, although the two walls share the same mean height. Thus, the considered irregular 3D roughness is more effective in reducing the flow velocity with respect to the 2D roughness, coherently with the literature results that identified a clear dependence of the roughness function on the effective slope (see ), higher in the generated 3D rough wall. The analysis of higher-order statistics shows that the effects of the roughness, independently on its two- or three-dimensional shape, are mainly confined in the inner

  20. Drag-reducing performance of obliquely aligned superhydrophobic surface in turbulent channel flow

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Sho; Fukagata, Koji [Department of Mechanical Engineering, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522 (Japan); Mamori, Hiroya, E-mail: fukagata@mech.keio.ac.jp [Department of Mechanical Engineering, Tokyo University of Science, Niijuku 6-3-1, Katsushika-ku, Tokyo 125-8585 (Japan)

    2017-04-15

    Friction drag reduction effect by superhydrophobic surfaces in a turbulent channel flow is investigated by means of direct numerical simulation. The simulations are performed under a constant pressure gradient at the friction Reynolds number of 180. A special focus is laid upon the influence of the angle of microridge structure to flow direction, while the gas area fraction on the surface is kept at 50% and the groove width is kept constant at 33.75 wall units. Larger drag reduction effect is observed for a smaller angle: the bulk-mean velocity is increased about 15% when the microridge is parallel to the flow. The drag reduction effect is found to deteriorate rapidly with the microridge angle due to a decrease in the slip velocity. The Reynolds stress budgets show that the modification in each physical effect is qualitatively similar but more pronounced when the microridge is aligned with the stream. (paper)

  1. Three-dimensional continuous particle focusing in a microfluidic channel via standing surface acoustic waves (SSAW).

    Science.gov (United States)

    Shi, Jinjie; Yazdi, Shahrzad; Lin, Sz-Chin Steven; Ding, Xiaoyun; Chiang, I-Kao; Sharp, Kendra; Huang, Tony Jun

    2011-07-21

    Three-dimensional (3D) continuous microparticle focusing has been achieved in a single-layer polydimethylsiloxane (PDMS) microfluidic channel using a standing surface acoustic wave (SSAW). The SSAW was generated by the interference of two identical surface acoustic waves (SAWs) created by two parallel interdigital transducers (IDTs) on a piezoelectric substrate with a microchannel precisely bonded between them. To understand the working principle of the SSAW-based 3D focusing and investigate the position of the focal point, we computed longitudinal waves, generated by the SAWs and radiated into the fluid media from opposite sides of the microchannel, and the resultant pressure and velocity fields due to the interference and reflection of the longitudinal waves. Simulation results predict the existence of a focusing point which is in good agreement with our experimental observations. Compared with other 3D focusing techniques, this method is non-invasive, robust, energy-efficient, easy to implement, and applicable to nearly all types of microparticles.

  2. A nine-dimensional ab initio global potential energy surface for the H2O+ + H2 → H3O+ + H reaction

    Science.gov (United States)

    Li, Anyang; Guo, Hua

    2014-06-01

    An accurate full-dimensional global potential energy surface (PES) is developed for the title reaction. While the long-range interactions in the reactant asymptote are represented by an analytical expression, the interaction region of the PES is fit to more than 81 000 of ab initio points at the UCCSD(T)-F12b/AVTZ level using the permutation invariant polynomial neural network approach. Fully symmetric with respect to permutation of all four hydrogen atoms, the PES provides a faithful representation of the ab initio points, with a root mean square error of 1.8 meV or 15 cm-1. The reaction path for this exoergic reaction features an attractive and barrierless entrance channel, a submerged saddle point, a shallow H4O+ well, and a barrierless exit channel. The rate coefficients for the title reaction and kinetic isotope effect have been determined on this PES using quasi-classical trajectories, and they are in good agreement with available experimental data. It is further shown that the H2O+ rotational enhancement of reactivity observed experimentally can be traced to the submerged saddle point. Using our recently proposed Sudden Vector Projection model, we demonstrate that a rotational degree of freedom of the H2O+ reactant is strongly coupled with the reaction coordinate at this saddle point, thus unraveling the origin of the pronounced mode specificity in this reaction.

  3. A nine-dimensional ab initio global potential energy surface for the H2O+ + H2 → H3O+ + H reaction

    International Nuclear Information System (INIS)

    Li, Anyang; Guo, Hua

    2014-01-01

    An accurate full-dimensional global potential energy surface (PES) is developed for the title reaction. While the long-range interactions in the reactant asymptote are represented by an analytical expression, the interaction region of the PES is fit to more than 81 000 of ab initio points at the UCCSD(T)-F12b/AVTZ level using the permutation invariant polynomial neural network approach. Fully symmetric with respect to permutation of all four hydrogen atoms, the PES provides a faithful representation of the ab initio points, with a root mean square error of 1.8 meV or 15 cm −1 . The reaction path for this exoergic reaction features an attractive and barrierless entrance channel, a submerged saddle point, a shallow H 4 O + well, and a barrierless exit channel. The rate coefficients for the title reaction and kinetic isotope effect have been determined on this PES using quasi-classical trajectories, and they are in good agreement with available experimental data. It is further shown that the H 2 O + rotational enhancement of reactivity observed experimentally can be traced to the submerged saddle point. Using our recently proposed Sudden Vector Projection model, we demonstrate that a rotational degree of freedom of the H 2 O + reactant is strongly coupled with the reaction coordinate at this saddle point, thus unraveling the origin of the pronounced mode specificity in this reaction

  4. Interactions between β-catenin and the HSlo potassium channel regulates HSlo surface expression.

    Directory of Open Access Journals (Sweden)

    Shumin Bian

    Full Text Available The large conductance calcium-activated potassium channel alpha-subunit (Slo is widely distributed throughout the body and plays an important role in a number of diseases. Prior work has shown that Slo, through its S10 region, interacts with β-catenin, a key component of the cytoskeleton framework and the Wnt signaling pathway. However, the physiological significance of this interaction was not clear.Using a combination of proteomic and cell biology tools we show the existence of additional multiple binding sites in Slo, and explore in detail β-catenin interactions with the S10 region. We demonstrate that deletion of this region reduces Slo surface expression in HEK cells, which indicates that interaction with beta-catenin is important for Slo surface expression. This is confirmed by reduced expression of Slo in HEK cells and chicken (Gallus gallus domesticus leghorn white hair cells treated with siRNA to β-catenin. HSlo reciprocally co-immunoprecipitates with β-catenin, indicating a stable binding between these two proteins, with the S10 deletion mutant having reduced binding with β-catenin. We also observed that mutations of the two putative GSK phosphorylation sites within the S10 region affect both the surface expression of Slo and the channel's voltage and calcium sensitivities. Interestingly, expression of exogenous Slo in HEK cells inhibits β-catenin-dependent canonical Wnt signaling.These studies identify for the first time a central role for β-catenin in mediating Slo surface expression. Additionally we show that Slo overexpression can lead to downregulation of Wnt signaling.

  5. Correlations of Surface Deformation and 3D Flow Field in a Compliant Wall Turbulent Channel Flow.

    Science.gov (United States)

    Wang, Jin; Zhang, Cao; Katz, Joseph

    2015-11-01

    This study focuses on the correlations between surface deformation and flow features, including velocity, vorticity and pressure, in a turbulent channel flow over a flat, compliant Polydimethylsiloxane (PDMS) wall. The channel centerline velocity is 2.5 m/s, and the friction Reynolds number is 2.3x103. Analysis is based on simultaneous measurements of the time resolved 3D velocity and surface deformation using tomographic PIV and Mach-Zehnder Interferometry. The volumetric pressure distribution is calculated plane by plane by spatially integrating the material acceleration using virtual boundary, omni-directional method. Conditional sampling based on local high/low pressure and deformation events reveals the primary flow structures causing the deformation. High pressure peaks appear at the interface between sweep and ejection, whereas the negative deformations peaks (dent) appear upstream, under the sweeps. The persistent phase lag between flow and deformations are presumably caused by internal damping within the PDMS. Some of the low pressure peaks and strong ejections are located under the head of hairpin vortices, and accordingly, are associated with positive deformation (bump). Others bumps and dents are correlated with some spanwise offset large inclined quasi-streamwise vortices that are not necessarily associated with hairpins. Sponsored by ONR.

  6. 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.

  7. Channel coupling in A(e,e N)B reactions

    CERN Document Server

    Kell, J

    1999-01-01

    The sensitivity of momentum distributions, recoil polarization observables, and response functions for nucleon knockout by polarized electron scattering to channel coupling in final-state interactions is investigated using a model in which both the distorting and the coupling potentials are constructed by folding density-dependent nucleon-nucleon effective interactions with nuclear transition densities. Elastic reorientation, inelastic scattering, and charge exchange are included for all possible couplings within the model space. Calculations for sup 1 sup 6 O are presented for 200 and 433 MeV ejectile energies, corresponding to proposed experiments at MAMI and TJNAF, and for sup 1 sup 2 C at 70 and 270 MeV, corresponding to experiments at NIKHEF and MIT-Bates. The relative importance of charge exchange decreases as the ejectile energy increases, but remains significant for 200 MeV. Both proton and neutron knockout cross sections for large recoil momenta, p sub m greater than 300 MeV/c, are substantially affe...

  8. Study of hydrogen in metal and alloy by nuclear reaction channeling method

    International Nuclear Information System (INIS)

    Yagi, Eiichi

    1998-01-01

    The position of hydrogen in the lattice was determined by the combination method of 1 H( 11 B, α)αα with a channeling effect of 11 B ion in the crystal. When the concentration of hydrogen in V single crystal was VH 0.1 at the room temperature, hydrogen occupied T position in the body-centered cubic lattice. The position was shifted to the displaced-T by the thermal treatment. Hydrogen in V is oversensitive to a stress, so that it located the displaced-T or 4T state under 7 kg/mm 2 of compressive stress. Hydrogen in Nb and Ta located T position, too. But their displaced states were not observed by the thermal treatment. All hydrogen in Nb-3 at % Mo-2 at % H alloy were captured by Mo and they located the positions of 0.62A displaced from T in the direction of Mo. In Nb-3 at % Mo-5 at % H alloy, a part of hydrogen were captured by Mo, but the other located T positions. At 100degC, hydrogen was free from capture of Mo and moved to T position. (S.Y.)

  9. 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).

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. A mathematical model for surface roughness of fluidic channels produced by grinding aided electrochemical discharge machining (G-ECDM

    Directory of Open Access Journals (Sweden)

    Ladeesh V. G.

    2017-01-01

    Full Text Available Grinding aided electrochemical discharge machining is a hybrid technique, which combines the grinding action of an abrasive tool and thermal effects of electrochemical discharges to remove material from the workpiece for producing complex contours. The present study focuses on developing fluidic channels on borosilicate glass using G-ECDM and attempts to develop a mathematical model for surface roughness of the machined channel. Preliminary experiments are conducted to study the effect of machining parameters on surface roughness. Voltage, duty factor, frequency and tool feed rate are identified as the significant factors for controlling surface roughness of the channels produced by G-ECDM. A mathematical model was developed for surface roughness by considering the grinding action and thermal effects of electrochemical discharges in material removal. Experiments are conducted to validate the model and the results obtained are in good agreement with that predicted by the model.

  15. 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

  16. 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.

  17. Predicting the impact of vegetations in open channels with different distributaries' operations on water surface profile using artificial neural networks

    International Nuclear Information System (INIS)

    Abdeen, Mostafa A. M.

    2008-01-01

    Most of the open water irrigation channels in Egypt suffer from the infestation of aquatic weeds, especially the submerged ones that cause numerous hydraulic problems for the open channels themselves and their water distributaries such as increasing water losses, obstructing water flow, and reducing channels' water distribution efficiencies. Accurate simulation and prediction of flow behavior in such channels is very essential for water distribution decision makers. Artificial neural networks (ANN) have proven to be very successful in the simulation of several physical phenomena, in general, and in the water research field in particular. Therefore, the current study aims towards introducing the utilization of ANN in simulating the impact of vegetation in main open channel, which supplies water to different distributaries, on the water surface profile in this main channel. Specifically, the study, presented in the current paper utilizes ANN technique for the development of various models to simulate the impact of different submerged weeds' densities, different flow discharges, and different distributaries operation scheduling on the water surface profile in an experimental main open channel that supplies water to different distributaries. In the investigated experiment, the submerged weeds were simulated as branched flexible elements. The investigated experiment was considered as an example for implementing the same methodology and technique in a real open channel system. The results showed that the ANN technique is very successful in simulating the flow behavior of the pre-mentioned open channel experiment with the existence of the submerged weeds. In addition, the developed ANN models were capable of predicting the open channel flow behavior in all the submerged weeds' cases that were considered in the ANN development process

  18. 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.)

  19. Magnetic field integral equation analysis of surface plasmon scattering by rectangular dielectric channel discontinuities.

    Science.gov (United States)

    Chremmos, Ioannis

    2010-01-01

    The scattering of a surface plasmon polariton (SPP) by a rectangular dielectric channel discontinuity is analyzed through a rigorous magnetic field integral equation method. The scattering phenomenon is formulated by means of the magnetic-type scalar integral equation, which is subsequently treated through an entire-domain Galerkin method of moments (MoM), based on a Fourier-series plane wave expansion of the magnetic field inside the discontinuity. The use of Green's function Fourier transform allows all integrations over the area and along the boundary of the discontinuity to be performed analytically, resulting in a MoM matrix with entries that are expressed as spectral integrals of closed-form expressions. Complex analysis techniques, such as Cauchy's residue theorem and the saddle-point method, are applied to obtain the amplitudes of the transmitted and reflected SPP modes and the radiated field pattern. Through numerical results, we examine the wavelength selectivity of transmission and reflection against the channel dimensions as well as the sensitivity to changes in the refractive index of the discontinuity, which is useful for sensing applications.

  20. Turbulent flow and heat transfer in channels with combined rough and smooth surfaces

    International Nuclear Information System (INIS)

    Aytekin, A.

    1978-01-01

    A two-part experimental investigation is reported on the effects of transverse square rib roughening on fluid flow and heat transfer in channels with uniform and non-uniform boundary conditions. The first part of the experimental programme consisted of providing detailed measurements of mean and basic turbulent characteristics of fully developed flow in two rectangular ducts of aspect ratios 1.63 and 3.0. In each duct only one wall was roughened. In channels having low aspect ratios secondary flows play an important part in momentum transfer, and an interpretation of their effect on the measured Reynolds shear stress distribution has been attempted. In the second part of the experimental programme mean velocity and temperature profiles, friction factors and Stanton numbers were measured in an internally roughened pipe and annuli composed of a rough inner rod and either a smooth or a rough outer pipe. Heating was always applied on the outer surface. In all the geometries the mean velocities near the rough walls were found to be represented by logarithmic straight lines. The gradients of these lines were independent of Reynolds number but differed for various geometries. The mean temperature profiles, measured in the rough pipe and the fully rough annulus, showed that these could also be represented by logarithmic straight lines, but the slopes of these profiles were markedly different from those of the velocity profiles. (author)

  1. 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.

  2. The golden-mean surface pattern to enhance flow mixing in micro-channel.

    Science.gov (United States)

    Wang, J F; Liu, Y; Xu, Y S

    2009-04-01

    Mixing of analytes and reagents in microfluidic devices is often crucial to the effective functioning of lab-on-a-chip. It is possible to affect the mixing in microfluidics by intelligently controlling the thermodynamic and chemical properties of the substrate surface. Numerous studies have shown that the phase behavior of mixtures is significantly affected by surface properties of microfluidics. For example, the phase separation between the fluids can be affected by heterogeneous patterns on the substrate. The patterned substrate can offer an effective means to control fluid behavior and in turn to enhance mixing. The golden mean is a ratio that is present in the growth patterns of many biological systems--the spiral formed by a shell or the curve of a fern, for example. The golden mean or golden section was derived by the ancient Greeks. Like "pi" the golden mean ratio is an irrational number 1.618, or (square root{5} + 1) / 2. It was found that the golden mean was an optimum ratio in natural convection heat transfer problem (Liu and Phan-Thien, Numer Heat Transf 37:613-630, 2000). In this study, we numerically studied the effect of optimum surface pattern on mixing in a micro channel and found that the flow oscillation and chaotic mixing were enhanced apparently when the ratio of hydrophobic and hydrophilic boundary follows the golden mean.

  3. Surface viscosity effects on the motion of self-propelling boat in a channel

    Science.gov (United States)

    Aliperio, M. G.; Nolan Confesor, Mark

    2015-06-01

    Self-propelled droplets have been conceived as simple chemical toy models to mimic motile biological samples such as bacteria. The motion of these droplets is believe to be due to the surface tension gradient in the boundary of the droplet. We performed experiments to look at the effect of varying the medium viscosity to the speed of a circular boat that was soaked in Pentanol. We found that the boats undergo oscillatory type of motion inside a channel. Moreover we found the maximum speed of the boat is independent on the viscosity of the medium. On the other a time scale describing the width of the velocity profile of the boat was found to increase with increasing viscosity.

  4. [Analysis of the Muscle Fatigue Based on Band Spectrum Entropy of Multi-channel Surface Electromyography].

    Science.gov (United States)

    Liu, Jian; Zou, Renling; Zhang, Dongheng; Xu, Xiulin; Hu, Xiufang

    2016-06-01

    Exercise-induced muscle fatigue is a phenomenon that the maximum voluntary contraction force or power output of muscle is temporarily reduced due to muscular movement.If the fatigue is not treated properly,it will bring about a severe injury to the human body.With multi-channel collection of lower limb surface electromyography signals,this article analyzes the muscle fatigue by adoption of band spectrum entropy method which combined electromyographic signal spectral analysis and nonlinear dynamics.The experimental result indicated that with the increase of muscle fatigue,muscle signal spectrum began to move to low frequency,the energy concentrated,the system complexity came down,and the band spectrum entropy which reflected the complexity was also reduced.By monitoring the entropy,we can measure the degree of muscle fatigue,and provide an indicator to judge fatigue degree for the sports training and clinical rehabilitation training.

  5. Charge state distributions from highly charged ions channeled at a metal surface

    International Nuclear Information System (INIS)

    Folkerts, L.; Meyer, F.W.; Schippers, S.

    1994-01-01

    The vast majority of the experimental work in the field of multicharged ion-surface interactions, to date, has focused on x-ray and particularly on electron emission. These experiments include measurements of the total electron yield, the emission statistics of the electrons, and, most of all, the electron energy distributions. So far, little attention has been paid to the fate of the multicharged projectile ions after the scattering. To our knowledge, the only measurement of the charge state distribution of the scattered ions is the pioneering experiment of de Zwart et al., who measured the total yield of scattered 1+, 2+, and 3+ ions as a function of the primary charge state q (q = 1--11) for 20 key Ne, Ar, and Kr ions after reflection from a polycrystalline tungsten target. Their main finding is the sudden onset of scattered 3+ ions when inner-shell vacancies are present in the primary particles. This suggests that a certain fraction of the inner-shell vacancies survives the entire collision event, and decays via autoionization on the outgoing path. Since the projectiles scattered in the neutral charge state could not be detected in the experiment of de Zwart et al., they were not able to provide absolute charge state fractions. In our present experiment, we focus on the scattered projectiles, measuring both the final charge state and the total scattering angle with a single 2D position sensitive detector (PSD). This method gives us the number of positive, as well as neutral and negative, scattered ions, thus allowing us to extract absolute charge state fractions. Using a well-prepared single Au(110) crystal and a grazing incidence geometry, we were able to observe surface channeling along the [001] channels

  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. Age, distribution, and significance within a sediment budget, of in-channel depositional surfaces in the Normanby River, Queensland, Australia

    Science.gov (United States)

    Pietsch, T. J.; Brooks, A. P.; Spencer, J.; Olley, J. M.; Borombovits, D.

    2015-06-01

    We present the results of investigations into alluvial deposition in the catchment of the Normanby River, which flows into Princess Charlotte Bay (PCB) in the northern part of the Great Barrier Reef Lagoon. Our focus is on the fine fraction (bank attached bars or inset or inner floodplains, these more or less flat-lying surfaces within the macro-channel have hitherto received little attention in sediment budgeting models. We use high resolution LiDAR based mapping combined with optical dating of exposures cut into these in-channel deposits to compare their aggradation rates with those found in other depositional zones in the catchment, namely the floodplain and coastal plain. In total 59 single grain OSL dates were produced across 21 stratigraphic profiles at 14 sites distributed though the 24 226 km2 catchment. In-channel storage in these inset features is a significant component of the contemporary fine sediment budget (i.e. recent decades/last century), annually equivalent to more than 50% of the volume entering the channel network from hillslopes and subsoil sources. Therefore, at the very least, in-channel storage of fine material needs to be incorporated into sediment budgeting exercises. Furthermore, deposition within the channel has occurred in multiple locations coincident in time with accelerated sediment production following European settlement. Generally, this has occurred on a subset of the features we have examined here, namely linear bench features low in the channel. This suggests that accelerated aggradation on in-channel depositional surfaces has been in part a response to accelerated erosion within the catchment. The entire contribution of ~ 370 kilotonnes per annum of fine sediment estimated to have been produced by alluvial gully erosion over the last ~ 100 years can be accounted for by that stored as in-channel alluvium. These features therefore can play an important role in mitigating the impact on the receiving water of accelerated erosion.

  9. 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.

  10. 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

  11. 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....

  12. The hydrogen abstraction reaction O(3P) + CH4: A new analytical potential energy surface based on fit to ab initio calculations

    International Nuclear Information System (INIS)

    González-Lavado, Eloisa; Corchado, Jose C.; Espinosa-Garcia, Joaquin

    2014-01-01

    Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system

  13. Effect of Channel Orientation and Rib Pitch-to-Height Ratio on Pressure Drop in a Rotating Square Channel with Ribs on Two Opposite Surfaces

    Directory of Open Access Journals (Sweden)

    Prabhu S. V.

    2005-01-01

    Full Text Available The effect of channel orientation and rib pitch-to-height ratio on the pressure drop distribution in a rib-roughened channel is an important issue in turbine blade cooling. The present investigation is a study of the overall pressure drop distribution in a square cross-sectioned channel, with rib turbulators, rotating about an axis normal to the free stream. The ribs are configured in a symmetric arrangement on two opposite surfaces with a rib angle of 90 ∘ to the mainstream flow. The study has been conducted for three Reynolds numbers, namely, 13 000, 17 000, and 22 000 with the rotation number varying from 0– 0.38 . Experiments have been carried out for various rib pitch-to-height ratios ( P/e with a constant rib height-to-hydraulic diameter ratio ( e/D of 0.1 . The test section in which the ribs are placed on the leading and trailing surfaces is considered as the base case ( orientation angle= 0 ∘ , Coriolis force vector normal to the ribbed surfaces. The channel is turned about its axis in steps of 15 ∘ to vary the orientation angle from 0 ∘ to 90 ∘ . The overall pressure drop does not change considerably under conditions of rotation for the base case. However, for the other cases tested, it is observed that the overall pressure drop increases with an increase in the rotation number for a given orientation angle and also increases with an increase in the orientation angle for a given rotation number. This change is attributed to the variation in the separation zone downstream of the ribs due to the presence of the Coriolis force—local pressure drop data is presented which supports this idea. At an orientation angle of 90 ∘ (ribs on the top and bottom surfaces, Coriolis force vector normal to the smooth surfaces, the overall pressure drop is observed to be maximum during rotation. The overall pressure drop for a case with a rib pitch-to-height ratio of 5 on both surfaces is found to be the highest

  14. 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.

  15. 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.

  16. 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.

  17. 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)

  18. 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.

  19. 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.)

  20. 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...

  1. 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.

  2. 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.

  3. 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....

  4. 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.

  5. 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.

  6. 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

  7. Coupled-channel calculation for cross section of fusion and barrier distribution of {}^{16,17,18}O + {}^{16}O reactions

    Science.gov (United States)

    Fereidonnejad, R.; Sadeghi, H.; Ghambari, M.

    2018-03-01

    In this work, the effect of multi-phonon excitation on heavy-ion fusion reactions has been studied and fusion barrier distributions of energy intervals near and below the Coulomb barrier have been studied for 16,17,18O + 16O reactions. The structure and deformation of nuclear projectiles have been studied. Given the adaptation of computations to experimental data, our calculations predict the behavior of reactions in intervals of energy in which experimental measurements are not available. In addition the S-factor for these reactions has been calculated. The results showed that the structure and deformation of a nuclear projectile are important factors. The S-factor, obtained in the coupled-channel calculations for the {}^{16}O + {}^{16}O, {}^{17}O +{}^{16}O and {}^{18}O +{}^{16}O reactions, showed good agreement with the experimental data and had a maximum value at an energy near 5, 4.5 and 4 MeV, respectively.

  8. 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.

  9. A waveless two-dimensional flow in a channel against an inclined wall with surface tension effect

    International Nuclear Information System (INIS)

    Merzougui, Abdelkrim; Mekias, Hocine; Guechi, Fairouz

    2007-01-01

    Surface tension effect on a two-dimensional channel flow against an inclined wall is considered. The flow is assumed to be steady, irrotational, inviscid and incompressible. The effect of surface tension is taken into account and the effect of gravity is neglected. Numerical solutions are obtained via series truncation procedure. The problem is solved numerically for various values of the Weber number α and for various values of the inclination angle β between the horizontal bottom and the inclined wall

  10. A waveless two-dimensional flow in a channel against an inclined wall with surface tension effect

    Energy Technology Data Exchange (ETDEWEB)

    Merzougui, Abdelkrim [Departement de Mathematiques, Faculte des sciences, Universite Mohamed Boudiaf, M' sila, 28000 (Algeria); Mekias, Hocine [Departement de Mathematiques, Faculte des sciences, Universite Farhat Abbas Setif 19000 (Algeria); Guechi, Fairouz [Departement de Mathematiques, Faculte des sciences, Universite Farhat Abbas Setif 19000 (Algeria)

    2007-11-23

    Surface tension effect on a two-dimensional channel flow against an inclined wall is considered. The flow is assumed to be steady, irrotational, inviscid and incompressible. The effect of surface tension is taken into account and the effect of gravity is neglected. Numerical solutions are obtained via series truncation procedure. The problem is solved numerically for various values of the Weber number {alpha} and for various values of the inclination angle {beta} between the horizontal bottom and the inclined wall.

  11. Validation of simulations of an underwater acoustic communication channel characterized by wind-generated surface waves and bubbles

    NARCIS (Netherlands)

    Dol, H.S.; Colin, M.E.G.D.; Ainlie, M.A.; Gerdes, F.; Schäfke, A.; Özkan Sertlekc, H.

    2013-01-01

    This paper shows that it is possible to simulate realistic shallow-water acoustic communication channels using available acoustic propagation models. Key factor is the incorporation of realistic time-dependent sea surface conditions, including both waves and bubbles due to wind.

  12. Use of 198 Au, with surface labelling, in the study of solid transport by bed load in large natural channels

    International Nuclear Information System (INIS)

    Nakahira, S.

    1987-01-01

    The present study aims to present a method of measuring the bed load transport using a radioisotope technique in large natural channels. This study describes the basic principles of radioisotope application in this field, emphasizing the use of 198 Au for surface labelling of a natural sediment. Moreover, it presents the theoretical aspects, critical analysis, recommendations and comments on the methodology proposed. (author)

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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-.

  19. Role of Aquaporin Water Channels in Airway Fluid Transport, Humidification, and Surface Liquid Hydration

    Science.gov (United States)

    Song, Yuanlin; Jayaraman, Sujatha; Yang, Baoxue; Matthay, Michael A.; Verkman, A.S.

    2001-01-01

    Several aquaporin-type water channels are expressed in mammalian airways and lung: AQP1 in microvascular endothelia, AQP3 in upper airway epithelia, AQP4 in upper and lower airway epithelia, and AQP5 in alveolar epithelia. Novel quantitative methods were developed to compare airway fluid transport–related functions in wild-type mice and knockout mice deficient in these aquaporins. Lower airway humidification, measured from the moisture content of expired air during mechanical ventilation with dry air through a tracheotomy, was 54–56% efficient in wild-type mice, and reduced by only 3–4% in AQP1/AQP5 or AQP3/AQP4 double knockout mice. Upper airway humidification, measured from the moisture gained by dry air passed through the upper airways in mice breathing through a tracheotomy, decreased from 91 to 50% with increasing ventilation from 20 to 220 ml/min, and reduced by 3–5% in AQP3/AQP4 knockout mice. The depth and salt concentration of the airway surface liquid in trachea was measured in vivo using fluorescent probes and confocal and ratio imaging microscopy. Airway surface liquid depth was 45 ± 5 μm and [Na+] was 115 ± 4 mM in wild-type mice, and not significantly different in AQP3/AQP4 knockout mice. Osmotic water permeability in upper airways, measured by an in vivo instillation/sample method, was reduced by ∼40% by AQP3/AQP4 deletion. In doing these measurements, we discovered a novel amiloride-sensitive isosmolar fluid absorption process in upper airways (13% in 5 min) that was not affected by aquaporin deletion. These results establish the fluid transporting properties of mouse airways, and indicate that aquaporins play at most a minor role in airway humidification, ASL hydration, and isosmolar fluid absorption. PMID:11382807

  20. Visualization of an air-water interface on superhydrophobic surfaces in turbulent channel flows

    Science.gov (United States)

    Kim, Hyunseok; Park, Hyungmin

    2017-11-01

    In the present study, three-dimensional deformation of air-water interface on superhydrophobic surfaces in turbulent channel flows at the Reynolds numbers of Re = 3000 and 10000 is measured with RICM (Reflection Interference Contrast Microscopy) technique. Two different types of roughness feature of circular hole and rectangular grate are considered, whose depth is 20 μm and diameter (or width) is varied between 20-200 μm. Since the air-water interface is always at de-pinned state at the considered condition, air-water interface shape and its sagging velocity is maintained to be almost constant as time goes one. In comparison with the previous results under the laminar flow, due to turbulent characteristics of the flow, sagging velocity is much faster. Based on the measured sagging profiles, a modified model to describe the air-water interface dynamics under turbulent flows is suggested. Supported by City of Seoul through Seoul Urban Data Science Laboratory Project (Grant No 0660-20170004) administered by SNU Big Data Institute.

  1. 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.

  2. 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.)

  3. Study of the dissipative binary channels in the {sup 107}Ag + {sup 58}Ni reaction at 52 MeV/nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Steckmeyer, J.C. [Caen Univ., 14 (France). Lab. de Physique Corpusculaire; Aiello, S. [Catania Univ., INFN (Italy); Anzalone, A. [Catania Univ., LNS (Italy)] [and others

    2002-03-01

    The binary dissipative channels are characterized by the presence of two main fragments in the exit channel. They have been studied in the {sup 107}Ag+{sup 58}Ni reaction at 52 MeV/nucleon of bombarding energy. For that purpose a modified version of the Indra multidetector has been used in conjunction with a part of the Chimera multidetector. Preliminary results on the excitation energy and intrinsic angular momentum of the quasi-projectile are reported and compared to a dynamical calculation. (authors)

  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. 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.

  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

    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.

  7. 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 .

  8. Acid-Sensing Ion Channel 2a (ASIC2a) Promotes Surface Trafficking of ASIC2b via Heteromeric Assembly

    OpenAIRE

    Kweon, Hae-Jin; Kim, Dong-Il; Bae, Yeonju; Park, Jae-Yong; Suh, Byung-Chang

    2016-01-01

    Acid-sensing ion channels (ASICs) are proton-activated cation channels that play important roles as typical proton sensors during pathophysiological conditions and normal synaptic activities. Among the ASIC subunits, ASIC2a and ASIC2b are alternative splicing products from the same gene, ACCN1. It has been shown that ASIC2 isoforms have differential subcellular distribution: ASIC2a targets the cell surface by itself, while ASIC2b resides in the ER. However, the underlying mechanism for this d...

  9. Charge and spin transport in edge channels of a ν=0 quantum Hall system on the surface of topological insulators.

    Science.gov (United States)

    Morimoto, Takahiro; Furusaki, Akira; Nagaosa, Naoto

    2015-04-10

    Three-dimensional topological insulators of finite thickness can show the quantum Hall effect (QHE) at the filling factor ν=0 under an external magnetic field if there is a finite potential difference between the top and bottom surfaces. We calculate energy spectra of surface Weyl fermions in the ν=0 QHE and find that gapped edge states with helical spin structure are formed from Weyl fermions on the side surfaces under certain conditions. These edge channels account for the nonlocal charge transport in the ν=0 QHE which is observed in a recent experiment on (Bi_{1-x}Sb_{x})_{2}Te_{3} films. The edge channels also support spin transport due to the spin-momentum locking. We propose an experimental setup to observe various spintronics functions such as spin transport and spin conversion.

  10. Zika virus RNA polymerase chain reaction on the utility channel of a commercial nucleic acid testing system.

    Science.gov (United States)

    Boujnan, Mohamed; Duits, Ashley J; Koppelman, Marco H G M

    2018-03-01

    Several countries have implemented safety strategies to reduce the risk of Zika virus (ZIKV) transmission through blood transfusion. These strategies have included nucleic acid amplification testing (NAT) of blood donations. In this study, a new real-time polymerase chain reaction (PCR) assay including internal control for the detection of ZIKV on the cobas omni Utility Channel (UC) on the cobas 6800 system is presented. PCR conditions and primer/probe concentrations were optimized on the LightCycler 480 instrument. Optimized conditions were transferred to the cobas omni UC on the cobas 6800 system. Subsequently, the limit of detection (LOD) in plasma and urine, genotype inclusivity, specificity, cross-reactivity, and clinical sensitivity were determined. The 95% LOD of the ZIKV PCR assay on the cobas 6800 system was 23.0 IU/mL (95% confidence interval [CI], 16.5-37.5) in plasma and 24.5 IU/mL (95% CI, 13.4-92.9) in urine. The assay detected African and Asian lineages of ZIKV. The specificity was 100%. The clinical concordance between the newly developed ZIKV PCR assay and the investigational Roche cobas Zika NAT test was 83% (24/29). We developed a sensitive ZIKV PCR assay on the cobas omni UC on the cobas 6800 system. The assay can be used for large-scale screening of blood donations for ZIKV or for testing of blood donors returning from areas with ZIKV to avoid temporal deferral. This study also demonstrates that the cobas omni UC on the cobas 6800 system can be used for in-house-developed PCR assays. © 2018 AABB.

  11. Toward prethreshold gate-based quantum simulation of chemical dynamics: using potential energy surfaces to simulate few-channel molecular collisions

    Science.gov (United States)

    Sornborger, Andrew T.; Stancil, Phillip; Geller, Michael R.

    2018-05-01

    One of the most promising applications of an error-corrected universal quantum computer is the efficient simulation of complex quantum systems such as large molecular systems. In this application, one is interested in both the electronic structure such as the ground state energy and dynamical properties such as the scattering cross section and chemical reaction rates. However, most theoretical work and experimental demonstrations have focused on the quantum computation of energies and energy surfaces. In this work, we attempt to make the prethreshold (not error-corrected) quantum simulation of dynamical properties practical as well. We show that the use of precomputed potential energy surfaces and couplings enables the gate-based simulation of few-channel but otherwise realistic molecular collisions. Our approach is based on the widely used Born-Oppenheimer approximation for the structure problem coupled with a semiclassical method for the dynamics. In the latter the electrons are treated quantum mechanically but the nuclei are classical, which restricts the collisions to high energy or temperature (typically above ≈ 10 eV). By using operator splitting techniques optimized for the resulting time-dependent Hamiltonian simulation problem, we give several physically realistic collision examples, with 3-8 channels and circuit depths < 1000.

  12. 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.

  13. The study of contamination of discharged runoff from surface water disposal channels of Bushehr city in 2012-2013

    Directory of Open Access Journals (Sweden)

    Vaheid Noroozi-Karbasdehi

    2016-09-01

    Full Text Available Background: In coastal cities, wastewater discharge into the sea is one of the options for sewage disposal that in case of non-compliance with health standards  in wastewater disposal will be led to the spread of infection and disease. On the other hand, water resources preservation and using them efficiently are the principles of sustainable development of each country. This study was aimed to investigate the contamination of discharged runoff from the surface water disposal channels of Bushehr city in 2012 - 13. Materials and Methods: In this study, Sampling was conducted by composite sampling method from output of the five main surface water disposal channels leading to the Persian Gulf located in the coastal region of Bushehr city during two seasons including wet (winter and dry (summer in 2012- 13. Then, experimental tests of BOD5, total coliform and fecal coliform were done on any of the 96 samples according to the standard method. Results: Analysis of the data showed that the BOD5, total coliform and fecal coliform of effluent runoff of the channels were more than the national standard output of disposal wastewaters into the surface waters, and the highest and lowest amount of BOD5 which obtained were 160 mg/L and 28 mg/L, respectively. Conclusion: considering the fact that discharged runoff from surface water disposal channels link from shoreline to sea in close distance and they often are as natural swimming sites and even fishing sites of Bushehr city, and also according to high level of organic and bacterial load of these channels, it is urgently required to be considered by the authorities.

  14. Investigating the astrophysical 22Ne(p, γ23Na and 22Mg(p, γ23Al reactions with a multi-channel scattering formalism

    Directory of Open Access Journals (Sweden)

    Fraser P. R.

    2014-03-01

    Full Text Available The reaction 22Ne(p, γ23Na is key to the NeNa cycle of stellar nucleogenesis, and better understanding of the 22Mg(p, γ23Al reaction is needed to understand the 22Na puzzle in ONe white dwarf novae. We aim to study these reactions using a multi-channel algebraic scattering (MCAS formalism for low-energy nucleon-nucleus scattering, recently expanded to investigate radiative capture. As a first step towards this goal, we here calculate the energy levels of the mass-23 (Ne, Mg, Na, Al nuclei. This is not only because the resonant structure of these nuclei are related to the astrophysical -rates of interest, but also because the interaction parameters determined for describing the energy levels are an integral part of the future calculation of the astrophysical reactions when using the MCAS scheme.

  15. 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.

  16. 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

  17. 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

  18. Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O((3)P) + Ethylene Reaction at High Collision Energy.

    Science.gov (United States)

    Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio; Fu, Bina; Bowman, Joel M

    2015-12-17

    The combustion relevant O((3)P) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs), which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy Ec of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135°. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by synergic full-dimensional quasiclassical trajectory surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical study extends and complements our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to vinoxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, with a clear tendency of the

  19. 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.

  20. 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

  1. 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)

  2. A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH4 system

    International Nuclear Information System (INIS)

    Li, Jun; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H.; Xie, Daiqian; Guo, Hua

    2015-01-01

    We report a permutationally invariant global potential energy surface (PES) for the H + CH 4 system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J tot = 0) including the abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)

  3. Organic Matter in the Surface Microlayer: Insights From a Wind Wave Channel Experiment

    Directory of Open Access Journals (Sweden)

    Anja Engel

    2018-06-01

    Full Text Available The surface microlayer (SML is the uppermost thin layer of the ocean and influencing interactions between the air and sea, such as gas exchange, atmospheric deposition and aerosol emission. Organic matter (OM plays a key role in air-sea exchange processes, but studying how the accumulation of organic compounds in the SML relates to biological processes is impeded in the field by a changing physical environment, in particular wind speed and wave breaking. Here, we studied OM dynamics in the SML under controlled physical conditions in a large annular wind wave channel, filled with natural seawater, over a period of 26 days. Biology in both SML and bulk water was dominated by bacterioneuston and -plankton, respectively, while autotrophic biomass in the two compartments was very low. In general, SML thickness was related to the concentration of dissolved organic carbon (DOC but not to enrichment of DOC or of specific OM components in the SML. Pronounced changes in OM enrichment and molecular composition were observed in the course of the study and correlated significantly to bacterial abundance. Thereby, hydrolysable amino acids, in particular arginine, were more enriched in the SML than combined carbohydrates. Amino acid composition indicated that less degraded OM accumulated preferentially in the SML. A strong correlation was established between the amount of surfactants coverage and γ-aminobutric acid, suggesting that microbial cycling of amino acids can control physiochemical traits of the SML. Our study shows that accumulation and cycling of OM in the SML can occur independently of recent autotrophic production, indicating a widespread biogenic control of process across the air-sea exchange.

  4. Velocity and thermal slip effects on MHD third order blood flow in an irregular channel though a porous medium with homogeneous/ heterogeneous reactions

    Science.gov (United States)

    Gnaneswara Reddy, M.

    2017-09-01

    This communication presents the transportation of third order hydromagnetic fluid with thermal radiation by peristalsis through an irregular channel configuration filled a porous medium under the low Reynolds number and large wavelength approximations. Joule heating, Hall current and homogeneous-heterogeneous reactions effects are considered in the energy and species equations. The Second-order velocity and energy slip restrictions are invoked. Final dimensionless governing transport equations along the boundary restrictions are resolved numerically with the help of NDsolve in Mathematica package. Impact of involved sundry parameters on the non-dimensional axial velocity, fluid temperature and concentration characteristics have been analyzed via plots and tables. It is manifest that an increasing porosity parameter leads to maximum velocity in the core part of the channel. Fluid velocity boosts near the walls of the channel where as the reverse effect in the central part of the channel for higher values of first order slip. Larger values of thermal radiation parameter R reduce the fluid temperature field. Also, an increase in heterogeneous reaction parameter Ks magnifies the concentration profile. The present study has the crucial application of thermal therapy in biomedical engineering.

  5. 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)

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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)

  12. Numerical Simulation of Dual-Channel Communication of Column Plasma Antenna Excited by a Surface Wave

    International Nuclear Information System (INIS)

    Duanmu Gang; Zhao Changming; Liang Chao; Xu Yuemin

    2014-01-01

    This paper focuses on the application of plasma as wireless antenna. In order to reveal the radiation characteristics of column plasma antenna, we chose the finite-difference time-domain (FDTD) numerical analysis method to simulate radiation impedance and efficiencies of each channel for a few sets of plasma densities and plasma collision frequencies. Simulation results demonstrate that a plasma antenna shares similar characteristics with a metallic antenna in radiation impedance and efficiency of each channel when an appropriate setting is adopted. Unlike a metallic antenna, a plasma antenna is capable of realizing such functions as dynamic reconfiguration, digital control and dual-channel communication. Thus it is possible to carry out dual-channel communication by plasma antenna, indicating a new path for modern intelligent communication. (plasma technology)

  13. Origins of Stratal Surfaces in Channel Fills on the New Jersey Continental Shelf

    National Research Council Canada - National Science Library

    Sommerfield, Christopher K

    2006-01-01

    The goal of this project was to advance an understanding of acoustic anomalies created by sub-seafloor paleochannels by investigating the geologic properties of channel-rich strata on the New Jersey continental shelf...

  14. "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.

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

    Science.gov (United States)

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

    2018-04-12

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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. The Human Acid-Sensing Ion Channel ASIC1a: Evidence for a Homotetrameric Assembly State at the Cell Surface.

    Directory of Open Access Journals (Sweden)

    Miguel Xavier van Bemmelen

    Full Text Available The chicken acid-sensing ion channel ASIC1 has been crystallized as a homotrimer. We address here the oligomeric state of the functional ASIC1 in situ at the cell surface. The oligomeric states of functional ASIC1a and mutants with additional cysteines introduced in the extracellular pore vestibule were resolved on SDS-PAGE. The functional ASIC1 complexes were stabilized at the cell surface of Xenopus laevis oocytes or CHO cells either using the sulfhydryl crosslinker BMOE, or sodium tetrathionate (NaTT. Under these different crosslinking conditions ASIC1a migrates as four distinct oligomeric states that correspond by mass to multiples of a single ASIC1a subunit. The relative importance of each of the four ASIC1a oligomers was critically dependent on the availability of cysteines in the transmembrane domain for crosslinking, consistent with the presence of ASIC1a homo-oligomers. The expression of ASIC1a monomers, trimeric or tetrameric concatemeric cDNA constructs resulted in functional channels. The resulting ASIC1a complexes are resolved as a predominant tetramer over the other oligomeric forms, after stabilization with BMOE or NaTT and SDS-PAGE/western blot analysis. Our data identify a major ASIC1a homotetramer at the surface membrane of the cell expressing functional ASIC1a channel.

  2. 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.

  3. 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.

  4. Surface pH changes suggest a role for H+/OH- channels in salinity response of Chara australis.

    Science.gov (United States)

    Absolonova, Marketa; Beilby, Mary J; Sommer, Aniela; Hoepflinger, Marion C; Foissner, Ilse

    2018-05-01

    To understand salt stress, the full impact of salinity on plant cell physiology has to be resolved. Electrical measurements suggest that salinity inhibits the proton pump and opens putative H + /OH - channels all over the cell surface of salt sensitive Chara australis (Beilby and Al Khazaaly 2009; Al Khazaaly and Beilby 2012). The channels open transiently at first, causing a characteristic noise in membrane potential difference (PD), and after longer exposure remain open with a typical current-voltage (I/V) profile, both abolished by the addition of 1 mM ZnCl 2 , the main known blocker of animal H + channels. The cells were imaged with confocal microscopy, using fluorescein isothiocyanate (FITC) coupled to dextran 70 to illuminate the pH changes outside the cell wall in artificial fresh water (AFW) and in saline medium. In the early saline exposure, we observed alkaline patches (bright fluorescent spots) appearing transiently in random spatial distribution. After longer exposure, some of the spots became fixed in space. Saline also abolished or diminished the pH banding pattern observed in the untreated control cells. ZnCl 2 suppressed the alkaline spot formation in saline and the pH banding pattern in AFW. The osmotic component of the saline stress did not produce transient bright spots or affect banding. The displacement of H + from the cell wall charges, the H + /OH - channel conductance/density, and self-organization are discussed. No homologies to animal H + channels were found. Salinity activation of the H + /OH - channels might contribute to saline response in roots of land plants and leaves of aquatic angiosperms.

  5. An Improved Single-Channel Method to Retrieve Land Surface Temperature from the Landsat-8 Thermal Band

    Directory of Open Access Journals (Sweden)

    Jordi Cristóbal

    2018-03-01

    Full Text Available Land surface temperature (LST is one of the sources of input data for modeling land surface processes. The Landsat satellite series is the only operational mission with more than 30 years of archived thermal infrared imagery from which we can retrieve LST. Unfortunately, stray light artifacts were observed in Landsat-8 TIRS data, mostly affecting Band 11, currently making the split-window technique impractical for retrieving surface temperature without requiring atmospheric data. In this study, a single-channel methodology to retrieve surface temperature from Landsat TM and ETM+ was improved to retrieve LST from Landsat-8 TIRS Band 10 using near-surface air temperature (Ta and integrated atmospheric column water vapor (w as input data. This improved methodology was parameterized and successfully evaluated with simulated data from a global and robust radiosonde database and validated with in situ data from four flux tower sites under different types of vegetation and snow cover in 44 Landsat-8 scenes. Evaluation results using simulated data showed that the inclusion of Ta together with w within a single-channel scheme improves LST retrieval, yielding lower errors and less bias than models based only on w. The new proposed LST retrieval model, developed with both w and Ta, yielded overall errors on the order of 1 K and a bias of −0.5 K validated against in situ data, providing a better performance than other models parameterized using w and Ta or only w models that yielded higher error and bias.

  6. 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.

  7. 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

  8. 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

  9. 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.)

  10. 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

  11. 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...

  12. 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)

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. 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.

  18. 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.

  19. The effects of processing parameters on the properties of micro-scale porous surface for a micro-channel reactor

    International Nuclear Information System (INIS)

    Feng, Yanbing; Mei, Deqing; Qian, Miao; Yi, Zoudongyi; Chen, Zichen

    2017-01-01

    To improve the performance of hydrogen production via a microchannel reactor with a porous surface, the process of layered powder sintering and dissolution method is optimized, and the effects of processing parameters on the morphological and mechanical properties of the porous surface structure are studied. Based on the preliminary experiments, three key parameters in the process are the size of the NaCl particle, the compaction pressure, and the sintering temperature. Besides, the porous surface structures are evaluated by the specific surface area and compression strength to optimize the influencing variables. Results show that the specific surface area of porous surface structure is determined mainly by the size of NaCl particle, while the pressure and temperature have little influence unexpectedly within the range of experimental condition. With the increase of temperature and pressure, the compression strength will be enhanced, but the increase of the size of NaCl particles will cause the decrease of compression strength. The optimum compaction pressure, sintering temperature, and size of the NaCl particle are obtained respectively. Finally, the optimum parameters have been used to manufacture the micro-channel catalyst support with a porous surface, and its hydrogen production can be maximumly enhanced by 90% compared with the surface fabricated with NaCl particles of 125–150 µ m. (paper)

  20. 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.

  1. 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.

  2. Effect of Equal Channel Angular Pressing on the Surface Roughness of Solid State Recycled Aluminum Alloy 6061 Chips

    Directory of Open Access Journals (Sweden)

    Adel Taha Abbas

    2017-01-01

    Full Text Available Solid state recycling through hot extrusion is a promising technique to recycle machining chips without remelting. Furthermore, equal channel angular pressing (ECAP technique coupled with the extruded recycled billet is introduced to enhance the mechanical properties of recycled samples. In this paper, the surface roughness of solid state recycled aluminum alloy 6061 turning chips was investigated. Aluminum chips were cold compacted and hot extruded under an extrusion ratio (ER of 5.2 at an extrusion temperature (ET of 425°C. In order to improve the properties of the extruded samples, they were subjected to ECAP up to three passes at room temperature using an ECAP die with a channel die angle (Φ of 90°. Surface roughness (Ra and Rz of the processed recycled billets machined by turning was investigated. Box-Behnken experimental design was used to investigate the effect of three machining parameters (cutting speed, feed rate, and depth of cut on the surface roughness of the machined specimens for four materials conditions, namely, extruded billet and postextrusion ECAP processed billets to one, two, and three passes. Quadratic models were developed to relate the machining parameters to surface roughness, and a multiobjective optimization scheme was conducted to maximize material removal rate while maintaining the roughness below a preset practical value.

  3. Charge loss experiments in surface channel CCD's explained by the McWhorter interface states model

    NARCIS (Netherlands)

    Penning De Vries, R.G.M.; Wallinga, Hans

    1985-01-01

    On the basis of the McWhorter interface states model the CCD charge loss is derived as a function of bias charge, signal charge and channel width. As opposed to existing models, the charge loss is now attributed to interface states in the entire gate area, even for high bias charge levels.

  4. Synthesis, characterization, and evaluation of a superficially porous particle with unique, elongated pore channels normal to the surface.

    Science.gov (United States)

    Wei, Ta-Chen; Mack, Anne; Chen, Wu; Liu, Jia; Dittmann, Monika; Wang, Xiaoli; Barber, William E

    2016-04-01

    In recent years, superficially porous particles (SPPs) have drawn great interest because of their special particle characteristics and improvement in separation efficiency. Superficially porous particles are currently manufactured by adding silica nanoparticles onto solid cores using either a multistep multilayer process or one-step coacervation process. The pore size is mainly controlled by the size of the silica nanoparticles and the tortuous pore channel geometry is determined by how those nanoparticles randomly aggregate. Such tortuous pore structure is also similar to that of all totally porous particles used in HPLC today. In this article, we report on the development of a next generation superficially porous particle with a unique pore structure that includes a thinner shell thickness and ordered pore channels oriented normal to the particle surface. The method of making the new superficially porous particles is a process called pseudomorphic transformation (PMT), which is a form of micelle templating. Porosity is no longer controlled by randomly aggregated nanoparticles but rather by micelles that have an ordered liquid crystal structure. The new particle possesses many advantages such as a narrower particle size distribution, thinner porous layer with high surface area and, most importantly, highly ordered, non-tortuous pore channels oriented normal to the particle surface. This PMT process has been applied to make 1.8-5.1μm SPPs with pore size controlled around 75Å and surface area around 100m(2)/g. All particles with different sizes show the same unique pore structure with tunable pore size and shell thickness. The impact of the novel pore structure on the performance of these particles is characterized by measuring van Deemter curves and constructing kinetic plots. Reduced plate heights as low as 1.0 have been achieved on conventional LC instruments. This indicates higher efficiency of such particles compared to conventional totally porous and

  5. 16-Channel surface coil for 13C-hyperpolarized spectroscopic imaging of cardiac metabolism in pig heart

    DEFF Research Database (Denmark)

    Frijia, Francesca; Santarelli, Maria Filomena; Koellisch, Ulrich

    2016-01-01

    Magnetic resonance spectroscopy (MRS) of hyperpolarized 13C pyruvate and its metabolites in large animal models is a powerful tool for assessing cardiac metabolism in patho-physiological conditions. In 13C studies, a high signal-to-noise ratio (SNR) is crucial to overcome the intrinsic data quality...... both targets. In this study, a 16-channel receive surface coil was designed for 13C hyperpolarized studies of the pig heart with a clinical 3-T scanner. The coil performance was characterized by phantom experiments and compared with that of a birdcage coil used in transmit/receive mode. Segmental...... of the 16-channel coil is recommended for studies of septal and anterior LV walls....

  6. Modelling of subcritical free-surface flow over an inclined backward-facing step in a water channel

    Directory of Open Access Journals (Sweden)

    Šulc Jan

    2012-04-01

    Full Text Available The contribution deals with the experimental and numerical modelling of subcritical turbulent flow in an open channel with an inclined backward-facing step. The step with the inclination angle α = 20° was placed in the water channel of the cross-section 200×200 mm. Experiments were carried out by means of the PIV and LDA measuring techniques. Numerical simulations were executed by means of the commercial software ANSYS CFX 12.0. Numerical results obtained for twoequation models and EARSM turbulence model completed by transport equations for turbulent energy and specific dissipation rate were compared with experimental data. The modelling was concentrated particularly on the development of the flow separation and on the corresponding changes of free surface.

  7. Channel separation using the transversity parameter in the pi /sup +/n to p pi /sup +/ pi /sup -/ reaction at 9 GeV/c

    CERN Document Server

    Armenise, N

    1978-01-01

    To solve the problem of separating competitive channels in a multiparticle final state the use of a parameter, called A(*), measuring the 'event transversity' has been suggested. The A parameter is found to be as powerful as prism plot analysis in separating different channels and economic with respect to the computer time. The transversity method is applied to the three-body reaction p/sup +/n to p pi /sup +/ pi /sup -/ at 9 TeV/c selected in pi /sup +/d interactions obtained in 2m-DBC exposed at CERN-PS. The main contributions in the final state are rho /sup 0/, f, g/sup 0/ (a dipion mass resonance) resonance production and neutron diffraction dissociation. (5 refs).

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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...

  13. 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.

  14. 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

  15. 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).

  16. Control of magnetism by electrical charge doping or redox reactions in a surface-oxidized Co thin film with a solid-state capacitor structure

    Science.gov (United States)

    Hirai, T.; Koyama, T.; Chiba, D.

    2018-03-01

    We have investigated the electric field (EF) effect on magnetism in a Co thin film with a naturally oxidized surface. The EF was applied to the oxidized Co surface through a gate insulator layer made of HfO2, which was formed using atomic layer deposition (ALD). The efficiency of the EF effect on the magnetic anisotropy in the sample with the HfO2 layer deposited at the appropriate temperature for the ALD process was relatively large compared to the previously reported values with an unoxidized Co film. The coercivity promptly and reversibly followed the variation in gate voltage. The modulation of the channel resistance was at most ˜0.02%. In contrast, a dramatic change in the magnetic properties including the large change in the saturation magnetic moment and a much larger EF-induced modulation of the channel resistance (˜10%) were observed in the sample with a HfO2 layer deposited at a temperature far below the appropriate temperature range. The response of these properties to the gate voltage was very slow, suggesting that a redox reaction dominated the EF effect on the magnetism in this sample. The frequency response for the capacitive properties was examined to discuss the difference in the mechanism of the EF effect observed here.

  17. 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...

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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)

  3. 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.

  4. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. A nine-dimensional ab initio global potential energy surface for the H{sub 2}O{sup +} + H{sub 2} → H{sub 3}O{sup +} + H reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Anyang; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2014-06-14

    An accurate full-dimensional global potential energy surface (PES) is developed for the title reaction. While the long-range interactions in the reactant asymptote are represented by an analytical expression, the interaction region of the PES is fit to more than 81 000 of ab initio points at the UCCSD(T)-F12b/AVTZ level using the permutation invariant polynomial neural network approach. Fully symmetric with respect to permutation of all four hydrogen atoms, the PES provides a faithful representation of the ab initio points, with a root mean square error of 1.8 meV or 15 cm{sup −1}. The reaction path for this exoergic reaction features an attractive and barrierless entrance channel, a submerged saddle point, a shallow H{sub 4}O{sup +} well, and a barrierless exit channel. The rate coefficients for the title reaction and kinetic isotope effect have been determined on this PES using quasi-classical trajectories, and they are in good agreement with available experimental data. It is further shown that the H{sub 2}O{sup +} rotational enhancement of reactivity observed experimentally can be traced to the submerged saddle point. Using our recently proposed Sudden Vector Projection model, we demonstrate that a rotational degree of freedom of the H{sub 2}O{sup +} reactant is strongly coupled with the reaction coordinate at this saddle point, thus unraveling the origin of the pronounced mode specificity in this reaction.

  10. 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

  11. Rayleigh waves ellipticity and mode mis-identification in multi-channel analysis of surface waves

    DEFF Research Database (Denmark)

    Boaga, Jacopo; Cassiani, Giorgio; Strobbia, Claudio

    dispersion curve which is then inverted. Typically, single component vertical and multi channel receivers are used. In most cases the inversion of the dispersion properties is carried out assuming that the experimental dispersion curve corresponds to a single mode, mostly the fundamental Rayleigh mode...... to each other reaching similar Rayleigh velocity. It is known ‘osculation’ happens generally in presence of strong velocity contrasts, typically with a fast bedrock underlying loose sediments. The practical limitations of the acquired data affect the spectral and modal resolution, making it often...

  12. A very fast program for visualizing protein surfaces, channels and cavities

    NARCIS (Netherlands)

    Voorintholt, Richard; Kosters, M.T.; Vegter, G.; Vriend, Gerrit; Hol, W.G.J.

    1989-01-01

    A method for visualizing molecular surfaces is described that uses a grid to store the distance to the nearest atom. Using on-the-fly three-dimensional (3D) contouring of a molecular graphics program such as FRODO, one can obtain a good impression of van der Waals surfaces and solvent-accessible

  13. Impact of the new HNO3-forming channel of the HO2+NO reaction on tropospheric HNO3, NOx, HOx and ozone

    Directory of Open Access Journals (Sweden)

    A. Kukui

    2008-07-01

    Full Text Available We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM. Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT. Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

  14. 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.

  15. 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.

  16. Research on optimization design of conformal cooling channels in hot stamping tool based on response surface methodology and multi-objective optimization

    Directory of Open Access Journals (Sweden)

    He Bin

    2016-01-01

    Full Text Available In order to optimize the layout of the conformal cooling channels in hot stamping tools, a response surface methodology and multi-objective optimization technique are proposed. By means of an Optimal Latin Hypercube experimental design method, a design matrix with 17 factors and 50 levels is generated. Three kinds of design variables, the radius Rad of the cooling channel, the distance H from the channel center to tool work surface and the ratio rat of each channel center, are optimized to determine the layout of cooling channels. The average temperature and temperature deviation of work surface are used to evaluate the cooling performance of hot stamping tools. On the basis of the experimental design results, quadratic response surface models are established to describe the relationship between the design variables and the evaluation objectives. The error analysis is performed to ensure the accuracy of response surface models. Then the layout of the conformal cooling channels is optimized in accordance with a multi-objective optimization method to find the Pareto optimal frontier which consists of some optimal combinations of design variables that can lead to an acceptable cooling performance.

  17. Radial dependence of surface streamer-channel luminosity: experimental evidence of Gaussian radiative profiles in Ar and N2

    International Nuclear Information System (INIS)

    Šimek, M; Ambrico, P F

    2012-01-01

    Radial distributions of electronically excited species produced during surface streamer propagation were obtained by applying the Abel inverse transform to projected luminosities of single streamers. The streamers were generated in an argon and nitrogen surface coplanar dielectric barrier discharge at atmospheric pressure and their magnified microscopic images were registered with high time resolution. Selected regions of the projected luminosities were processed by the Abel inverse transform procedure based on the Hankel–Fourier method assuming cylindrical symmetry of the streamer channel. Projected as well as Abel-inverted profiles were fitted by Gaussian functions. It is shown that the projected profiles, in addition to the Abel-inverted ones, can be well approximated by the sum of two coaxial Gaussians with two different half-widths and weights. The sharper Gaussian component with higher weight characterizes the radial dependence of the primary cathode-directed streamer-channel luminosity. The second (broader) Gaussian component probably originates either from the pre-breakdown Townsend phase or from the second wave propagating towards the anode. (paper)

  18. Three-channel false colour AFM images for improved interpretation of complex surfaces: A study of filamentous cyanobacteria

    International Nuclear Information System (INIS)

    Kurk, Toby; Adams, David G.; Connell, Simon D.; Thomson, Neil H.

    2010-01-01

    Imaging signals derived from the atomic force microscope (AFM) are typically presented as separate adjacent images with greyscale or pseudo-colour palettes. We propose that information-rich false-colour composites are a useful means of presenting three-channel AFM image data. This method can aid the interpretation of complex surfaces and facilitate the perception of information that is convoluted across data channels. We illustrate this approach with images of filamentous cyanobacteria imaged in air and under aqueous buffer, using both deflection-modulation (contact) mode and amplitude-modulation (tapping) mode. Topography-dependent contrast in the error and tertiary signals aids the interpretation of the topography signal by contributing additional data, resulting in a more detailed image, and by showing variations in the probe-surface interaction. Moreover, topography-independent contrast and topography-dependent contrast in the tertiary data image (phase or friction) can be distinguished more easily as a consequence of the three dimensional colour-space.

  19. Three-channel false colour AFM images for improved interpretation of complex surfaces: A study of filamentous cyanobacteria

    Energy Technology Data Exchange (ETDEWEB)

    Kurk, Toby, E-mail: phytak@leeds.ac.uk [School of Physics and Astronomy, University of Leeds, Leeds, West Yorkshire LS2 9JT (United Kingdom); Adams, David G., E-mail: D.G.Adams@leeds.ac.uk [Faculty of Biological Sciences, University of Leeds, Leeds, West Yorkshire LS2 9JT (United Kingdom); Connell, Simon D., E-mail: S.D.A.Connell@leeds.ac.uk [School of Physics and Astronomy, University of Leeds, Leeds, West Yorkshire LS2 9JT (United Kingdom); Thomson, Neil H., E-mail: N.H.Thomson@leeds.ac.uk [School of Physics and Astronomy, University of Leeds, Leeds, West Yorkshire LS2 9JT (United Kingdom); Dental Institute, University of Leeds, Leeds, West Yorkshire LS2 9JT (United Kingdom)

    2010-05-15

    Imaging signals derived from the atomic force microscope (AFM) are typically presented as separate adjacent images with greyscale or pseudo-colour palettes. We propose that information-rich false-colour composites are a useful means of presenting three-channel AFM image data. This method can aid the interpretation of complex surfaces and facilitate the perception of information that is convoluted across data channels. We illustrate this approach with images of filamentous cyanobacteria imaged in air and under aqueous buffer, using both deflection-modulation (contact) mode and amplitude-modulation (tapping) mode. Topography-dependent contrast in the error and tertiary signals aids the interpretation of the topography signal by contributing additional data, resulting in a more detailed image, and by showing variations in the probe-surface interaction. Moreover, topography-independent contrast and topography-dependent contrast in the tertiary data image (phase or friction) can be distinguished more easily as a consequence of the three dimensional colour-space.

  20. 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.

  1. 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.

  2. 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

  3. 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)

  4. 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.

  5. Experimental results on one-pion neutral current reaction in all channels induced by antineutrinos at CERN PS

    CERN Document Server

    Erriquez, O; Bullock, F W; Cavalli, D; Engel, J P; Fogli-Muciaccia, M T; Gamba, D; Guyonnet, J L; Halsteinslid, A; Henderson, R C W; Huss, D; Jones, T W; Marzari-Chiesa, A; Myklebost, K; Natali, S; Nuzzo, S; Paty, M; Pullia, A; Riccati, L; Riester, J L; Rognebakke, A; Rollier, M; Romero, A

    1980-01-01

    Single pion production, in antineutrino-nucleon interactions via the neutral current, has been studied in the bubble chamber Gargamelle, filled with propane. Complete analysis of the secondaries, including pi /sup 0/'s, has allowed a detailed study of all channels. After background and nuclear corrections, results are obtained which can be interpreted in terms of isospin structure of the neutral weak current and of the Salam-Weinberg angle. Agreement is found with the currently accepted value of sin/sup 2/ theta /sub w/ and the data suggest an important contribution of I=/sup 3///sub 2/ final states. (11 refs).

  6. Proper surface channelling of low energy argon ions incident on a nickel (110) crystal

    International Nuclear Information System (INIS)

    Evdokimov, I.N.; Berg, J.A. van den; Armour, D.G.

    1979-01-01

    The scattering behaviour of 6 keV argon ions from a nickel (110) surface has been investigated for specular reflection under grazing incidence conditions. The occurrence of an anomalously high energy loss has been confirmed and the transition from chain scattering at large scattering angles to a distinctly different type of scattering at small angles has been investigated. The characteristics of the low angle scattering phenomena, which dominate the observed spectra at scattering angles below about 18 0 , may be explained in terms of a surface hyperchannelling model in which the incident ions are confined to move within the shallow 'potential valleys' between two atomic rows in the surface. The critical angle for occurrence of this phenomena which is distinctly different from surface semichannelling has been evaluated with Lindhard's standard string potential. The experimentally measured critical angles are in good agreement with the calculated ones. (author)

  7. Ion channeling

    International Nuclear Information System (INIS)

    Erramli, H.; Blondiaux, G.

    1994-01-01

    Channeling phenomenon was predicted, many years ago, by stark. The first channeling experiments were performed in 1963 by Davies and his coworkers. Parallely Robinson and Oen have investigated this process by simulating trajectories of ions in monocrystals. This technique has been combined with many methods like Rutherford Backscattering Spectrometry (R.B.S.), Particles Induced X-rays Emission (P.I.X.E) and online Nuclear Reaction (N.R.A.) to localize trace elements in the crystal or to determine crystalline quality. To use channeling for material characterization we need data about the stopping power of the incident particle in the channeled direction. The ratios of channeled to random stopping powers of silicon for irradiation in the direction have been investigated and compared to the available theoretical results. We describe few applications of ion channeling in the field of materials characterization. Special attention is given to ion channeling combined with Charged Particle Activation Analysis (C.P.A.A.) for studying the behaviour of oxygen atoms in Czochralski silicon lattices under the influence of internal gettering and in different gaseous atmospheres. Association between ion channeling and C.P.A.A was also utilised for studying the influence of the growing conditions on concentration and position of carbon atoms at trace levels in the MOVPE Ga sub (1-x) Al sub x lattice. 6 figs., 1 tab., 32 refs. (author)

  8. Treatment for the recoil effects of the multi-step heavy-ion nucleon transfers with the orthogonalized coupled-reaction-channel theory

    International Nuclear Information System (INIS)

    Misono, S.; Imanishi, B.

    1997-02-01

    We have investigated recoil effects in heavy-ion reactions for the nucleon transfers, and the validity of the spatially local approximation for the non-local transfer interaction defined by the orthogonalized coupled-reaction-channel (OCRC) theory. This approximation makes it easier to treat multi-step transfer processes with the coupled channel method and makes it possible to define the nucleon molecular orbitals with the inclusion of the recoil effects. The transfer interaction is expanded in a power series of the momentum operator, and is approximated by the first order term, i.e., the spatially local term. The numerical calculation for the core-symmetric systems 12 C+ 13 C and 16 O+ 17 O with this approximation shows that the recoil effects are well included in the results at energies lower than a few MeV/nucleon. Furthermore, the OCRC formalism allows us even to employ the complete no-recoil approximation for the calculation of cross sections, even though it is not adequate to use this approximation in the distorted wave Born approximation (DWBA) method. As to polarization, however, the no-recoil approximation is not good even in the OCRC formalism. We discuss the recoil effects on nucleon molecular-orbital states. It is shown that states of the covalent molecular orbitals of the valence (transferred) nucleon are little affected by the recoil effects, as already suggested by Korotky et al. in the full finite-range DWBA analysis of the transfer reaction, 13 C( 13 C, 12 C) 14 C. (author). 59 refs

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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

  14. Control of Ambipolar Transport in SnO Thin-Film Transistors by Back-Channel Surface Passivation for High Performance Complementary-like Inverters.

    Science.gov (United States)

    Luo, Hao; Liang, Lingyan; Cao, Hongtao; Dai, Mingzhi; Lu, Yicheng; Wang, Mei

    2015-08-12

    For ultrathin semiconductor channels, the surface and interface nature are vital and often dominate the bulk properties to govern the field-effect behaviors. High-performance thin-film transistors (TFTs) rely on the well-defined interface between the channel and gate dielectric, featuring negligible charge trap states and high-speed carrier transport with minimum carrier scattering characters. The passivation process on the back-channel surface of the bottom-gate TFTs is indispensable for suppressing the surface states and blocking the interactions between the semiconductor channel and the surrounding atmosphere. We report a dielectric layer for passivation of the back-channel surface of 20 nm thick tin monoxide (SnO) TFTs to achieve ambipolar operation and complementary metal oxide semiconductor (CMOS) like logic devices. This chemical passivation reduces the subgap states of the ultrathin channel, which offers an opportunity to facilitate the Fermi level shifting upward upon changing the polarity of the gate voltage. With the advent of n-type inversion along with the pristine p-type conduction, it is now possible to realize ambipolar operation using only one channel layer. The CMOS-like logic inverters based on ambipolar SnO TFTs were also demonstrated. Large inverter voltage gains (>100) in combination with wide noise margins are achieved due to high and balanced electron and hole mobilities. The passivation also improves the long-term stability of the devices. The ability to simultaneously achieve field-effect inversion, electrical stability, and logic function in those devices can open up possibilities for the conventional back-channel surface passivation in the CMOS-like electronics.

  15. Vapor-Liquid-Solid Etch of Semiconductor Surface Channels by Running Gold Nanodroplets.

    Science.gov (United States)

    Nikoobakht, Babak; Herzing, Andrew; Muramoto, Shin; Tersoff, Jerry

    2015-12-09

    We show that Au nanoparticles spontaneously move across the (001) surface of InP, InAs, and GaP when heated in the presence of water vapor. As they move, the particles etch crystallographically aligned grooves into the surface. We show that this process is a negative analogue of the vapor-liquid-solid (VLS) growth of semiconductor nanowires: the semiconductor dissolves into the catalyst and reacts with water vapor at the catalyst surface to create volatile oxides, depleting the dissolved cations and anions and thus sustaining the dissolution process. This VLS etching process provides a new tool for directed assembly of structures with sublithographic dimensions, as small as a few nanometers in diameter. Au particles above 100 nm in size do not exhibit this process but remain stationary, with oxide accumulating around the particles.

  16. Introduction of inclined open channels for the control of surface runoff of slopes in road structures

    Directory of Open Access Journals (Sweden)

    Hniad O.

    2018-01-01

    Full Text Available The phenomenon of water erosion induced by runoff speeds at the surface of the embankments causes their instability. Particularly in road environments, gullying on the slope's surface due to runoffs causes landslides, which in turn cause considerable damage and consequent disorders to the road network. The aim of this research is to put in place a new technology for superficial water drainage on slope surfaces. Our study has developed a methodology involving the change of the geometric configuration of the water flow, aiming at velocity control of the flows by choosing slanting waterways with small slopes coupled to vertical drains. A modelling of the proposed solution will evaluate its effectiveness as to prevent the erosive factor and to identify other factors that are responsible for slope disorders.

  17. Defect and dopant depth profiles in boron-implanted silicon studied with channeling and nuclear reaction analysis

    NARCIS (Netherlands)

    Vos, M.; Boerma, D.O.; Smulders, P.J.M.; Oosterhoff, S.

    1986-01-01

    Single crystals of silicon were implanted at RT with 1 MeV boron ions to a dose of 1 × 1015 ions/cm2. The depth profile of the boron was measured using the 2060-keV resonance of the 11B(α, n)14N nuclear reaction. The distribution of the lattice disorder as a function of depth was determined from

  18. 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

  19. Study of 24Mg(18O,16O)26Mg reaction at Esub(180)=50MeV including scattering in entrance and exit channel

    International Nuclear Information System (INIS)

    Bernas, M.; Pougheon, F.; Roy-Stephan, M.; Berg, G.P.A.; Kernforschungsanlage Juelich G.m.b.H.; Berthier, B.; Le Fevre, J.P.; Wildenthal, B.H.

    1980-01-01

    Cross section angular distributions of 24 Mg( 18 O, 16 O) 26 Mg reaction at 50 MeV incident energy leading to the first four excited states in 26 Mg and the elastic and inelastic scattering for 18 O + 24 Mg at 50 MeV and 16 O + 26 Mg at 56 MeV have been measured in order to investigate the reaction mechanism of the two-nucleon transfer reaction including the analysis of incident and exit channels. The measured angular distributions were analyzed in the framework of the EFR-DWBA. Two neutron transfer amplitudes were determined using the 2s-1d shell model amplitudes calculated by Chung and Wildenthal. The large experimental cross section in contrast to the smallness of the direct transfer amplitude and the peculiar shape of the measured angular distribution of the lowest 2 1 + state suggests that this level is mainly excited by two-step processes. It is shown that a CCBA calculation describes successfully the angular distributions of the ground state and the 2 1 + state in 26 Mg

  20. Surface expression, single-channel analysis and membrane topology of recombinant Chlamydia trachomatis Major Outer Membrane Protein

    Directory of Open Access Journals (Sweden)

    McClafferty Heather

    2005-01-01

    Full Text Available Abstract Background Chlamydial bacteria are obligate intracellular pathogens containing a cysteine-rich porin (Major Outer Membrane Protein, MOMP with important structural and, in many species, immunity-related roles. MOMP forms extensive disulphide bonds with other chlamydial proteins, and is difficult to purify. Leaderless, recombinant MOMPs expressed in E. coli have yet to be refolded from inclusion bodies, and although leadered MOMP can be expressed in E. coli cells, it often misfolds and aggregates. We aimed to improve the surface expression of correctly folded MOMP to investigate the membrane topology of the protein, and provide a system to display native and modified MOMP epitopes. Results C. trachomatis MOMP was expressed on the surface of E. coli cells (including "porin knockout" cells after optimizing leader sequence, temperature and medium composition, and the protein was functionally reconstituted at the single-channel level to confirm it was folded correctly. Recombinant MOMP formed oligomers even in the absence of its 9 cysteine residues, and the unmodified protein also formed inter- and intra-subunit disulphide bonds. Its topology was modeled as a (16-stranded β-barrel, and specific structural predictions were tested by removing each of the four putative surface-exposed loops corresponding to highly immunogenic variable sequence (VS domains, and one or two of the putative transmembrane strands. The deletion of predicted external loops did not prevent folding and incorporation of MOMP into the E. coli outer membrane, in contrast to the removal of predicted transmembrane strands. Conclusions C. trachomatis MOMP was functionally expressed on the surface of E. coli cells under newly optimized conditions. Tests of its predicted membrane topology were consistent with β-barrel oligomers in which major immunogenic regions are displayed on surface-exposed loops. Functional surface expression, coupled with improved understanding of MOMP

  1. Free-Molecular Gas Flow in Channels (Pores) with Physico-Chemical Transformation on the Surface

    Czech Academy of Sciences Publication Activity Database

    Levdansky, V.V.; Smolík, Jiří; Moravec, Pavel

    2006-01-01

    Roč. 49, 13-14 (2006), s. 2356-2365 ISSN 0017-9310 Institutional research plan: CEZ:AV0Z40720504 Keywords : free-molecular flow * surface * spatial distribution Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.482, year: 2006

  2. Visualization of pre-set vortices in boundary layer flow over wavy surface in rectangular channel

    KAUST Repository

    Budiman, Alexander Christantho; Mitsudharmadi, Hatsari; Bouremel, Yann; Winoto, Sonny H.; Low, H. T.

    2014-01-01

    structures on the cross-sectional plane normal to the wavy surface. To obtain uniform spanwise vortex wavelength which will result in uniform vortex size, two types of spanwise disturbances were used: a series of perturbation wires placed prior and normal

  3. Novel concept of multi-channel fiber optic surface plasmon resonance sensor

    Czech Academy of Sciences Publication Activity Database

    Špačková, Barbora; Piliarik, Marek; Kvasnička, Pavel; Rajarajan, M.; Homola, Jiří

    2009-01-01

    Roč. 139, č. 1 (2009), s. 199-203 ISSN 0925-4005 R&D Projects: GA AV ČR KAN200670701 Institutional research plan: CEZ:AV0Z20670512 Keywords : . Surface plasmon resonance * Fiber optic * Bragg grating * Biosensor Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 3.083, year: 2009

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. Influence of Surface Phenomena on Free-Molecule Gas Flow in Fine Channels.

    Czech Academy of Sciences Publication Activity Database

    Levdansky, V.V.; Smolík, Jiří; Moravec, Pavel

    2007-01-01

    Roč. 34, 7 (2007) , s. 796-800 ISSN 0735-1933 R&D Projects: GA ČR(CZ) GA101/05/2214; GA ČR(CZ) GA101/05/2524 Institutional research plan: CEZ:AV0Z40720504 Keywords : adsorption * surface diffusion * sticking coefficient Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.945, year: 2007

  9. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2012-09-13 to 2012-09-25 (NCEI Accession 0157385)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157385 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  10. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2013-09-10 to 2013-10-02 (NCEI Accession 0157366)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157366 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  11. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2013-05-08 to 2013-05-28 (NCEI Accession 0157373)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157373 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  12. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2013-04-19 to 2013-05-08 (NCEI Accession 0157305)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157305 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  13. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2012-09-27 to 2012-10-04 (NCEI Accession 0157267)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157267 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  14. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2013-02-03 to 2013-02-13 (NCEI Accession 0157382)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157382 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  15. Partial pressure (or fugacity) of carbon dioxide, salinity and other variables collected from Surface underway observations using Carbon dioxide (CO2) gas analyzer, Shower head chamber equilibrator for autonomous carbon dioxide (CO2) measurement and other instruments from CEFAS ENDEAVOUR in the Bristol Channel, English Channel and others from 2012-10-23 to 2012-11-09 (NCEI Accession 0157241)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NCEI Accession 0157241 includes Surface underway, chemical, meteorological and physical data collected from CEFAS ENDEAVOUR in the Bristol Channel, English Channel,...

  16. Impact of feed additives on surface mucosal health and columnaris susceptibility in channel catfish fingerlings, Ictalurus punctatus.

    Science.gov (United States)

    Zhao, Honggang; Li, Chao; Beck, Benjamin H; Zhang, Ran; Thongda, Wilawan; Davis, D Allen; Peatman, Eric

    2015-10-01

    One of the highest priority areas for improvement in aquaculture is the development of dietary additives and formulations which provide for complete mucosal health and protection of fish raised in intensive systems. Far greater attention has been paid to dietary impact on gut health than to protective effects at other mucosal surfaces such as skin and gill. These exterior surfaces, however, are important primary targets for pathogen attachment and invasion. Flavobacterium columnare, the causative agent of columnaris disease, is among the most prevalent of all freshwater disease-causing bacteria, impacting global aquaculture of catfish, salmonids, baitfish and aquaria-trade species among others. This study evaluated whether the feeding of a standard catfish diet supplemented with Alltech dietary additives Actigen(®), a concentrated source of yeast cell wall-derived material and/or Allzyme(®) SSF, a fermented strain of Aspergillus niger, could offer protection against F. columnare mortality. A nine-week feeding trial of channel catfish fingerlings with basal diet (B), B + Allzyme(®) SSF, B + Actigen(®) and B + Actigen(®)+Allzyme(®) SSF revealed good growth in all conditions (FCR additives may provide protection extending beyond the gut to surface mucosa. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Cross channel isospin amplitude analysis of the reaction pN→NNπ at 19 GeV/c

    International Nuclear Information System (INIS)

    Bakken, V.; Gennow, H.; Hansen, J.D.; Lundborg, P.; Maekelae, J.; Pimiae, M.; Sellden, B.; Skjevling, G.; Sundell, E.

    1976-10-01

    The reaction N 1 N 2 →N 3 (N 4 π) is analysed in terms of three isospin amplitudes Msub(I)sup(Isub(x)) where Isub(x) and I are the isospin of the exchanged particle and the N 4 π combination respectively. The amplitudes are studied as functions of the momentum transfer to and the mass of the N 4 π system. The M 0 sub(1/2) amplitude exhibits the characteristics of diffraction dissociation with a broad low mass enhancement centered around 1.35 GeV. The dsigma/dt' distribution of M 0 sub(1/2) shows a clear break around 0.2 (GeV/c) 2 for masses smaller than 1.36 GeV. For higher masses the break disappears and the slope of the forward peak becomes smaller. The interference between M 0 sub(1/2) and M 1 sub(1/2) is zero for small values of t' and becomes large in magnitude and negative for larger t' values. The other interference terms are consistent with being zero. The hypothesis of factorization is tested for the M 0 sub(1/2) amplitude by comparison with the corresponding amplitude of π +- N reactions. The agreement is excellent over the whole mass range. (Auth.)

  18. 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

  19. 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...

  20. 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.

  1. Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things.

    Directory of Open Access Journals (Sweden)

    Murat Kuscu

    Full Text Available We consider a microfluidic molecular communication (MC system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA. However, analytical models are key for the information and communication technology (ICT, as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics.

  2. Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things.

    Science.gov (United States)

    Kuscu, Murat; Akan, Ozgur B

    2018-01-01

    We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics.

  3. A New Alternative in Urban Geophysics: Multi-Channel Analysis of Surface Waves (MASW) Method

    International Nuclear Information System (INIS)

    Ozcep, F.

    2007-01-01

    Geophysical studies are increasingly being applied to geotechnical investigations as they can identify soil properties and soil boundaries. Other advantage is that many of these methods are non-invasive and environment friendly. Soil stiffness is one of the critical material parameters considered during an early stage of most foundation construction. It is related directly to the stability of structural load, especially as it relates to possible earthquake hazard. Soil lacking sufficient stiffness for a given load can experience a significant reduction in strength under earthquake shaking resulting in liquefaction, a condition responsible for tremendous amounts of damage from earthquakes around the world The multichannel analysis of surface waves (MASW) method originated from the traditional seismic exploration approach that employs multiple (twelve or more) receivers placed along a linear survey line. Main advantage is its capability of recognizing different types of seismic waves based on wave propagation characteristics such as velocity and attenuation. The MASW method utilizes this capability to discriminate the fundamental-mode Rayleigh wave against all other types of surface and body waves generated not only from the active seismic source but also from the ambient site conditions. Dispersive characteristics of seismic waves are imaged from an objective 2-D wave field transformation. The present paper indicates results from MASW survey at different urban site in Turkey. MASW techniques will prove to be important tools for obtaining shear wave velocity and evaluating liquefaction potential, soil bearing capacity and soil amplification, etc. for future geophysical and geotechnical engineering community

  4. 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.

  5. 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.

  6. 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)

  7. 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

  8. Site Classification using Multichannel Channel Analysis of Surface Wave (MASW) method on Soft and Hard Ground

    Science.gov (United States)

    Ashraf, M. A. M.; Kumar, N. S.; Yusoh, R.; Hazreek, Z. A. M.; Aziman, M.

    2018-04-01

    Site classification utilizing average shear wave velocity (Vs(30) up to 30 meters depth is a typical parameter. Numerous geophysical methods have been proposed for estimation of shear wave velocity by utilizing assortment of testing configuration, processing method, and inversion algorithm. Multichannel Analysis of Surface Wave (MASW) method is been rehearsed by numerous specialist and professional to geotechnical engineering for local site characterization and classification. This study aims to determine the site classification on soft and hard ground using MASW method. The subsurface classification was made utilizing National Earthquake Hazards Reduction Program (NERHP) and international Building Code (IBC) classification. Two sites are chosen to acquire the shear wave velocity which is in the state of Pulau Pinang for soft soil and Perlis for hard rock. Results recommend that MASW technique can be utilized to spatially calculate the distribution of shear wave velocity (Vs(30)) in soil and rock to characterize areas.

  9. Lattice location of O{sup 18} in ion implanted Fe crystals by Rutherford backscattering spectrometry, channeling and nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Vairavel, Mathayan; Sundaravel, Balakrishnan, E-mail: bsundar@igcar.gov.in; Panigrahi, Binaykumar

    2016-09-15

    There are contradictory theoretical predictions of lattice location of oxygen interstitial atom at tetrahedral and octahedral interstices in bcc Fe. For validating these predictions, 300 keV O{sup 18} ions with fluence of 5 × 10{sup 15} ions/cm{sup 2} are implanted into bcc Fe single crystals at room temperature and annealed at 400 °C. The Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA)/channeling measurements are carried out with 850 keV protons. The lattice location of implanted O{sup 18} is analysed using the α-particles yield from O{sup 18}(p,α)N{sup 15} nuclear reaction. The tilt angular scans of α-particle yield along 〈110〉 and 〈100〉 axial directions are performed at room temperature. Lattice location of O{sup 18} is found to be at tetrahedral interstitial site by comparing the experimental scan with simulated scans using FLUX7 software.

  10. Analysis of the reaction γp → K{sup 0}Σ{sup +} in the neutral decay channel at the BGO-OD experiment using kinematic fitting

    Energy Technology Data Exchange (ETDEWEB)

    Alef, Stefan [Physikalisches Institut, Universitaet Bonn (Germany); Collaboration: BGO-OD-Collaboration

    2016-07-01

    The BGO-OD experiment at the ELSA facility in Bonn is built to investigate nucleon excitations via meson photoproduction. One research objective is associated strangeness production, which includes the reaction channel γp → K{sup 0}Σ{sup +}. Results of the analysis for the neutral decay channel K{sup 0}Σ{sup +} → π{sup 0}π{sup 0}π{sup 0}p will be presented. Due to the small production cross section and branching ratio kinematic fitting is used to discriminate the reaction against background.

  11. 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.

  12. 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.

  13. 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.

  14. Suppression of surface-originated gate lag by a dual-channel AlN/GaN high electron mobility transistor architecture

    International Nuclear Information System (INIS)

    Deen, David A.; Storm, David F.; Scott Katzer, D.; Bass, R.; Meyer, David J.

    2016-01-01

    A dual-channel AlN/GaN high electron mobility transistor (HEMT) architecture is demonstrated that leverages ultra-thin epitaxial layers to suppress surface-related gate lag. Two high-density two-dimensional electron gas (2DEG) channels are utilized in an AlN/GaN/AlN/GaN heterostructure wherein the top 2DEG serves as a quasi-equipotential that screens potential fluctuations resulting from distributed surface and interface states. The bottom channel serves as the transistor's modulated channel. Dual-channel AlN/GaN heterostructures were grown by molecular beam epitaxy on free-standing hydride vapor phase epitaxy GaN substrates. HEMTs fabricated with 300 nm long recessed gates demonstrated a gate lag ratio (GLR) of 0.88 with no degradation in drain current after bias stressed in subthreshold. These structures additionally achieved small signal metrics f_t/f_m_a_x of 27/46 GHz. These performance results are contrasted with the non-recessed gate dual-channel HEMT with a GLR of 0.74 and 82 mA/mm current collapse with f_t/f_m_a_x of 48/60 GHz.

  15. Suppression of surface-originated gate lag by a dual-channel AlN/GaN high electron mobility transistor architecture

    Science.gov (United States)

    Deen, David A.; Storm, David F.; Scott Katzer, D.; Bass, R.; Meyer, David J.

    2016-08-01

    A dual-channel AlN/GaN high electron mobility transistor (HEMT) architecture is demonstrated that leverages ultra-thin epitaxial layers to suppress surface-related gate lag. Two high-density two-dimensional electron gas (2DEG) channels are utilized in an AlN/GaN/AlN/GaN heterostructure wherein the top 2DEG serves as a quasi-equipotential that screens potential fluctuations resulting from distributed surface and interface states. The bottom channel serves as the transistor's modulated channel. Dual-channel AlN/GaN heterostructures were grown by molecular beam epitaxy on free-standing hydride vapor phase epitaxy GaN substrates. HEMTs fabricated with 300 nm long recessed gates demonstrated a gate lag ratio (GLR) of 0.88 with no degradation in drain current after bias stressed in subthreshold. These structures additionally achieved small signal metrics ft/fmax of 27/46 GHz. These performance results are contrasted with the non-recessed gate dual-channel HEMT with a GLR of 0.74 and 82 mA/mm current collapse with ft/fmax of 48/60 GHz.

  16. Suppression of surface-originated gate lag by a dual-channel AlN/GaN high electron mobility transistor architecture

    Energy Technology Data Exchange (ETDEWEB)

    Deen, David A., E-mail: david.deen@alumni.nd.edu; Storm, David F.; Scott Katzer, D.; Bass, R.; Meyer, David J. [Naval Research Laboratory, Electronics Science and Technology Division, Washington, DC 20375 (United States)

    2016-08-08

    A dual-channel AlN/GaN high electron mobility transistor (HEMT) architecture is demonstrated that leverages ultra-thin epitaxial layers to suppress surface-related gate lag. Two high-density two-dimensional electron gas (2DEG) channels are utilized in an AlN/GaN/AlN/GaN heterostructure wherein the top 2DEG serves as a quasi-equipotential that screens potential fluctuations resulting from distributed surface and interface states. The bottom channel serves as the transistor's modulated channel. Dual-channel AlN/GaN heterostructures were grown by molecular beam epitaxy on free-standing hydride vapor phase epitaxy GaN substrates. HEMTs fabricated with 300 nm long recessed gates demonstrated a gate lag ratio (GLR) of 0.88 with no degradation in drain current after bias stressed in subthreshold. These structures additionally achieved small signal metrics f{sub t}/f{sub max} of 27/46 GHz. These performance results are contrasted with the non-recessed gate dual-channel HEMT with a GLR of 0.74 and 82 mA/mm current collapse with f{sub t}/f{sub max} of 48/60 GHz.

  17. 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

  18. 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

  19. Loss of ATP-Sensitive Potassium Channel Surface Expression in Heart Failure Underlies Dysregulation of Action Potential Duration and Myocardial Vulnerability to Injury.

    Directory of Open Access Journals (Sweden)

    Zhan Gao

    Full Text Available The search for new approaches to treatment and prevention of heart failure is a major challenge in medicine. The adenosine triphosphate-sensitive potassium (KATP channel has been long associated with the ability to preserve myocardial function and viability under stress. High surface expression of membrane KATP channels ensures a rapid energy-sparing reduction in action potential duration (APD in response to metabolic challenges, while cellular signaling that reduces surface KATP channel expression blunts APD shortening, thus sacrificing energetic efficiency in exchange for greater cellular calcium entry and increased contractile force. In healthy hearts, calcium/calmodulin-dependent protein kinase II (CaMKII phosphorylates the Kir6.2 KATP channel subunit initiating a cascade responsible for KATP channel endocytosis. Here, activation of CaMKII in a transaortic banding (TAB model of heart failure is coupled with a 35-40% reduction in surface expression of KATP channels compared to hearts from sham-operated mice. Linkage between KATP channel expression and CaMKII is verified in isolated cardiomyocytes in which activation of CaMKII results in downregulation of KATP channel current. Accordingly, shortening of monophasic APD is slowed in response to hypoxia or heart rate acceleration in failing compared to non-failing hearts, a phenomenon previously shown to result in significant increases in oxygen consumption. Even in the absence of coronary artery disease, failing myocardium can be further injured by ischemia due to a mismatch between metabolic supply and demand. Ischemia-reperfusion injury, following ischemic preconditioning, is diminished in hearts with CaMKII inhibition compared to wild-type hearts and this advantage is largely eliminated when myocardial KATP channel expression is absent, supporting that the myocardial protective benefit of CaMKII inhibition in heart failure may be substantially mediated by KATP channels. Recognition of Ca

  20. Material and surface - Course synergy as a channel towards a more encompassing view of learning

    Directory of Open Access Journals (Sweden)

    Ana Nuutinen

    2016-02-01

    Full Text Available The course Material and Surface is a combination of four minor courses: Experiential Textile Design, Dyeing, Textile Printing and Embroidery. The course combination is offered to first-year textile teacher students. Through combining courses, the aim has been to support integrated learning and transform fragmented education into a thematically coherent whole. The four courses form an intertwined and progressive structure in which each course is based on the knowledge learned from the previous course. The creative basis of the Experiential Textile Design course applies David Kolb’s theory (1984. The creative ideas are then applied to assignments in Dyeing, Textile Printing and Embroidery. Following the courses, students collect assignments in a learning portfolio. They organize their assignments in a progressive order to self-assess personal development, the creative process and changes in learning and thinking. The aims of this research were to find out 1 how the course combination reinforced students’ understanding of their own learning, 2 in which ways students’ own experiences strengthened their personal development and 3 what effect the collaboration had on teachers and their working. Data collected during the years 2008–2013 consisted of students’ portfolios (N=152, teachers' self-reflections as notes and diary remarks and notes from the final critiques. Data were analyzed using qualitative content analysis. The results indicate that the learning portfolio serves as feedback for the teachers. During the courses, the students worked in groups and shared experiences which strengthened collective values and meanings. Mutual sharing built the group’s cohesion, which was observable in students’ vivid and increasing discussions: they shared more of their ideas, they encouraged and inspired each other.  Diversity appeared to be the most important feature that arose from the data – all experiences were evaluated equally true and

  1. 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)

  2. Surface morphology and surface energy of anode materials influence power outputs in a multi-channel mediatorless bio-photovoltaic (BPV) system.

    Science.gov (United States)

    Bombelli, Paolo; Zarrouati, Marie; Thorne, Rebecca J; Schneider, Kenneth; Rowden, Stephen J L; Ali, Akin; Yunus, Kamran; Cameron, Petra J; Fisher, Adrian C; Ian Wilson, D; Howe, Christopher J; McCormick, Alistair J

    2012-09-21

    Bio-photovoltaic cells (BPVs) are a new photo-bio-electrochemical technology for harnessing solar energy using the photosynthetic activity of autotrophic organisms. Currently power outputs from BPVs are generally low and suffer from low efficiencies. However, a better understanding of the electrochemical interactions between the microbes and conductive materials will be likely to lead to increased power yields. In the current study, the fresh-water, filamentous cyanobacterium Pseudanabaena limnetica (also known as Oscillatoria limnetica) was investigated for exoelectrogenic activity. Biofilms of P. limnetica showed a significant photo response during light-dark cycling in BPVs under mediatorless conditions. A multi-channel BPV device was developed to compare quantitatively the performance of photosynthetic biofilms of this species using a variety of different anodic conductive materials: indium tin oxide-coated polyethylene terephthalate (ITO), stainless steel (SS), glass coated with a conductive polymer (PANI), and carbon paper (CP). Although biofilm growth rates were generally comparable on all materials tested, the amplitude of the photo response and achievable maximum power outputs were significantly different. ITO and SS demonstrated the largest photo responses, whereas CP showed the lowest power outputs under both light and dark conditions. Furthermore, differences in the ratios of light : dark power outputs indicated that the electrochemical interactions between photosynthetic microbes and the anode may differ under light and dark conditions depending on the anodic material used. Comparisons between BPV performances and material characteristics revealed that surface roughness and surface energy, particularly the ratio of non-polar to polar interactions (the CQ ratio), may be more important than available surface area in determining biocompatibility and maximum power outputs in microbial electrochemical systems. Notably, CP was readily outperformed by all

  3. 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.

  4. Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface.

    Science.gov (United States)

    Li, Yang; Klippenstein, Stephen J; Zhou, Chong-Wen; Curran, Henry J

    2017-10-12

    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ 4 H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ 4 H 7 1-3) and 3-buten-1-yl (Ċ 4 H 7 1-4) radicals and C 2 H 4 + Ċ 2 H 3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4 H 6 + Ḣ → products and C 2 H 4 + Ċ 2 H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is

  5. Study for the charge symmetric systems, 12C+13N and 12C+13C with the orthogonalized coupled-reaction-channel method

    International Nuclear Information System (INIS)

    Imanishi, B.; Denisov, V.; Motobayashi, T.

    1996-10-01

    The charge-symmetric scattering systems, 12 C+ 13 N and 12 C+ 13 C have been investigated by using the orthogonalized coupled-reaction-channel (OCRC) method with the basis functions of the elastic, inelastic and transfer channels defined by the single-particle states, 1p1/2, 2s1/2, 1d5/2 and 1d3/2 of the valence nucleon in 13 N or 13 C. The data of the elastic scattering of 13 N on 12 C measured by Lienard et al. have been explained consistently with the data of the elastic and inelastic scattering of the 12 C+ 13 C system. The CRC effects both on the above systems are very strong, although those on the 12 C+ 13 N system are fairly weaker than the 12 C+ 13 C system. The role of the highly excited single-particle states 1d3/2 is particularly important in the formation of a specific CRC scheme, i.e., the formation of the covalent molecules due to the hybridization caused by the mixing of the different parity single-particle states. The fusion cross sections of the 12 C+ 13 C system at energies below the Coulomb barrier are strongly enhanced as a result of the strong CRC effects as compared with those of the 12 C+ 12 C system, while in 12 C+ 13 N system the enhancement of the sub-barrier fusion has not been observed. The above absorption mechanism for the 12 C+ 13 C system explains the lack of the molecular-resonance phenomena observed in the 12 C+ 12 C system. We check the effects of the dipole (E1) transition of the valence nucleon in 13 N (and also in 13 C) due to the core-core Coulomb interaction in the scattering at sub-barrier energies. The effects are not appreciable. (author)

  6. Achieving more efficient operation of the nozzle vane and rotor blade rows of gas turbines through using nonaxisymmetric end wall surfaces of interblade channels

    Science.gov (United States)

    Inozemtsev, A. A.; Samokhvalov, N. Yu.; Tikhonov, A. S.

    2012-09-01

    Results from a numerical study of three versions of the end-wall generatrix of the interblade channel used in the second-stage nozzle vanes of a prospective engine's turbine are presented. Recommendations for designing nonaxisymmetric end-wall surfaces are suggested based on the obtained data.

  7. Separation followed by direct SERS detection of explosives on a novel black silicon multifunctional nanostructured surface prepared in a microfluidic channel

    DEFF Research Database (Denmark)

    Talian, Ivan; Hübner, Jörg

    2013-01-01

    The article describes the multifunctionality of a novel black silicon (BS) nanostructured surface covered with a thin layer of noble metal prepared in the a microfluidic channel. It is focused on the separation properties of the BS substrate with direct detection of the separated analytes utilizing...

  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. Analysis of the reaction γp → K{sup 0}Σ{sup +} by the identification of the charged K* decay channel at the BGO-OD experiment using kinematic fitting

    Energy Technology Data Exchange (ETDEWEB)

    Reitz, Bjoern-Eric [Physikalisches Institut Bonn (Germany); Collaboration: BGO-OD-Collaboration

    2016-07-01

    The BGO-OD experiment at the ELSA facility in Bonn is built to investigate nucleon excitations via meson photoproduction. A program of measurements of reactions of associated strangeness in the final state has begun, one of which is γp → K{sup 0}Σ{sup +}. One research objective is associated production of strange particles. An interesting reaction channel is γp → K{sup 0}Σ{sup +}. This talk shows the preliminary results of the analysis for the charged decay channel K{sup 0}Σ{sup +} → π{sup -}π{sup +}π{sup 0}p. Due to the small production cross section kinematic fitting has been used to discriminate the wanted channel against background.

  13. 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

  14. Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors.

    Science.gov (United States)

    Lenz, Thomas; Schmaltz, Thomas; Novak, Michael; Halik, Marcus

    2012-10-02

    In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (n-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α'-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics.

  15. 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.)

  16. 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

  17. 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.

  18. 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.

  19. Warpage optimisation on the moulded part with straight-drilled and conformal cooling channels using response surface methodology (RSM) and glowworm swarm optimisation (GSO)

    Science.gov (United States)

    Hazwan, M. H. M.; Shayfull, Z.; Sharif, S.; Nasir, S. M.; Zainal, N.

    2017-09-01

    In injection moulding process, quality and productivity are notably important and must be controlled for each product type produced. Quality is measured as the extent of warpage of moulded parts while productivity is measured as a duration of moulding cycle time. To control the quality, many researchers have introduced various of optimisation approaches which have been proven enhanced the quality of the moulded part produced. In order to improve the productivity of injection moulding process, some of researches have proposed the application of conformal cooling channels which have been proven reduced the duration of moulding cycle time. Therefore, this paper presents an application of alternative optimisation approach which is Response Surface Methodology (RSM) with Glowworm Swarm Optimisation (GSO) on the moulded part with straight-drilled and conformal cooling channels mould. This study examined the warpage condition of the moulded parts before and after optimisation work applied for both cooling channels. A front panel housing have been selected as a specimen and the performance of proposed optimisation approach have been analysed on the conventional straight-drilled cooling channels compared to the Milled Groove Square Shape (MGSS) conformal cooling channels by simulation analysis using Autodesk Moldflow Insight (AMI) 2013. Based on the results, melt temperature is the most significant factor contribute to the warpage condition and warpage have optimised by 39.1% after optimisation for straight-drilled cooling channels and cooling time is the most significant factor contribute to the warpage condition and warpage have optimised by 38.7% after optimisation for MGSS conformal cooling channels. In addition, the finding shows that the application of optimisation work on the conformal cooling channels offers the better quality and productivity of the moulded part produced.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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...

  5. 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)

  6. 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).

  7. 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.

  8. 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.

  9. 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)

  10. 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.

  11. 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...

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. 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)

  17. Simultaneous estimation of vitamin K1 and heparin with low limit of detection using cascaded channels fiber optic surface plasmon resonance.

    Science.gov (United States)

    Tabassum, Rana; Gupta, Banshi D

    2016-12-15

    We report an approach for the simultaneous estimation of vitamin K1 (VK1) and heparin via cascaded channel multianalyte sensing probe employing fiber optic surface plasmon resonance technique. Cladding from two well separated portions of the fiber is removed and are respectively coated with thin films of silver (channel-1) and copper (channel-2). The nanohybrid of multiwalled carbon nanotube in chitosan is fabricated over silver layer for the sensing of VK1 whereas core shell nanostructure of polybrene@ZnO is coated over copper layer for the sensing of heparin. Spectral interrogation method is used for the characterization of the sensor. Analyte selectivity of both the channels is performed by carrying out experiments using independent solutions of VK1 and heparin. Experiments performed on the solution of the mixture of VK1 and heparin show red shifts in both the channels on changing the concentration of both the analytes in the mixture. The operating range of both VK1 and heparin is from 0 to 10(-3)g/l. The limit of detection of the sensor is 2.66×10(-4)µg/l and 2.88×10(-4)µg/l for VK1 and heparin respectively which are lower than the reported ones. The additional advantages of the present sensor are low cost, possibility of online monitoring and remote sensing. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. The influence of hydrodynamic factors, membrane surface properties and channel geometries on membrane performance and fouling mechanisms

    Directory of Open Access Journals (Sweden)

    Pervov Alexey

    2016-01-01

    Full Text Available Modern theoretical understanding of colloidal and suspended matter membrane fouling mechanisms are presented and discussed. State-of-the-art simulation models of concentration polarization calculations for different channel conditions are described and influence of the fouling layers on the flux and rejection decrease are evaluated. Results of experimental investigations are presented that suggest a quantitative evaluation of fouling rates and membrane flux prognosis due to colloidal fouling with time. The influence of channel geometry on fouling is demonstrated and discussed. The main disadvantage of spiral wounded membrane modules which is attributed to the presence of a separation spacer mesh in the feed channel is discussed.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. 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)

  10. [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.

  11. 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.

  12. 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.

  13. 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%.

  14. Ion backscattering, channeling and nuclear reaction analysis study of passive films formed on FeCrNi and FeCrNiMo (100) single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, C; Schmaus, D [Paris-7 Univ., 75 (France). Groupe de Physique des Solides de l' ENS; Elbiache, A; Marcus, P [Ecole Nationale Superieure de Chimie, 75 - Paris (France)

    1990-01-01

    The compositions of passive films formed on Fe-17Fr-13Ni (at. %) and Fe-18.5Cr-14Ni-1.5Mo (100) single crystals have been determined and the structure of the alloy under the film has been investigated. The alloys were passivated in 0.05M H{sub 2}SO{sub 4} at 250 mV/SHE for 30 min. The oxygen content was measured by nuclear microanalysis using the {sup 16}O(d,p) {sup 17}O* reaction. The oxygen content in the passive film is similar for the two alloys and equal to (12{plus minus}2) 10{sup 15} O/cm{sup 2}. The cationic compositions of the passive films have been determined by {sup 4}He channeling at two incident beam energies: 0.8 and 2.0 MeV. For the two alloys studied, a total cation content of (5{plus minus}2)10{sup 15} at/cm{sup 2} is found in the passive films. The corresponding thickness is about 12 A. There is an excess of oxygen, which can be attributed to the presence of hydroxyls and sulfate. A strong chromium enrichment is found in the passive film formed on both alloys: chromium represents about 50% of the cations. There is no evidence of molybdenum enrichment in the passive film formed on the Mo-alloyed stainless steel. The comparison of the results obtained at the two different incident beam energies (0.8MeV and 2MeV) reveals the existence of defects at the alloy/passive film interface. (author).

  15. 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

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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...

  1. 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...

  2. 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

  3. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using 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 to 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. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  4. Local Multi-Channel RF Surface Coil versus Body RF Coil Transmission for Cardiac Magnetic Resonance at 3 Tesla: Which Configuration Is Winning the Game?

    Science.gov (United States)

    Weinberger, Oliver; Winter, Lukas; Dieringer, Matthias A; Els, Antje; Oezerdem, Celal; Rieger, Jan; Kuehne, Andre; Cassara, Antonino M; Pfeiffer, Harald; Wetterling, Friedrich; Niendorf, Thoralf

    2016-01-01

    The purpose of this study was to demonstrate the feasibility and efficiency of cardiac MR at 3 Tesla using local four-channel RF coil transmission and benchmark it against large volume body RF coil excitation. Electromagnetic field simulations are conducted to detail RF power deposition, transmission field uniformity and efficiency for local and body RF coil transmission. For both excitation regimes transmission field maps are acquired in a human torso phantom. For each transmission regime flip angle distributions and blood-myocardium contrast are examined in a volunteer study of 12 subjects. The feasibility of the local transceiver RF coil array for cardiac chamber quantification at 3 Tesla is demonstrated. Our simulations and experiments demonstrate that cardiac MR at 3 Tesla using four-channel surface RF coil transmission is competitive versus current clinical CMR practice of large volume body RF coil transmission. The efficiency advantage of the 4TX/4RX setup facilitates shorter repetition times governed by local SAR limits versus body RF coil transmission at whole-body SAR limit. No statistically significant difference was found for cardiac chamber quantification derived with body RF coil versus four-channel surface RF coil transmission. Our simulation also show that the body RF coil exceeds local SAR limits by a factor of ~2 when driven at maximum applicable input power to reach the whole-body SAR limit. Pursuing local surface RF coil arrays for transmission in cardiac MR is a conceptually appealing alternative to body RF coil transmission, especially for patients with implants.

  5. 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.

  6. 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.

  7. 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

  8. 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).

  9. 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.

  10. 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.

  11. On the Efficiency of the Multi-Channel Analysis of Surface Wave Method for Shallow and Semi-Deep Loose Soil Layers

    Directory of Open Access Journals (Sweden)

    Kasgin Khaheshi Banab

    2010-01-01

    Full Text Available The multi-channel analysis of surface waves (MASWs method was used to obtain the shear wave velocity variations through near surface (depth 2,300 m/s is very large. The MASW velocity results compared with those of other geophysical approaches, such as seismic reflection/refraction methods and borehole data, where available, mostly confirming the capability of the MASW method to distinguish the high shear wave velocity contrast in the study area. We have found that, of the inversion procedures of MASW data, the random search inversion technique provides better results than the analytical generalized inversion method.

  12. 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.

  13. 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).

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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

  6. Surface Clutter Suppression Techniques Applied to P-band Multi-Channel SAR Ice Sounder Data from East Antarctica

    DEFF Research Database (Denmark)

    Lin, Chung-Chi; Bekaert, David; Gebert, Nicolas

    ., Lausanne, developed and built the radiator-elements of the enhanced POLARIS. Several datasets were acquired in the multi-channel configuration during the Feb. 2011 campaign over East Antarctica. The POLARIS instrument will be briefly introduced, followed by an overview of the sounding campaign. Finally...

  7. A localized interaction surface for voltage-sensing domains on the pore domain of a K+ channel.

    Science.gov (United States)

    Li-Smerin, Y; Hackos, D H; Swartz, K J

    2000-02-01

    Voltage-gated K+ channels contain a central pore domain and four surrounding voltage-sensing domains. How and where changes in the structure of the voltage-sensing domains couple to the pore domain so as to gate ion conduction is not understood. The crystal structure of KcsA, a bacterial K+ channel homologous to the pore domain of voltage-gated K+ channels, provides a starting point for addressing this question. Guided by this structure, we used tryptophan-scanning mutagenesis on the transmembrane shell of the pore domain in the Shaker voltage-gated K+ channel to localize potential protein-protein and protein-lipid interfaces. Some mutants cause only minor changes in gating and when mapped onto the KcsA structure cluster away from the interface between pore domain subunits. In contrast, mutants producing large changes in gating tend to cluster near this interface. These results imply that voltage-sensing domains interact with localized regions near the interface between adjacent pore domain subunits.

  8. 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.

  9. 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).

  10. Acoustic streaming in a microfluidic channel with a reflector: Case of a standing wave generated by two counterpropagating leaky surface waves.

    Science.gov (United States)

    Doinikov, Alexander A; Thibault, Pierre; Marmottant, Philippe

    2017-07-01

    A theory is developed for the modeling of acoustic streaming in a microfluidic channel confined between an elastic solid wall and a rigid reflector. A situation is studied where the acoustic streaming is produced by two leaky surface waves that propagate towards each other in the solid wall and thus form a combined standing wave in the fluid. Full analytical solutions are found for both the linear acoustic field and the field of the acoustic streaming. A dispersion equation is derived that allows one to calculate the wave speed in the system under study. The obtained solutions are used to consider particular numerical examples and to reveal the structure of the acoustic streaming. It is shown that two systems of vortices are established along the boundaries of the microfluidic channel.

  11. 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

  12. Development and field example of multi channel surface wave data acquisition and processing system (SWS-1); Multi channel hyomenha data shutoku shori system (SWS-1) no kaihatsu to jikkenrei

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Y [Huashui Institute of Geophysical Exploration, (China); Wang, Z [Bureauof Engineering MGMR, (China); Zhang, Z [STG Corp., (China); Tanaka, Y

    1996-05-01

    A report is given here about the use of a newly-developed multi-channel surface wave data acquisition and processing system different from the conventional surface wave exploration device. This system enables the on-site pickup of a dispersion curve out of the multi-component surface wave data and, in the analysis of underground structure, performs the forward modeling and inversion. The system, furthermore, acquires and analyzes the data obtained from reflection earthquake exploration and constant microtremor observation. During a survey conducted along the highway from Port Ren-un to Xuzhou, China, estimation of the basement boundary was made by use of dynamite, and what was obtained agreed with the result of boring though with an error of 3m. In addition, this system could probe levels deeper than 100m using the instantaneous Rayleigh wave exploration method. This system and the conventional surface exploration device were compared in a soft ground in Fukui Prefecture, the former using a 10kg hammer and the latter using a 350kg exciter, when it was verified that the results produced by both techniques excellently agree with the geologic columnar section and changes in the N-value. 4 refs., 4 figs.

  13. 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)

  14. 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.

  15. 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

  16. 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

  17. 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, w