WorldWideScience

Sample records for surface reactions lead

  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. Recyclization reactions leading to benzimidazoles

    International Nuclear Information System (INIS)

    Mamedov, Vakhid A; Murtazina, Anna M

    2011-01-01

    The published data on the recyclization reactions that afford benzimidazoles are generalized and systematized. Both classical and new methods of benzimidazole synthesis are considered. Attention is focused on the publications over the recent 10-15 years; of the earlier publications, only those unknown to the wide circle of chemists are analyzed.

  3. Recyclization reactions leading to benzimidazoles

    Science.gov (United States)

    Mamedov, Vakhid A.; Murtazina, Anna M.

    2011-05-01

    The published data on the recyclization reactions that afford benzimidazoles are generalized and systematized. Both classical and new methods of benzimidazole synthesis are considered. Attention is focused on the publications over the recent 10-15 years; of the earlier publications, only those unknown to the wide circle of chemists are analyzed.

  4. Tissue reactions to bacteria-inoculated rat lead samples .2. Effect of local gentamicin release through surface-modified polyurethane tubing

    NARCIS (Netherlands)

    vanWachem, PB; vanLuyn, MJA; deWit, AW; Raatjes, D; Hendriks, M; Verhoeven, MLPM; Cahalan, PT

    A surface modification technique was developed to achieve controlled release of gentamicin from implanted polyurethane (PU) rat lead samples. PU tubing first was provided with an acrylic acid/acrylamide copolymer surface graft and then loaded with gentamicin. This surface modification technique

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

    Science.gov (United States)

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

    2015-10-20

    -functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

  6. Radiation effects on lead silicate glass surfaces

    International Nuclear Information System (INIS)

    Wang, P.W.; Zhang, L.P.; Borgen, N.; Pannell, K.

    1996-01-01

    Radiation-induced changes in the microstructure of lead silicate glass were investigated in situ under Mg K α irradiation in an ultra-high vacuum (UHV) environment by X-ray photoelectron spectroscopy (XPS). Lead-oxygen bond breaking resulting in the formation of pure lead was observed. The segregation, growth kinetics and the structural relaxation of the lead, with corresponding changes in the oxygen and silicon on the glass surfaces were studied by measuring the time-dependent changes in concentration, binding energy shifts, and the full width at half maximum. A bimodal distribution of the oxygen XPS signal, caused by bridging and non-bridging oxygens, was found during the relaxation process. All experimental data indicate a reduction of the oxygen concentration, a phase separation of the lead from the glass matrix, and the metallization of the lead occurred during and after the X-ray irradiation. (author)

  7. 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.

  8. 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)

  9. Low Energy Nuclear Reaction Products at Surfaces

    Science.gov (United States)

    Nagel, David J.

    2008-03-01

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

  10. 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.

  11. Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

    Science.gov (United States)

    Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

    2012-01-01

    Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

  12. Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

    Directory of Open Access Journals (Sweden)

    Ziya Kalay

    Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

  13. 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)

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. Highly reversible lead-carbon battery anode with lead grafting on the carbon surface

    KAUST Repository

    Yin, Jian; Lin, Nan; Zhang, Wenli; Lin, Zheqi; Zhang, Ziqing; Wang, Yue; Shi, Jun; Bao, Jinpeng; Lin, Haibo

    2018-01-01

    A novel C/Pb composite has been successfully prepared by electroless plating to reduce the hydrogen evolution and achieve the high reversibility of the anode of lead-carbon battery (LCB). The deposited lead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Because lead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogen evolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead. Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge–discharge reversibility, which is attributed to the good connection between carbon additives and lead that has been stuck on the surface of C/Pb composite during the preparation process. The addition of C/Pb composite maintains a solid anode structure with high specific surface area and power volume, and thereby, it plays a significant role in the highly reversible lead-carbon anode.

  1. Highly reversible lead-carbon battery anode with lead grafting on the carbon surface

    KAUST Repository

    Yin, Jian

    2018-03-27

    A novel C/Pb composite has been successfully prepared by electroless plating to reduce the hydrogen evolution and achieve the high reversibility of the anode of lead-carbon battery (LCB). The deposited lead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Because lead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogen evolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead. Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge–discharge reversibility, which is attributed to the good connection between carbon additives and lead that has been stuck on the surface of C/Pb composite during the preparation process. The addition of C/Pb composite maintains a solid anode structure with high specific surface area and power volume, and thereby, it plays a significant role in the highly reversible lead-carbon anode.

  2. Lead concentrations and risk exposure assessment in surface soils ...

    African Journals Online (AJOL)

    Lead concentrations and risk exposure assessment in surface soils at residential lands previously used for auto-mechanic and auto-welding activities in Port Harcourt, Nigeria. ... Journal of Applied Sciences and Environmental Management.

  3. Lead Concentrations and Risk Exposure Assessment in Surface ...

    African Journals Online (AJOL)

    ADOWIE PERE

    µm, < 250 µm, and < 75 µm of surface soils at undeveloped residential lands leased to ... mechanic yards may still be point sources of lead ..... therefore need to conduct a source apportionment ... heavy metals in soil profiles of automobile.

  4. 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.

  5. Aging of residual surface resistance of superconducting lead cavities

    DEFF Research Database (Denmark)

    Danielsen, M.

    1972-01-01

    Measurements of the residual surface resistance of superconducting lead cavities as a function of time during a period of a month showed an oscillating variation. An explanation of the ageing curves is proposed. ©1972 The American Institute of Physics......Measurements of the residual surface resistance of superconducting lead cavities as a function of time during a period of a month showed an oscillating variation. An explanation of the ageing curves is proposed. ©1972 The American Institute of Physics...

  6. Investigations on organolead compounds V. Lead---lead bond cleavage reactions of hexaphenyldilead

    NARCIS (Netherlands)

    Willemsens, L.C.; Kerk, G.J.M. van der

    1968-01-01

    It has been shown that a number of nucleophilic and weakly electrophilic reagents (organolithium and organomagnesium compounds, metallic lithium, potassium permanganate, sodium ethoxide, diaryl disulphides, sulphur, ozone, hypochlorous acid and iodine/iodide) selectively cleave the lead---lead bond

  7. 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)

  8. 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

  9. A novel surface cleaning method for chemical removal of fouling lead layer from chromium surfaces

    International Nuclear Information System (INIS)

    Gholivand, Kh.; Khosravi, M.; Hosseini, S.G.; Fathollahi, M.

    2010-01-01

    Most products especially metallic surfaces require cleaning treatment to remove surface contaminations that remain after processing or usage. Lead fouling is a general problem which arises from lead fouling on the chromium surfaces of bores and other interior parts of systems which have interaction with metallic lead in high temperatures and pressures. In this study, a novel chemical solution was introduced as a cleaner reagent for removing metallic lead pollution, as a fouling metal, from chromium surfaces. The cleaner aqueous solution contains hydrogen peroxide (H 2 O 2 ) as oxidizing agent of lead layer on the chromium surface and acetic acid (CH 3 COOH) as chelating agent of lead ions. The effect of some experimental parameters such as acetic acid concentration, hydrogen peroxide concentration and temperature of the cleaner solution during the operation on the efficiency of lead cleaning procedure was investigated. The results of scanning electron microscopy (SEM) showed that using this procedure, the lead pollution layer could be completely removed from real chromium surfaces without corrosion of the original surface. Finally, the optimum conditions for the complete and fast removing of lead pollution layer from chromium surfaces were proposed. The experimental results showed that at the optimum condition (acetic acid concentration 28% (V/V), hydrogen peroxide 8% (V/V) and temperature 35 deg. C), only 15-min time is needed for complete removal of 3 g fouling lead from a chromium surface.

  10. 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

  11. 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.)

  12. 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

  13. Centrality in Hadron-Carbon, Hadron-Lead, and Lead-Lead Reactions at 158 GeV/c

    International Nuclear Information System (INIS)

    Rybicki, A.

    2006-08-01

    A study of centrality in p + C, π + C, p + Pb, π + Pb, and Pb + Pb reactions is made. The analysis is performed by means of a simple geometrical model. The mean number of elementary collisions, , is estimated in minimum bias p + C reactions. For the specific case of the carbon nucleus, estimates on appear to depend strongly on assumed nuclear densities. Most realistic of the presented assumptions result in a value of 1.71 ± 0.05. Additional quantities, like predictions for the total inelastic cross-section in p + C reactions, or the number of participants in minimum bias C + C collisions, are given. The analysis is subsequently extended to minimum bias π + C, π + Pb, and p + Pb reactions. Estimates are given for the mean number of elementary collisions as well as for the contribution of single collisions P(1). A comparison with experimental data is made. Finally, the impact parameter dependence of p + Pb and Pb + Pb collisions is discussed. In view of future studies, various aspects of the analysis are discussed in detail; a bibliography of used references is included. (author)

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Surface treatment and history-dependent corrosion in lead alloys

    International Nuclear Information System (INIS)

    Li Ning; Zhang Jinsuo; Sencer, Bulent H.; Koury, Daniel

    2006-01-01

    In oxygen-controlled lead and lead-bismuth eutectic (LBE), steel corrosion may be strongly history dependent. This is due to the competition between liquid metal dissolution corrosion and oxidation as a 'self-healing' protection barrier. Such effects can be observed from corrosion testing of a variety of surface-treated materials, such as cold working, shot peening, pre-oxidation, etc. Shot peening of austenitic steels produces surface-layer microstructural damages and grain compression, which could contribute to increased Cr migration to the surface and enhance the protection through an impervious oxide. Pre-oxidation under conditions different from operating ones may form more protective oxides, reduce oxygen and metal ion migration through the oxides, and achieve better protection for longer durations. Corrosion and oxidation modeling and analysis reveal the potential for significantly reducing long-term corrosion rates by initial and early-stage conditioning of steels for Pb/LBE services

  19. Surface treatment and history-dependent corrosion in lead alloys

    Energy Technology Data Exchange (ETDEWEB)

    Li Ning [Los Alamos National Laboratory, Los Alamos, NM (United States)]. E-mail: ningli@lanl.gov; Zhang Jinsuo [Los Alamos National Laboratory, Los Alamos, NM (United States); Sencer, Bulent H. [Los Alamos National Laboratory, Los Alamos, NM (United States); Koury, Daniel [University of Nevada, Las Vegas, NV (United States)

    2006-06-23

    In oxygen-controlled lead and lead-bismuth eutectic (LBE), steel corrosion may be strongly history dependent. This is due to the competition between liquid metal dissolution corrosion and oxidation as a 'self-healing' protection barrier. Such effects can be observed from corrosion testing of a variety of surface-treated materials, such as cold working, shot peening, pre-oxidation, etc. Shot peening of austenitic steels produces surface-layer microstructural damages and grain compression, which could contribute to increased Cr migration to the surface and enhance the protection through an impervious oxide. Pre-oxidation under conditions different from operating ones may form more protective oxides, reduce oxygen and metal ion migration through the oxides, and achieve better protection for longer durations. Corrosion and oxidation modeling and analysis reveal the potential for significantly reducing long-term corrosion rates by initial and early-stage conditioning of steels for Pb/LBE services.

  20. 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.

  1. 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...

  2. 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).

  3. 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)

  4. Molecular extinction coefficients of lead sulfide and polymerized diaminobenzidine as final reaction products of histochemical phosphatase reactions

    NARCIS (Netherlands)

    van Noorden, C. J.; Jonges, G. N.

    1992-01-01

    Molar extinction coefficients of precipitated lead sulfide (PbS) and polymerized diaminobenzidine (polyDAB) have been determined at wavelengths of 450 nm and 480 nm, respectively, for quantitative histochemical analysis of phosphatase reactions. These values are essential for the conversion of

  5. Lead concentrations and risk exposure assessment in surface soils ...

    African Journals Online (AJOL)

    This study investigated lead concentrations in < 250 μm and < 75 μm of deposited dust and< 2000 μm, < 250 μm, and < 75 μm of surface soils at undeveloped residential lands leased to auto-mechanic artisans for a minimum of ten years and estimated exposure risk for children that will reside on the polluted lands after the ...

  6. 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.

  7. 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

  8. Surface passivation of high purity granular metals: zinc, cadmium, lead

    Directory of Open Access Journals (Sweden)

    Pirozhenko L. A.

    2017-10-01

    Full Text Available For the high purity metals (99.9999%, such as zinc, cadmium, and lead, which are widely used as initial components in growing semiconductor and scintillation crystals (CdTe, CdZnTe, ZnSe, (Cd, Zn, Pb WO4, (Cd, Zn, Pb MoO4 et al., it is very important to ensure reliable protection of the surface from oxidation and adsorption of impurities from the atmosphere. The specific features of surface passivation of high purity cadmium, lead and zinc are not sufficiently studied and require specific methodologies for further studies. The use of organic solutions in the schemes of chemical passivation of the investigated metals avoids hydrolysis of the obtained protective films. The use of organic solvents with pure cation and anion composition as the washing liquid prevents chemisorption of ions present in the conventionally used distilled water. This keeps the original purity of the granular metals. Novel compositions of etchants and etching scheme providing simultaneous polishing and passivation of high purity granular Zn, Cd and Pb are developed. Chemical passivation allows storing metals in the normal atmospheric conditions for more than half a year for Zn and Cd and up to 30 days for Pb without changing the state of the surface. The use of the glycerol-DMF solution in the processes for obtaining Pb granules provides self-passivation of metal surfaces and eliminates the additional chemical processing while maintaining the quality of corrosion protection.

  9. 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

  10. 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

  11. 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.)

  12. Removing antimony from waste lead storage batteries alloy by vacuum displacement reaction technology.

    Science.gov (United States)

    Liu, Tiantian; Qiu, Keqiang

    2018-04-05

    With the wide application of lead acid battery, spent lead acid battery has become a serious problem to environmental protection and human health. Though spent battery can be a contaminant if not handled properly, it is also an important resource to obtain refined lead. Nowadays, the Sb-content in lead storage batteries is about 0.5-3 wt%, which is higher than the Sb-content in the crude lead. However, there are few reports about the process of removing antimony from high-antimony lead bullion. In this study, vacuum displacement reaction technology, a new process for removing antimony from high-antimony lead melts, was investigated. During this process, lead oxide was added to the system and antimony from lead melts was converted into antimony trioxide, which easily was evaporated under vacuum so that antimony was removed from lead melts. The experimental results demonstrated that Sb-content in lead melts decreased from 2.5% to 23 ppm under following conditions: mass ratio of PbO/lead bullion of 0.33, residual gas pressure of 30 Pa, melt temperature of 840 °C, reaction time of 60 min. The distillate gotten can be used as by-product to produce antimony white. Moreover, this study is of importance to recycling of waste lead storage batteries alloy. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. 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...

  14. 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.

  15. 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

  16. 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

  17. Computer-assisted study on the reaction between pyruvate and ylide in the pathway leading to lactyl-ThDP.

    Science.gov (United States)

    Alvarado, Omar; Jaña, Gonzalo; Delgado, Eduardo J

    2012-08-01

    In this study the formation of the lactyl-thiamin diphosphate intermediate (L-ThDP) is addressed using density functional theory calculations at X3LYP/6-31++G(d,p) level of theory. The study includes potential energy surface scans, transition state search, and intrinsic reaction coordinate calculations. Reactivity is analyzed in terms of Fukui functions. The results allow to conclude that the reaction leading to the formation of L-ThDP occurs via a concerted mechanism, and during the nucleophilic attack on the pyruvate molecule, the ylide is in its AP form. The calculated activation barrier for the reaction is 19.2 kcal/mol, in agreement with the experimental reported value.

  18. 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.

  19. 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.

  20. A facile and expedient one-pot three-component reaction leading to ...

    Indian Academy of Sciences (India)

    Sci. Vol. 124, No. 5, September 2012, pp. 1007–1012. c Indian Academy of Sciences. A facile and expedient one-pot three-component reaction leading to multifunctionalized stabilized phosphorus ylides. ZAHRA HASSANI. ∗ and ZEINAB ESFANDIARPOUR. Department of New Materials, International Center for Science, ...

  1. 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.

  2. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico) and Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada - IPN, Legaria 694, Col. Irrigacion, Del. Miguel Hidalgo (Mexico); Reyes-Carmona, F. [Facultad de Quimica - UNAM, Circuito de la Investigacion Cientifica s/n, C.U. Del. Coyoacan (Mexico); Jaramillo-Vigueras, D. [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico)

    2011-10-15

    Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  3. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    International Nuclear Information System (INIS)

    Rojas-Chavez, H.; Reyes-Carmona, F.; Jaramillo-Vigueras, D.

    2011-01-01

    Highlights: → PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. → During high-energy milling oxygen has to be chemically reduced from the lead oxide. → Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  4. Method of determining paper-deposited materials, eg. lead, by their reaction with radioactive krypton

    International Nuclear Information System (INIS)

    Tolgyessy, J.; Pruzinec, J.

    1976-01-01

    The invention claims a method of determining substances on a paper carrier based on the substance reaction with 85 Kr gas and the measurement of radioactivity of the kryptonate formed. Lead is shown as an example. Different amounts of lead acetate were deposited on Whatman 2 chromatographic paper as was an unknown sample of Pb salt. The paper was exposed to a 2.5 mCi 85 Kr atmosphere for 48 hours. The activity of the individual spots was then measured, a calibration curve established and the amount of lead in the analyzed sample read-out. (Ha)

  5. 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

  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. Evidence for leading mesons in anti p4He reactions at 0.6 GeV/c incident momentum

    International Nuclear Information System (INIS)

    Breivik, F.O.; Haatuft, A.; Halsteinslid, A.

    1990-05-01

    In a previous report, evidence has been shown for leading mesons in anti p Ne - reactions at 0.6 Gev/c incident momentum. In this report evidence is shown for leading mesons in anti p 4 He reactions at the same incident momentum, based on data from the same detector. In anti p Ne - reactions, only kaons are observed as leading mesons in K o s-events, and only pions are observed as leading mesons in Λ o -events. In anti p He - reactions this is not longer true, since also pions behave as leading mesons in K o s-events. 5 refs., 9 figs

  8. 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.

  9. 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.

  10. 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

  11. Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

    Energy Technology Data Exchange (ETDEWEB)

    Hafsteinsdottir, Erla G., E-mail: erla.hafsteinsdottir@gmail.com [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); White, Duanne A., E-mail: duanne.white@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Gore, Damian B., E-mail: damian.gore@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Stark, Scott C., E-mail: scott.stark@aad.gov.au [Environmental Protection and Change, Australian Antarctic Division, Department of Sustainability, Environment, Water, Population and Communities, Tasmania 7050 (Australia)

    2011-12-15

    Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H{sub 2}PO{sub 4}){sub 2}] or sodium phosphate [Na{sub 3}PO{sub 4}]) reacts with lead (PbSO{sub 4} or PbCl{sub 2}) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO{sub 4} and Na{sub 3}PO{sub 4} were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: > Formation of lead phosphate products in cold environments is identified. > Potential change in formation during freeze-thaw cycling is assessed. > Lead phosphate reaction efficiency varies according to phosphate and lead source. > Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

  12. Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

    International Nuclear Information System (INIS)

    Hafsteinsdottir, Erla G.; White, Duanne A.; Gore, Damian B.; Stark, Scott C.

    2011-01-01

    Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H 2 PO 4 ) 2 ] or sodium phosphate [Na 3 PO 4 ]) reacts with lead (PbSO 4 or PbCl 2 ) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO 4 and Na 3 PO 4 were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: → Formation of lead phosphate products in cold environments is identified. → Potential change in formation during freeze-thaw cycling is assessed. → Lead phosphate reaction efficiency varies according to phosphate and lead source. → Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

  13. Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Yun-Lin.

    1990-09-21

    The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

  14. 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

  15. Double Charged Surface Layers in Lead Halide Perovskite Crystals

    KAUST Repository

    Sarmah, Smritakshi P.

    2017-02-01

    Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

  16. 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.

  17. 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

  18. 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...

  19. 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.

  20. 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

  1. Determination of the shapes and sizes of the regions in which in hadron-nucleus collisions reactions leading to the nucleon emission, particle production, and fragment evaporation occur

    International Nuclear Information System (INIS)

    Strugalski, Z.

    1985-01-01

    Shapes and sizes of the regions in target-nuclei in which reactions leading to the nucleon emission, particle production and fragment evaporation occur are determined. The region of nucleon emission is of cylindrical shape, with the diameter as large as two nucleon diameters, centered on the incident hadron course. The reactions leading to the particle production happen predominantly along the incident hadron course in nuclear matter. The fragment evaporation goes from the surface layer of the part of the target-nucleus damaged in nucleon emission process

  2. 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.

  3. Pacing Lead-Induced Granuloma in the Atrium: A Foreign Body Reaction to Polyurethane

    Directory of Open Access Journals (Sweden)

    Shinagawa Yoko

    2013-01-01

    Full Text Available We described a case of an 82-year-old male who presented with a granuloma entrapping the polyurethane-coated pacing lead at the site of contact on the atrium. He had been paced for 8 years without symptoms or signs suggestive of an allergic reaction to the pacemaker system and died from thrombosis of the superior mesenteric artery and heart failure. A histological examination of the nodule showed an incidental granuloma with multinucleated giant cells. No granuloma was found in the heart or the lung.

  4. Asian industrial lead inputs to the North Pacific evidenced by lead concentrations and isotopic compositions in surface waters and aerosols.

    Science.gov (United States)

    Gallon, Céline; Ranville, Mara A; Conaway, Christopher H; Landing, William M; Buck, Clifton S; Morton, Peter L; Flegal, A Russell

    2011-12-01

    Recent trends of atmospheric lead deposition to the North Pacific were investigated with analyses of lead in aerosols and surface waters collected on the fourth Intergovernmental Oceanographic Commission Contaminant Baseline Survey from May to June, 2002. Lead concentrations of the aerosols varied by 2 orders of magnitude (0.1-26.4 pmol/m(3)) due in part to variations in dust deposition during the cruise. The ranges in lead aerosol enrichment factors relative to iron (1-119) and aluminum (3-168) were similar, evidencing the transport of Asian industrial lead aerosols across the North Pacific. The oceanic deposition of some of those aerosols was substantiated by the gradient of lead concentrations of North Pacific waters, which varied 3-fold (32.7-103.5 pmol/kg), were highest along with the Asian margin of the basin, and decreased eastward. The hypothesized predominance of Asian industrial lead inputs to the North Pacific was further corroborated by the lead isotopic composition of ocean surface waters ((206)Pb/(207)Pb = 1.157-1.169; (208)Pb/(206)Pb = 2.093-2.118), which fell within the range of isotopic ratios reported in Asian aerosols that are primarily attributed to Chinese industrial lead emissions.

  5. 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...

  6. 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

  7. 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

  8. Tunable surface plasmon instability leading to emission of radiation

    Energy Technology Data Exchange (ETDEWEB)

    Gumbs, Godfrey [Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States); Donostia International Physics Center (DIPC), P de Manuel Lardizabal, 4, 20018 San Sebastian, Basque Country (Spain); Iurov, Andrii, E-mail: aiurov@chtm.unm.edu [Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States); Center for High Technology Materials, University of New Mexico, Albuquerque, New Mexico 87106 (United States); Huang, Danhong [Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117 (United States); Pan, Wei [Sandia National Laboratory, Albuquerque, New Mexico 87185 (United States)

    2015-08-07

    We propose a new approach for energy conversion from a dc electric field to tunable terahertz emission based on hybrid semiconductors by combining two-dimensional (2D) crystalline layers and a thick conducting material with possible applications for chemical analysis, security scanning, medical (single-molecule) imaging, and telecommunications. The hybrid nano-structure may consist of a single or pair of sheets of graphene, silicene, or a 2D electron gas. When an electric current is passed through a 2D layer, we discover that two low-energy plasmon branches exhibit a characteristic loop in their dispersion before they merge into an unstable region beyond a critical wave vector q{sub c}. This finite q{sub c} gives rise to a wavenumber cutoff in the emission dispersion of the surface plasmon induced instability and emission of radiation (spiler). However, there is no instability for a single driven layer far from the conductor, and the instability of an isolated pair of 2D layers occurs without a wavenumber cutoff. The wavenumber cutoff is found to depend on the conductor electron density, layer separation, distances of layers from the conductor surface, and the driving-current strength.

  9. 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.

  10. 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.

  11. Interfacial Reaction of Sn-Ag-Cu Lead-Free Solder Alloy on Cu: A Review

    Directory of Open Access Journals (Sweden)

    Liu Mei Lee

    2013-01-01

    Full Text Available This paper reviews the function and importance of Sn-Ag-Cu solder alloys in electronics industry and the interfacial reaction of Sn-Ag-Cu/Cu solder joint at various solder forms and solder reflow conditions. The Sn-Ag-Cu solder alloys are examined in bulk and in thin film. It then examines the effect of soldering conditions to the formation of intermetallic compounds such as Cu substrate selection, structural phases, morphology evolution, the growth kinetics, temperature and time is also discussed. Sn-Ag-Cu lead-free solder alloys are the most promising candidate for the replacement of Sn-Pb solders in modern microelectronic technology. Sn-Ag-Cu solders could possibly be considered and adapted in miniaturization technologies. Therefore, this paper should be of great interest to a large selection of electronics interconnect materials, reliability, processes, and assembly community.

  12. 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

  13. 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)

  14. 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...

  15. 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....

  16. 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.

  17. Study on the properties of leading protons and antiprotons from exclusive anti pp reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskij, M.Yu.; Borovikov, A.A.; Boos, Eh.G.

    1986-01-01

    The leading properties of protons and antiprotons from the nondiffractive events are studied for p-barp-exclusive reactions at 32 GeV/c. It is found that the relative leading effect of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal moments of the leading hadrons are uncorrelated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another leading hadron. It is shown that these experimental facts are described well by a statistical jet-independent model but contradict the Lund string-fragmentation model

  18. New MCRs: The first 4-component reaction leading to 2,4-disubstituted thiazoles

    NARCIS (Netherlands)

    Kolb, Jürgen; Beck, Barbara; Almstetter, Michael; Heck, Stefan; Herdtweck, Eberhardt; Dömling, Alexander

    2003-01-01

    New organic reactions allow chemical transformations which were previously not possible. Therefore, new reactions are important contributions to the progress in the field of organic synthesis. In this series we describe the design, scope, and limitations of newly-discovered multi-component reactions

  19. 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.

  20. Photonuclear reactions in the GNASH code: Benchmarking model calculations for reactions on lead up to 140 MeV

    International Nuclear Information System (INIS)

    Chadwick, M.B.; Young, P.G.

    1994-08-01

    The authors have developed the GNASH code to include photonuclear reactions for incident energies up to 140 MeV. Photoabsorption is modeled through the giant resonance at the lower energies, and the quasideuteron mechanism at the higher energies, and the angular momentum coupling of the incident photon to the target is properly accounted for. After the initial interaction, primary and multiple preequilibrium emission of fast particles can occur before compound nucleus decay from the equilibrated compound nucleus. The angular distributions from compound nucleus decay are taken as isotropic, and those from preequilibrium emission (which they obtain from a phase-space model which conserves momentum) are forward-peaked. To test the new modeling they apply the code to calculate photonuclear reactions on 208 Pb for incident energies up to 140 MeV

  1. 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.

  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. 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 ...

  4. 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.

  5. 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...

  6. 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)

  7. 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....

  8. Corrosive microenvironments at lead solder surfaces arising from galvanic corrosion with copper pipe.

    Science.gov (United States)

    Nguyen, Caroline K; Stone, Kendall R; Dudi, Abhijeet; Edwards, Marc A

    2010-09-15

    As stagnant water contacts copper pipe and lead solder (simulated soldered joints), a corrosion cell is formed between the metals in solder (Pb, Sn) and the copper. If the resulting galvanic current exceeds about 2 μA/cm(2), a highly corrosive microenvironment can form at the solder surface, with pH chloride concentrations at least 11 times higher than bulk water levels. Waters with relatively high chloride tend to sustain high galvanic currents, preventing passivation of the solder surface, and contributing to lead contamination of potable water supplies. The total mass of lead corroded was consistent with predictions based on the galvanic current, and lead leaching to water was correlated with galvanic current. If the concentration of sulfate in the water increased relative to chloride, galvanic currents and associated lead contamination could be greatly reduced, and solder surfaces were readily passivated.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Skin and surface lead contamination, hygiene programs, and work practices of bridge surface preparation and painting contractors.

    Science.gov (United States)

    Virji, M Abbas; Woskie, Susan R; Pepper, Lewis D

    2009-02-01

    A 2005 regulatory review of the lead in construction standard by the Occupational Safety and Health Administration (OSHA) noted that alternative pathways of exposure can be as significant as inhalation exposure and that noncompliance with the standard pertaining to hygiene facilities and practices was the second most commonly violated section of the standard. Noncompliance with provisions of the standard and unhealthy work and hygiene practices likely increase the likelihood of take-home lead via contaminated clothing, automobiles, and skin, thus contributing to elevated blood lead levels (BLL) among construction workers and their family members. We performed a cross-sectional study of bridge painters working for small contractors in Massachusetts to investigate causes of persistent elevated BLLs and to assess lead exposures. Thirteen work sites were evaluated for a 2-week period during which surface and skin wipe samples were collected and qualitative information was obtained on personal hygiene practices, decontamination and hand wash facilities, and respiratory protection programs. Results showed lead contamination on workers' skin, respirators, personal automobiles, and the decontamination unit, indicating a significant potential for take-home lead exposure. Overall, the geometric mean (GM) skin lead levels ranged from 373 microg on workers' faces at end of shift to 814 microg on hands at break time. The overall GM lead level inside respirators was 143 microg before work and 286 microg after work. Lead contamination was also present inside workers' personal vehicles as well as on surfaces inside the clean side of the decontamination unit. Review of the respiratory protection programs, work site decontamination and hand wash facilities, and personal hygiene practices indicated that these factors had significant impact on skin and surface contamination levels and identified significant opportunities for improving work site facilities and personal practices

  14. Palladium-catalyzed three-component reaction of N-tosyl hydrazones, isonitriles and amines leading to amidines.

    Science.gov (United States)

    Dai, Qiang; Jiang, Yan; Yu, Jin-Tao; Cheng, Jiang

    2015-12-04

    A palladium-catalyzed three-component reaction between N-tosyl hydrazones, aryl isonitriles and amines was developed, leading to amidines in moderate to good yields. This procedure features the rapid construction of amidine frameworks with high diversity and complexity. Ketenimines serve as intermediates, which encounter nucleophilic attack by amines to produce amidines.

  15. 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

  16. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  17. 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

  18. 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 ...

  19. 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....

  20. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  1. Reaction 12C(16O,α)24Mg leading to nuclear molecular resonances

    International Nuclear Information System (INIS)

    Nagatani, K.; Shimoda, T.; Tanner, D.; Tribble, R.; Yamaya, T.

    1979-01-01

    The reactions 12 C( 16 O,α) 24 Mg and 13 C( 16 O,α) 25 Mg were investigated at an incident energy of 145 MeV. In the reaction with the 12 C target, broad peaks are observed at forward angles which correspond to the molecular resonance states of the 12 C+ 12 C system, while the spectra with 13 C target show only a smooth continuum

  2. 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.

  3. Blaming for a better future: future orientation and associated intolerance of personal uncertainty lead to harsher reactions toward innocent victims.

    Science.gov (United States)

    Bal, Michèlle; van den Bos, Kees

    2012-07-01

    People are often encouraged to focus on the future and strive for long-term goals. This noted, the authors argue that this future orientation is associated with intolerance of personal uncertainty, as people usually cannot be certain that their efforts will pay off. To be able to tolerate personal uncertainty, people adhere strongly to the belief in a just world, paradoxically resulting in harsher reactions toward innocent victims. In three experiments, the authors show that a future orientation indeed leads to more negative evaluations of an innocent victim (Study 1), enhances intolerance of personal uncertainty (Study 2), and that experiencing personal uncertainty leads to more negative evaluations of a victim (Study 3). So, while a future orientation enables people to strive for long-term goals, it also leads them to be harsher toward innocent victims. One underlying mechanism causing these reactions is intolerance of personal uncertainty, associated with a future orientation.

  4. Numerical investigation of mist/air impingement cooling on ribbed blade leading-edge surface.

    Science.gov (United States)

    Bian, Qingfei; Wang, Jin; Chen, Yi-Tung; Wang, Qiuwang; Zeng, Min

    2017-12-01

    The working gas turbine blades are exposed to the environment of high temperature, especially in the leading-edge region. The mist/air two-phase impingement cooling has been adopted to enhance the heat transfer on blade surfaces and investigate the leading-edge cooling effectiveness. An Euler-Lagrange particle tracking method is used to simulate the two-phase impingement cooling on the blade leading-edge. The mesh dependency test has been carried out and the numerical method is validated based on the available experimental data of mist/air cooling with jet impingement on a concave surface. The cooling effectiveness on three target surfaces is investigated, including the smooth and the ribbed surface with convex/concave columnar ribs. The results show that the cooling effectiveness of the mist/air two-phase flow is better than that of the single-phase flow. When the ribbed surfaces are used, the heat transfer enhancement is significant, the surface cooling effectiveness becomes higher and the convex ribbed surface presents a better performance. With the enhancement of the surface heat transfer, the pressure drop in the impingement zone increases, but the incremental factor of the flow friction is smaller than that of the heat transfer enhancement. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. 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.

  6. 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.

  7. Errors in Postural Preparation Lead to Increased Choice Reaction Times for Step Initiation in Older Adults

    Science.gov (United States)

    Nutt, John G.; Horak, Fay B.

    2011-01-01

    Background. This study asked whether older adults were more likely than younger adults to err in the initial direction of their anticipatory postural adjustment (APA) prior to a step (indicating a motor program error), whether initial motor program errors accounted for reaction time differences for step initiation, and whether initial motor program errors were linked to inhibitory failure. Methods. In a stepping task with choice reaction time and simple reaction time conditions, we measured forces under the feet to quantify APA onset and step latency and we used body kinematics to quantify forward movement of center of mass and length of first step. Results. Trials with APA errors were almost three times as common for older adults as for younger adults, and they were nine times more likely in choice reaction time trials than in simple reaction time trials. In trials with APA errors, step latency was delayed, correlation between APA onset and step latency was diminished, and forward motion of the center of mass prior to the step was increased. Participants with more APA errors tended to have worse Stroop interference scores, regardless of age. Conclusions. The results support the hypothesis that findings of slow choice reaction time step initiation in older adults are attributable to inclusion of trials with incorrect initial motor preparation and that these errors are caused by deficits in response inhibition. By extension, the results also suggest that mixing of trials with correct and incorrect initial motor preparation might explain apparent choice reaction time slowing with age in upper limb tasks. PMID:21498431

  8. Some studies of lead and iron adsorption on the W(100) surface by field emission microscopy

    International Nuclear Information System (INIS)

    Jones, J.P.; Roberts, E.W.

    1978-01-01

    The behaviour of lead and iron adsorbed on the W(100) surface has been studied by probe hole field emission microscopy, field desorption, and by measurement of the total energy distribution (TED) of field-emitted electrons. Lead adsorbed at 300 K which reduces the work function of W(100) can be completely removed at 78 K by field desorption below 3.2 V A -1 and the resulting surface has both the work function and TED, which are characteristic of the clean plane. Condensation at 800 K followed by field desorption, results in a plane surface of work function 4.17 eV and an altered TED. This effect is attributed to the microfacetting, which is observed by LEED. The Swanson peak in the W(100) TED which is removed by submonolayer amounts of lead re-emerges at monolayer coverage when lead adopts the (1 X 1) structure. Such behaviour is consistent with the model proposed by Kar and Soven. A spectral peak observed when lead is adsorbed on the reconstructed W(100) surface is thought to derive for the atomic 1 D state. Adsorption of iron on a W(100) surface reduces phi considerably due to dipole formation and efficiently quenches the Swanson peak. (Auth.)

  9. PHYSIOLOGICAL REACTION OF COMMON OSIER (SALIX VIMINIALIS L. VAR. JORR TO THE PRESENCE OF LEAD IN THE SUBSOIL

    Directory of Open Access Journals (Sweden)

    Katarzyna Malinowska

    2015-02-01

    Full Text Available The effect of lead ions of the concentrations within the range of 15–1000 mg∙dm-3 on the physiological reaction of common osier var. Jorr was examined. The content of assimilation pigments, the rate the CO2 assimilation, transpiration, the indices of relative water content and the deficit of water saturation and the content of lead in the nutrient solution. The studied physiological parameters in common osier var. Jorr were differentiated by the rate of lead ions in the nutrient solution. The Jorr variety of common osier was characterised by good values of the determined physiological parameters under stressful conditions at a large accumulation of lead. This suggests that it shows quite a high tolerance to the stress caused by contamination of the subsoil with lead.

  10. Dosimetric perturbations of a lead shield for surface and interstitial high-dose-rate brachytherapy

    International Nuclear Information System (INIS)

    Candela-Juan, Cristian; Granero, Domingo; Vijande, Javier; Ballester, Facundo; Perez-Calatayud, Jose; Rivard, Mark J

    2014-01-01

    In surface and interstitial high-dose-rate brachytherapy with either 60 Co, 192 Ir, or 169 Yb sources, some radiosensitive organs near the surface may be exposed to high absorbed doses. This may be reduced by covering the implants with a lead shield on the body surface, which results in dosimetric perturbations. Monte Carlo simulations in Geant4 were performed for the three radionuclides placed at a single dwell position. Four different shield thicknesses (0, 3, 6, and 10 mm) and three different source depths (0, 5, and 10 mm) in water were considered, with the lead shield placed at the phantom surface. Backscatter dose enhancement and transmission data were obtained for the lead shields. Results were corrected to account for a realistic clinical case with multiple dwell positions. The range of the high backscatter dose enhancement in water is 3 mm for 60 Co and 1 mm for both 192 Ir and 169 Yb. Transmission data for 60 Co and 192 Ir are smaller than those reported by Papagiannis et al (2008 Med. Phys. 35 4898–4906) for brachytherapy facility shielding; for 169 Yb, the difference is negligible. In conclusion, the backscatter overdose produced by the lead shield can be avoided by just adding a few millimetres of bolus. Transmission data provided in this work as a function of lead thickness can be used to estimate healthy organ equivalent dose saving. Use of a lead shield is justified. (paper)

  11. 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.

  12. 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

  13. Coral-based history of lead and lead isotopes of the surface Indian Ocean since the mid-20th century

    Science.gov (United States)

    Lee, Jong-Mi; Boyle, Edward A.; Suci Nurhati, Intan; Pfeiffer, Miriam; Meltzner, Aron J.; Suwargadi, Bambang

    2014-07-01

    Anthropogenic lead (Pb) from industrial activities has greatly altered the distribution of Pb in the present-day oceans, but no continuous temporal Pb evolution record is available for the Indian Ocean despite rapidly emerging industries around the region. Here, we present the coral-inferred annual history of Pb concentration and isotope ratios in the surface Indian Ocean since the mid-20th century (1945-2010). We analyzed Pb in corals from the Chagos Archipelago, western Sumatra and Strait of Singapore - which represent the central Indian Ocean via nearshore sites. Overall, coral Pb/Ca increased in the mid-1970s at all the sites. However, coral Pb isotope ratios evolve distinctively at each site, suggesting Pb contamination arises from different sources in each case. The major source of Pb in the Chagos coral appears to be India's Pb emission from leaded gasoline combustion and coal burning, whereas Pb in western Sumatra seems to be largely affected by Indonesia's gasoline Pb emission with additional Pb inputs from other sources. Pb in the Strait of Singapore has complex sources and its isotopic composition does not reflect Pb from leaded gasoline combustion. Higher 206Pb/207Pb and 208Pb/207Pb ratios found at this site may reflect the contribution of Pb from coals and ores from southern China, Indonesia, and Australia, and local Pb sources in the Strait of Singapore. It is also possible that the Pb isotope ratios of Singapore seawater were elevated through isotope exchange with natural fluvial particles considering its delta setting.

  14. 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.

  15. 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)

  16. A facile and expedient one-pot three-component reaction leading to ...

    Indian Academy of Sciences (India)

    A three-component reaction between triphenylphosphine, a dialkyl acetylenedicarboxylate and phthalazin-1(2H)-ones that affords novel organic phosphorane derivatives in good to excellent yields is reported. FTIR, 1H, 13C and 31P NMR and elemental analyses have been utilized to characterize the synthesized ...

  17. Atomization of magnesium, strontium, barium and lead nitrates on surface of graphite atomizers

    International Nuclear Information System (INIS)

    Nagdaev, V.K.; Pupyshev, A.A.

    1982-01-01

    Modelling of the processes on graphite surface using differential-thermal analysis and graphite core with identification of decomposition products of magnesium, strontium, barium and lead nitrates by X-ray analysis has shown that carbon promotes the formation of strontium, barium and lead carbonates. The obtained temperatures of strontium and barium carbonate decomposition to oxides agree satisfactorily with calculation ones. Magnesium nitrate does not react with carbon. Formation of strontium and barium carbonates results in considerable slowing down of the process of gaseous oxide dissociation. Lead carbonate is unstable and rapidly decomposes to oxide with subsequent reduction to free metal. Formation of magnesium, strontium and barium free atoms is connected with appearance of gaseous oxides in analytical zone. Oxide and free metal lead are present on graphite surface simultaneously

  18. Surface characterization of a corroded bronze-leaded alloy in a salt spray cabinet

    International Nuclear Information System (INIS)

    Cura D'Ars de Figueiredo Junior, Joao; Freitas Cunha Lins, Vanessa de; Bellis, Vito Modesto de

    2007-01-01

    The corrosion products of a TM 23 bronze-leaded alloy (Cu 72%, Pb 15%, Zn 8% and Sn 5%) were obtained in a salt spray cabinet after exposition during 120 h and 1000 h. The products obtained were studied using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. The major products of bronze-leaded corrosion were oxides and basic salts of Cu, CuCl 2 .3Cu(OH) 2 , and Pb, Pb(OH)Cl. The results can be attributed to a kinetic control of the corrosion reactions

  19. Lead extraction from waste funnel cathode-ray tubes glasses by reaction with silicon carbide and titanium nitride

    International Nuclear Information System (INIS)

    Yot, Pascal G.; Mear, Francois O.

    2009-01-01

    As a possibility to clean waste CRT glass, treatment of lead-containing glass with a reducing agent, SiC or TiN, leads to a porous material containing metallic lead, Pb(0), located on the surface of the pore, and unreduced lead, Pb(II). The influences of reducing agent content, of the time, and at last of the temperature on lead reduction were analysed. Our investigations have pointed out significant differences as a function of the used reducing agent. CRT glass heat treated with SiC lead to less Pb(0), compared to TiN as shown by X-ray diffraction, and differential scanning calorimetry (DSC). It has been also evidenced that lead reduction occurs on randomized zones inside the sample leading to macroscopic lead beads inside glassy samples. XPS and XAS measurements were also carried out to investigate the local structure of lead and have evidenced a change of role of lead inside the glassy framework in function of the used conditions.

  20. Lessons learned from surface wipe sampling for lead in three workplaces.

    Science.gov (United States)

    Beaucham, Catherine; Ceballos, Diana; King, Bradley

    2017-08-01

    Surface wipe sampling in the occupational environment is a technique widely used by industrial hygienists. Although several organizations have promulgated standards for sampling lead and other metals, uncertainty still exists when trying to determine an appropriate wipe sampling strategy and how to interpret sampling results. Investigators from the National Institute for Occupational Safety and Health (NIOSH) Health Hazard Evaluation Program have used surface wipe sampling as part of their exposure assessment sampling strategies in a wide range of workplaces. This article discusses wipe sampling for measuring lead on surfaces in three facilities: (1) a battery recycling facility; (2) a firing range and gun store; and (3) an electronic scrap recycling facility. We summarize our findings from the facilities and what we learned by integrating wipe sampling into our sampling plan. Wiping sampling demonstrated lead in non-production surfaces in all three workplaces and that the potential that employees were taking lead home to their families existed. We also found that the presence of metals such as tin can interfere with the colorimetric results. We also discuss the advantages and disadvantages of colorimetric analysis of surface wipe samples and the challenges we faced when interpreting wipe sampling results.

  1. 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.

  2. Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu, E-mail: lis@atm.neu.edu.cn

    2014-10-30

    Graphical abstract: - Highlights: • A uniform MnO{sub 2} layer was anchored onto diatomite surface. • Kinetics and isotherms over MnO{sub 2} modified diatomite were studied. • The Pb(II) adsorption is based on ion-exchange mechanism. - Abstract: A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO{sub 2} is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO{sub 2} was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO{sub 2} modification increased more than six times. And the adsorption of Pb{sup 2+} on the MnO{sub 2} surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

  3. 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

  4. Dissipative effects in fission investigated with proton-on-lead reactions

    Directory of Open Access Journals (Sweden)

    Rodríguez-Sánchez J. L.

    2016-01-01

    Full Text Available The complete kinematic measurement of the two fission fragments permitted us to investigate dissipative effects at large deformations, between the saddle-point and the corresponding scission configurations. Up to now, this kind of study has only been performed with fusionfission reactions using a limited number of observables, such as the mass distribution of the fission fragments or the neutron multiplicities. However, the large angular momenta gained by the compound nucleus could affect the conclusions drawn from such experiments. In this work, the use of spallation reactions, where the fissioning systems are produced with low angular momentum, small deformations and high excitation energies, favors the study of dissipation, and allowed us to define new observables, such as postscission neutron multiplicities and the neutron excess of the final fission fragments as a function of the atomic number of the fissioning system. These new observables are used to investigate the dissipation at large deformations.

  5. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  6. High spin states excited by the (p, t) reaction on lead isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kumabe, I.; Hyakutake, M. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Yuasa, K.; Yamagata, T.; Kishimoto, S.; Ikegami, H.; Muraoka, M [eds.

    1980-01-01

    In order to find high spin states the sup(204, 206, 208)Pb (p, t) reactions have been investigated with RCNP isochronous cyclotron and a high resolution magnetic spectrograph ''RAIDEN''. The experimental angular distributions were analyzed by DWBA calculations, and the lowest 10/sup +/, 12/sup +/ (i sub(13/2))/sup 2/ and 11/sup -/ (i sub(13/2), h sub(9/2)) states in /sup 202/Pb, /sup 204/Pb and /sup 206/Pb were established.

  7. Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels.

    Science.gov (United States)

    Vigier-Carrière, Cécile; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loïc

    2018-02-05

    Localized molecular self-assembly processes leading to the growth of nanostructures exclusively from the surface of a material is one of the great challenges in surface chemistry. In the last decade, several works have been reported on the ability of modified or unmodified surfaces to manage the self-assembly of low-molecular-weight hydrogelators (LMWH) resulting in localized supramolecular hydrogel coatings mainly based on nanofiber architectures. This Minireview highlights all strategies that have emerged recently to initiate and localize LMWH supramolecular hydrogel formation, their related fundamental issues and applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  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. Cross sections of (p, xn) reactions in the isotopes of lead and bismuth

    Energy Technology Data Exchange (ETDEWEB)

    Bell, R E [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Skarsgard, H M [Atomic Energy Research Establishment, Reactor Research Div., Harwell (United Kingdom)

    1956-07-01

    Measurements have been made by the activation method of cross sections of (p, xn) reactions in Bi{sup 209}, Pb{sup 206}, Pb{sup 207}, and Pb{sup 208}. The present results cover x = 3 to 7 in Bi{sup 209}, 2 to 6 in Pb{sup 206}, 2 to 4 in Pb{sup 207}, and 3 and 4 in Pb{sup 208}, over a total proton energy range from 12 to 85 Mev. The absolute accuracy is about 15%. Each cross section plotted as a function of proton energy rises above its threshold to a peak whose height is of the order of one barn, and then falls again to a low and fairly constant value. The results from x = 3 to 7 are consistent with a compound nucleus plus prompt nucleon-nucleon cascade model using reasonable nuclear parameters, but the experimental (p, 2n) cross section appears to be almost double the value so predicted. Since (p, xn) reactions are dominant in the energy range 10 to 40 Mev., their sum approximates the total reaction cross section; the experimental sum fluctuates around the smooth curve computed for the compound nucleus model with r{sub 0} = 1.3 X 10{sup -13} cm. The fluctuations are similar to, but more marked than, those in the total neutron cross section of heavy elements in the same energy range. A more detailed theoretical discussion of these results is given by Jackson in the paper immediately following. (author)

  11. 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.

  12. 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.

  13. 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.

  14. The reaction of Lupinus angustifolius L. root meristematic cell nucleoli to lead.

    Science.gov (United States)

    Balcerzak, Lucja; Glińska, Sława; Godlewski, Mirosław

    2011-04-01

    The effect of 2-48 h treatment of Lupinus angustifolius L. roots with lead nitrate at the concentration of 10(-4) M on the nucleoli in meristematic cells was investigated. In the lead presence the number of ring-shaped as well as segregated nucleoli increased especially after 12-48 h of treatment, while spindle-shaped nucleoli appeared after 24 h and 48 h. Lead presence also increased the frequency of cells with silver-stained particles in the nucleus and the number of these particles especially from the 12th hour of treatment. It was accompanied by significant decline of nucleolar area. Analysis of these cells in transmission electron microscope confirmed the presence of ring-shaped and segregated nucleoli. Moreover, electron microscopy revealed compact structure nucleoli without granular component. Additionally, one to three oval-shaped fibrillar structures attached to nucleolus or lying free in the nucleoplasm were visible. The possible mechanism of lead toxicity to the nucleolus is briefly discussed.

  15. Reaction of winter oilseed rape varieties to elevated concentrations of lead

    Directory of Open Access Journals (Sweden)

    Oreščanin Bojana

    2012-01-01

    Full Text Available Remediation methods allow the removal of metals from contaminated soil, and phytoremediation a technology for cleaning contaminated soil and waste material by plants, is becoming increasingly used. Brassica napus L., as one of the main oilcrops and high-biomass producing species, is becoming more and more interesting for the use in phytoextraction as it is proved to be tolerant to higher concentrations of heavy metals. The aim of this study was to examine the specific responses of three commercial winter rapeseed varieties, Banaćanka, Slavica and Kata, to the increased concentrations of lead in vitro. Significant reduction in root length of plants treated with lead was observed only in the variety Slavica, indicating susceptibility of this variety to the increased concentrations of this heavy metal. As in variety Kata a significant reduction in the length of the above-ground part due to the treatment with lead was detected, it could be concluded that the variety Banaćanka is the most tolerant to the applied concentrations of lead since there were no significant changes in the growth and biomass accumulation in all treatments except one, and could be recommended for further use in phytoremediation studies. [Projekat Ministarstva nauke Republike Srbije, br. TR31025 i br. III43007

  16. 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.

  17. 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

  18. Production of He-, Ne-, Ar-, Kr-, and Xe-isotopes by proton-induced reactions on lead

    International Nuclear Information System (INIS)

    Leya, I.; Michel, R.

    2003-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr-, and Xe-isotopes from lead from the respective reaction thresholds up to 2.6 GeV. The production of noble gas isotopes in lead by proton-induced reactions is of special importance for design studies of accelerator driven systems and energy amplifiers. In order to minimise the influences of secondary particles on the production of residual nuclides a new Mini-Stack approach was used instead of the well-known stacked-foil techniques for all experiments with proton energies above 200 MeV. With some exceptions our database for the proton-induced production of noble gas isotopes from lead is consistent and nearly complete. In contradistinction to the production of He from Al and Fe, where the cross sections obtained by thin-target irradiation experiments are up to a factor of 2 higher than the NESSI data, both datasets agree for the He production from lead. (orig.)

  19. Negative plate macropore surfaces in lead-acid batteries: Porosity, Brunauer-Emmett-Teller area, and capacity

    Energy Technology Data Exchange (ETDEWEB)

    D' Alkaine, C.V.; de O. Brito, G.A. [Group of Electrochemistry and Polymers, DQ-UFSCar, Rodovia Washington Luis, Km 235, CP 676, 13565-905 Sao Carlos (SP) (Brazil)

    2009-06-01

    We propose an explanation for the production of an electrochemically active area during the electrochemical formation of lead-acid battery negative plates based on solid-state reactions. Our proposal is supported by experimental data. This study includes a critical review of the literature on charge/discharge mechanisms, porosity, and BET area. The critical review, through the latter two parameters, indicates the existence of both macro and micropores in positive plates, but only macropores in negative plates, with characteristic surface roughness. In the present paper the surface sulfation of the precursor is controlled using various acidic, neutral and alkaline solutions during an electrochemical formation process that does not include soaking. Our results confirm that variable roughness can be produced at the negative plate macropore surfaces. The morphological changes produced by different formation conditions are assessed by measuring the macroporosity, BET area, and capacity of single negative plates. Based on these concepts, a method was developed and applied to measure independently the contributions of geometrical surface macroporosity and roughness to the negative plate capacity. (author)

  20. 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

  1. Surface Electronic Structure of Hybrid Organo Lead Bromide Perovskite Single Crystals

    KAUST Repository

    Komesu, Takashi

    2016-08-24

    The electronic structure and band dispersion of methylammonium lead bromide, CH3NH3PbBr3, has been investigated through a combination of angle-resolved photoemission spectroscopy (ARPES) and inverse photoemission spectroscopy (IPES), as well as theoretical modeling based on density functional theory. The experimental band structures are consistent with the density functional calculations. The results demonstrate the presence of a dispersive valence band in MAPbBr3 that peaks at the M point of the surface Brillouin zone. The results also indicate that the surface termination of the CH3NH3PbBr3 is the methylammonium bromide (CH3NH3Br) layer. We find our results support models that predict a heavier hole effective mass in the region of -0.23 to -0.26 me, along the Γ (surface Brillouin center) to M point of the surface Brillouin zone. The surface appears to be n-type as a result of an excess of lead in the surface region. © 2016 American Chemical Society.

  2. Effects of reaction conditions on the emission behaviors of arsenic, cadmium and lead during sewage sludge pyrolysis.

    Science.gov (United States)

    Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun

    2017-07-01

    Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. 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.

  4. 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.)

  5. In situ X-ray diffraction study of the electrochemical reaction on lead electrodes in sulphate electrolytes

    International Nuclear Information System (INIS)

    Angerer, P.; Mann, R.; Gavrilovic, A.; Nauer, G.E.

    2009-01-01

    The anodic oxidation of pure lead in two acidic sulphate electrolytes with identical ionic strength (pH ∼ 0 and pH ∼ -0.1) was studied by in situ grazing incidence X-ray diffraction method (GIXD). Crystalline products such as lead sulphate (anglesite, PbSO 4 , orthorhombic), α- and β-lead dioxide (α-PbO 2 , orthorhombic, and β-PbO 2 , tetragonal), and tribasic lead sulphate hydrate with the stoichiometric composition 3PbO.PbSO 4 .H 2 O (triclinic) were detected at defined potentials. A method for the semi-quantitative determination of the thickness of the deposited layer from diffraction data is described. After the in situ measurement, the washed and dried working electrodes were additionally characterized ex situ by GIXD measurements at different angles of incidence. The phase litharge (lead oxide, t-PbO, tetragonal) and lead sulphate were observed at the surface of the lead substrate. The quantitative evaluation of the diffraction intensity of this measurement series enables the modelling of a qualitative depth profile of the layer generated during the electrochemical treatment. The anglesite phase is located in the uppermost layer, while the litharge phase was detected closer to the lead substrate

  6. 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.

  7. 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.

  8. Reversible surface binding of cadmium and lead by lactic acid and bifidobacteria.

    Science.gov (United States)

    Teemu, Halttunen; Seppo, Salminen; Jussi, Meriluoto; Raija, Tahvonen; Kalle, Lertola

    2008-07-15

    Extensive cadmium and lead contamination of water has been reported to occur locally as a result of human activities. Lactic acid bacteria have been reported to remove cadmium and lead from water. The aim of this work was to clarify the mechanisms of cadmium and lead removal from water. In addition, the effect of other metals, reversibility of binding and recyclability of the biomass was assessed. Based on our earlier data, the two most promising lactic acid bacteria, Lactobacillus fermentum ME3 and Bifidobacterium longum 46, were selected for these experiments. The results showed that the presence of other cationic metals and blocking of carboxyl and phosphoryl groups reduced cadmium and lead removal. These results suggest involvement of electrostatic interactions in cadmium and lead removal, and support our earlier findings. Transmission electron micrographs showed large deposits of lead on the bacterial surface suggesting formation of metallic lead precipitates. Both cadmium and lead removal were reversible processes established by full recovery of removed metal after desorption with dilute solutions of EDTA and HNO(3). Resorption capacity of both biomasses tested was reduced after regeneration with 10 mM EDTA and 15 mM HNO(3). Taken together, the results suggest involvement of several reversible mechanisms such as ion exchange and precipitation in cadmium and lead binding by lactic acid bacteria. The results show that specific lactic acid bacteria have the potential for removal of cadmium and lead from water although reduction in resorption capacity after regeneration of the biomass may form a problem. Since the studies so far have mainly focused on removal of single metals from pure water, metal removal in conditions of natural waters should be assessed in further experiments.

  9. 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.

  10. Sleep restriction may lead to disruption in physiological attention and reaction time

    Directory of Open Access Journals (Sweden)

    Arbind Kumar Choudhary

    2016-07-01

    Full Text Available Sleepiness is the condition where for some reason fails to go into a sleep state and will have difficulty in remaining awake even while carrying out activities. Sleep restriction occurs when an individual fails to get enough sleep due to high work demands. The mechanism between sleep restriction and underlying brain physiology deficits is not well assumed. The objective of the present study was to investigate the mental attention (P300 and reaction time [visual (VRT and auditory (ART] among night watchmen, at subsequent; first (1st day, fourth (4th day and seventh (7th day of restricted sleep period. After exclusion and inclusion criteria, the study was performed among 50 watchmen (age=18–35 years (n=50 after providing written informed consent and divided into two group. Group I-(Normal sleep (n=28 working in day time and used to have normal sleep in night (≥8 h; Group II-(Restricted sleep (n=22 - working in night time and used to have less sleep in night (≤3 h. Statistical significance between the different groups was determined by the independent student ʻtʼ test and the significance level was fixed at p≤0.05. We observed that among all normal and restricted sleep watchmen there was not any significant variation in Karolinska Sleepiness Scale (KSS score, VRT and ART, along with latency and amplitude of P300 on 1st day of restricted sleep. However at subsequent on 4th day and 7th day of restricted sleep, there was significant increase in (KSSscore, and prolongation of VRT and ART as well as alteration in latency and amplitude of P300 wave in restricted sleep watchmen when compare to normal sleep watchmen. The present finding concludes that loss of sleep has major impact in dynamic change in mental attention and reaction time among watchmen employed in night shift. Professional regulations and work schedules should integrate sleep schedules before and during the work period as an essential dimension for their healthy life.

  11. Sleep restriction may lead to disruption in physiological attention and reaction time.

    Science.gov (United States)

    Choudhary, Arbind Kumar; Kishanrao, Sadawarte Sahebrao; Dadarao Dhanvijay, Anup Kumar; Alam, Tanwir

    2016-01-01

    Sleepiness is the condition where for some reason fails to go into a sleep state and will have difficulty in remaining awake even while carrying out activities. Sleep restriction occurs when an individual fails to get enough sleep due to high work demands. The mechanism between sleep restriction and underlying brain physiology deficits is not well assumed. The objective of the present study was to investigate the mental attention (P300) and reaction time [visual (VRT) and auditory (ART)] among night watchmen, at subsequent; first (1st) day, fourth (4th) day and seventh (7th) day of restricted sleep period. After exclusion and inclusion criteria, the study was performed among 50 watchmen (age=18-35 years) (n=50) after providing written informed consent and divided into two group. Group I-(Normal sleep) (n=28) working in day time and used to have normal sleep in night (≥8 h); Group II-(Restricted sleep) (n=22) - working in night time and used to have less sleep in night (≤3 h). Statistical significance between the different groups was determined by the independent student ' t ' test and the significance level was fixed at p≤0.05. We observed that among all normal and restricted sleep watchmen there was not any significant variation in Karolinska Sleepiness Scale (KSS) score, VRT and ART, along with latency and amplitude of P300 on 1st day of restricted sleep. However at subsequent on 4th day and 7th day of restricted sleep, there was significant increase in (KSS)score, and prolongation of VRT and ART as well as alteration in latency and amplitude of P300 wave in restricted sleep watchmen when compare to normal sleep watchmen. The present finding concludes that loss of sleep has major impact in dynamic change in mental attention and reaction time among watchmen employed in night shift. Professional regulations and work schedules should integrate sleep schedules before and during the work period as an essential dimension for their healthy life.

  12. Screening hydroxyapatite for cadmium and lead immobilization in aqueous solution and contaminated soil: The role of surface area.

    Science.gov (United States)

    Li, Hongying; Guo, Xisheng; Ye, Xinxin

    2017-02-01

    Hydroxyapatite (HAP) has been widely used to immobilize many cationic metals in water and soils. The specific reason why an increase in the surface area of HAP enhances cadmium (Cd) uptake, but has no effect on lead (Pb) uptake, is not clear. The aim of this study was to determine the factors causing the differences in sorption behavior between Cd and Pb by evaluating HAPs with different surface areas. We synthesized HAPs with two different surface areas, which were characterized by X-ray diffraction, N 2 adsorption, and scanning electron microscopy, and then evaluated them as sorbents for Cd and Pb removal by testing in single and binary systems. The sorption capacity of large surface area HAP (1.85mmol/g) for Cd in the single-metal system was higher than that of small surface area HAP (0.64mmol/g), but there were no differences between single- and binary-metal solutions containing Pb. After the Cd experiments, the HAP retained a stable structure and intact morphology, which promotes the accessibility of reactive sites for Cd. However, a newly formed precipitate covered the surface and blocked the channels in the presence of Pb, which reduced the number of potential adsorption sites on HAP for Cd and Pb. Remediation experiments using Cd- and Pb-contaminated soil produced similar results to the solution tests. These results indicate that alterations of the structure and morphology during the reaction is an important factor influencing metal sorption to HAP. Copyright © 2016. Published by Elsevier B.V.

  13. A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

    Science.gov (United States)

    Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

    2015-04-30

    Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

  14. A chemometric method to identify enzymatic reactions leading to the transition from glycolytic oscillations to waves

    Science.gov (United States)

    Zimányi, László; Khoroshyy, Petro; Mair, Thomas

    2010-06-01

    In the present work we demonstrate that FTIR-spectroscopy is a powerful tool for the time resolved and noninvasive measurement of multi-substrate/product interactions in complex metabolic networks as exemplified by the oscillating glycolysis in a yeast extract. Based on a spectral library constructed from the pure glycolytic intermediates, chemometric analysis of the complex spectra allowed us the identification of many of these intermediates. Singular value decomposition and multiple level wavelet decomposition were used to separate drifting substances from oscillating ones. This enabled us to identify slow and fast variables of glycolytic oscillations. Most importantly, we can attribute a qualitative change in the positive feedback regulation of the autocatalytic reaction to the transition from homogeneous oscillations to travelling waves. During the oscillatory phase the enzyme phosphofructokinase is mainly activated by its own product ADP, whereas the transition to waves is accompanied with a shift of the positive feedback from ADP to AMP. This indicates that the overall energetic state of the yeast extract determines the transition between spatially homogeneous oscillations and travelling waves.

  15. Dimensional and Compositional Change of 1D Chalcogen Nanostructures Leading to Tunable Localized Surface Plasmon Resonances.

    Science.gov (United States)

    Min, Yuho; Seo, Ho Jun; Choi, Jong-Jin; Hahn, Byung-Dong; Moon, Geon Dae

    2018-05-31

    As the oxygen family, chalcogen (Se, Te) nanostructures have been considered important elements for various practical fields and further exploited to constitute metal chalcogenides for each targeted application. Here we report a controlled synthesis of well-defined one-dimensional chalcogen nanostructures such as nanowries, nanorods, and nanotubes by controlling reduction reaction rate to fine-tune the dimension and composition of the products. Tunable optical properties (localized surface plasmon resonances) of these chalcogen nanostructures are observed depending on their morphological, dimensional, and compositional variation. © 2018 IOP Publishing Ltd.

  16. Effect of surface oxide on the melting behavior of lead-free solder nanowires and nanorods

    International Nuclear Information System (INIS)

    Gao Fan; Rajathurai, Karunaharan; Cui, Qingzhou; Zhou, Guangwen; NkengforAcha, Irene; Gu Zhiyong

    2012-01-01

    Lead-free nanosolders have shown promise in nanowire and nanoelectronics assembly. Among various important parameters, melting is the most fundamental property affecting the assembly process. Here we report that the melting behavior of tin and tin/silver nanowires and nanorods can be significantly affected by the surface oxide of nanosolders. By controlling the nanosolder reflow atmosphere using a flux, the surface oxide of the nanowires/nanorods can be effectively removed and complete nanosolder melting can be achieved. The complete melting of the nanosolders leads to the formation of nanoscale to microscale spherical solder balls, followed by Ostwald ripening phenomenon. The contact angle of the microscale solder balls formed on Si substrate was measured by direct electron microscopic imaging. These results provide new insights into micro- and nanoscale phase transition and liquid droplet coalescence from nanowires/nanorods to spheroids, and are relevant to nanoscale assembly and smaller ball grid array formation.

  17. Influence of surface effects on the performance of lead-niobium-germanate optical waveguides

    International Nuclear Information System (INIS)

    Munoz-Martin, D.; Gonzalo, J.; Fernandez-Navarro, J.M.; Siegel, J.; Afonso, C.N.

    2007-01-01

    Lead-niobium-germanate planar waveguides have been produced by pulsed laser deposition. The composition of the waveguides is found to be relatively weakly dependent on the laser fluence, while their surface morphology is affected dramatically. Smooth surfaces are obtained for a narrow fluence range centered at 2.0 J/cm 2 , while particulates having typical diameters of 2 , which is close to the value of the bulk glass, and remains constant at higher fluences. Propagation losses show instead a minimum (∼6.5 dB/cm) at 2.0 J/cm 2 . The characteristics of the ablation process that leads to the ejection of solid particulates or molten droplets as well as the increase of the waveguides density on increasing the fluence are discussed to be responsible for the observed optical behavior

  18. Lead-free, bronze-based surface layers for wear resistance in axial piston hydraulic pumps

    Energy Technology Data Exchange (ETDEWEB)

    Vetterick, Gregory Alan [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    Concerns regarding the safety of lead have provided sufficient motivation to develop substitute materials for the surface layer on a thrust bearing type component known as a valve plate in axial piston hydraulic pumps that consists of 10% tin, 10% lead, and remainder cooper (in wt. %). A recently developed replacement material, a Cu-10Sn-3Bi (wt.%) P/M bronze, was found to be unsuitable as valve plate surface layer, requiring the development of a new alloy. A comparison of the Cu-1-Sn-10Pb and Cu-10Sn-3Bi powder metal valve plates showed that the differences in wear behavior between the two alloys arose due to the soft phase bismuth in the alloy that is known to cause both solid and liquid metal embrittlement of copper alloys.

  19. 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.

  20. 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

  1. Stabilizing lead bullets in shooting range soil by phosphate-based surface coating

    Directory of Open Access Journals (Sweden)

    Bin Hua

    2016-08-01

    Full Text Available Soil lead (Pb is well known as a threat to human health and ecosystem. Although relatively insoluble, lead bullets in shooting range soil can be readily released into soluble forms through natural weathering processes and thus pose significant human and environmental risks. In this study, laboratory experiments were conducted to investigate if the Pb bullets in shooting range soil can be stabilized through surface coating of phosphate-based materials. Results indicated that FePO4 or AlPO4 coatings, insoluble metal phosphates, have been successfully formed on the surface of the Pb bullets. The EPA Toxicity Characteristic Leaching Procedure (TCLP test showed that FePO4 or AlPO4 surface coating would effectively reduce the Pb solubility or leachability of the bullets. The surface coating under pH of <5.5 for 7 days could achieve 92–100% reduction, with 85–98% by FePO4 coating and 77–98% by AlPO4 coating as compared with the non-coating. Leachable Pb concentration in the contaminated shooting range soil was reduced by 85–98% or 77–98% as a result of the FePO4 or AlPO4 solution treatment. This study demonstrated that the FePO4 or AlPO4–based surface coating on lead bullets can effectively inhibit the Pb weathering and significantly reduce the Pb release from soil through in situ chemical stabilization, which could be potentially applicable as a cost-effective and environmental-sound technology for the remediation of Pb-contaminated shooting range soil.

  2. 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....

  3. Partial strands synthesizing leads to inevitable aborting and complicated products in consecutive polymerase chain reactions (PCRs)

    Institute of Scientific and Technical Information of China (English)

    LUO Rui; ZHANG DaMing

    2007-01-01

    Various abnormal phenomena have been observed during PCR so far. The present study performed a series of consecutive PCRs (including many rounds of re-amplification continuously) and found that the abortion of re-amplification was inevitable as long as a variety of complicated product appeared.The aborting stages varied, according to the lengths of targets. Longer targets reached the abortion earlier than the shorter ones, marked by appearance of the complex that was immobile in electrophoresis. Denatured gel-electrophoresis revealed that the complex was mainly made up of shorter or partially synthesized strands, together with small amounts of full-length ones. Able to be digested by S1 nuclease but unable by restriction endonucleases (REs), the complex was proved to consist of both single regions and double-helix regions that kept the complex stable thermodynamically. Simulations gave evidence that partial strands, even at lower concentration, could disturb re-amplification effectively and lead to the abortion of re-amplifications finally. It was pointed out that the partial strands formed chiefly via polymerase's infidelity, and hence the solution to lighten the abnormality was also proposed.

  4. Partial strands synthesizing leads to inevitable aborting and complicated products in consecutive polymerase chain reactions (PCRs)

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Various abnormal phenomena have been observed during PCR so far. The present study performed a series of consecutive PCRs (including many rounds of re-amplification continuously) and found that the abortion of re-amplification was inevitable as long as a variety of complicated product appeared. The aborting stages varied, according to the lengths of targets. Longer targets reached the abortion earlier than the shorter ones, marked by appearance of the complex that was immobile in electropho-resis. Denatured gel-electrophoresis revealed that the complex was mainly made up of shorter or partially synthesized strands, together with small amounts of full-length ones. Able to be digested by S1 nuclease but unable by restriction endonucleases (REs), the complex was proved to consist of both single regions and double-helix regions that kept the complex stable thermodynamically. Simulations gave evidence that partial strands, even at lower concentration, could disturb re-amplification effec- tively and lead to the abortion of re-amplifications finally. It was pointed out that the partial strands formed chiefly via polymerase’s infidelity, and hence the solution to lighten the abnormality was also proposed.

  5. The effect of oxygen molecule adsorption on lead iodide perovskite surface by first-principles calculation

    Science.gov (United States)

    Ma, Xia-Xia; Li, Ze-Sheng

    2018-01-01

    Oxygen molecule has a negative effect on perovskite solar cells, which has been investigated experimentally. However, detailed theoretical research is still rare. This study presents a microscopic view to reveal the interaction mechanism between O2 and perovskite based on the first-principles calculation. The results show that O2 is adsorbed on the (100) surface of MAPbI3 perovskite mainly by Van der Waals force. O2 adsorption makes the MAPbI3 surface generate a small number of positive charges, which leads to the increase of the work function of the MAPbI3 surface. This is in agreement with the experimental measurement. And increased work function of MAPbI3 surface is not beneficial to electron transfer from perovskite to electronic extraction layer (such as TiO2). Comparison of the density of states (DOS) of the clean (100) surface and the adsorbed system shows that an in-gap state belonging to O2 appears, which can explain the phenomenon observed from experiments that electron transfers from the surface of perovskite to O2 to form superoxide. The theoretical power conversion efficiency of the system with and without O2 adsorption is evaluated, and it turns out that the power conversion efficiency of the system with O2 adsorption is slightly lower than that of the system without O2 adsorption. This result indicates that avoiding the introduction of O2 molecules between perovskite and electronic extraction layer is beneficial to the perovskite solar cell.

  6. Laser-based surface preparation of composite laminates leads to improved electrodes for electrical measurements

    KAUST Repository

    Almuhammadi, Khaled; Selvakumaran, Lakshmi; Alfano, Marco; Yang, Yang; Bera, Tushar Kanti; Lubineau, Gilles

    2015-01-01

    Electrical impedance tomography (EIT) is a low-cost, fast and effective structural health monitoring technique that can be used on carbon fiber reinforced polymers (CFRP). Electrodes are a key component of any EIT system and as such they should feature low resistivity as well as high robustness and reproducibility. Surface preparation is required prior to bonding of electrodes. Currently this task is mostly carried out by traditional sanding. However this is a time consuming procedure which can also induce damage to surface fibers and lead to spurious electrode properties. Here we propose an alternative processing technique based on the use of pulsed laser irradiation. The processing parameters that result in selective removal of the electrically insulating resin with minimum surface fiber damage are identified. A quantitative analysis of the electrical contact resistance is presented and the results are compared with those obtained using sanding.

  7. Laser-based surface preparation of composite laminates leads to improved electrodes for electrical measurements

    KAUST Repository

    Almuhammadi, Khaled

    2015-10-19

    Electrical impedance tomography (EIT) is a low-cost, fast and effective structural health monitoring technique that can be used on carbon fiber reinforced polymers (CFRP). Electrodes are a key component of any EIT system and as such they should feature low resistivity as well as high robustness and reproducibility. Surface preparation is required prior to bonding of electrodes. Currently this task is mostly carried out by traditional sanding. However this is a time consuming procedure which can also induce damage to surface fibers and lead to spurious electrode properties. Here we propose an alternative processing technique based on the use of pulsed laser irradiation. The processing parameters that result in selective removal of the electrically insulating resin with minimum surface fiber damage are identified. A quantitative analysis of the electrical contact resistance is presented and the results are compared with those obtained using sanding.

  8. Insect Residue Contamination on Wing Leading Edge Surfaces: A Materials Investigation for Mitigation

    Science.gov (United States)

    Lorenzi, Tyler M.; Wohl, Christopher J.; Penner, Ronald K.; Smith, Joseph G.; Siochi, Emilie J.

    2011-01-01

    Flight tests have shown that residue from insect strikes on aircraft wing leading edge surfaces may induce localized transition of laminar to turbulent flow. The highest density of insect populations have been observed between ground level and 153 m during light winds (2.6 -- 5.1 m/s), high humidity, and temperatures from 21 -- 29 C. At a critical residue height, dependent on the airfoil and Reynolds number, boundary layer transition from laminar to turbulent results in increased drag and fuel consumption. Although this represents a minimal increase in fuel burn for conventional transport aircraft, future aircraft designs will rely on maintaining laminar flow across a larger portion of wing surfaces to reduce fuel burn during cruise. Thus, insect residue adhesion mitigation is most critical during takeoff and initial climb to maintain laminar flow in fuel-efficient aircraft configurations. Several exterior treatments investigated to mitigate insect residue buildup (e.g., paper, scrapers, surfactants, flexible surfaces) have shown potential; however, implementation has proven to be impractical. Current research is focused on evaluation of wing leading edge surface coatings that may reduce insect residue adhesion. Initial work under NASA's Environmentally Responsible Aviation Program focused on evaluation of several commercially available products (commercial off-the-shelf, COTS), polymers, and substituted alkoxy silanes that were applied to aluminum (Al) substrates. Surface energies of these coatings were determined from contact angle data and were correlated to residual insect excrescence on coated aluminum substrates using a custom-built "bug gun." Quantification of insect excrescence surface coverage was evaluated by a series of digital photographic image processing techniques.

  9. Surface dust wipes are the best predictors of blood leads in young children with elevated blood lead levels

    Energy Technology Data Exchange (ETDEWEB)

    Gulson, Brian, E-mail: brian.gulson@mq.edu.au [Graduate School of the Environment, Macquarie University, North Ryde NSW 2109 (Australia); CSIRO Earth Science and Resource Engineering, North Ryde NSW 2113 (Australia); Anderson, Phil [Information and Statistics Group, Australian Institute of Health and Welfare, Canberra ACT 2601 (Australia); Faculty of Health, University of Canberra, Canberra ACT 2601 (Australia); Taylor, Alan [Department of Psychology, Macquarie University, Sydney NSW 2109 (Australia)

    2013-10-15

    Background: As part of the only national survey of lead in Australian children, which was undertaken in 1996, lead isotopic and lead concentration measurements were obtained from children from 24 dwellings whose blood lead levels were ≥15 µg/dL in an attempt to determine the source(s) of their elevated blood lead. Comparisons were made with data for six children with lower blood lead levels (<10 µg/dL). Methods: Thermal ionisation and isotope dilution mass spectrometry were used to determine high precision lead isotopic ratios ({sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb and {sup 206}Pb/{sup 204}Pb) and lead concentrations in blood, dust from floor wipes, soil, drinking water and paint (where available). Evaluation of associations between blood and the environmental samples was based on the analysis of individual cases, and Pearson correlations and multiple regression analyses based on the whole dataset. Results and discussion: The correlations showed an association for isotopic ratios in blood and wipes (r=0.52, 95% CI 0.19–0.74), blood and soil (r=0.33, 95% CI −0.05–0.62), and blood and paint (r=0.56, 95% CI 0.09–0.83). The regression analyses indicated that the only statistically significant relationship for blood isotopic ratios was with dust wipes (B=0.65, 95% CI 0.35–0.95); there were no significant associations for lead concentrations in blood and environmental samples. There is a strong isotopic correlation of soils and house dust (r=0.53, 95% CI 0.20–0.75) indicative of a common source(s) for lead in soil and house dust. In contrast, as with the regression analyses, no such association is present for bulk lead concentrations (r=−0.003, 95% CI −0.37–0.36), the most common approach employed in source investigations. In evaluation of the isotopic results on a case by case basis, the strongest associations were for dust wipes and blood. -- Highlights: • Children with elevated blood lead ≥15 µg/dL compared with a group with <10

  10. 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.

  11. 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.

  12. 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.

  13. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  14. 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)

  15. 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.

  16. 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.)

  17. Concentration dependence of surface properties and molar volume of multicomponent system indium-tin-lead-bismuth

    Energy Technology Data Exchange (ETDEWEB)

    Dadashev, R; Kutuev, R [Complex Science Research Institute of the Science Academy of the Chechen Republic, 21 Staropromisl. shosse, Grozny 364096 (Russian Federation); Elimkhanov, D [Science Academy of the Chechen Republic (Russian Federation)], E-mail: edzhabrail@mail.ru

    2008-02-15

    The results of an experimental research of surface properties of the four-component system indium-tin-lead-bismuth are presented. The researches under discussion were carried out in a combined device in which the surface tension ({sigma}) is measured by the method of maximum pressure in a drop, and density ({rho}) is measured by advanced aerometry. Measurement errors are 0.7 % for surface tension measurement, and 0.2 % for density measurement. The study of the concentration dependence of {sigma} in this system has revealed the influence of the third and fourth components upon the characteristics of surface tension isotherms of the binary system indium-tin. It was found out that with an increase in the content of the third and fourth components the depth of the minimum on the surface tension isotherms of the indium-tin system {sigma} decreases. On the basis of the concentration dependence of the phenomenon of concentration bufferity is revealed. It is shown that despite the complex character, isotherms of {sigma} on beam sections of a multicomponent system do not contain qualitatively new features in comparison with the isotherms of these properties in lateral binary systems.

  18. 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...

  19. 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.

  20. 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.

  1. 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....

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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-.

  11. Investigation of reaction mechanisms during electroreduction of carbon dioxide on lead electrode for the production of organic compounds

    International Nuclear Information System (INIS)

    Innocent, B.

    2008-09-01

    The aim of this work was to promote the reduction of CO 2 through its electrochemical conversion (electro-synthesis) on a lead electrode into high added value products. Depending on the nature of electrolyte, the electro-reduction of carbon dioxide leads to different products. Various electrolytes (aqueous or organic, protic or aprotic) were used to study two mechanisms: hydrogenation (formation of formate) and electro-dimerization (synthesis of oxalate). Cyclic voltammetry studies have been carried out for electrochemically characterizing CO 2 reduction on Pb. The electrochemical investigation of the electrode electrolyte interface has shown that the process of CO 2 electro-reduction is a mass transfer control both in the organic and aqueous media. Electrochemical experiments (cyclic voltammetry, chrono-amperometry) coupled with in situ infrared reflectance spectroscopic techniques (SPAIRS, SNIFTIRS) have also shown that in aqueous medium (7 ≤pH≤9) hydrogeno-carbonate ions were reduced to formate. The modification of solvent (propylene carbonate) leads selectively to oxalate as the main reaction product. Long-term electrolyses were performed in a filter-press cell to deal large volumes. In aqueous medium, the reduction of HCO 3 - to HCOO - (R F = 89% at -2.5 mA cm -2 and 4 C) is always accompanied by the production of H 2 . (author)

  12. Surface bond contraction and its effect on the nanometric sized lead zirconate titanate

    International Nuclear Information System (INIS)

    Haitao Huang; Sun, Chang Q.; Hing, Peter

    2000-01-01

    The grain size effect of lead zirconate titanate PbZr 1-x Ti x O 3 (PZT, x≥0.6) caused by surface bond contraction has been investigated by using the Landau-Ginsburg-Devonshire (LGD) phenomenological theory. It has been shown that, due to the surface bond contraction, both the Curie temperature and the spontaneous polarization of tetragonal PZT decrease with decreasing grain size. These effects become more significant when the grain size is in the nanometre range. A dielectric anomaly appears with decreasing grain size, which corresponds to a size dependent phase transformation. The ferroelectric critical size below which a loss of ferroelectricity will happen is estimated from the results obtained. (author). Letter-to-the-editor

  13. 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.

  14. 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.

  15. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xinye [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Huang, Yaji, E-mail: heyyj@seu.edu.cn [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Pan, Zhigang [College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009 (China); Wang, Yongxing; Liu, Changqi [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China)

    2015-09-15

    Highlights: • Al surface after dehydroxylation is active while Si surface is inert. • The active sites are the unsaturated Al atoms and O atoms losing H atom. • PbO is the most suitable species for adsorption. • Increasing the activities of Al atoms can enhance the performance of kaolinite. • Produce of amorphous silica is a potential path to enhance the performance of kaolinite. - Abstract: Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl{sub 2} molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl{sub 2}. Considering the energy barriers, it is easy for PbO and PbCl{sub 2} to adsorb on Al surfaces but difficult to escape. The high energy barriers of de–HCl process cause the difficulties of PbCl{sub 2} to form PbO·Al{sub 2}O{sub 3}·2SiO{sub 2} with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent.

  16. 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.

  17. Survivability and Fusibility in Reactions Leading to Heavy Nuclei in the Vicinity of the N=126 Closed Shell

    International Nuclear Information System (INIS)

    Sagaidak, R. N.

    2009-01-01

    Nuclear fission is well suited to study the dynamic properties and dissipative processes in cold and moderately excited nuclei. It is also a unique tool to explore level density and shell effects at an extreme deformation. Despite the significant progress in the fission studies, the isospin dependence of fission properties and, in particular, of fission barrier heights still remains an open problem. Theoretical fission model parameters are tuned by using the experimental nuclear and fission data close to stability [1]. The models provide a reasonable description of the fission barriers close to the stability line. However, large deviations are observed between predictions of different models for the fission barriers of very neutron-deficient and neutron-rich nuclei. These discrepancies (by as much as 20-30 MeV, see, e.g. [2]) become especially important in the r-process calculations for extremely neutron-rich nuclei, whose fission barriers determine the termination of the r-process by fission [3]. Unfortunately, such neutron-rich nuclei will probably not become accessible in the nearest experiments. Therefore, fission properties of exotic nuclei and especially their isospin dependence can be investigated in alternative regions of the Nuclide Chart, which are accessible for such studies now. Fusion-evaporation cross sections for heavy fissile nuclei obtained in heavy ion induced reactions as well as their fission cross sections are mainly determined by statistical properties of decaying compound nuclei (CN) and first of all by the fission-barrier heights of nuclei involved in the de-excitation chains leading to observable evaporation residues (ER). At the same time, the ER production and fission in nearly symmetric projectile-target fusion reactions leading to the most neutron-deficient CN could be strongly suppressed due to the quasi-fission (QF) effect [4], as observed recently in the 4 8C a induced reactions leading to Ra [5] and Pb [6] CN. The production of

  18. 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...

  19. 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.

  20. 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.

  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. 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 .

  3. 16 CFR 1145.2 - Paint (and other similar surface-coating materials) containing lead; toys, children's articles...

    Science.gov (United States)

    2010-01-01

    ... materials) containing lead; toys, children's articles, and articles of furniture bearing such paint (or... materials) containing lead; toys, children's articles, and articles of furniture bearing such paint (or...) Paint and other similar surface-coating materials containing lead and toys, children's articles, and...

  4. 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.

  5. Modification of surface texture by grinding and polishing lead zirconate titanate ceramics

    International Nuclear Information System (INIS)

    Cheng, S.; Lloyd, I.K.

    1992-01-01

    This paper reports that grinding and polishing affected the orientation of 90 degrees domains at the surface of lead zirconate titanate (PZT) ceramics. This was quantified by using changes in the intensity ratio of the (002) and (200) X-ray reflections. Grinding unpoled PZT with 600-grit SiC paper gave X-ray intensity ratios similar to those of poled material. This implies that 90 degrees domain realignments had occurred in the near surface region probed by the X-rays. Grinding poled samples with 600-grit SiC further increased the X-ray intensity ratio beyond that caused by poling, indicating that additional surface reorientation of 90 degrees domains had occurred. The effects of diamond polishing depended on the size of the diamond particles. The use of 6-μm diamond had no effect on the (002)/(200) intensity ratio of either poled or unpoled samples, while polishing with 15- or 45-μm diamond significantly enhanced the 90 degrees domain rotation. In unpoled samples, the increase in the X-ray intensity ratio then approached that induced by poling or grinding with 600-grit SiC paper. While the observed increase in X-ray intensity ratio upon grinding is attributed to the rotation of 90 degrees domains, the simultaneous formation of 180 degrees domains appears to minimize or reduce the increase in electrical polarization

  6. Surface plasmon resonance sensing detection of mercury and lead ions based on conducting polymer composite.

    Directory of Open Access Journals (Sweden)

    Mahnaz M Abdi

    Full Text Available A new sensing area for a sensor based on surface plasmon resonance (SPR was fabricated to detect trace amounts of mercury and lead ions. The gold surface used for SPR measurements were modified with polypyrrole-chitosan (PPy-CHI conducting polymer composite. The polymer layer was deposited on the gold surface by electrodeposition. This optical sensor was used for monitoring toxic metal ions with and without sensitivity enhancement by chitosan in water samples. The higher amounts of resonance angle unit (ΔRU were obtained for PPy-CHI film due to a specific binding of chitosan with Pb(2+ and Hg(2+ ions. The Pb(2+ ion bind to the polymer films most strongly, and the sensor was more sensitive to Pb(2+ compared to Hg(2+. The concentrations of ions in the parts per million range produced the changes in the SPR angle minimum in the region of 0.03 to 0.07. Data analysis was done by Matlab software using Fresnel formula for multilayer system.

  7. 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.

  8. 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

  9. Effect of trace elements on the interface reactions between two lead-free solders and copper or nickel substrates

    Directory of Open Access Journals (Sweden)

    Soares D.

    2007-01-01

    Full Text Available Traditional Sn-Pb solder alloys are being replaced, because of environmental and health concerns about lead toxicity. Among some alternative alloy systems, the Sn-Zn and Sn-Cu base alloy systems have been studied and reveal promising properties. The reliability of a solder joint is affected by the solder/substrate interaction and the nature of the layers formed at the interface. The solder/substrate reactions, for Sn-Zn and Sn-Cu base solder alloys, were evaluated in what concerns the morphology and chemical composition of the interface layers. The effect of the addition of P, at low levels, on the chemical composition of the layers present at the interface was studied. The phases formed at the interface between the Cu or Ni substrate and a molten lead-free solder at 250ºC, were studied for different stage times and alloy compositions. The melting temperatures, of the studied alloys, were determined by Differential Scanning Calorimetry (DSC. Identification of equilibrium phases formed at the interface layer, and the evaluation of their chemical composition were performed by Scanning Electron Microscopy (SEM/EDS. Different interface characteristics were obtained, namely for the alloys containing Zn. The obtained IML layer thickness was compared, for both types of alloy systems.

  10. 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

  11. 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.

  12. 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

  13. Investigation of corrosion, water reaction, polonium evaporation and bismuth resource in liquid metal lead-bismuth technology

    Energy Technology Data Exchange (ETDEWEB)

    Takano, Hideki; Takizuka, Takakazu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kitano, Teruaki [Mitsui Shipbuilding and Engineering Co. Ltd., Tokyo (Japan)

    2000-10-01

    Lead-bismuth is the first candidate material for liquid metal target find coolant of fueled blanket system in accelerator-driven system (ADS) studied at JAERI. Advantages of the lead-bismuth utilization are non-active material, very low capture cross section, low melting point of 125degC and high boiling point of 1670degC, and beside coolant void reactivity become negative. But problems are due to the high corrosivity to most of the structural materials and the corrosive data are scarcity. In this report, corrosivity, reaction with water, thermal-hydraulics, chemical toxicity etc. are studied by investigating some facilities utilized and researched really for lead or lead-bismuth. And, furthermore, polonium evaporation rate and bismuth resource are investigated. Main results obtained are as follows: (1) In a refinery, there are enough employment experience for liquid Pb-Bi in period of about 17 years and not corrosion for the thermal conductive materials (1Cr-0.5Mo steel) used under the condition of natural convection with temperature around 400degC. (2) In Russia, extensive experience in the use as Russian submarines and in R and D during about 50 years are available. And as a result, it will be able to lead approximately zero corrosion for Cr-Si materials by adjusting oxygen film with oxygen concentration control between 10{sup -7} to 10{sup -5}% mass. However, the corrosion data are not enough systematically collected involving them in radiation dose field. (3) In liquid-dropping experiment, it is shown that interaction between water and high temperature liquid Pb-Bi is reduced steeply with rising of atmosphere pressure. But, in order to design the second circuit removal model of ADS, the interaction should be evaluated by water continuous injection experiment. (4) Polonium forms PbPo in Pb-Bi, and the evaporation rate become less three factor than that of Po, and furthermore, the rate decreases in the atmosphere. The effects of Po on employee and environment

  14. Photo-induced surface modification to improve the performance of lead sulfide quantum dot solar cell.

    Science.gov (United States)

    Tulsani, Srikanth Reddy; Rath, Arup Kumar

    2018-07-15

    The solution-processed quantum dot (QD) solar cell technology has seen significant advancements in recent past to emerge as a potential contender for the next generation photovoltaic technology. In the development of high performance QD solar cell, the surface ligand chemistry has played the important role in controlling the doping type and doping density of QD solids. For instance, lead sulfide (PbS) QDs which is at the forefront of QD solar cell technology, can be made n-type or p-type respectively by using iodine or thiol as the surfactant. The advancements in surface ligand chemistry enable the formation of p-n homojunction of PbS QDs layers to attain high solar cell performances. It is shown here, however, that poor Fermi level alignment of thiol passivated p-type PbS QD hole transport layer with the n-type PbS QD light absorbing layer has rendered the photovoltaic devices from realizing their full potential. Here we develop a control surface oxidation technique using facile ultraviolet ozone treatment to increase the p-doping density in a controlled fashion for the thiol passivated PbS QD layer. This subtle surface modification tunes the Fermi energy level of the hole transport layer to deeper values to facilitate the carrier extraction and voltage generation in photovoltaic devices. In photovoltaic devices, the ultraviolet ozone treatment resulted in the average gain of 18% in the power conversion efficiency with the highest recorded efficiency of 8.98%. Copyright © 2018 Elsevier Inc. All rights reserved.

  15. 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)

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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)

  2. Pion-transfer (n,d) and (d, 3He) reactions leading to deeply bound pionic atoms

    International Nuclear Information System (INIS)

    Toki, H.; Hirenzaki, S.; Yamazaki, T.

    1990-11-01

    Theoretical studies are given on the (n,d) and (d, 3 He) reactions leading to deeply bound pionic atoms in heavy nuclei of configuration [(nl) π ·j n -1 ]J. The cross sections for various pionic and neutron-hole configurations in the case of a 208 Pb target are calculated at incident energies 300-1000 MeV/u by using the effective number approach and the eikonal approximation for distortion. The effective number with a pion in the 1s or 2p state and a neutron hole in the i 13/2 orbit peaks around the same incident energy (T n =600 MeV) as the elementary cross section n+n→d+π - , where the momentum transfer matches the angular-momentum transfer of L=5∼7. The DWIA cross section for (n,d) producing a pion in the 1s or 2p orbit at T n =600 MeV is found to be around 42 or 75 μb/sr, respectively. At T n =350 MeV, where the momentum transfer is small, quasi-substitutional states of configurations [(2p) π (3p 1/2 ) n -1 ]L=0 and [(2p) π (3p 3/2 ) n -1 ]L=0 are preferentially populated with cross sections of 190 and 380 μb/sr, respectively. The (d, 3 He) cross sections are estimated to be an order of magnitude smaller than the (n,d) cross sections. Thus, the (n,d) and (d, 3 He) reactions are found to be suited for the production of deeply bound pionic atoms. (author)

  3. Surface Treatment to Improve Corrosion Resistance in Lead-Alloy Coolants

    International Nuclear Information System (INIS)

    Todd R. Allen; Kumar Sridharan; McLean T. Machut; Lizhen Tan

    2007-01-01

    One of the six proposed advanced reactor designs of the Generation IV Initiative, the Lead-cooled Fast Reactor (LFR) possesses many characteristics that make it a desirable candidate for future nuclear energy production and responsible actinide management. These characteristics include favorable heat transfer, fluid dynamics, and neutronic performance compared to other candidate coolants. However, the use of a heavy liquid metal coolant presents a challenge for reactor designers in regards to reliable structural and fuel cladding materials in both a highly corrosive high temperature liquid metal and an intense radiation field. Flow corrosion studies at the University of Wisconsin have examined the corrosion performance of candidate materials for application in the LFR concept as well as the viability of various surface treatments to improve the materials compatibility. To date this research has included several focus areas, which include the formulation of an understanding of corrosion mechanisms and the examination of the effects of chemical and mechanical surface modifications on the materials performance in liquid lead-bismuth by experimental testing in Los Alamos National Laboratory's DELTA Loop, as well as comparison of experimental findings to numerical and physical models for long term corrosion prediction. This report will first review the literature and introduce the experiments and data that will be used to benchmark theoretical calculations. The experimental results will be followed by a brief review of the underlying theory and methodology for the physical and theoretical models. Finally, the results of theoretical calculations as well as experimentally obtained benchmarks and comparisons to the literature are presented

  4. Leading survey and research report for fiscal 1999. Survey and research on chemical reaction simulator technology; 1999 nendo kagaku hanno simulator gijutsu no chosa kenkyu hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Although various chemical reactions are made use of at scenes of chemical industry for the acquisition of desired chemicals, the control of reaction process governing factors, such as temperature, pressure, catalysts, solutions, etc., is found to be carried out only on the empirical basis. At the present time, rational or optimum reaction designs are not to be prepared in a short period of time in the presence of the widespread shortage of knowledge about chemical reactions and of the shortage of understanding of chemical reactions at the micro level. Leading survey and research are conducted for the development of a 'chemical reaction simulator' technology to enable the acquisition of optimum reaction designing guidelines in a short period of time. Using the simulator, a chemical of his choice is inputted by a researcher engaged in the study of an real chemical reaction and then various techniques of computer science are mobilized for the preparation of a huge number of feasible reaction routes, and high-precision simulations are conducted for the feasible reaction routes. The results achieved this fiscal year are reported. The purpose of this research and its ripple effect on new product industry creation are stated. Then the positioning, mission, and concept of such a chemical reaction simulator are described. Finally, the result of research and survey of knowledge databases and the result of research and survey of computational chemistry are stated. (NEDO)

  5. Leading survey and research report for fiscal 1999. Survey and research on chemical reaction simulator technology; 1999 nendo kagaku hanno simulator gijutsu no chosa kenkyu hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Although various chemical reactions are made use of at scenes of chemical industry for the acquisition of desired chemicals, the control of reaction process governing factors, such as temperature, pressure, catalysts, solutions, etc., is found to be carried out only on the empirical basis. At the present time, rational or optimum reaction designs are not to be prepared in a short period of time in the presence of the widespread shortage of knowledge about chemical reactions and of the shortage of understanding of chemical reactions at the micro level. Leading survey and research are conducted for the development of a 'chemical reaction simulator' technology to enable the acquisition of optimum reaction designing guidelines in a short period of time. Using the simulator, a chemical of his choice is inputted by a researcher engaged in the study of an real chemical reaction and then various techniques of computer science are mobilized for the preparation of a huge number of feasible reaction routes, and high-precision simulations are conducted for the feasible reaction routes. The results achieved this fiscal year are reported. The purpose of this research and its ripple effect on new product industry creation are stated. Then the positioning, mission, and concept of such a chemical reaction simulator are described. Finally, the result of research and survey of knowledge databases and the result of research and survey of computational chemistry are stated. (NEDO)

  6. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and Adverse Drug Reactions.

    Science.gov (United States)

    Böhm, Ingrid; Nairz, Knud; Morelli, John N; Keller, Patricia Silva Hasembank; Heverhagen, Johannes T

    2017-04-01

    Purpose  To test the hypothesis that the incomplete diagnosis "iodine allergy" is a possibly dangerous concept for patients under routine radiologic conditions. Materials and Methods  300 patients with a history of an "iodine allergy" were retrospectively screened and compared with two age-, sex-, and procedure-matched groups of patients either diagnosed with a nonspecific "iodine contrast medium (ICM) allergy" or an allergy to a specific ICM agent. For all groups, the clinical symptoms of the most recent past adverse drug reaction (ADR), prophylactic actions taken for subsequent imaging, and ultimate outcome were recorded and analyzed. Results  The diagnosis "iodine allergy" was not otherwise specified in 84.3 % patients. For this group, in most cases, the symptoms of the previous ADRs were not documented. In contrast, the type of ADR was undocumented in only a minority of patients in the comparison groups. In the group of patients with an "iodine allergy" the percentage of unenhanced CT scans was greater than within the other two groups (36.7 % vs. 28.7 %/18.6 %). ADRs following prophylactic measures were only observed in the "iodine allergy" group (OR of 9.24 95 % CI 1.16 - 73.45; p contrast media containing covalently bound iodine.. · There is a clear correlation between the exactness of the diagnosis - from the alleged "iodine allergy" to "contrast media allergy" to naming the exact culprit CM - and the quality of documentation of the symptoms.. · Management of patients diagnosed with "iodine allergy" was associated with uncertainty leading to unenhanced scans and sometimes unnecessary prophylactic actions.. · The term "iodine allergy" should be omitted, because it is potentially dangerous and can decrease the quality of radiology exams.. Citation Format · Böhm Ingrid, Nairz Knud, Morelli John N et al. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and

  7. "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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.)

  20. 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

  1. Surface ECG and Fluoroscopy are Not Predictive of Right Ventricular Septal Lead Position Compared to Cardiac CT.

    Science.gov (United States)

    Rowe, Matthew K; Moore, Peter; Pratap, Jit; Coucher, John; Gould, Paul A; Kaye, Gerald C

    2017-05-01

    Controversy exists regarding the optimal lead position for chronic right ventricular (RV) pacing. Placing a lead at the RV septum relies upon fluoroscopy assisted by a surface 12-lead electrocardiogram (ECG). We compared the postimplant lead position determined by ECG-gated multidetector contrast-enhanced computed tomography (MDCT) with the position derived from the surface 12-lead ECG. Eighteen patients with permanent RV leads were prospectively enrolled. Leads were placed in the RV septum (RVS) in 10 and the RV apex (RVA) in eight using fluoroscopy with anteroposterior and left anterior oblique 30° views. All patients underwent MDCT imaging and paced ECG analysis. ECG criteria were: QRS duration; QRS axis; positive or negative net QRS amplitude in leads I, aVL, V1, and V6; presence of notching in the inferior leads; and transition point in precordial leads at or after V4. Of the 10 leads implanted in the RVS, computed tomography (CT) imaging revealed seven to be at the anterior RV wall, two at the anteroseptal junction, and one in the true septum. For the eight RVA leads, four were anterior, two septal, and two anteroseptal. All leads implanted in the RVS met at least one ECG criteria (median 3, range 1-6). However, no criteria were specific for septal position as judged by MDCT. Mean QRS duration was 160 ± 24 ms in the RVS group compared with 168 ± 14 ms for RVA pacing (P = 0.38). We conclude that the surface ECG is not sufficiently accurate to determine RV septal lead tip position compared to cardiac CT. © 2017 Wiley Periodicals, Inc.

  2. 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...

  3. 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

  4. 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)

  5. Spatial distribution of lead concentrations in urban surface soils of New Orleans, Louisiana USA.

    Science.gov (United States)

    Abel, Michael T; Suedel, Burton; Presley, Steven M; Rainwater, Thomas R; Austin, Galen P; Cox, Stephen B; McDaniel, Les N; Rigdon, Richard; Goebel, Timothy; Zartman, Richard; Leftwich, Blair D; Anderson, Todd A; Kendall, Ronald J; Cobb, George P

    2010-10-01

    Immediately following hurricane Katrina concern was raised over the environmental impact of floodwaters on the city of New Orleans, especially in regard to human health. Several studies were conducted to determine the actual contaminant distribution throughout the city and surrounding wetlands by analyzing soil, sediment, and water for a variety of contaminants including organics, inorganics, and biologics. Preliminary investigations by The Institute of Environmental and Human Health at Texas Tech University concluded that soils and sediments contained pesticides, semi-volatiles, and metals, specifically arsenic, iron, and lead, at concentrations that could pose a significant risk to human health. Additional studies on New Orleans floodwaters revealed similar constituents as well as compounds commonly found in gasoline. More recently, it has been revealed that lead (Pb), arsenic, and vanadium are found intermittently throughout the city at concentrations greater than the human health soil screening levels (HHSSLs) of 400, 22 (non-cancer endpoint) and 390 μg/g, respectively. Of these, Pb appears to present the greatest exposure hazard to humans as a result of its extensive distribution in city soils. In this study, we spatially evaluated Pb concentrations across greater New Orleans surface soils. We established 128 sampling sites throughout New Orleans at approximately half-mile intervals. A soil sample was collected at each site and analyzed for Pb by ICP-AES. Soils from 19 (15%) of the sites had Pb concentrations exceeding the HHSSL threshold of 400 μg/g. It was determined that the highest concentrations of Pb were found in the south and west portions of the city. Pb concentrations found throughout New Orleans in this study were then incorporated into a geographic information system to create a spatial distribution model that can be further used to predict Pb exposure to humans in the city.

  6. 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.

  7. 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.

  8. 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...

  9. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

    Science.gov (United States)

    Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

    2011-12-21

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  10. Surface Treatment to Improve Corrosion Resistance in Lead-Alloy Coolants

    Energy Technology Data Exchange (ETDEWEB)

    Todd R. Allen; Kumar Sridharan; McLean T. Machut; Lizhen Tan

    2007-08-29

    One of the six proposed advanced reactor designs of the Generation IV Initiative, the Leadcooled Fast Reactor (LFR) possesses many characteristics that make it a desirable candidate for future nuclear energy production and responsible actinide management. These characteristics include favorable heat transfer, fluid dynamics, and neutronic performance compared to other candidate coolants. However, the use of a heavy liquid metal coolant presents a challenge for reactor designers in regards to reliable structural and fuel cladding materials in both a highly corrosive high temperature liquid metal and an intense radiation fieldi. Flow corrosion studies at the University of Wisconsin have examined the corrosion performance of candidate materials for application in the LFR concept as well as the viability of various surface treatments to improve the materials’ compatibility. To date this research has included several focus areas, which include the formulation of an understanding of corrosion mechanisms and the examination of the effects of chemical and mechanical surface modifications on the materials’ performance in liquid lead-bismuth by experimental testing in Los Alamos National Laboratory’s DELTA Loop, as well as comparison of experimental findings to numerical and physical models for long term corrosion prediction. This report will first review the literature and introduce the experiments and data that will be used to benchmark theoretical calculations. The experimental results will be followed by a brief review of the underlying theory and methodology for the physical and theoretical models. Finally, the results of theoretical calculations as well as experimentally obtained benchmarks and comparisons to the literature are presented.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Catalytic effects of silver plasmonic nanoparticles on the redox reaction leading to ABTS˙+ formation studied using UV-visible and Raman spectroscopy.

    Science.gov (United States)

    Garcia-Leis, A; Jancura, D; Antalik, M; Garcia-Ramos, J V; Sanchez-Cortes, S; Jurasekova, Z

    2016-09-29

    ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) is a compound extensively employed to evaluate the free radical trapping capacity of antioxidant agents and complex mixtures such as biological fluids or foods. This evaluation is usually performed by using a colourimetric experiment, where preformed ABTS radical cation (ABTS˙ + ) molecules are reduced in the presence of an antioxidant causing an intensity decrease of the specific ABTS˙ + UV-visible absorption bands. In this work we report a strong effect of silver plasmonic nanoparticles (Ag NPs) on ABTS leading to the formation of ABTS˙ + . The reaction of ABTS with Ag NPs has been found to be dependent on the interfacial and plasmonic properties of NPs. Specifically, this reaction is pronounced in the presence of spherical nanoparticles prepared by the reduction of silver nitrate with hydroxylamine (AgH) and in the case of star-shaped silver nanoparticles (AgNS). On the other hand, spherical nanoparticles prepared by the reduction of silver nitrate with citrate apparently do not react with ABTS. Additionally, the formation of ABTS˙ + is investigated by surface-enhanced Raman scattering (SERS) and the assignment of the most intense vibrational bands of this compound is performed. The SERS technique enables us to detect this radical cation at very low concentrations of ABTS (∼2 μM). Altogether, these findings allow us to suggest the use of ABTS/Ag NPs-systems as reliable and easy going substrates to test the antioxidant capacity of various compounds, even at concentrations much lower than those usually used in the spectrophotometric assays. Moreover, we have suggested that ABTS could be employed as a suitable agent to investigate the interfacial and plasmonic properties of the metal nanoparticles and, thus, to characterize the nanoparticle metal systems employed for various purposes.

  16. Nickel, Lead and Zinc Contamination in the Surface Sediments of Agh Gel Wetland, Iran

    Directory of Open Access Journals (Sweden)

    Soheil Sobhan Ardakani

    2016-07-01

    Full Text Available Background & Aims of the Study: Due to the increased human activities around the Agh Gel wetland, this study aimed to measured accumulations of heavy metals (Ni, Pb and Zn in the surface sediment samples taken from this wetland. Materials & Methods: Samples were taken from 10 stations and exposed to bulk digestion and chemical partitioning. Finally, Ni, Pb and Zn concentrations were monitored with ICP-OES in the sediments. Also, geo-accumulation index, contamination factor and pollution load index were used to evaluate the magnitude of contaminants in the sediment profile. Results: The results showed, the average of metal concentration in samples (mg kg-1 wet weight were 34.20±3.58 for Ni, 25.37±2.52 for Pb and 127.20±15.21 for Zn, respectively. Therefore, the pattern of metal concentrations in sediment was determined as Zinc>Nickel >Lead. According to the mean I-geo values, sediments' qualities are classified as unpolluted category for Ni and Pb. Also, sediment's quality is classified as unpolluted to moderately polluted for Zn. The CF values for all elements are classified as moderate contamination. The PLI values indicated that metal pollution exists for all sampling stations. Conclusions: The obtained results indicated that the Agh Gel wetland has a potential to threaten by chemical pollutants such as agricultural effluent. So, in order to preserve the environment of the Agh Gel wetland from deterioration, monitoring of water and sediment qualities is recommended periodically.

  17. Study of the properties of leading protons and antiprotons produced in p-barp exclusive reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskii, M.Y.; Boos, E.G.; Borovikov, A.A.

    1986-01-01

    We study the properties of leading protons and antiprotons from nondiffractive events in p-barp exclusive reactions at 32 GeV/c. It is found that the relative leading of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal momenta of leading hadrons are not correlated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another hadron. It is shown that these experimental data are well described by the statistical model of independent particle emission but contradict the Lund string-fragmentation model

  18. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Directory of Open Access Journals (Sweden)

    G. Li

    2016-08-01

    Full Text Available Gaseous formaldehyde (HCHO is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs. Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of  ∼  10 to 40 ppbv. For the determination of uptake coefficients (γ, we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity  =  0 %, an initial γ of (1.1 ± 0.05  ×  10−4 is determined, which gradually drops to (5.5 ± 0.4  ×  10−5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition at the atmosphere–soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  19. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Science.gov (United States)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  20. 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.

  1. Molecular binding mechanisms of aqueous cadmium and lead to siderophores, bacteria and mineral surfaces

    Science.gov (United States)

    Mishra, Bhoopesh

    Recent studies have shown that diverse groups of bacteria adsorb metals to similar extents and uptake can be modeled using a universal adsorption model. In this study, XAFS has been used to resolve whether binding sites determined for single species systems are responsible for adsorption in more complex natural bacterial assemblages. Results obtained from a series of XAFS experiments on pure Gram positive and Gram negative bacterial strains and consortia of bacteria as a function of pH and Cd loading suggests that every bacterial strain has a complex physiology and they are all slightly different from each other. Nevertheless from the metal adsorption chemistry point of view, the main difference between them lies in the site ratio of three fundamental sites only - carboxyl, phosphoryl and sulfide. Two completely different consortia of bacteria (obtained from natural river water, and soil system with severe organic contamination) were successfully modeled in the pH range 3.4--7.8 using the EXAFS models developed for single species systems. Results thus obtained can potentially have very high impact on the modeling of the complex bacterial systems in realistic geological settings, leading to further refinement and development of robust remediation strategies for metal contamination at macroscopic level. In another study, solution speciation of Pb and Cd with DFO-B has been examined using a combination of techniques (ICP, TOC, thermodynamic modeling and XAFS). Results indicate that Pb does not complex with DFO-B at all until about pH 3.5, but forms a totally caged structure at pH 7.5. At intermediate pH conditions, mixture of species (one and two hydroxamate groups complexed) is formed. Cd on the other hand, does not complex until pH 5, forms intermediate complexes at pH 8 and is totally chelated at pH 9. Further studies were conducted for Pb sorption to mineral surface kaolinite with and without DFO-B. In the absence of DFO-B, results suggest outer sphere and inner

  2. 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

  3. 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.

  4. 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.

  5. 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...

  6. 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.

  7. 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

  8. 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).

  9. Quantifying the contribution of airborne lead (Pb) to surface waters in northeastern Oklahoma

    Science.gov (United States)

    Li, J. J.; McDonald, J.; Curtis, H.

    2017-12-01

    The northeastern Oklahoma, home to a number of Native American Tribes, is part of the well-known Tri-State Mining District (TSMD). One hundred years of mining production in this area has left numerous, large chat piles on the surrounding environment, directly affecting the town of Picher and many other tribe communities. Byproducts of the mining, including lead (Pb)-contain dust have been transported to the atmosphere and seeped into groundwater, lakes, ponds and rivers. Due to this contamination, many children in the area have elevated levels of Pb in their bodies. Despite a substantial number of studies and efforts on the restoration of heavy metal contamination in this area (e.g. The Tar Creek Superfund Site, EPA), no studies have attempted to distinguish the contributions of different sources, particularly from the atmospheric deposition, of heavy metals to the aquatic environment. In this study, we analyzed the atmospheric deposition of Pb from 4 sites located close to the chat piles for the period of 2010 to 2016. Our preliminary analysis showed that atmospheric Pb has a strong seasonal pattern with two peak times in early spring and late fall, which largely correspond with the dry periods in the this area. Atmospheric concentrations of Pb monitored at these sites frequently exceeded 0.15 μg/m3, the National Ambient Air Quality Standards (NAAQS) standard for ambient air Pb, and was generally 10 times higher than atmospheric Pb monitored in Tulsa, OK, a major metropolitan area 150 km southwest of the monitoring sites. With the known Pb flux to the sediments of the water bodies, we estimated that the contribution of Pb from the atmospheric deposition to the surface waters is up to 25%, depending on the distance of the water bodies to concentrated distribution of the chat piles.

  10. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver; Kanoun, Mohammed; Scaranto, Jessica; Hedhili, Mohamed Nejib; Khalid, Syed; Laveille, Paco; D'Souza, Lawrence; Clo, Alain M.; Basset, Jean-Marie

    2015-01-01

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  11. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  12. 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.

  13. 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.

  14. 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.

  15. 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)

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  1. Evidence for leading mesons in anti p sup 4 He reactions at 0. 6 GeV c sup -1 incident momentum

    Energy Technology Data Exchange (ETDEWEB)

    Balestra, F.; Bossolasco, S.; Bussa, M.P.; Busso, L.; Fava, L.; Ferrero, L.; Grasso, A.; Maggiora, A.; Panzieri, D.; Piragino, G.; Piragino, R.; Tosello, F. (Ist. di Fisica Generale ' A. Avogadro' , Univ. of Turin (Italy) INFN, Sezione di Torino (Italy)); Bendiscioli, G.; Filippini, V.; Rotondi, A.; Salvini, P.; Venaglioni, A.; Zenoni, A. (Dipt. di Fisica Nucleare e Teoria, Univ. of Pavia (Italy) INFN, Sezione di Pavia (Italy)); Batusov, Yu.; Bunyatov, S.A.; Falomkin, I.V.; Nichitiu, F.; Pontecorvo, G.B.; Rozhdestvensky, A.M.; Sapozhnikov, M.G.; Tretyak, V.I. (Joint Inst. of Nuclear Research, Dubna (USSR)); Guaraldo, C. (Lab. Nazionali di Frascati dell' INFN (Italy)); Lodi Rizzini, E. (Dipt. di Automazione Industriale, Univ. of Brescia (Italy) INFN, Sezione di Pavia (Italy)); Haatuft, A.; Halsteinslid, A.; Myklebost, K.; Olsen, J.M. (Physics Dept., Univ. of Bergen (Norway)); Breivik, F.O.; Danielsen, K.M.; Jacobsen, T.; Soerensen, S.O. (Inst. of Physics, Univ. of Oslo (Norway))

    1991-01-01

    Leading mesons are seen in anti p {sup 4}He {yields} neutral strange particles at 0.6 GeV c{sup -1} incident momentum. These results differ somewhat from our previous results from anti p Ne-reactions. The concept of an ''effective target'' is useless. (orig.).

  2. An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I2 and TBHP: access to lead molecules for biomedical applications.

    Science.gov (United States)

    Mahato, Karuna; Arora, Neha; Ray Bagdi, Prasanta; Gattu, Radhakrishna; Ghosh, Siddhartha Sankar; Khan, Abu T

    2018-02-06

    A metal-free I 2 /TBHP induced highly atom economic and operationally simple oxidative cross-coupling reaction has been developed for the direct synthesis of sulfenamides/sulfanes/disulfides from the reaction of 4-hydroxydithiocoumarin and amines/thiols. The novelties of the present protocol are unprecedented S-C bond formation in addition to S-N and S-S bonds, shorter reaction time, mild and environmentally benign reaction conditions, functional group tolerance and moderate to excellent yields. Moreover, the four newly synthesized compounds namely 4q, 6d, 6e and 7a exhibit anti-proliferative activity against the breast cancer cell line MCF7, and may be lead molecules for future drug development.

  3. Method and System for Weakening Shock Wave Strength at Leading Edge Surfaces of Vehicle in Supersonic Atmospheric Flight

    Science.gov (United States)

    Daso, Endwell O. (Inventor); Pritchett, Victor E., II (Inventor); Wang, Ten-See (Inventor); Farr, Rebecca Ann (Inventor); Auslender, Aaron Howard (Inventor); Blankson, Isaiah M. (Inventor); Plotkin, Kenneth J. (Inventor)

    2015-01-01

    A method and system are provided to weaken shock wave strength at leading edge surfaces of a vehicle in atmospheric flight. One or more flight-related attribute sensed along a vehicle's outer mold line are used to control the injection of a non-heated, non-plasma-producing gas into a local external flowfield of the vehicle from at least one leading-edge surface location along the vehicle's outer mold line. Pressure and/or mass flow rate of the gas so-injected is adjusted in order to cause a Rankine-Hugoniot Jump Condition along the vehicle's outer mold line to be violated.

  4. 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.

  5. Histopathology and immune histochemistry of red tattoo reactions. Interface dermatitis is the lead pathology, with increase in T-lymphocytes and Langerhans cells suggesting an allergic pathomechanism.

    Science.gov (United States)

    Høgsberg, T; Thomsen, B M; Serup, J

    2015-11-01

    The majority of tattoo reactions are affiliated to red pigmented areas and often suspected to be allergic in nature. A sizeable series of biopsies of such reactions has not previously been performed. The aim of this study was to type and grade epidermal and dermal changes in tattoo reactions to red/red nuances by microscopy and immunochemistry relevant for the assessment of a possible allergic pathomechanism. Skin biopsies were taken from red tattoo reactions, graded by conventional microscopy and stained for T and B-lymphocytes, Langerhans cells, macrophages and tumour necrosis factor (TNF)-α. The study included 19 biopsies from 19 patients. The culprit colours were red/pink (n = 15) and purple/bordeaux (n = 4). Interface dermatitis was clearly the lead pathology found in 78% of samples, overlapped with granulomatous (in 32%) and pseudolymphomatous reaction patterns (in 32%). Epidermal hyperkeratosis (in 89%) was common as was leakage of red pigment across the dermo-epidermal junction, with transepidermal elimination (in 28%). The dermal cellular infiltration was dominated by T-lymphocytes (in 100%), Langerhans cells (in 95%) and macrophages (in 100%). TNF-α was common. The predominant histological pattern of chronic tattoo reactions in red/red nuances is interface dermatitis. T-lymphocytes and Langerhans cells are increased suggesting an allergic pathomechanism. TNF-α may contribute to reactions. In many cases, overlapping reactive patterns were identified. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. 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.

  7. 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.

  8. 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.

  9. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  10. 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.

  11. 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

  12. 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)

  13. Micro-EDXRF surface analyses of a bronze spear head: Lead content in metal and corrosion layers

    International Nuclear Information System (INIS)

    Figueiredo, E.; Valerio, P.; Araujo, M.F.; Senna-Martinez, J.C.

    2007-01-01

    A bronze spear head from Central Portugal dated to Late Bronze Age has been analyzed by non-destructive micro-EDXRF in the metal surface and corrosion layers. The artifact had previously been analyzed using a conventional EDXRF spectrometer having a larger incident beam. The quantification of the micro-EDXRF analyses showed that lead content in corrosion layers can reach values up to four times higher than the content determined in the metal surface. Results obtained with the higher energy incident beam from the EDXRF equipment, although referring mainly to the corrosion layers, seem to suffer some influence from the surface composition of the metallic alloy

  14. A zinc enolate of amide: Preparation and application in reformasky-like reaction leading to β-hydroxy amides

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hyun Hee; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of)

    2015-04-15

    One of the best known functionalized organic complexes is the β-hydroxy carbonyl compound. This unique functionality has been frequently found in naturally occurring bioactive derivatives. The cross-coupling reaction of A with aldehydes were carried out in the absence of any catalyst and completed in most cases within 1.0 h at room temperature. We have developed an efficient synthetic route for the preparation of β-hydroxy amides. The method involved the preparation of room-temperature-stable organo zinc reagents (A, B, and C) in THF and their subsequent coupling reactions with various carbonyl derivatives under mild conditions. Significantly, this approach using zinc enolate of amides could expand the scope of Reformatsky-like reactions. Further studies to elucidate this synthetic protocol are currently under way in our laboratory.

  15. 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

  16. 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.

  17. Stimulated emission of surface plasmon polaritons by lead-sulphide quantum dots at near infra-red wavelengths

    DEFF Research Database (Denmark)

    Radko, Ilya P.; Nielsen, Michael Grøndahl; Albrektsen, Ole

    2010-01-01

    Amplification of surface plasmon polaritons (SPPs) in planar metal-dielectric structure through stimulated emission is investigated using leakage-radiation microscopy configuration. The gain medium is a thin polymethylmethacrylate layer doped with lead-sulphide nanocrystals emitting at near-infrared...

  18. 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.

  19. 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

  20. Lead extraction from Cathode Ray Tube (CRT) funnel glass: Reaction mechanisms in thermal reduction with addition of carbon (C).

    Science.gov (United States)

    Lu, Xingwen; Ning, Xun-An; Chen, Da; Chuang, Kui-Hao; Shih, Kaimin; Wang, Fei

    2018-06-01

    This study quantitatively determined the extraction of lead from CRT funnel glass and examined the mechanisms of thermally reducing lead in the products of sintering Pb-glass with carbon in the pre-heated furnace. The experimentally derived results indicate that a 90.3 wt% lead extraction efficiency can be achieved with 20 wt% of C addition at 950 °C for 3 min under air. The formation of viscous semi-liquid glass blocked the oxygen supply between the interaction of C and Pb-glass, and was highly effective for the extraction of metallic Pb. A maximum of 87.3% lead recover was obtained with a C to Na 2 CO 3 ratio of 1/3 at 1200 °C. The decrease of C/Na 2 CO 3 ratio enhanced the metallic lead recovery by increasing the glass viscosity for effective sedimentation of metallic lead in the bottom. However, with the further increase of temperature and treatment time, re-vitrification of lead back to silicate-glass matrix was detected in both Pb-glass/C and Pb-glass/C/Na 2 CO 3 systems. The findings indicated that with proper controls, using C as an inexpensive reagent can effectively reduce treatment time and energy, which is crucial to a waste-to-resource technology for economically recovering lead from the waste CRT glass. Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. Lead adsorption study on combustion derived γ-Fe2O3 surface

    Indian Academy of Sciences (India)

    2016-08-26

    AAS) and solution conductivity (SC). Reduction in the concentration and increase in conductance of eluent lead solution is observed. The potential use of solid adsorbents for the adsorption of heavy metal pollutants is envisaged ...

  2. Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

    Science.gov (United States)

    Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

    2018-06-01

    Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

  3. Lead and polycyclic aromatic hydrocarbons (PAHs) in surface soil from day care centres in the city of Bergen, Norway

    International Nuclear Information System (INIS)

    Haugland, Toril; Ottesen, Rolf Tore; Volden, Tore

    2008-01-01

    Surface soil (0-2 cm) quality in 87 day care centres in the city of Bergen, Norway has been studied. Approximately 45% of the day care centres contained Pb and PAH values above recommended action levels. There are clear variations between different areas of the city. The old central part of the city hosts most of the contaminated day care centres. In suburban areas most of the day care centres have Pb and PAH concentrations below action levels. City fires, gas work emission, lead-based paint, and traffic are probably important anthropogenic contamination sources, together with uncontrolled transportation of soil from contaminated to clean areas. Geological or other natural sources are probably not an important contributor to the high levels of lead and PAH. - Surface soil in 45% of the studied day care centres was contaminated by lead and PAH

  4. 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.

  5. 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

  6. Surface analysis and depth profiling of corrosion products formed in lead pipes used to supply low alkalinity drinking water.

    Science.gov (United States)

    Davidson, C M; Peters, N J; Britton, A; Brady, L; Gardiner, P H E; Lewis, B D

    2004-01-01

    Modern analytical techniques have been applied to investigate the nature of lead pipe corrosion products formed in pH adjusted, orthophosphate-treated, low alkalinity water, under supply conditions. Depth profiling and surface analysis have been carried out on pipe samples obtained from the water distribution system in Glasgow, Scotland, UK. X-ray diffraction spectrometry identified basic lead carbonate, lead oxide and lead phosphate as the principal components. Scanning electron microscopy/energy-dispersive x-ray spectrometry revealed the crystalline structure within the corrosion product and also showed spatial correlations existed between calcium, iron, lead, oxygen and phosphorus. Elemental profiling, conducted by means of secondary ion mass spectrometry (SIMS) and secondary neutrals mass spectrometry (SNMS) indicated that the corrosion product was not uniform with depth. However, no clear stratification was apparent. Indeed, counts obtained for carbonate, phosphate and oxide were well correlated within the depth range probed by SIMS. SNMS showed relationships existed between carbon, calcium, iron, and phosphorus within the bulk of the scale, as well as at the surface. SIMS imaging confirmed the relationship between calcium and lead and suggested there might also be an association between chloride and phosphorus.

  7. Neutron production in spallation reactions of 0.9 and 1.5 GeV protons on a thick lead target. Comparison between experimental data and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    Krasa, A.; Krizek, F.; Wagner, V.; Kugler, A.; Henzl, V.; Henzlova, D.; Majerle, M.; Adam, J.; Caloun, P.; Bradnova, V.; Chultem, D.; Kalinnikov, V.G.; Krivopustov, M.I.; Solnyshkin, A.A.; Stegajlov, V.I.; Tsupko-Sitnikov, V.M.; Tumehndehlgehr, Ts.; Vasil'ev, S.I.

    2005-01-01

    This paper reports on two experiments performed at the Synchrophasotron/Nuclotron accelerator complex at JINR. Relativistic protons with energies 885 MeV and 1.5 GeV hit a massive cylindrical lead target. The spatial and energetic distributions of the neutron field produced by the spallation reactions were measured by the activation of Al, Au, Bi, Co, and Cu foils placed on the surface of the target and close to it. The yields of the radioactive nuclei produced by threshold reactions in these foils were determined by the analyses of their γ spectra. The comparison with Monte-Carlo based simulations was performed both with the LAHET+MCNP code and the MCNPX code

  8. Neutron Production in Spallation Reactions of 0.9 and 1.5 GeV Protons on a Thick Lead Target. Comparison between Experimental Data and Monte-Carlo Simulations

    CERN Document Server

    Krasa, A; Bradnova, V; Caloun, P; Chultem, D; Henzl, V; Henzlová, D; Kalinnikov, V G; Krivopustov, M I; Krízek, F; Kugler, A; Majerle, M; Solnyshkin, A A; Stegailov, V I; Tsoupko-Sitnikov, V M; Tumendelger, T; Vasilev, S I; Wagner, V; Nuclear Physics Institute of Academy of Sciences of Czech Republic, Rez, Czech Republic

    2005-01-01

    This paper reports on two experiments performed at the Synchrophasotron/Nuclotron accelerator complex at JINR. Relativistic protons with energies 885 MeV and 1.5 GeV hit a massive cylindrical lead target. The spatial and energetic distributions of the neutron field produced by the spallation reactions were measured by the activation of Al, Au, Bi, Co, and Cu foils placed on the surface of the target and close to it. The yields of the radioactive nuclei produced by threshold reactions in these foils were determined by the analyses of their $\\gamma$ spectra. The comparison with Monte-Carlo based simulations was performed both with the LAHET+MCNP code and the MCNPX code.

  9. 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

  10. 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.

  11. The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

    Science.gov (United States)

    Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

    2018-05-01

    Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.

  12. 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

  13. Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces.

    Science.gov (United States)

    Cha, Jihoon; Cui, Mingcan; Jang, Min; Cho, Sang-Hyun; Moon, Deok Hyun; Khim, Jeehyeong

    2011-01-01

    This study examines the adsorption isotherms, kinetics and mechanisms of Pb²(+) sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²(+) in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²(+) with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²(+) and PO₄³⁻ concentrations during the metal sorption processes. The Pb²(+) sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb(+). The sorption isotherm results indicated that Pb²(+) sorption onto the Langmuir and Freundlich constant q(max) and K( F ) is 9.52 and 8.18 mg g⁻¹, respectively. Sorption kinetics results indicated that Pb²(+) sorption onto WCBP was pseudo-second-order rate constants K₂ was 1.12 g mg⁻¹ h⁻¹. The main mechanism is adsorption or surface complexation (≡POPb(+): 61.6%), co-precipitation or ion exchange [Ca₃(.)₉₃ Pb₁(.)₀₇ (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L⁻¹ and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²(+) removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²(+) indicates its potential as another promising way to remediate Pb²(+)-contaminated media.

  14. Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films

    Science.gov (United States)

    Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E.; Malko, Anton V.; Chabal, Yves J.

    2016-01-01

    The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (~1017 cm-3) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state

  15. Effects of blending of desalinated water with treated surface drinking water on copper and lead release.

    Science.gov (United States)

    Liu, Haizhou; Schonberger, Kenneth D; Korshin, Gregory V; Ferguson, John F; Meyerhofer, Paul; Desormeaux, Erik; Luckenbach, Heidi

    2010-07-01

    This study examined effects of desalinated water on the corrosion of and metal release from copper and lead-containing materials. A jar test protocol was employed to examine metal release from copper and lead-tin coupons exposed to water chemistries with varying blending ratios of desalinated water, alkalinities, pHs and orthophosphate levels. Increasing fractions of desalinated water in the blends resulted in non-monotonic changes of copper and lead release, with generally lower metal concentrations in the presence of desalinated water, especially when its contribution increased from 80% to 100%. SEM examination showed that the increased fractions of desalinated water were associated with pronounced changes of the morphology of the corrosion scales, likely due to the influence of natural organic matter. This hypothesis was corroborated by the existence of correlations between changes of the zeta-potential of representative minerals (malachite and hydrocerussite) and metal release. For practical applications, maintaining pH at 7.8 and adding 1 mg/L orthophosphate as PO(4) were concluded to be adequate to decrease copper and lead release. Lower alkalinity of desalinated water was beneficial for blends containing 50% or more desalinated water. Copyright 2010 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  18. Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

    Science.gov (United States)

    Lobo-Lapidus, Rodrigo J; Gates, Bruce C

    2010-10-04

    Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

  19. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    Science.gov (United States)

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2001-01-01

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

  2. 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.

  3. Reliability of lead-free solder joints with different PCB surface finishes under thermal cycling

    Energy Technology Data Exchange (ETDEWEB)

    Xia Yanghua [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)], E-mail: xia_yanghua@hotmail.com; Xie Xiaoming [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)

    2008-04-24

    The reliability of lead-free electronic assemblies under thermal cycling was investigated. Thin small outline package (TSOP) devices with FeNi leads were reflow soldered on FR4 PCB (printed circuit board) with Sn3.0Ag0.5Cu (wt%) solder. The effects of different PCB finishes (organic solderability preservative (OSP) and electroless nickel immersion gold (ENIG)) were studied. The results show that OSP finish reveals better performance than its ENIG counterparts. The crack originates at the fringe of heel fillet in both cases. The propagation of crack in the ENIG case is along the device/solder interface, while in the case of OSP, the crack extends parallel to the solder/PCB interface. When the OSP finishes are employed, many Cu6Sn5 precipitates form inside the bulk solder and have a strengthening effect on the solder joint, resulting in better reliability performance as compared to those with ENIG finishes.

  4. Lead-silicate glass surface sputtered by an argon cluster ion beam investigated by XPS

    Czech Academy of Sciences Publication Activity Database

    Zemek, Josef; Jiříček, Petr; Houdková, Jana; Jurek, Karel; Gedeon, O.

    2017-01-01

    Roč. 469, Aug (2017), s. 1-6 ISSN 0022-3093 R&D Projects: GA MŠk LM2015088; GA ČR(CZ) GA15-12580S Institutional support: RVO:68378271 Keywords : lead-silicate glass * XPS * BO * NBO * Argon duster ion beam sputtering * X-ray irradiation Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.124, year: 2016

  5. Lead-210 analyses of sediment accumulation rates in five Southern Illinois surface mine lakes

    International Nuclear Information System (INIS)

    Brugam, R.B.; Carlson, M.A.

    1981-01-01

    210 Pb is a naturally occurring radionuclide with a short half-life (22 yrs) which can be used to determine sedimentation rates in lakes. The technique was applied in 5 Southern Illinois surface mine lakes where it revealed past sedimentation rates to have been extremely variable. In some of the lakes there was evidence for extensive slumping immediately after mining ceased followed by a more regular sedimentary regime that continued until the present. In others there have been one or more changes in sediment accumulation rates since lacustrine sedimentation began. These results suggest that simply measuring the amount of sediment that has accumulated in a surface mine lake since mining ceased is inadequate to determine filling rates. Sedimentation rates in the 5 lakes varied from .60 +- .19 to 1.46 +- .19 cm/y. These rates are similar to natural lakes with moderately disturbed watersheds

  6. Fusability and survivability in reactions leading to heavy nuclei in the vicinity of the N = 126 shell

    International Nuclear Information System (INIS)

    Sagajdak, R.N.

    2008-01-01

    The production of heavy nuclei from Rn to Th around the N = 126 neutron shell in complete fusion reactions of nuclei has been considered in a systematic way in the framework of the conventional barrier-passing fusion model coupled with the Standard Statistical Model (SSM). Available data on the excitation functions for fusion and production of evaporation residues obtained in very asymmetric combinations are described with these models rather well. In the interaction of massive projectiles with heavy target nuclei quasi-fission effects appear in the entrance reaction channel. The quantity of the fusion probability introduced empirically has been used to reproduce excitation functions with the same SSM parameters (fission barriers) as those obtained in the analysis of very asymmetric combinations. A lack of stabilization against fission around N = 126 for Th nuclei was earlier explained with a reduced collective contribution to the level density in spherical nuclei. However, the present analysis shows severe inhibition for fusion, i.e., the drop in production cross sections of Th nuclei in the vicinity of N = 126 is mainly caused by entrance channel effects. The macroscopic component of fission barriers for nuclei involved in a deexcitation cascade has been derived and compared with the theoretical model predictions and available data

  7. Influence of exogenous lead pollution on enzyme activities and organic matter degradation in the surface of river sediment.

    Science.gov (United States)

    Huang, Danlian; Xu, Juanjuan; Zeng, Guangming; Lai, Cui; Yuan, Xingzhong; Luo, Xiangying; Wang, Cong; Xu, Piao; Huang, Chao

    2015-08-01

    As lead is one of the most hazardous heavy metals in river ecosystem, the influence of exogenous lead pollution on enzyme activities and organic matter degradation in the surface of river sediment with high moisture content were studied at laboratory scale. The dynamic changes of urease, catalase, protease activities, organic matter content, and exchangeable or ethylenediaminetetraacetic acid (EDTA)-extractable Pb concentration in sediment were monitored during different levels of exogenous lead infiltrating into sediment. At the early stage of incubation, the activities of catalase and protease were inhibited, whereas the urease activities were enhanced with different levels of exogenous lead. Organic matter content in polluted sediment with exogenous lead was lower than control and correlated with enzyme activities. In addition, the effects of lead on the three enzyme activities were strongly time-dependent and catalase activities showed lower significant difference (P < 0.05) than urease and protease. Correlations between catalase activities and EDTA-extractable Pb in the experiment were significantly negative. The present findings will improve the understandings about the ecotoxicological mechanisms in sediment.

  8. 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.

  9. 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)

  10. 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

  11. Surface decoration through electrostatic interaction leading to enhanced reactivity: Low temperature synthesis of nanostructured chromium borides (CrB and CrB2)

    International Nuclear Information System (INIS)

    Menaka,; Kumar, Bharat; Kumar, Sandeep; Ganguli, A.K.

    2013-01-01

    The present study describes a novel low temperature route at ambient pressure for the synthesis of nanocrystalline chromium borides (CrB and CrB 2 ) without using any flux or additives. The favorable and intimate mixing of nanoparticles of chromium acetate (Cr source) and boron forms an active chromium–boron precursor which decomposes at much lower temperature (400 °C) to form CrB (which is ∼1000 °C less than the known ambient pressure synthesis). The chromium acetate nanoparticles (∼5 nm) decorate the larger boron particles (150–200 nm) due to electrostatic interactions resulting from opposing surface charges of boron (zeta potential:+48.101 mV) and chromium acetate (zeta potential:−4.021 mV) in ethanolic medium and is evident in the TEM micrographs. The above method leads to the formation of pure CrB film like structure at 400 °C and nanospheres (40–60 nm) at 600 °C. Also, chromium diboride (CrB 2 ) nanoparticles (25 nm) could be obtained at 1000 °C. - Graphical abstract: Variation of surface charge of reactants, precursor and the products, chromium borides (CrB and CrB 2 ). Highlights: ► Novel borothermal reduction process for synthesis of chromium boride. ► Significant lowering of reaction temperature to obtain nanocrystalline chromium boride. ► Enhanced reactivity due to appropriate surface interactions

  12. Arsenic, cadmium, lead, and mercury in surface soils, Pueblo, Colorado: Implications for population health risk

    Science.gov (United States)

    Diawara, D.M.; Litt, J.S.; Unis, D.; Alfonso, N.; Martinez, L.A.; Crock, J.G.; Smith, D.B.; Carsella, J.

    2006-01-01

    Decades of intensive industrial and agricultural practices as well as rapid urbanization have left communities like Pueblo, Colorado facing potential health threats from pollution of its soils, air, water and food supply. To address such concerns about environmental contamination, we conducted an urban geochemical study of the city of Pueblo to offer insights into the potential chemical hazards in soil and inform priorities for future health studies and population interventions aimed at reducing exposures to inorganic substances. The current study characterizes the environmental landscape of Pueblo in terms of heavy metals, and relates this to population distributions. Soil was sampled within the city along transects and analyzed for arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb). We also profiled Pueblo's communities in terms of their socioeconomic status and demographics. ArcGIS 9.0 was used to perform exploratory spatial data analysis and generate community profiles and prediction maps. The topsoil in Pueblo contains more As, Cd, Hg and Pb than national soil averages, although average Hg content in Pueblo was within reported baseline ranges. The highest levels of As concentrations ranged between 56.6 and 66.5 ppm. Lead concentrations exceeded 300 ppm in several of Pueblo's residential communities. Elevated levels of lead are concentrated in low-income Hispanic and African-American communities. Areas of excessively high Cd concentration exist around Pueblo, including low income and minority communities, raising additional health and environmental justice concerns. Although the distribution patterns vary by element and may reflect both industrial and non-industrial sources, the study confirms that there is environmental contamination around Pueblo and underscores the need for a comprehensive public health approach to address environmental threats in urban communities. ?? Springer 2006.

  13. Optical and surface morphological properties of triethylamine passivated lead sulphide nanoparticles

    International Nuclear Information System (INIS)

    Navaneethan, M.; Nisha, K.D.; Ponnusamy, S.; Muthamizhchelvan, C.

    2009-01-01

    The triethylamine capped lead sulphide (PbS) nanoparticles were successfully synthesized by simple wet chemical method. The synthesized product has been characterized by powder X-ray diffraction (XRD), UV-vis spectrophotometry, FTIR spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and photoluminescence studies. The size of the PbS nanoparticles was determined from AFM, TEM, XRD and from these studies it is found that the size of the particles of the order of 10-15 nm. Significant 'blue shift' from bulk material was observed on the PbS nanoparticles using UV-vis and photoluminescence spectrum.

  14. Unraveling surface and bulk trap states in lead halide perovskite solar cells using impedance spectroscopy

    Science.gov (United States)

    Han, Changfeng; Wang, Kai; Zhu, Xixiang; Yu, Haomiao; Sun, Xiaojuan; Yang, Qin; Hu, Bin

    2018-03-01

    Organic-inorganic hybrid perovskites (OIHPs) have been widely recognized as an excellent candidate for next-generation photovoltaic materials because of their highly efficient power conversion. Acquiring a complete understanding of trap states and dielectric properties in OIHP-based solar cells at the steady state is highly desirable in order to further explore and improve their optoelectronic functionalities and properties. We report CH3NH3PbI3-x Cl x -based planar solar cells with a power conversion efficiency (PCE) of 15.8%. The illumination intensity dependence of the current density-voltage (J-V) revealed the presence of trap-assisted recombination at low fluences. Non-destructive ac impedance spectroscopy (ac-IS) was applied to characterize the device at the steady state. The capacitance-voltage (C-V) spectra exhibited some distinct variations at a wide range of ac modulation frequencies with and without photo-excitations. Since the frequency-dependent chemical capacitance ({{C}μ }) is concerned with the surface and bulk related density of states (DOS) in CH3NH3PbI3-x Cl x , we verified this by fitting the corresponding DOS by a Gaussian distribution function. We ascertained that the electronic sub-gap trap states present in the solution processed CH3NH3PbI3-x Cl x and their distribution differs from the surface to the bulk. In fact, we demonstrated that both surfaces that were adjacent to the electron and hole transport layers featured analogous DOS. Despite this, photo- and bias-induced giant dielectric responses (i.e. both real and imaginary parts) were detected. A remarkable reduction of {{C}μ } at higher frequencies (i.e. more than 100 kHz) was ascribed to the effect of dielectric loss in CH3NH3PbI3-x Cl x .

  15. Overexpression of NRPS4 leads to increased surface hydrophobicity in fusarium graminearum

    DEFF Research Database (Denmark)

    Hansen, Frederik Teilfeldt; Droce, Aida; Sørensen, Jens Laurids

    2012-01-01

    ). Most of these are unknown as F. graminearum contains 19 NRPS encoding genes, but only three have been assigned products. For the first time, we use deletion and overexpression mutants to investigate the functions and product of NRPS4 in F. graminearum. Deletion of NRPS4 homologues in Alternaria...... brassicicola and Cochloibolus heterostrophus has been shown to result in mutants unable to repel water. In a time study of surface hydrophobicity we observed that water droplets could penetrate 7 d old colonies of the NRPS4 deletion mutants. Loss in ability to repel water was first observed on 13 d old...

  16. Optimization of Lead Removal via Napier Grass in Synthetic Brackish Water using Response Surface Model

    Science.gov (United States)

    Hongsawat, P.; Suttiarporn, P.; Wutsanthia, K.; Kongsiri, G.

    2018-03-01

    The efficiency of the lead (Pb) phytoremediation by Napier grass was studied on the plant’s growth and plant’s tolerance on the Pb toxicity in synthetic brackish water. It was found that the plant was high tolerance to high level of Pb concentration (10 mg/l) in synthetic brackish water. Which revealed on the possibilities of plant’s growth under the presence of Pb contaminated condition. According to the Pb removal efficiency, the highest one (88.63±4.9%) was found at 10 ppm Pb concentration, 0.3 g/l NaCl concentration during the period 45 day. However, this study investigated the optimum condition for lead (Pb) removal from synthetic brackish water using phytoremediation treatment with Napier grass through a Box-Behnken Design. Three operational variables, i.e. Pb concentration (1, 5.5, 10 mg/l), NaCl (0.1, 0.3, 0.5 g/l) and period time (7, 26, 45 day), were determined. The results were provided evidence that the highest Pb removal efficiency (93.56%) from synthetic brackish water via Napier grass was Pb and NaCl concentration at 10 mg/l and 0.5 g/l during 45 day.

  17. Measurements and Evaluation of Nuclear Reaction Cross Sections Leading to Various Practical Applications in Science and Technology

    Energy Technology Data Exchange (ETDEWEB)

    Khandaker, Mayeen Uddin; Lee, Young Ouk; Cho, Young Sik

    2008-07-15

    This report contains the measurements and evaluation of production cross sections of some medically and technologically important radionuclides over the energy range 1-40 MeV by using a conventional stacked-foil activation technique combined with high purity germanium (HPGe) -ray spectrometry. The irradiations were done by using the external beam line of the MC-50 cyclotron at the Korea Institute of Radiological and Medical Sciences (KIRAMS). The standard cross sections for monitor reactions were taken from IAEA web site. Integral yields for the investigated radionuclides were deduced using the measured cross-sections. Reported data were compared with the available literature data, theoretical calculations by the codes TALYS and ALICE-IPPE, and a good overall agreement among them was found.

  18. Measurements and Evaluation of Nuclear Reaction Cross Sections Leading to Various Practical Applications in Science and Technology

    International Nuclear Information System (INIS)

    Khandaker, Mayeen Uddin; Lee, Young Ouk; Cho, Young Sik

    2008-07-01

    This report contains the measurements and evaluation of production cross sections of some medically and technologically important radionuclides over the energy range 1-40 MeV by using a conventional stacked-foil activation technique combined with high purity germanium (HPGe) -ray spectrometry. The irradiations were done by using the external beam line of the MC-50 cyclotron at the Korea Institute of Radiological and Medical Sciences (KIRAMS). The standard cross sections for monitor reactions were taken from IAEA web site. Integral yields for the investigated radionuclides were deduced using the measured cross-sections. Reported data were compared with the available literature data, theoretical calculations by the codes TALYS and ALICE-IPPE, and a good overall agreement among them was found

  19. Polysiloxane surface modified with bipyrazolic tripodal receptor for quantitative lead adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Radi, Smaail, E-mail: radi_smaail@yahoo.fr [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Tighadouini, Said; Toubi, Yahya [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Bacquet, Maryse [Universite des Sciences et Technologies de Lille, UMET: Unite Materiaux et Transformations UMR8207, Equipe Ingenierie des Systemes Polymeres, Batiment C6 salle 119-59655 Villeneuve d' Ascq (France)

    2011-01-15

    A new silica gel compound modified N,N-bis(3,5-dimethylpyrazol-1-ylmethyl) amine (SiN{sub 2}Pz) was synthesized and characterized by elemental analysis, FT-IR, {sup 13}C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area and BJH pore sizes. The new surface exhibits good chemical and thermal stability determined by thermogravimetry curves (TGA). The effect of pH and stirring time on the adsorption of Pb(II) were studied. The process of metal retention was followed by batch method and the optimum pH value for the quantitative adsorption of this toxic metal ion was 7. At this pH value, the new functionalized polysiloxane presents further improvements and shows higher affinity (123 mg of Pb{sup 2+}/g of silica) for the effective adsorption of Pb(II) compared to others described sorbents. The extracted amounts of Pb(II) were determined by atomic absorption measurements.

  20. 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.

  1. 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.

  2. Surface air concentration and deposition of lead-210 in French Guiana: two years of continuous monitoring

    International Nuclear Information System (INIS)

    Melieres, Marie-Antoinette; Pourchet, Michel; Richard, Sandrine

    2003-01-01

    To make up for the lack of data on 210 Pb aerosol deposition in tropical regions and to use this radionuclide as an aerosol tracer,a monitoring station was run for two years at Petit-Saut, French Guiana. Lead-210 concentration in air at ground level was monitored continuously together with atmospheric total deposition. The air concentration has a mean value of 0.23±0.02 mBq m -3 during both wet and dry seasons, and it is only weakly affected by the precipitation mechanism. This result was unexpected in a wet tropical region, with a high precipitation rate. In contrast, deposition clearly correlates with precipitation for low/moderate rainfall ( -2 y -1 . This provides a procedure fo estimating this mean flux at other sites in French Guiana

  3. 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

  4. 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

  5. Bacteroides fragilis interferes with iNOS activity and leads to pore formation in macrophage surface

    International Nuclear Information System (INIS)

    Vieira, Jessica Manya B.D.; Vallim, Deyse C.; Ferreira, Eliane O.; Seabra, Sergio H.; Vommaro, Rossiane C.; Avelar, Katia E.S.; De Souza, Wanderley; Ferreira, Maria Ca-hat ndida S.; Domingues, Regina M.C.P.

    2005-01-01

    Bacteroides fragilis is the anaerobe most commonly recoverable from clinical specimens. The wide genetic diversity of this bacterium related with virulence potential is still an open question. In this study, we analyzed the morphological aspects and microbicide action of MO during interactions with B. fragilis. A filamentous cytoplasm content release and a different actin organization colocalized with iNOS were detected. It was also possible to observe the reduction of NO production in the same conditions. The scanning electron microscopy showed the formation of pore-like structures in the surface of macrophages in the bacterial presence and by transmission electron microscopy we could observe the extrusion of cytoplasm contents as well as the condensation of chromatin in the nucleus periphery. These data suggest the existence of an inhibitory mechanism developed by B. fragilis strains for one of the macrophage microbicide actions

  6. 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)

  7. Assessing the speciation pattern of lead and zinc in surface water collected from Abegede creek, Ijora and Lagos

    International Nuclear Information System (INIS)

    Adeniyi, A.A.; Okedeyi, O.O.

    2004-01-01

    A two stage sequential extraction procedure for the speciation of zinc and lead has been applied to surface water randomly collected from three sites in Abegede Creek, Ijora and Lagos. The determination of the labile and non-labile metals species was carried out by flame atomic absorption spectrophotometry (FAAS). The mean values of non-labile zinc and lead concentrations from the three sites, A, B and Care 0.54 minus plus 0.25 mg/l; 0.55 plus minus 0.26 mg/l;1.13 plus 0.76 mg/l; respectively for zinc and 0.13 plus minus 0.09 mg/l; 0.17 plus minus 0.07 mg/l;0.42 plus minus 0.23 mg/l respectively for lead. These are higher than for the labile species in the three sites;0.14 plus minus 0.07 mg/l; 0.21 plus minus 0.22 mg/l; 0.73 plus minus 0.82 mg/l, respectively for zinc and ND; 0.02 plus minus 0.04 mg/l; 0.16 plus minus 0.22 mg/l, respectively for lead. The statistical analysis of variance of the distribution of zinc and lead in the three sites were estimated at 95% confidence level. The values of metal and obtained were compared with Nigeria's background values for some rivers and the World Health Organization limits for drinking water respectively and found to be generally higher especially for lead levels. The probable sources of zinc and lead in the Creek are from natural and point sources, although there could be non-point source contributions from urban run-offs and vehicular exhaust. (author)

  8. Surface modified MXene Ti3C2 multilayers by aryl diazonium salts leading to large-scale delamination

    Science.gov (United States)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-10-01

    Herein we report a simple and facile method to delaminate MXene Ti3C2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti3AlC2 and the exfoliation of Ti3AlC2 into Ti3C2 multilayers, followed by Na+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti3C2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti3C2 sheets disperse well in water and the solutions obey Lambert-Beer's law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti3C2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti3C2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  9. Surface air concentration and deposition of lead-210 in French Guiana: two years of continuous monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Melieres, Marie-Antoinette E-mail: melieres@glaciog.ujf-grenoble.fr; Pourchet, Michel; Richard, Sandrine

    2003-07-01

    To make up for the lack of data on {sup 210}Pb aerosol deposition in tropical regions and to use this radionuclide as an aerosol tracer,a monitoring station was run for two years at Petit-Saut, French Guiana. Lead-210 concentration in air at ground level was monitored continuously together with atmospheric total deposition. The air concentration has a mean value of 0.23{+-}0.02 mBq m{sup -3} during both wet and dry seasons, and it is only weakly affected by the precipitation mechanism. This result was unexpected in a wet tropical region, with a high precipitation rate. In contrast, deposition clearly correlates with precipitation for low/moderate rainfall (<15 cm per 15-day), while this correlation is masked by strong fluctuations at high rainfall. The estimated mean annual deposition over the last ten years is 163{+-}75 Bq m{sup -2} y{sup -1}. This provides a procedure fo estimating this mean flux at other sites in French Guiana.

  10. Theoretical estimates of supernova-neutrino cross sections for the stable even-even lead isotopes: Charged-current reactions

    Science.gov (United States)

    Almosly, W.; Carlsson, B. G.; Suhonen, J.; Toivanen, J.; Ydrefors, E.

    2016-10-01

    A detailed study of the charged-current supernova electron neutrino and electron antineutrino scattering off the stable even-mass lead isotopes A =204 , 206, and 208 is reported in this work. The proton-neutron quasiparticle random-phase approximation (pnQRPA) is adopted to construct the nuclear final and initial states. Three different Skyrme interactions are tested for their isospin and spin-isospin properties and then applied to produce (anti)neutrino-nucleus scattering cross sections for (anti)neutrino energies below 80 MeV. Realistic estimates of the nuclear responses to supernova (anti)neutrinos are computed by folding the computed cross sections with a two-parameter Fermi-Dirac distribution of the electron (anti)neutrino energies. The computed cross sections are compared with earlier calculations and the analyses are extended to take into account the effects coming from the neutrino oscillations.

  11. Surface modified MXene Ti_3C_2 multilayers by aryl diazonium salts leading to large-scale delamination

    International Nuclear Information System (INIS)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-01-01

    Highlights: • A novel and simple method to delaminate MXene Ti_3C_2 multilayers. • Surface modification using aryl diazonium salts induced swelling that conversely weakened the bonds between MXene layers. • The grafting of phenylsulfonic acid groups on MXene surfaces resulted in excellent water dispersibility. - Abstract: Herein we report a simple and facile method to delaminate MXene Ti_3C_2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti_3AlC_2 and the exfoliation of Ti_3AlC_2 into Ti_3C_2 multilayers, followed by Na"+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti_3C_2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti_3C_2 sheets disperse well in water and the solutions obey Lambert–Beer’s law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti_3C_2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti_3C_2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  12. 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.

  13. Boson states in the reaction π-p → π-π-π+p with leading π+ meson at 25 GeV/c

    International Nuclear Information System (INIS)

    Antipov, Yu.M.; Baud, R.

    1975-01-01

    The reaction π - + p → p + π - + π - + π + at 25 GeV/c was studied in the mass region M sub(3π) >>= 1.8 GeV with leading π + in the final state. The mass spectrum of π 1 π - -system evidently shows peaks rho deg, f, g deg resonances and an enhancement in S'-region. It is shown that the g deg and π - mesons are mainly in A4 state J sub(P) = 3 + S-wave g degπ - like A1(sup(rhoπ)) and A3(sup(fπ))

  14. 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

  15. 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.

  16. 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

  17. 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

  18. 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

  19. A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

    Science.gov (United States)

    Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

    2016-09-21

    Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

  20. 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.)

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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...

  8. 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)

  9. 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).

  10. 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.

  11. Thermal and non-thermal lattice gas models for a dimer-trimer surface catalytic reaction: a Monte-Carlo simulation study

    International Nuclear Information System (INIS)

    Iqbal, K.; Khand, P.A.

    2012-01-01

    The kinetics of an irreversible dimer-trimer reaction of the type 2 A/sub 3/ +3 B/sub 2/ -- 6 AB by considering the precursor motion of the dimer (B/sub 2) on a square, as well as on a hexagonal surface, by using a Monte Carlo simulation have been studied. When the movement of precursors is limited to the first nearest neighborhood, the model gives reactive window widths of the order of 0.22 and 0.29 for the square and the hexagonal lattices, respectively, which are quite large compared to those predicted by the LH model. In our model, the reactive window width for a square lattice increases significantly as compared to that for the LH models of the same system on square and hexagonal lattices. The width of the reactive region increases when the precursor motion is extended to the second and the third nearest neighborhood. The continuous transition disappears when the precursor motion is extended to the third nearest neighborhood. The diffusion of B atoms does not change the situation qualitatively for both the precursor and the LH models. However, desorption of the dimer changes the situation significantly; i.e., the width of the reactive window shows an exponential growth with respect to the desorption probability of the dimer for both the precursor and the LH models. In our opinion, the inclusion of precursors in the LH model of the dimer-trimer reactions leads to a better and more realistic description of the heterogeneous catalytic reactions. Consequently, further numerical and theoretical activity in this field will be very useful for understanding complex heterogeneous reactions. (orig./A.B.)

  12. Photocatalysis of irradiated semiconductor surfaces: Its application to water splitting and some organic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sakata, T

    1985-05-01

    Hydrogen production from organic compounds and water was investigated using powdered semiconductor photocatalysts. The complete decomposition observed for several organic compounds demonstrated that water is involved in the reactions as an oxidizing agent. Photocatalyses of dyes and semiconductors were found to be applicable to amino acid synthesis. The quantum yields of photocatalytic amino acid synthesis using visible light are about 20%-40% in the absence of a metal catalyst such as platinum. Moreover the reactions are highly selective and depend strongly on the type of semiconductor. This method was applied to the asymmetric synthesis of amino acids using asymmetric catalysts. Rather high optical yields of 50% were achieved for the synthesis of L-phenylalanine.

  13. Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

    International Nuclear Information System (INIS)

    Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

    1994-01-01

    CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

  14. Shaping surface of palladium nanospheres through the control of reaction parameters

    International Nuclear Information System (INIS)

    Wang Lianmeng; Tan Enzhong; Guo Lin; Wang Lihua; Han Xiaodong

    2011-01-01

    Solid, cracked, and flower-shaped surfaces of palladium nanospheres with high yields and good uniformity were successfully prepared by a wet chemical method. On the basis of the experimental data, the same size of palladium nanosphere with different surface morphologies can be regulated only by changing the amount of ammonium hydroxide and reductant in one experimental system. The as-prepared products were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and x-ray diffraction (XRD). In addition, surface-enhanced Raman scattering (SERS) spectra on the as-prepared different surface of palladium nanospheres exhibit high activity towards p-aminothiophenol (PATP) detection, and the result further reveals that the predominance of the a1 vibration mode in the SERS spectra via an electromagnetic (EM) mechanism is significant.

  15. Characterisation and surface reactions of iron oxides and fluorapatite in aqueous suspensions

    OpenAIRE

    Jarlbring, Mathias

    2004-01-01

    The final objective of this study is to produce chemical models of flotation- like systems, including oxidation products of magnetite (maghemite and hematite) together with apatite. This is started by investigating the acid base properties, surface complexation and surface characteristics of the systems hematite-H+ and maghemite-H+ (paper I), fluorapatite-OH- (paper II) and a mixed system of maghemite-fluorapatite-OH- (paper III). Synthetic minerals were prepared and characterised with BET, S...

  16. Solar Atmosphere to Earth's Surface: Long Lead Time dB/dt Predictions with the Space Weather Modeling Framework

    Science.gov (United States)

    Welling, D. T.; Manchester, W.; Savani, N.; Sokolov, I.; van der Holst, B.; Jin, M.; Toth, G.; Liemohn, M. W.; Gombosi, T. I.

    2017-12-01

    The future of space weather prediction depends on the community's ability to predict L1 values from observations of the solar atmosphere, which can yield hours of lead time. While both empirical and physics-based L1 forecast methods exist, it is not yet known if this nascent capability can translate to skilled dB/dt forecasts at the Earth's surface. This paper shows results for the first forecast-quality, solar-atmosphere-to-Earth's-surface dB/dt predictions. Two methods are used to predict solar wind and IMF conditions at L1 for several real-world coronal mass ejection events. The first method is an empirical and observationally based system to estimate the plasma characteristics. The magnetic field predictions are based on the Bz4Cast system which assumes that the CME has a cylindrical flux rope geometry locally around Earth's trajectory. The remaining plasma parameters of density, temperature and velocity are estimated from white-light coronagraphs via a variety of triangulation methods and forward based modelling. The second is a first-principles-based approach that combines the Eruptive Event Generator using Gibson-Low configuration (EEGGL) model with the Alfven Wave Solar Model (AWSoM). EEGGL specifies parameters for the Gibson-Low flux rope such that it erupts, driving a CME in the coronal model that reproduces coronagraph observations and propagates to 1AU. The resulting solar wind predictions are used to drive the operational Space Weather Modeling Framework (SWMF) for geospace. Following the configuration used by NOAA's Space Weather Prediction Center, this setup couples the BATS-R-US global magnetohydromagnetic model to the Rice Convection Model (RCM) ring current model and a height-integrated ionosphere electrodynamics model. The long lead time predictions of dB/dt are compared to model results that are driven by L1 solar wind observations. Both are compared to real-world observations from surface magnetometers at a variety of geomagnetic latitudes

  17. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  18. An integrated high temperature environmental cell for atom probe tomography studies of gas-surface reactions: Instrumentation and results

    International Nuclear Information System (INIS)

    Dumpala, S.; Broderick, S.R.; Bagot, P.A.J.; Rajan, K.

    2014-01-01

    An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument. - Highlights: • Designed and built atom probe environmental cell for in situ reactions. • Investigated Al oxidation, and demonstrated improvement with new cell. • in situ APT analysis of Pt-alloys showed surface segregation of Rh and Ir

  19. Corrosion of ferritic steels by molten lithium: Influence of competing thermal gradient mass transfer and surface product reactions

    International Nuclear Information System (INIS)

    Tortorelli, P.F.

    1987-10-01

    An Fe-12Cr-1MoVW steel was exposed to thermally convective lithium for 6962 h. Results showed that the weight change profile of Fe-12Cr-1MoVW steel changed substantially as the maximum loop temperature was raised from 500 to 600 0 C. Furthermore, for a particular loop experiment, changes in the structure and composition of the exposed surfaces did not reflect typical thermal gradient mass transfer effects for all elements: the surface concentration of chromium was often a maximum at intermediate temperatures, while nickel (present at low concentrations in the starting material) tended to be transported to the coldest part of the loop. Such data were interpreted in terms of a qualitative model in which there are different dominant reactions or the various constituents of the ferritic steels (surface product formation involving nitrogen and/or carbon and solubility-driven elemental transport). This competition among different reactions is important in evaluating overall corrosion behavior and the effects of temperature. The overall corrosion rate of the 12Cr-1MoVW steel was relatively low when compared to that for austenitic stainless steel exposed under similar conditions

  20. Assessment Of Surface-Catalyzed Reaction Products From High Temperature Materials In Plasmas

    Science.gov (United States)

    Allen, Luke Daniel

    Current simulations of atmospheric entry into both Mars and Earth atmospheres for the design of thermal protections systems (TPS) typically invoke conservative assumptions regarding surface-catalyzed recombination and the amount of energy deposited on the surface. The need to invoke such assumptions derives in part from lack of adequate experimental data on gas-surface interactions at trajectory relevant conditions. Addressing this issue, the University of Vermont's Plasma Test and Diagnostics Laboratory has done extensive work to measure atomic specie consumption by measuring the concentration gradient over various material surfaces. This thesis extends this work by attempting to directly diagnose molecular species production in air plasmas. A series of spectral models for the A-X and B-X systems of nitric oxide (NO), and the B-X system of boron monoxide (BO) have been developed. These models aim to predict line positions and strengths for the respective molecules in a way that is best suited for the diagnostic needs of the UVM facility. From the NO models, laser induced fluorescence strategies have been adapted with the intent of characterizing the relative quantity and thermodynamic state of NO produced bysurface-catalyzed recombination, while the BO model adds a diagnostic tool for the testing of diboride-based TPS materials. Boundary layer surveys of atomic nitrogen and NO have been carried out over water-cooled copper and nickel surfaces in air/argon plasmas. Translation temperatures and relative number densities throughout the boundary layer are reported. Additional tests were also conducted over a water-cooled copper surface to detect evidence of highly non-equilibrium effects in the form of excess population in elevated vibrational levels of the A-X system of NO. The tests showed that near the sample surface there is a much greater population in the upsilon'' = 1ground state than is predicted by a Boltzmann distribution.

  1. Evaluation of the cross-sections of threshold reactions leading to the production of long-lived radionuclides during irradiation of steels by thermonuclear spectrum neutrons

    CERN Document Server

    Blokhin, A I; Manokhin, V N; Mikhajlyukova, M V; Nasyrova, S M; Skripova, M V

    2001-01-01

    The present paper analyses and evaluates the cross-sections of threshold reactions leading to the production of long-lived radionuclides during the irradiation, by thermonuclear spectrum neutrons, of steels containing V, Ti, Cr, Fe and Ni. On the basis of empirical systematics. a new evaluation of the (n,2n), (n,p), (n,np), (n,alpha) and (n,n alpha) excitation functions is made for all isotopes of V, Ti, Cr, Fe and Ni and for intermediate isotopes produced in the chain from irradiated isotopes up to production of the long-lived radionuclides sup 3 sup 9 Ar, sup 4 sup 2 Ar, sup 4 sup 1 Ca, sup 5 sup 3 Mn, sup 6 sup 0 Fe, sup 6 sup 0 Co, sup 5 sup 9 Ni and sup 6 sup 3 Ni. A comparison is made with the experimental and other evaluated data.

  2. Evaluation of the cross-sections of threshold reactions leading to the production of long-lived radionuclides during irradiation of steels by thermonuclear spectrum neutrons

    International Nuclear Information System (INIS)

    Blokhin, A.I.; Buleeva, N.N.; Manokhin, V.N.; Mikhajlyukova, M.V.; Nasyrova, S.M.; Skripova, M.V.

    2002-01-01

    The present paper analyses and evaluates the cross-sections of threshold reactions leading to the production of long-lived radionuclides during the irradiation, by thermonuclear spectrum neutrons, of steels containing V, Ti, Cr, Fe and Ni. On the basis of empirical systematics. a new evaluation of the (n,2n), (n,p), (n,np), (n,α) and (n,nα) excitation functions is made for all isotopes of V, Ti, Cr, Fe and Ni and for intermediate isotopes produced in the chain from irradiated isotopes up to production of the long-lived radionuclides 39 Ar, 42 Ar, 41 Ca, 53 Mn, 60 Fe, 60 Co, 59 Ni and 63 Ni. A comparison is made with the experimental and other evaluated data. (author)

  3. Measurement of activation reaction rate distribution on a mercury target with a lead-reflector and light-water-moderator for high energy proton bombardment using AGS accelerator

    International Nuclear Information System (INIS)

    Kasugai, Yoshimi; Takada, Hiroshi; Meigo, Shin-ichiro

    2001-02-01

    Characteristic of spallation neutrons driven by GeV protons from a mercury target with a lead-reflector and light-water-moderator was studied experimentally using the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Several reaction rates along with the mercury target were measured with the activation method at incident proton energies of 1.94, 12 and 24 GeV. Indium, niobium, aluminum, cobalt, nickel and bismuth were used as activation detectors to cover the threshold energy of between 0.33 and 40.9 MeV. This report summarizes the experimental procedure with all the measured data. (author)

  4. 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.

  5. 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.

  6. Lead-chalcogenide mid-infrared vertical external cavity surface emitting lasers with improved threshold: Theory and experiment

    Science.gov (United States)

    Fill, Matthias; Debernardi, Pierluigi; Felder, Ferdinand; Zogg, Hans

    2013-11-01

    Mid-infrared Vertical External Cavity Surface Emitting Lasers (VECSEL) based on narrow gap lead-chalcogenide (IV-VI) semiconductors exhibit strongly reduced threshold powers if the active layers are structured laterally for improved optical confinement. This is predicted by 3-d optical calculations; they show that lateral optical confinement is needed to counteract the anti-guiding features of IV-VIs due to their negative temperature dependence of the refractive index. An experimental proof is performed with PbSe quantum well based VECSEL grown on a Si-substrate by molecular beam epitaxy and emitting around 3.3 μm. With proper mesa-etching, the threshold intensity is about 8-times reduced.

  7. Lead-chalcogenide mid-infrared vertical external cavity surface emitting lasers with improved threshold: Theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Fill, Matthias [ETH Zurich, Laser Spectroscopy and Sensing Lab, 8093 Zurich (Switzerland); Phocone AG, 8005 Zurich (Switzerland); Debernardi, Pierluigi [IEIIT-CNR, Torino 10129 (Italy); Felder, Ferdinand [Phocone AG, 8005 Zurich (Switzerland); Zogg, Hans [ETH Zurich (Switzerland)

    2013-11-11

    Mid-infrared Vertical External Cavity Surface Emitting Lasers (VECSEL) based on narrow gap lead-chalcogenide (IV-VI) semiconductors exhibit strongly reduced threshold powers if the active layers are structured laterally for improved optical confinement. This is predicted by 3-d optical calculations; they show that lateral optical confinement is needed to counteract the anti-guiding features of IV-VIs due to their negative temperature dependence of the refractive index. An experimental proof is performed with PbSe quantum well based VECSEL grown on a Si-substrate by molecular beam epitaxy and emitting around 3.3 μm. With proper mesa-etching, the threshold intensity is about 8-times reduced.

  8. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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)

  15. [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.

  16. 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.

  17. 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.

  18. 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%.

  19. 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

  20. "Turn-on" fluorescence detection of lead ions based on accelerated leaching of gold nanoparticles on the surface of graphene.

    Science.gov (United States)

    Fu, Xiuli; Lou, Tingting; Chen, Zhaopeng; Lin, Meng; Feng, Weiwei; Chen, Lingxin

    2012-02-01

    A novel platform for effective "turn-on" fluorescence sensing of lead ions (Pb(2+)) in aqueous solution was developed based on gold nanoparticle (AuNP)-functionalized graphene. The AuNP-functionalized graphene exhibited minimal background fluorescence because of the extraordinarily high quenching ability of AuNPs. Interestingly, the AuNP-functionalized graphene underwent fluorescence restoration as well as significant enhancement upon adding Pb(2+), which was attributed to the fact that Pb(2+) could accelerate the leaching rate of the AuNPs on graphene surfaces in the presence of both thiosulfate (S(2)O(3)(2-)) and 2-mercaptoethanol (2-ME). Consequently, this could be utilized as the basis for selective detection of Pb(2+). With the optimum conditions chosen, the relative fluorescence intensity showed good linearity versus logarithm concentration of Pb(2+) in the range of 50-1000 nM (R = 0.9982), and a detection limit of 10 nM. High selectivity over common coexistent metal ions was also demonstrated. The practical application had been carried out for determination of Pb(2+) in tap water and mineral water samples. The Pb(2+)-specific "turn-on" fluorescence sensor, based on Pb(2+) accelerated leaching of AuNPs on the surface of graphene, provided new opportunities for highly sensitive and selective Pb(2+) detection in aqueous media.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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...

  6. 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...

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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).

  12. 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.

  13. 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.

  14. 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.

  15. 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).

  16. Assessment of lead, cadmium, and zinc contamination of roadside soils, surface films, and vegetables in Kampala City, Uganda

    International Nuclear Information System (INIS)

    Nabulo, Grace; Oryem-Origa, Hannington; Diamond, Miriam

    2006-01-01

    The relationship between traffic density and trace metal concentrations in roadside soils, surface films, and a selected vegetable weed, Amaranthus dubius Mart. Ex Thell., was determined in 11 farming sites along major highways around Kampala City in Uganda. Surface soil, atmospherically deposited surface films on windows, and leaves of Amaranthus dubius were sampled at known distances from the roads and analyzed for lead (Pb), zinc (Zn), and cadmium (Cd) using flame atomic absorption spectrophotometry. Atmospherically deposited trace metal particulates were sampled using window glass as an inert, passive collector. Total trace metal concentrations in soils ranged from 30.0±2.3 to 64.6±11.7 mg/kg Pb, 78.4±18.4 to 265.6±63.2 mg/kg Zn, and 0.8±0.13 to 1.40±0.16 mg/kg Cd. Total trace metal levels in soil decreased rapidly with distance from the road. Total Pb decreased with distance up to 30 m from the road, where it reached a background soil concentration of 28 mg/kg dry weight. The study found background values of 50 and 1.4 mg/kg for Zn and Cd in roadside soils, respectively. Similarly, Pb concentration in Amaranthus dubius leaves decreased with increasing distance from the road edge. The dominant pathway for Pb contamination was from atmospheric deposition, which was consistent with Pb concentrations in surface films. The mean Pb concentrations in leaves of roadside crops were higher than those in their respective roots, with the highest leaf-to-root ratio observed in the Brassica oleraceae acephala group. The lowest Pb and Zn concentrations were found in the fruit compared to the leaves of the same crops. Leaves of roadside vegetables were therefore considered a potential source of heavy metal contamination to farmers and consumers in urban areas. It is recommended that leafy vegetables should be grown 30 m from roads in high-traffic, urban areas

  17. 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.

  18. 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

  19. 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

  20. Spectroscopic factors measurement of the five first energy levels of lead 208 nucleus using the 208Pb(e,e'p207Tl* huge pulse transfer reaction

    International Nuclear Information System (INIS)

    Medaglia, R.

    1999-08-01

    In this work, the spectral functions and the spectroscopic factors of the first five energy levels of the lead 208 nucleus have been measured using the 208 Pb(e,e'p) 207 Tl * reaction. The aim is to characterize the effect of the nuclear environment on pulse and energy distributions of protons. In order to minimize the ejected proton-residual nucleus interactions in the final state, the measurement has been performed at 750 and 570 MeV/c pulse transfers, and thus for proton kinetic energies of 263 MeV and 161 MeV, contrarily to a previous measurement performed at 100 MeV. A kinematics with a transverse electromagnetic coupling, instead of a longitudinal one, has been used because of the important coupling dependence observed for medium nuclei. The experiment has been carried out at the NIKHEF electron accelerator and smoothing ring. The pulse distributions of the first five energy levels for a proton pulse range of 0 to 300 MeV/c have been extracted from the (e,e'p) cross sections. An integration of model-dependent distributions gives the spectroscopic factors which indicate the number of protons of each level. These data rae compared to models that include both the proton interactions in the final state and the coulomb distortions. The Pavie model reproduces well the observed distributions and the transfer dependence, while the Ohio model does not. The spectroscopic factors obtained with the Pavie model are the same for both transfers and are 20% higher as an average than the previous experiment performed at 450 MeV/c. However, they are 30% below the shell model. The uncertain estimation of the reaction mechanisms does not allow to consider this reduction as being due exclusively to nuclear structure effects. (J.S.)

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gopalan, Srikanth [Boston Univ., MA (United States)

    2017-04-06

    This final report for project FE0009656 covers the period from 10/01/2012 to 09/30/2015 and covers research accomplishments on the effects of carbon dioxide on the surface composition and structure of cathode materials for solid oxide fuel cells (SOFCs), specifically La1-xSrxFeyCo1- yO3-δ (LSCF). Epitaxially deposited thin films of LSCF on various single-crystal substrates have revealed the selective segregation of strontium to the surface thereby resulting in a surface enrichment of strontium. The near surface compositional profile in the films have been measured using total x-ray fluorescence (TXRF), and show that the kinetics of strontium segregation are higher at higher partial pressures of carbon dioxide. Once the strontium segregates to the surface, it leads to the formation of precipitates of SrO which convert to SrCO3 in the presence of even modest concentrations of carbon dioxide in the atmosphere. This has important implications for the performance of SOFCs which is discussed in this report. These experimental observations have also been verified by Density Functional Theory calculations (DFT) which predict the conditions under which SrO and SrCO3 can occur in LSCF. Furthermore, a few cathode compositions which have received attention in the literature as alternatives to LSCF cathodes have been studied in this work and shown to be thermodynamically unstable under the operating conditions of the SOFCs.

  6. 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

  7. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip

    Science.gov (United States)

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-01

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7 × 108) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8 × 109) was 2.5 times greater than the experimental enhancement factor (1.1 × 109). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9 × 1011), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  8. 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

  9. 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

  10. 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.

  11. 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

  12. Using Monoclonal Antibody to Determine Lead Ions with a Localized Surface Plasmon Resonance Fiber-optic Biosensor

    Directory of Open Access Journals (Sweden)

    Mon-Fu Chung

    2008-01-01

    Full Text Available A novel reflection-based localized surface plasmon resonance (LSPR fiber-optic probe has been developed to determine the heavy metal lead ion concentration. Monoclonal antibody as the detecting probe containing massive amino groups to capture Pb(II-chelate complexes was immobilized onto gold nanoparticle-modified optical fiber (NMAuOF. The optimal immobilizing conditions of monoclonal antibody on to the NMAuOF are 189 μg/mL in pH7.4 PBS for 2 h at 25°C. The absorbability of the functionalized NMAuOF sensor increases to 12.2 % upon changing the Pb(II-EDTA level from 10 to 100 ppb with a detection limit of 0.27 ppb. The sensor retains 92.7 % of its original activity and gives reproducible results after storage in 5% D-( -Trehalose dehydrate solution at 4°C for 35 days. In conclusion, the monoclonal antibody-functionalized NMAuOF sensor shows a promising result for determining the concentration of Pb(II with high sensitivity.

  13. 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.

  14. 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).

  15. Development of a chemical kinetic measurement apparatus and the determination of the reaction rate constants for lithium-lead/water interaction

    International Nuclear Information System (INIS)

    Biney, P.O.

    1993-04-01

    An experimental set-up for accurate measurement of hydrogen generation rate in Lithium-Lead (Li 17 Pb 83 ) Steam or water interactions has been designed. The most important features of the design include a pneumatic actuated quick opening and closing high temperature all stainless steel valve used to control the reaction time and the placement of most measuring devices below a water line to minimize leakage of the hydrogen collected. A PC based data acquisition and control system provides remote process sequencing, acquisition and control of all major components of the set-up. Initial tests indicate that the first design objective of maintaining leakproof gas collection chamber has been achieved. Initial pressure tests indicated that the pressure drop over a time span of 30 minutes was within the tolerance of the pressure transducer used to measure the pressure (within 0.690 kPa) at a nominal system pressure of 685 kPa. The experimental system hardware, data acquisition and control programs and data analysis program have been completed, tested and are currently functional

  16. HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

    International Nuclear Information System (INIS)

    Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

    2004-01-01

    We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

  17. Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate.

    Science.gov (United States)

    Tsai, Po-Yu; Chao, Meng-Hsuan; Kasai, Toshio; Lin, King-Chuen; Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo

    2014-02-21

    The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

  18. 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)

  19. 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.

  20. 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

  1. Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

    2003-01-01

    Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

  2. Optimization of Al-CVD process based on elementary reaction simulation and experimental verification: From the growth rate to the surface morphology

    International Nuclear Information System (INIS)

    Sugiyama, Masakazu; Iino, Tomohisa; Nakajima, Tohru; Tanaka, Takeshi; Egashira, Yasuyuki; Yamashita, Kohichi; Komiyama, Hiroshi; Shimogaki, Yukihiro

    2006-01-01

    We propose a method to reduce the surface roughness of Al film in the chemical vapor deposition (CVD) using dimethyl-aluminum-hydride (DMAH) as the precursor. An elementary reaction simulation was executed not only to predict the deposition rate but also to predict the coverage of the film by surface adsorbates. It was assumed that high surface coverage is essential in order to deposit smooth films because the adsorbates protect the surface from oxidation which causes discontinuous growth of crystal grains. According to this principle, the condition, that realizes both high surface coverage and high deposition rate at the same time by using the elementary reaction simulation, was sought. A nozzle inlet was used instead of a conventional showerhead. This drastically improved the surface morphology, showing the effectiveness of this theoretical optimization procedure

  3. Diagnosing the leading mode of interdecadal covariability between the Indian Ocean sea surface temperature and summer precipitation in southern China

    Science.gov (United States)

    Liu, Jingpeng; Ren, Hong-Li; Li, Weijing; Zuo, Jinqing

    2018-03-01

    Precipitation in southern China during boreal summer (June to August) shows a substantial interdecadal variability on the timescale longer than 8 years. In this study, based on the analysis of singular value decomposition, we diagnose the leading mode of interdecadal covariability between the observational precipitation in southern China and the sea surface temperature (SST) in the Indian Ocean. Results indicate that there exist a remarkable southern China zonal dipole (SCZD) pattern of interdecadal variability of summer precipitation and an interdecadal Indian Ocean basin mode (ID-IOBM) of SST. It is found that the SCZD is evidently covaried with the ID-IOBM, which may induce anomalous inter-hemispheric vertical circulation and atmospheric Kelvin waves. During the warm phase of the ID-IOBM, an enhanced lower-level convergence and upper-level divergence exist over the tropical Indian Ocean, which is a typical Gill-Matsuno-type response to the SST warming. Meanwhile, the accompanied upper-level outflow anomalies further converge over the Indo-China peninsula, resulting in a lower-level anticyclone that contributes to reduction of the eastward moisture transport from the Bay of Bengal to the west part of southern China. In addition, the Kelvin wave-like pattern, as a response of the warm ID-IOBM phase, further induces the lower-level anticyclonic anomaly over the South China Sea-Philippines. Such an anticyclonic circulation is favorable for more water vapor transport from the East China Sea into the east part of southern China. Therefore, the joint effects of the anomalous inter-hemispheric vertical circulation and the Kelvin wave-like pattern associated with the ID-IOBM may eventually play a key role in generating the SCZD pattern.

  4. Expression of the recombinant bacterial outer surface protein A in tobacco chloroplasts leads to thylakoid localization and loss of photosynthesis.

    Science.gov (United States)

    Hennig, Anna; Bonfig, Katharina; Roitsch, Thomas; Warzecha, Heribert

    2007-11-01

    Bacterial lipoproteins play crucial roles in host-pathogen interactions and pathogenesis and are important targets for the immune system. A prominent example is the outer surface protein A (OspA) of Borrelia burgdorferi, which has been efficiently used as a vaccine for the prevention of Lyme disease. In a previous study, OspA could be produced in tobacco chloroplasts in a lipidated and immunogenic form. To further explore the potential of chloroplasts for the production of bacterial lipoproteins, the role of the N-terminal leader sequence was investigated. The amount of recombinant OspA could be increased up to ten-fold by the variation of the insertion site in the chloroplast genome. Analysis of OspA mutants revealed that replacement of the invariant cysteine residue as well as deletion of the leader sequence abolishes palmitolyation of OspA. Also, decoration of OspA with an N-terminal eukaryotic lipidation motif does not lead to palmitoylation in chloroplasts. Strikingly, the bacterial signal peptide of OspA efficiently targets the protein to thylakoids, and causes a mutant phenotype. Plants accumulating OspA at 10% total soluble protein could not grow without exogenously supplied sugars and rapidly died after transfer to soil under greenhouse conditions. The plants were found to be strongly affected in photosystem II, as revealed by the analyses of temporal and spatial dynamics of photosynthetic activity by chlorophyll fluorescence imaging. Thus, overexpression of OspA in chloroplasts is limited by its concentration-dependent interference with essential functions of chloroplastic membranes required for primary metabolism.

  5. Decreased blood hepatitis B surface antibody levels linked to e-waste lead exposure in preschool children

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xijin [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Department of Cell Biology and Genetics, Shantou University Medical College, Shantou 515041, Guangdong (China); Chen, Xiaojuan; Zhang, Jian [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Guo, Pi [Department of Public Health, Shantou University Medical College, Shantou 515041, Guangdong (China); Fu, Tingzao; Dai, Yifeng [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China); Lin, Stanley L. [Department of Pathophysiology and Key Immunopathology Laboratory of Guangdong Province, Shantou University Medical College, Shantou 515041, Guangdong (China); Huo, Xia, E-mail: xhuo@stu.edu.cn [Laboratory of Environmental Medicine and Developmental Toxicology, and Guangdong Provincial Key Laboratory of Infectious Diseases, Shantou University Medical College, Shantou 515041, Guangdong (China)

    2015-11-15

    Highlights: • Secondary exploratory analyses displayed a correlation of blood Pb to HBsAb levels. • Generalized linear mixed models were used to analyze two-phase data. • Children from an e-waste area had higher blood Pb levels and lower HBsAb titers. • Nearly 50% of Pb-exposed children fail to develop sufficient HBV immunity. • Different vaccination strategies are required for in e-waste areas. - Abstract: Lead (Pb) is a widespread environmental contaminant that can profoundly affect the immune system in vaccinated children. To explore the association between blood Pb and HBsAb levels in children chronically exposed to Pb, we measured hepatitis B surface antibody (HBsAb) titers, to reflect the immune response in the children of Guiyu, an electronic and electrical waste (e-waste) recycling area well known for environmental Pb contamination. We performed secondary exploratory analyses of blood Pb levels and plasma HBsAb titers in samples, taken in two phases between 2011 and 2012, from 590 children from Guiyu (exposed group) and Haojiang (reference group). Children living in the exposed area had higher blood Pb levels and lower HBsAb titers compared with children from the reference area. At each phase, generalized linear mixed models (GLMMs) showed that HBsAb titers were significantly negatively associated with child blood Pb levels. This work shows that a decreased immune response to hepatitis B vaccine and immune system might have potential harm to children with chronic Pb exposure. Importantly, nearly 50% of chronically exposed children failed to develop sufficient immunity to hepatitis in response to vaccination. Thus different vaccination strategies are needed for children living under conditions of chronic Pb exposure.

  6. Transtendon rotator-cuff repair of partial-thickness articular surface tears can lead to medial rotator-cuff failure

    Directory of Open Access Journals (Sweden)

    Woods TC

    2014-06-01

    Full Text Available Tom C Woods,4 Michael J Carroll,1 Atiba A Nelson,2 Kristie D More,2 Randa Berdusco,1 Stephen Sohmer,3 Richard S Boorman,1,2 Ian KY Lo1,21Department of Surgery, 2Sport Medicine Centre, University of Calgary, Calgary, AB, Canada; 3Department of Orthopaedics, University of British Columbia, Vancouver, 4St Joseph's Hospital, Comox, BC, CanadaPurpose: The purpose of this study was to evaluate clinical and anatomic outcomes of patients following transtendon rotator-cuff repair of partial articular supraspinatus tendon avulsion (PASTA lesions.Patients and methods: Patients in the senior author's practice who had isolated PASTA lesions treated by transtendon rotator-cuff repair were included (n=8 and retrospectively reviewed. All patients were evaluated preoperatively and at a mean of 21.2 months (±9.7 months postoperatively using standardized clinical evaluation (physical exam, American Shoulder and Elbow Surgeons, and Simple Shoulder Test. All patients underwent postoperative imaging with a magnetic resonance imaging arthrogram.Results: There was a significant improvement in American Shoulder and Elbow Surgeons (42.7±17.5 to 86.9±25.2 and Simple Shoulder Test (4.6±3.2 to 10.1±3.8 scores from pre- to postoperative, respectively. Postoperative imaging demonstrated full-thickness medial cuff tearing in seven patients, and one patient with a persistent partial articular surface defect.Conclusion: Transtendon repair of PASTA lesions may lead to improvements in clinical outcome. However, postoperative imaging demonstrated a high incidence of full-thickness rotator-cuff defects following repair.Keywords: rotator cuff, PASTA lesion, transtendon repair

  7. Decreased blood hepatitis B surface antibody levels linked to e-waste lead exposure in preschool children

    International Nuclear Information System (INIS)

    Xu, Xijin; Chen, Xiaojuan; Zhang, Jian; Guo, Pi; Fu, Tingzao; Dai, Yifeng; Lin, Stanley L.; Huo, Xia

    2015-01-01

    Highlights: • Secondary exploratory analyses displayed a correlation of blood Pb to HBsAb levels. • Generalized linear mixed models were used to analyze two-phase data. • Children from an e-waste area had higher blood Pb levels and lower HBsAb titers. • Nearly 50% of Pb-exposed children fail to develop sufficient HBV immunity. • Different vaccination strategies are required for in e-waste areas. - Abstract: Lead (Pb) is a widespread environmental contaminant that can profoundly affect the immune system in vaccinated children. To explore the association between blood Pb and HBsAb levels in children chronically exposed to Pb, we measured hepatitis B surface antibody (HBsAb) titers, to reflect the immune response in the children of Guiyu, an electronic and electrical waste (e-waste) recycling area well known for environmental Pb contamination. We performed secondary exploratory analyses of blood Pb levels and plasma HBsAb titers in samples, taken in two phases between 2011 and 2012, from 590 children from Guiyu (exposed group) and Haojiang (reference group). Children living in the exposed area had higher blood Pb levels and lower HBsAb titers compared with children from the reference area. At each phase, generalized linear mixed models (GLMMs) showed that HBsAb titers were significantly negatively associated with child blood Pb levels. This work shows that a decreased immune response to hepatitis B vaccine and immune system might have potential harm to children with chronic Pb exposure. Importantly, nearly 50% of chronically exposed children failed to develop sufficient immunity to hepatitis in response to vaccination. Thus different vaccination strategies are needed for children living under conditions of chronic Pb exposure

  8. The Effect of Simulated Microgravity Environment of RWV Bioreactors on Surface Reactions and Adsorption of Serum Proteins on Bone-bioactive Microcarriers

    Science.gov (United States)

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

    2003-01-01

    Biomimetically modified bioactive materials with bone-like surface properties are attractive candidates for use as microcarriers for 3-D bone-like tissue engineering under simulated microgravity conditions of NASA designed rotating wall vessel (RWV) bioreactors. The simulated microgravity environment is attainable under suitable parametric conditions of the RWV bioreactors. Ca-P containing bioactive glass (BG), whose stimulatory effect on bone cell function had been previously demonstrated, was used in the present study. BG surface modification via reactions in solution, resulting formation of bone-like minerals at the surface and adsorption of serum proteins is critical for obtaining the stimulatory effect. In this paper, we report on the major effects of simulated microgravity conditions of the RWV on the BG reactions surface reactions and protein adsorption in physiological solutions. Control tests at normal gravity were conducted at static and dynamic conditions. The study revealed that simulated microgravity remarkably enhanced reactions involved in the BG surface modification, including BG dissolution, formation of bone-like minerals at the surface and adsorption of serum proteins. Simultaneously, numerical models were developed to simulate the mass transport of chemical species to and from the BG surface under normal gravity and simulated microgravity conditions. The numerical results showed an excellent agreement with the experimental data at both testing conditions.

  9. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  10. A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

    Science.gov (United States)

    Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

    2017-04-05

    The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

  11. Surface tectonics of nanoporous networks of melamine-capped molecular building blocks formed through interface Schiff-base reactions.

    Science.gov (United States)

    Liu, Xuan-He; Wang, Dong; Wan, Li-Jun

    2013-10-01

    Control over the assembly of molecules on a surface is of great importance for the fabrication of molecule-based miniature devices. Melamine (MA) and molecules with terminal MA units are promising candidates for supramolecular interfacial packing patterning, owing to their multiple hydrogen-bonding sites. Herein, we report the formation of self-assembled structures of MA-capped molecules through a simple on-surface synthetic route. MA terminal groups were successfully fabricated onto rigid molecular cores with 2-fold and 3-fold symmetry through interfacial Schiff-base reactions between MA and aldehyde groups. Sub-molecular scanning tunneling microscopy (STM) imaging of the resultant adlayer revealed the formation of nanoporous networks. Detailed structural analysis indicated that strong hydrogen-bonding interactions between the MA groups persistently drove the formation of nanoporous networks. Herein, we demonstrate that functional groups with strong hydrogen-bond-formation ability are promising building blocks for the guided assembly of nanoporous networks and other hierarchical 2D assemblies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces.

    Science.gov (United States)

    Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R; Sakai, Naomi; Matile, Stefan

    2016-03-18

    To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Overcoming Short-Circuit in Lead-Free CH3NH3SnI3 Perovskite Solar Cells via Kinetically Controlled Gas-Solid Reaction Film Fabrication Process.

    Science.gov (United States)

    Yokoyama, Takamichi; Cao, Duyen H; Stoumpos, Constantinos C; Song, Tze-Bin; Sato, Yoshiharu; Aramaki, Shinji; Kanatzidis, Mercouri G

    2016-03-03

    The development of Sn-based perovskite solar cells has been challenging because devices often show short-circuit behavior due to poor morphologies and undesired electrical properties of the thin films. A low-temperature vapor-assisted solution process (LT-VASP) has been employed as a novel kinetically controlled gas-solid reaction film fabrication method to prepare lead-free CH3NH3SnI3 thin films. We show that the solid SnI2 substrate temperature is the key parameter in achieving perovskite films with high surface coverage and excellent uniformity. The resulting high-quality CH3NH3SnI3 films allow the successful fabrication of solar cells with drastically improved reproducibility, reaching an efficiency of 1.86%. Furthermore, our Kelvin probe studies show the VASP films have a doping level lower than that of films prepared from the conventional one-step method, effectively lowering the film conductivity. Above all, with (LT)-VASP, the short-circuit behavior often obtained from the conventional one-step-fabricated Sn-based perovskite devices has been overcome. This study facilitates the path to more successful Sn-perovskite photovoltaic research.

  14. Histopathology and immune histochemistry of red tattoo reactions. Interface dermatitis is the lead pathology, with increase in T-lymphocytes and Langerhans cells suggesting an allergic pathomechanism

    DEFF Research Database (Denmark)

    Høgsberg, T; Thomsen, B M; Serup, J

    2015-01-01

    BACKGROUND: The majority of tattoo reactions are affiliated to red pigmented areas and often suspected to be allergic in nature. A sizeable series of biopsies of such reactions has not previously been performed. The aim of this study was to type and grade epidermal and dermal changes in tattoo re...

  15. Understanding Gender Differences in Children's Risk Taking and Injury: A Comparison of Mothers' and Fathers' Reactions to Sons and Daughters Misbehaving in Ways that Lead to Injury

    Science.gov (United States)

    Morrongiello, Barbara A.; Zdzieborski, Daniel; Normand, Jackie

    2010-01-01

    This study compared reactions of mothers and fathers to the risk taking behavior of sons and daughters. Mother-father pairs (N = 52) imagined their 2-year-old boy or girl behaving in risky ways in common home situations that could, and did, result in injury. Emotional and parenting reactions to the behaviors were assessed before and after injury.…

  16. State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface.

    Science.gov (United States)

    Li, Anyang; Guo, Hua; Sun, Zhigang; Kłos, Jacek; Alexander, Millard H

    2013-10-07

    The state-to-state reaction dynamics of the title reaction is investigated on the ground electronic state potential energy surface using two quantum dynamical methods. The results obtained using the Chebyshev real wave packet method are in excellent agreement with those obtained using the time-independent method, except at low translational energies. It is shown that this exothermic hydrogen abstraction reaction is direct, resulting in a strong back-scattered bias in the product angular distribution. The HF product is highly excited internally. Agreement with available experimental data is only qualitative. We discuss several possible causes of disagreement with experiment.

  17. Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.

    Science.gov (United States)

    Gao, Erping; Wang, Wenzhong

    2013-11-21

    Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2˙(-) anions as the major oxidation species instead of ˙OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25.

  18. A global model for SF6 plasmas coupling reaction kinetics in the gas phase and on the surface of the reactor walls

    International Nuclear Information System (INIS)

    Kokkoris, George; Panagiotopoulos, Apostolos; Gogolides, Evangelos; Goodyear, Andy; Cooke, Mike

    2009-01-01

    Gas phase and reactor wall-surface kinetics are coupled in a global model for SF 6 plasmas. A complete set of gas phase and surface reactions is formulated. The rate coefficients of the electron impact reactions are based on pertinent cross section data from the literature, which are integrated over a Druyvesteyn electron energy distribution function. The rate coefficients of the surface reactions are adjustable parameters and are calculated by fitting the model to experimental data from an inductively coupled plasma reactor, i.e. F atom density and pressure change after the ignition of the discharge. The model predicts that SF 6 , F, F 2 and SF 4 are the dominant neutral species while SF 5 + and F - are the dominant ions. The fit sheds light on the interaction between the gas phase and the reactor walls. A loss mechanism for SF x radicals by deposition of a fluoro-sulfur film on the reactor walls is needed to predict the experimental data. It is found that there is a net production of SF 5 , F 2 and SF 6 , and a net consumption of F, SF 3 and SF 4 on the reactor walls. Surface reactions as well as reactions between neutral species in the gas phase are found to be important sources and sinks of the neutral species.

  19. Comments on leading mesons in anti p Ne - reactions at 607 MeV/c incident momentum in terms of four-momentum transfers in two-vertex diagrams

    International Nuclear Information System (INIS)

    Breivik, F.O.; Haatuft, A.; Halsteinslid, A.

    1990-02-01

    Based on previous observations of anti p Ne - reactions the author discuss, in terms of four-momentum transfers, why only leading pions are seen in events detected by their Λ-decays, and only leading kaons in the events detected by their neutral K-decays. The experimental results are consistent with a two-vertex model with strange or non-strange baryon exchange. 3 refs.; 4 figs.; 1 tab

  20. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  1. Application of the response surface and desirability design to the Lambda-cyhalothrin degradation using photo-Fenton reaction.

    Science.gov (United States)

    Colombo, Renata; Ferreira, Tanare C R; Alves, Suellen A; Carneiro, Renato L; Lanza, Marcos R V

    2013-03-30

    Lambda-cyhalothrin is a potent pyrethroid insecticide used widely in pest management. Detectable levels of the pyrethroid in agricultural watersheds are potentially toxic to aquatic organisms. There is little information in the scientific literature about degradation in aqueous media of the Lambda-cyhalothrin by Advanced Oxidative Process. A mathematical approach for the degradation of this compound has not yet been fully explored… The Central composite design (CCD) and response surface method (RSM) were applied to evaluate and optimize the interactive effects of two operating variables. The initial dosages of H2O2 and Fe(2+) on photo-Fenton degradation of an aqueous solution of Lambda-cyhalothrin in a recirculation flow-through UV photoreactor were used. The remaining concentration of Lambda-cyhalothrin (y1) and the percentage removal of total organic carbon (y2) were the monitored factors since they are dependent parameters of y1 and y2. According to analysis of variances (ANOVA) results, two proposed models can be used to navigate the design space with regression coefficient R(2) - 0.834 and 0.843 for y1 and y2, respectively. A multi-response optimization procedure, based on the global desirability of the factors, was performed to establish the best concentrations of hydrogen peroxide and ferrous sulfate that would allow the most efficient degradation of Lambda-cyhalothrin concomitant with a maximal removal of total organic carbon. The global desirability surface revealed that 0.295 mmol L(-1) of ferrous sulfate and 3.85 mmol L(-1) of hydrogen peroxide were close to the optimum conditions to satisfy both factors simultaneously using minimal amounts of reagents. These photo-Fenton conditions promoted 100% of Lambda-cyhalothrin degradation and 79.83% TOC removal (mineralization) in 120 min of reaction time. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Photoreactivity of ZnO nanoparticles in visible light: Effect of surface states on electron transfer reaction

    International Nuclear Information System (INIS)

    Baruah, Sunandan; Dutta, Joydeep; Sinha, Sudarson Sekhar; Ghosh, Barnali; Pal, Samir Kumar; Raychaudhuri, A. K.

    2009-01-01

    Wide band gap metal oxide semiconductors such as zinc oxide (ZnO) show visible band photolysis that has been employed, among others, to degrade harmful organic contaminants into harmless mineral acids. Metal oxides show enhanced photocatalytic activity with the increase in electronic defects in the crystallites. By introducing defects into the crystal lattice of ZnO nanoparticles, we observe a redshift in the optical absorption shifting from the ultraviolet region to the visible region (400-700 nm), which is due to the creation of intermediate defect states that inhibit the electron hole recombination process. The defects were introduced by fast nucleation and growth of the nanoparticles by rapid heating using microwave irradiation and subsequent quenching during the precipitation reaction. To elucidate the nature of the photodegradation process, picosecond resolved time correlated single photon count (TCSPC) spectroscopy was carried out to record the electronic transitions resulting from the de-excitation of the electrons to their stable states. Photodegradation and TCSPC studies showed that defect engineered ZnO nanoparticles obtained through fast crystallization during growth lead to a faster initial degradation rate of methylene blue as compared to the conventionally synthesized nanoparticles

  3. Molecular dynamics simulation of sodium aluminosilicate glass structures and glass surface-water reactions using the reactive force field (ReaxFF)

    Science.gov (United States)

    Dongol, R.; Wang, L.; Cormack, A. N.; Sundaram, S. K.

    2018-05-01

    Reactive potentials are increasingly used to study the properties of glasses and glass water reactions in a reactive molecular dynamics (MD) framework. In this study, we have simulated a ternary sodium aluminosilicate glass and investigated the initial stages of the glass surface-water reactions at 300 K using reactive force field (ReaxFF). On comparison of the simulated glass structures generated using ReaxFF and classical Buckingham potentials, our results show that the atomic density profiles calculated for the surface glass structures indicate a bond-angle distribution dependency. The atomic density profiles also show higher concentrations of non-bridging oxygens (NBOs) and sodium ions at the glass surface. Additionally, we present our results of formation of silanol species and the diffusion of water molecules at the glass surface using ReaxFF.

  4. A computational study on the adsorption configurations and reactions of SiH{sub x}(x = 1-4) on clean and H-covered Si(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Le, Thong N-M [Molecular Science and Nano-Materials Laboratory, Institute for Computational Science and Technology, Quang Trung Software Park, Dist. 12, Ho Chi Minh City (Viet Nam); Raghunath, P. [Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan (China); Huynh, Lam K., E-mail: lamhuynh.us@gmail.com [Department of Applied Chemistry, School of Biotechnology,International University, VNU-HCMC, Quarter 6, Linh Trung, Thu Duc District, Ho Chi Minh City (Viet Nam); Lin, M.C., E-mail: chemmcl@emory.edu [Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan (China)

    2016-11-30

    Highlights: • Possible adsorption configurations of all adsorbates on Si(100) surface are systematically explored. • The mechanisms leading to the formation of silicon adatoms on the surface are proposed. • The barriers for hydrogen abstractions from the surface are negligible comparing to the barriers for the hydrogen migrations. • The barriers for hydrogen abstractions from the adsorbed speices are negligible comparing to the barriers for the decompositions. - Abstract: Possible adsorption configurations of H and SiH{sub x} (x = 1 − 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH{sub 3} radicals effectively adsorb on the top sites, while SiH and SiH{sub 2} prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiH{sub x} species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiH{sub x} precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiH{sub x} radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiH{sub x}, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.

  5. Effects of Thermal Radiation and Chemical Reaction on MHD Free Convection Flow past a Flat Plate with Heat Source and Convective Surface Boundary Condition

    OpenAIRE

    E.Hemalatha; N. Bhaskar Reddy

    2015-01-01

    This paper analyzes the radiation and chemical reaction effects on MHD steady two-dimensional laminar viscous incompressible radiating boundary layer flow over a flat plate in the presence of internal heat generation and convective boundary condition. It is assumed that lower surface of the plate is in contact with a hot fluid while a stream of cold fluid flows steadily over the upper surface with a heat source that decays exponentially. The Rosseland approximation is used to desc...

  6. Thermal decomposition of a molecular material {N(n-C4H94[FeIIFeIII(C2O43]}∞ leading to ferrite: A reaction kinetics study

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Ashis

    2013-01-01

    Full Text Available A multi-step thermal decomposition of a molecular precursor, {N(n-C4H94[FeIIFeIII(C2O43}∞ has been studied using non-isothermal thermogravimetry (TG measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1. The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

  7. Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

  8. Effect of surface reactions on steel, Al{sub 2}O{sub 3} and Si{sub 3}N{sub 4} counterparts on their tribological performance with polytetrafluoroethylene filled composites

    Energy Technology Data Exchange (ETDEWEB)

    Shen, J.T.; Top, M. [Materials Innovation Institute M2i, Department of Applied Physics, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands); Ivashenko, O.; Rudolf, P. [Department of Surfaces and Thin Films, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands); Pei, Y.T., E-mail: y.pei@rug.nl [Materials Innovation Institute M2i, Department of Applied Physics, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands); Department of Advanced Production Engineering, Engineering and Technology Institute Groningen, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands); De Hosson, J.Th.M., E-mail: j.t.m.de.hosson@rug.nl [Materials Innovation Institute M2i, Department of Applied Physics, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands)

    2015-03-15

    Highlights: • The influence of surface reactions with PTFE on the tribo-performance of different counterparts is revealed. • Experiments confirm that friction can be greatly reduced by two F-terminated surfaces sliding over each other. • Al−F and Fe−F chemical bonding form on the surface of alumina and steel counterpart balls during sliding against PTFE-containing composite. • No Si−F bonding formed on Si{sub 3}N{sub 4} ball under the same condition, leading to higher friction and wear. - Abstract: The influence of surface reactions on the tribo-performance of steel, Al{sub 2}O{sub 3} and Si{sub 3}N{sub 4} balls sliding against polytetrafluoroethylene/SiO{sub 2}/epoxy composites was investigated. Al{sub 2}O{sub 3} ball were found to exhibit the best tribo-performance, namely a low coefficient of friction and the lowest wear rates of both the composites and the counterpart ball, when sliding against the PTFE filled composites. The difference in the tribo-performance of the Al{sub 2}O{sub 3} ball and the Si{sub 3}N{sub 4} ball can neither be attributed to the different morphology of the worn composite surfaces nor to the amount of PTFE transferred onto the wear surfaces. Instead we found that the friction is greatly reduced in the case of the Al{sub 2}O{sub 3} ball because two fluoro-terminated surfaces are sliding over each other; in fact, the formation of Al−F bonding was confirmed by X-ray photoelectron spectroscopy.

  9. Study of the Reactions Controlling the Mobility of Uranium in Ground and Surface Water Systems in Contact with Apatite

    International Nuclear Information System (INIS)

    Taffet, M

    2004-01-01

    The objective of this project was to define the mechanisms, equilibria, kinetics, and extent of sorption of aqueous uranium onto hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)) for a range of pH, ionic strength, aqueous uranium concentration, dissolved carbon/air CO 2 , and mineral surface area. We conducted chemical modeling, batch and flow-through experiments, chemical analysis, x-ray absorption and diffraction measurement, and electron microscopy. Our motivation was the need to immobilize U in water and soil to prevent it's entry into water supplies and ultimately, biological systems. Applying hydroxyapatite to in-situ treatment of uranium-bearing ground water could be an effective, low cost technology. We found that hydroxyapatite quickly, effectively, and reversibly sorbed uranium at a high capacity by inner-sphere complexation over a wide range of conditions. Our results indicate that at aqueous uranium concentrations below 10-20 ppb: (1) equilibrium sorption of uranium to hydroxyapatite occurs in hours, regardless of pH; (2) in ambient and CO 2 -free atmospheres, over 98% of initial u