These are representative sample records from Science.gov related to your search topic.
For comprehensive and current results, perform a real-time search at Science.gov.
1

Image formation and contrast inversion in noncontact atomic force microscopy imaging of oxidized Cu(110) surfaces  

NASA Astrophysics Data System (ADS)

Joint experimental and theoretical investigation of image formation in noncontact atomic force microscopy (NC-AFM) of the c(6 × 2) and p(2 × 1) phases of the Cu(110):O surface is presented. We proposed previously that the c(6 × 2) reconstruction of the Cu(110):O surface may serve as a reference system allowing chemical identification of the tip apex atom during the course of NC-AFM experiments. The identification is possible due to the fact that two most likely possible contrasts that could be observed after intermittent contacts of the tip with the surface were found which can be attributed to the tip being either terminated by Cu or O atoms. In this paper the idea of exploiting the Cu(110):O surface in NC-AFM studies is further developed. Specifically, (i) we show that there must be an image contrast inversion when the c(6 × 2) surface reconstruction is scanned depending on the tip-surface distance: at the usual imaging conditions, at tip-sample distances of 2-5 Å, the previously reported contrast is observed; however, an opposite contrast is observed for larger separations with one of the two tip terminations. (ii) We study in detail also the image contrast formation of the p (2×1) surface, which is another common surface reconstruction, and show that tip identification for it is not possible. (iii) Finally, we discuss here possible effects of the actual tip atomic structure on the NC-AFM image. In particular, we show that the O-terminated tip will remain such even after picking up a Cu atom from the surface, experimentally a frequently observed process. Hence this type of the tip modification would only affect secondary features in the image.

Bamidele, J.; Kinoshita, Y.; Turanský, R.; Lee, S. H.; Naitoh, Y.; Li, Y. J.; Sugawara, Y.; Štich, I.; Kantorovich, L.

2014-07-01

2

Oxygen chemisorption-induced surface phase transitions on Cu(110)  

NASA Astrophysics Data System (ADS)

From an interplay between variable temperature scanning tunneling microscopy and density-functional theory calculations, the evolution of oxygen chemisorption-induced surface reconstructions of the Cu(110) surface is determined. The surface reconstructions proceed via a sequential pathway with increasing oxygen surface coverage. The (2 × 1) reconstruction occurs first and then transits to the c(6 × 2) phase with a higher oxygen coverage through a mechanism that consumes the existing (2 × 1) phase with the supply of Cu adatoms from step edges and terraces. The temperature dependence of the (2 × 1) ? c(6 × 2) transition demonstrates that the surface phase transition is an activated process for breaking up added Cu-O-Cu rows in the (2 × 1) structure. Comparison between the experimental observations and the theoretical surface phase diagram obtained from first-principles thermodynamic calculations reveals that the (2 × 1) ? c(6 × 2) transition takes place at the oxygen chemical potentials that are far above the chemical potential for Cu2O bulk oxide formation, reflecting the existence of kinetic limitations to the surface phase transition and the bulk oxide formation.

Liu, Qianqian; Li, Liang; Cai, Na; Saidi, Wissam A.; Zhou, Guangwen

2014-09-01

3

A Window on Surface Explosions: Tartaric Acid on Cu(110)  

SciTech Connect

Autocatalytic reaction mechanisms are observed in a range of important chemical processes including catalysis, radical-mediated explosions, and biosynthesis. Because of their complexity, the microscopic details of autocatalytic reaction mechanisms have been difficult to study on surfaces and heterogeneous catalysts. Autocatalytic decomposition reactions of S,S- and R,R-tartaric acid (TA) adsorbed on Cu(110) offer molecular-level insight into aspects of these processes, which until now, were largely a matter of speculation. The decomposition of TA/Cu(110) is initiated by a slow, irreversible process that forms vacancies in the adsorbed TA layer, followed by a vacancy-mediated, explosive decomposition process that yields CO{sub 2} and small hydrocarbon products. Initiation of the explosive decomposition of TA/Cu(110) has been studied by measurement of the reaction kinetics, time-resolved low energy electron diffraction (LEED), and time-resolved scanning tunneling microscopy (STM). Initiation results in a decrease in the local coverage of TA and a concomitant increase in the areal vacancy concentration. Observations of explosive TA decomposition on the Cu(651)S surface suggest that initiation does not occur at structural defects in the surface, as has been suggested in the past. Once the vacancy concentration reaches a critical value, the explosive, autocatalytic decomposition step dominates the TA decomposition rate. The onset of the explosive decomposition of TA on Cu(110) is accompanied by the extraction of Cu atoms from the surface to form a (±6,7; {-+}2,1) overlayer that is readily observable using LEED and STM. The explosive decomposition step is second-order in vacancy concentration and accelerates with increasing extent of reaction.

Mhatre, B. S.; Pushkarev, V.; Holsclaw, B.; Lawton, T. J.; Sykes, E. C. H.; Gellman, A. J.

2013-04-18

4

Epitaxially Grown Films of Standing and Lying Pentacene Molecules on Cu(110) Surfaces.  

PubMed

This study investigates epitaxially oriented pentacene films grown on Cu(110) surfaces crystallizing either in the "thin film" phase with standing molecules or in the "single crystal" structure with molecules lying with their long axes parallel to the substrate. PMID:21479111

Djuric, Tatjana; Ules, Thomas; Flesch, Heinz-Georg; Plank, Harald; Shen, Quan; Teichert, Christian; Resel, Roland; Ramsey, Michael G

2011-04-01

5

Chloride-induced morphology transformations of the Cu(110) surface in dilute HCl.  

PubMed

Morphological changes of a bare Cu(110) substrate in 10 mM HCl aqueous solution have been studied using cyclic voltammetry (CV), electrochemical scanning tunneling microscopy (EC-STM), and reflectance anisotropy spectroscopy (RAS). At cathodic potentials more positive than the hydrogen evolution reaction, a bare copper surface (1 × 1) structure is found by EC-STM. At anodic potentials more negative than the copper(II) dissolution reaction, a furrowed structure is found. The governing factor that rules Cu(110)-Cl interface processes is discussed as an interplay among Cl(-) adsorption/desorption, the dynamic rearrangement of the surface atoms on the substrate, and strain in order to reduce the surface energy. The information provided by EC-STM and RAS complements that of CV, supplies detailed information on the surface morphology, and correlates peaking Faraday currents to structural modifications. Furthermore, RAS and EC-STM show changes in the surface appearance in a potential range where no specific charge transfer is observed. CV indicates that the Cu(110) surface chemistry compares much better to that of amorphous Cu than to that of the more stable (100) and (111) surfaces, respectively. PMID:25383708

Barati, Gholamreza; Solokha, Vladyslav; Wandelt, Klaus; Hingerl, Kurt; Cobet, Christoph

2014-12-01

6

Surface structure of alanine on Cu(110) via grazing scattering of fast atoms and molecules  

NASA Astrophysics Data System (ADS)

We have studied structures of the chiral amino acid alanine adsorbed on Cu(110) via low-energy electron diffraction (LEED) as well as scattering of fast light atoms and molecules. The adsorption process was controlled in situ by the intensity of specularly reflected 2-keV He atoms. For projectile energies less than 1 keV, we applied the method of fast atom diffraction for studies on the structure of adsorbed alanine molecules on an atomically flat Cu(110) surface with focus on a p(3×2) adsorbate phase. The results are consistent with LEED and explain distortions in LEED patterns via an elongated surface unit cell with incommensurate c(3.16×2) symmetry of parts of the adsorbate. From triangulation using fast atoms via the azimuthal rotation of the target surface, the positions of protruding methyl groups are derived.

Seifert, J.; Busch, M.; Meyer, E.; Winter, H.

2014-02-01

7

Structure of N 2 adlayers on the highly corrugated Cu(110)-(2×1)O surface  

NASA Astrophysics Data System (ADS)

The adsorption and structure of molecular nitrogen on the reconstructed Cu(110)-(2×1)O surface has been studied by He-diffraction and temperature programmed desorption. Owing to the "added row" reconstruction, the Cu(110)-(2×1)0 surface exhibits a large corrugation along the [1 1¯0] direction, i.e. perpendicular to the Cu-O rows. This has a marked influence on the adsorption properties and structure compared with the bare Cu(110) surface. The N 2 molecules initially adsorb in a lattice gas phase which is stable up to rather high density. In this phase the desorption proceeds via first-order desorption kinetics. With increasing coverage the lattice gas eventually condenses into a (4×3) commensurate phase where the molecules are much more weakly bound. Potential calculations corroborate the existence of a low density phase in which the N 2 molecules adsorb along the troughs between Cu-O added rows with only negligible lateral interactions. The (4×3) phase is found to contain up to eight N 2 molecules per unit cell, half of which occupy sites on top of the Cu-O added rows. A possible novel desorption channel involving a metastable bi-molecular precursor is proposed that could provide a consistent explanation of the N 2 desorption data.

Zeppenfeld, P.; Diercks, V.; Halmer, R.; David, R.; Pouthier, V.; Ramseyer, C.; Girardet, C.

1999-03-01

8

Epitaxially Grown Films of Standing and Lying Pentacene Molecules on Cu(110) Surfaces  

PubMed Central

Here, it is shown that pentacene thin films (30 nm) with distinctively different crystallographic structures and molecular orientations can be grown under essentially identical growth conditions in UHV on clean Cu(110) surfaces. By X-ray diffraction, we show that the epitaxially oriented pentacene films crystallize either in the “thin film” phase with standing molecules or in the “single crystal” structure with molecules lying with their long axes parallel to the substrate. The morphology of the samples observed by atomic force microscopy shows an epitaxial alignment of pentacene crystallites, which corroborates the molecular orientation observed by X-ray diffraction pole figures. Low energy electron diffraction measurements reveal that these dissimilar growth behaviors are induced by subtle differences in the monolayer structures formed by slightly different preparation procedures. PMID:21479111

2011-01-01

9

Effects of Adsorbed Formate on Equilibrium Step Fluctuations on Cu(110) Surfaces  

NASA Astrophysics Data System (ADS)

We have used scanning tunneling microscopy (STM) to study the time dependence of step edge fluctuations on Cu(110) surfaces at room temperature. Analysis of the temporal autocorrelation functions, obtained by monitoring step position displacements using STM, was performed on a clean surface and on surfaces partially covered with adsorbed formate. The autocorrelation functions for all studied surfaces were found to be well approximated by <(f(t)-f(t_0))^2> =a ?^? , where 1/3 < ? < 1/2, over times ranging from 10-1 to 10^1 seconds. This range of exponents is consistent with a mass transport mechanism on the surface whereby a step-terrace system exchanges atoms in a nearly random fashion. The parameter a, related to the terrace gas diffusion constant and the step line tension, is known to demonstrates an Arrhenian dependence on temperature and is dependent on the choice of crystallographic surface and edge orientation. We have found that it also varies significantly and in a systematic fashion with changes in chemical potential associated with increasing concentrations of formate on the surface.

Harrington, Steven J.; Zhu, Da-Ming; Leibsle, F. M.; Phillips, James M.; Kilway, K. V.

2000-03-01

10

Lateral hopping and desorption of a single CO molecule on a Cu(110) surface induced by femtosecond laser pulses  

NASA Astrophysics Data System (ADS)

Lateral hopping and desorption of a single CO molecule on a Cu(110) surface [Bartels , ScienceSCIEAS0036-807510.1126/science.1099770 305, 648 (2004)] induced by femtosecond laser pulses are studied using an indirect heat-transfer model. In addition to a direct heating of the reaction coordinate (RC) mode [frustrated translation (FT) mode for hopping and center-of-mass (CM) mode for desorption] by laser-generated hot electrons in the substrate, we consider an indirect heating of the RC mode through intermode coupling between the frustrated rotation (FR) mode and the RC mode. We calculate the transient behavior of the effective temperature of the FT and the CM modes, and of the normalized reaction yield. The experimental result of a ratio of the hopping yield along and across a row on a Cu(110) surface is nicely calculated. Although no information is available for the attempt frequency in a form of the Arrhenius equation for thermally activated reactions, it is predicted under which condition the desorption rate becomes in the same order of magnitude as the hopping rate, although the barrier height for desorption is much higher than for hopping. The present analysis highlights the role of excitation of the FR mode in reactions of a CO molecule as has been confirmed in the real-time observation [Backus , ScienceSCIEAS0036-807510.1126/science.1120693 310, 1790 (2005)].

Ueba, H.; Ootsuka, Y.

2013-05-01

11

Chemistry of Cu(acac){sub 2} on Ni(110) and Cu(110) surfaces: Implications for atomic layer deposition processes  

SciTech Connect

The thermal chemistry of copper(II)acetylacetonate, Cu(acac){sub 2}, on Ni(110) and Cu(110) single-crystal surfaces was probed under vacuum by using x-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Some data for acetylacetone (Hacac, CH{sub 3}COCH{sub 2}COCH{sub 3}) adsorbed on Ni(110) are also reported as reference. Chemical transformations were identified in several steps covering a temperature range from 150 K to at least 630 K. The desorption of Hacac and a 3-oxobutanal (CH{sub 3}COCH{sub 2}CHO) byproduct was observed first at 150 and 180 K on Ni(110) and at 160 and 185 K on Cu(110), respectively. Partial loss of the acetylacetonate (acac) ligands and a likely change in adsorption geometry are seen next, with the possible production of HCu(acac), which desorbs at 200 and 235 K from the nickel and copper surfaces, respectively. Molecular Cu(acac){sub 2} desorption is observed on both surfaces at approximately 300 K, probably from recombination of Cu(acac) and acac surface species. The remaining copper atoms on the surface lose their remaining acac ligands to the substrate and become reduced directly to metallic copper. At the same time, the organic ligands follow a series of subsequent surface reactions, probably involving several C-C bond-scissions, to produce other fragments, additional Hacac and HCu(acac) in the gas phase in the case of the copper surface, and acetone on nickel. A significant amount of acac must nevertheless survive on the surface to high temperatures, because Hacac peaks are seen in the TPD at about 515 and 590 K and the C 1s XPS split associated with acac is seen up to close to 500 K. In terms of atomic layer deposition processes, this suggests that cycles could be design to run at such temperatures as long as an effective hydrogenation agent is used as the second reactant to remove the surface acac as Hacac. Only a small fraction of carbon is left behind on Ni after heating to 800 K, whereas more carbon and additional oxygen remains on the surface in the case of Cu.

Ma Qiang; Zaera, Francisco [Department of Chemistry, University of California, Riverside, California 92521 (United States)

2013-01-15

12

Long Range Chiral Imprinting of Cu(110) by Tartaric Acid  

SciTech Connect

Restructuring of metals by chiral molecules represents an important route to inducing and controlling enantioselective surface chemistry. Tartaric acid adsorption on Cu(110) has served as a useful system for understanding many aspects of chiral molecule adsorption and ordering on a metal surface, and a number of chiral and achiral unit cells have been reported. Herein, we show that given the appropriate annealing treatment, singly deprotonated tartaric acid monolayers can restructure the Cu metal itself, and that the resulting structure is both highly ordered and chiral. Molecular resolution scanning tunneling microscopy reveals that singly deprotonated tartaric acid extracts Cu atoms from the Cu(110) surface layer and incorporates them into highly ordered, chiral adatom arrays capped by a continuous molecular layer. Further evidence for surface restructuring comes from images of atom-deep trenches formed in the Cu(110) surface during the process. These trenches also run in low symmetry directions and are themselves chiral. Simulated scanning tunneling microscopy images are consistent with the appearance of the added atom rows and etched trenches. The chiral imprinting results in a long-range, highly ordered unit cell covering the whole surface as confirmed by low energy electron diffraction. Details of the restructuring mechanism were further investigated via time-lapse imaging at elevated temperature. This work reveals the stages of nanoscale surface restructuring and offers an interesting method for chiral modification of an achiral metal surface.

Lawton, T. J.; Pushkarev, V.; Wei, D.; Lucci, F. R.; Sholl, D. S.; Gellman, A. J.; Sykes, E. C. H.

2013-10-31

13

Autocatalytic water dissociation on Cu(110) at near ambient conditions  

SciTech Connect

Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated based on X-ray photoelectron spectroscopy studies carried out in-situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.

Mulleregan, Alice; Andersson, Klas; Ketteler, Guido; Bluhm, Hendrik; Yamamoto, Susumu; Ogasawara, Hirohito; Pettersson, Lars G.M.; Salmeron, Miquel; Nilsson, Anders

2007-05-16

14

Effects of laser irradiation on the morphology of Cu(110)  

SciTech Connect

The effects of pulsed laser irradiation on the morphology of the Cu(110) surface were investigated by means of reflectance difference spectroscopy (RDS) and spot profile analysis low-energy electron diffraction (SPA-LEED). The laser light induces surface defects (adatoms and islands) as well as subsurface dislocation lines. The high surface mobility leads to efficient annealing of the surface defects even at room temperature, whereas the subsurface dislocation lines persist up to temperatures T>800 K. SPA-LEED profiles of the (00) diffraction spot from the laser irradiated surface suggest an anisotropic distribution of the subsurface line defects related to the geometry of the fcc easy glide system, which is corroborated by STM measurements. Comparative experiments using conventional Ar ion bombardment point out the distinctiveness of the morphological changes induced by laser irradiation.

Brandstetter, T.; Draxler, M.; Hohage, M.; Zeppenfeld, P.; Stehrer, T.; Heitz, J.; Georgiev, N.; Martinotti, D.; Ernst, H.-J. [Institut fuer Experimentalphysik, Johannes Kepler Universitaet Linz, A-4040 Linz (Austria); Institut fuer Angewandte Physik, Johannes Kepler Universitaet Linz, A-4040 Linz (Austria); CEA Saclay, DSM/Drecam/SPCSI, 91191 Gif sur Yvette (France)

2008-07-15

15

Elementary Process for CVD Graphene on Cu(110): Size-selective Carbon Clusters  

NASA Astrophysics Data System (ADS)

Revealing the graphene growth mechanism at the atomic-scale is of great importance for achieving high quality graphene. However, the lack of direct experimental observation and density functional theory (DFT) verification hinders a comprehensive understanding of the structure of the carbon clusters and evolution of the graphene growth on surface. Here, we report an in-situ low-temperature scanning tunneling microscopy (LT-STM) study of the elementary process of chemical vapor deposition (CVD) graphene growth via thermal decomposition of methane on Cu(110), including the formation of monodispersed carbon clusters at the initial stage, the graphene nucleation and the ripening of graphene islands to form continuous graphene film. STM measurement, supported by DFT calculations, suggests that the carbon clusters on the surface are C2H5. It is found that graphene layers can be joined by different domains, with a relative misorientation of 30°. These graphene layers can be decoupled from Cu(110) through low temperature thermal cycling.

Zhang, Jialin; Wang, Zhunzhun; Niu, Tianchao; Wang, Shengnan; Li, Zhenyu; Chen, Wei

2014-03-01

16

Comparative study of phenol and thiophenol adsorption on Cu(110)  

NASA Astrophysics Data System (ADS)

Adsorption of phenol and thiophenol (benzenethiol) on Cu(110) is investigated by a scanning tunneling microscope and electron energy loss spectroscopy. Phenol adsorbs intact and forms a cyclic trimer at 78 K. It is dehydrogenated to yield a phenoxy (C6H5O) group at 300 K. On the other hand, thiophenol is dehydrogenated to a thiophenoxy (C6H5S) group even at 78 K. Both products are bonded via chalcogen atom to the short-bridge site with the phenyl ring oriented nearly parallel to the surface. The C6H5O and C6H5S groups are preferentially assembled into the chains along the [001] and [1bar{1}2] directions, respectively. Dipole-dipole interaction is responsible for the chain growth, while the chain direction is ruled by the steric repulsion between chalcogen atoms and adjacent phenyl ring. This work demonstrates a crucial role of chalcogen atom of phenol species in their overlayer growth on the surface.

Kitaguchi, Y.; Habuka, S.; Mitsui, T.; Okuyama, H.; Hatta, S.; Aruga, T.

2013-07-01

17

Rotationally anisotropic second-harmonic generation studies of the structure and electronic properties of bimetallic interfaces, Ag on Cu(110)  

SciTech Connect

Rotationally anisotropic surface second-harmonic generation (SHG) has been measured from a clean, well-ordered Cu(110) single-crystal surface as a function of both surface temperature and Ag coverage. For the clean Cu(110) surface, the temperature dependence of the SH response at a fixed azimuthal angle can be correlated with a surface phase transformation. A large decrease in the rotationally anisotropic SH response as a function of surface temperature can be related to changes in the surface disorder. The results are compared with other studies of Cu(110) surface structure using both x-ray and He-atom scattering. The rotationally anisotropic SH response has also been measured as a function of Ag coverage with the Cu(110) surface temperature fixed at 300 K. The results closely follow the formation of an ordered Ag(111)-like overlayer, the nucleation of three-dimensional Ag nanoclusters (<20 {angstrom} thick) that enhance the anisotropic SH response, and the subsequent growth of a {approximately}10 monolayer thick Ag film. Variations in the rotationally anisotropic SH response as a function of Ag coverage are used to separate the resonant surface electronic contributions to the nonlinear susceptibility of the interface. 22 refs., 4 figs.

Hoffbauer, M.A.; McVeigh, V.J.

1990-01-01

18

Elementary Process for CVD Graphene on Cu(110): Size-selective Carbon Clusters  

PubMed Central

Revealing the graphene growth mechanism at the atomic-scale is of great importance for achieving high quality graphene. However, the lack of direct experimental observation and density functional theory (DFT) verification hinders a comprehensive understanding of the structure of the carbon clusters and evolution of the graphene growth on surface. Here, we report an in-situ low-temperature scanning tunneling microscopy (LT-STM) study of the elementary process of chemical vapor deposition (CVD) graphene growth via thermal decomposition of methane on Cu(110), including the formation of monodispersed carbon clusters at the initial stage, the graphene nucleation and the ripening of graphene islands to form continuous graphene film. STM measurement, supported by DFT calculations, suggests that the carbon clusters on the surface are C2H5. It is found that graphene layers can be joined by different domains, with a relative misorientation of 30°. These graphene layers can be decoupled from Cu(110) through low temperature thermal cycling. PMID:24651211

Zhang, Jialin; Wang, Zhunzhun; Niu, Tianchao; Wang, Shengnan; Li, Zhenyu; Chen, Wei

2014-01-01

19

Adsorption of Benzene, Fluorobenzene and Meta-di-Fluorobenzene on Cu(110): A Computational Study  

E-print Network

Adsorption of Benzene, Fluorobenzene and Meta-di-Fluorobenzene on Cu(110): A Computational Study L.interscience.wiley.com). Abstract: We modelled the adsorption of benzene, fluorobenzene and meta-di-fluorobenzene on Cu(110) by Den geometry is favoured. Function- alizing the benzene ring with one or two fluorine atoms weakens the bonding

Gao, Hongjun

20

Adsorption behavior of Lander molecules on Cu,,110... studied by scanning tunneling microscopy  

E-print Network

Adsorption behavior of Lander molecules on Cu,,110... studied by scanning tunneling microscopy M organic molecule, named Lander, has been studied on a Cu 110 substrate by scanning tunneling microscopy may play an impor- tant role when for example measuring the conductance through a single molecule.18

21

Electronic structure at highly ordered organic/metal interfaces: Pentacene on Cu(110)  

NASA Astrophysics Data System (ADS)

The electronic structure at highly ordered pentacene monolayer prepared on Cu(110) substrate was studied by angle-resolved ultraviolet photoemission spectroscopy. The valence-level photoemission line shape showed the evidences of (i) formation of the interface states and (ii) two-dimensional energy-band dispersion of the resultant interface states. The lattice constant deduced from the observed energy-band dispersion is consistent with the reported one based on the low-energy electron diffraction experiments. Thus, the observed energy-band dispersion can be ascribed to the in-plane intermolecular energy-band dispersion in the pentacene monolayer on Cu(110). These phenomena may originate from the hybridization between the molecular orbital and the wave function of the substrate surface. Furthermore, work-function change of about -0.9eV by adsorption of pentacene was observed from the shift of the secondary-electron cutoff. Such a decrease of the work function indicates the formation of a dipole layer at the interface with the molecule positively charged. This direction is opposite to the naive expectation from the electron transfer from the substrate to the molecule, which was suggested from the previous work of core-level photoemission spectroscopy [McDonald , Surf. Sci. 600, 1909 (2006)]. This unexpected result may originate from the charge redistribution at the interface due to the induced image charge in the metal and the push back of electrons spilled out from the metal surface by the adsorbed molecules, which may overwhelm the effect of electron transfer.

Yamane, H.; Yoshimura, D.; Kawabe, E.; Sumii, R.; Kanai, K.; Ouchi, Y.; Ueno, N.; Seki, K.

2007-10-01

22

Theory of vibrationally assisted tunneling for hydroxyl monomer flipping on Cu(110)  

NASA Astrophysics Data System (ADS)

To describe vibrationally mediated configuration changes of adsorbates on surfaces we have developed a theory to calculate both reaction rates and pathways. The method uses the T-matrix to describe excitations of vibrational states by the electrons of the substrate, adsorbate, and tunneling electrons from a scanning tunneling probe. In addition to reaction rates, the theory also provides the reaction pathways by going beyond the harmonic approximation and using the full potential energy surface of the adsorbate which contains local minima corresponding to the adsorbates different configurations. To describe the theory, we reproduce the experimental results in [T. Kumagai et al., Phys. Rev. B 79, 035423 (2009), 10.1103/PhysRevB.79.035423], where the hydrogen/deuterium atom of an adsorbed hydroxyl (OH/OD) exhibits back and forth flipping between two equivalent configurations on a Cu(110) surface at T =6 K. We estimate the potential energy surface and the reaction barrier, ˜160 meV, from DFT calculations. The calculated flipping processes arise from (i) at low bias, tunneling of the hydrogen through the barrier, (ii) intermediate bias, tunneling electrons excite the vibrations increasing the reaction rate although over the barrier processes are rare, and (iii) higher bias, overtone excitations increase the reaction rate further.

Gustafsson, Alexander; Ueba, Hiromu; Paulsson, Magnus

2014-10-01

23

1D self-assembly of chemisorbed thymine on Cu(110) driven by dispersion forces  

NASA Astrophysics Data System (ADS)

Adsorption of thymine on a defined Cu(110) surface was studied using reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and scanning tunnelling microscopy (STM). In addition, density functional theory (DFT) calculations were undertaken in order to further understand the energetics of adsorption and self-assembly. The combination of RAIRS, TPD, and DFT results indicates that an upright, three-point-bonded adsorption configuration is adopted by the deprotonated thymine at room temperature. DFT calculations show that the upright configuration adopted by individual molecules arises as a direct result of strong O-Cu and N-Cu bonds between the molecule and the surface. STM data reveal that this upright thymine motif self-assembles into 1D chains, which are surprisingly oriented along the open-packed [001] direction of the metal surface and orthogonal to the alignment of the functional groups that are normally implicated in H-bonding interactions. DFT modelling of this system reveals that the molecular organisation is actually driven by dispersion interactions, which cause a slight tilt of the molecule and provide the major driving force for assembly into dimers and 1D chains. The relative orientations and distances of neighbouring molecules are amenable for ?-? stacking, suggesting that this is an important contributor in the self-assembly process.

Temprano, I.; Thomas, G.; Haq, S.; Dyer, M. S.; Latter, E. G.; Darling, G. R.; Uvdal, P.; Raval, R.

2015-03-01

24

Experimental and theoretical investigation of the electronic structure of Cu2O and CuO thin films on Cu(110) using x-ray photoelectron and absorption spectroscopy  

NASA Astrophysics Data System (ADS)

The electronic structure of Cu2O and CuO thin films grown on Cu(110) was characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The various oxidation states, Cu0, Cu+, and Cu2+, were unambiguously identified and characterized from their XPS and XAS spectra. We show that a clean and stoichiometric surface of CuO requires special environmental conditions to prevent loss of oxygen and contamination by background water. First-principles density functional theory XAS simulations of the oxygen K edge provide understanding of the core to valence transitions in Cu+ and Cu2+. A novel method to reference x-ray absorption energies based on the energies of isolated atoms is presented.

Jiang, Peng; Prendergast, David; Borondics, Ferenc; Porsgaard, Soeren; Giovanetti, Lisandro; Pach, Elzbieta; Newberg, John; Bluhm, Hendrik; Besenbacher, Flemming; Salmeron, Miquel

2013-01-01

25

Effect of oxygen surfactant on the magnetic and structural properties of Co films grown on Cu(110)  

SciTech Connect

It was found that atomically flat Co(110) film could be grown on Cu(110) using O as a surfactant. To obtain detailed knowledge on the effect of O on the growth, as well as on the magnetic properties of Co overlayer, we carried out an investigation on this system using Auger Electron Spectroscopy (AES), Low Energy Electron Diffraction (LEED), Surface Magneto-Optic Kerr Effect (SMOKE), and Scanning Tunneling Microscopy (STM). With O as a surfactant, the initial growth of Co (< 1 ML) results in a flat monolayer structure. When the Co is thicker than 1 ML, three-dimensional clusters begin to form. These clusters become ordered islands at 3 ML Co and coalesce at about 5 ML Co. Above 5 ML Co, layer-by-layer growth resumes. No Cu segregation is observed. SMOKE studies at room temperature show that the Co film is magnetic above about 5 ML Co, with the magnetization easy axis along the [001] direction. On the other hand, without using oxygen as a surfactant, Co grows three-dimensionally on Cu(110). The Co overlayer has its easy magnetization axis along the [001] direction, but the onset of the magnetization was observed at 11 ML Co at room temperature.

Ling, W.L.; Qiu, Z.Q.; Takeuchi, O.; Ogletree, D.F.; Salmeron, M.

2000-04-13

26

Effect of oxygen surfactant on the magnetic and structural properties of Co films grown on Cu(110)  

NASA Astrophysics Data System (ADS)

It was found that atomically flat Co(110) films could be grown on Cu(110) using O as a surfactant. To obtain detailed knowledge on the effect of O on the growth, as well as on the magnetic properties of Co overlayer, we carried out an investigation on this system using Auger electron spectroscopy, low-energy electron diffraction, surface magneto-optic Kerr effect (SMOKE), and scanning tunneling microscopy. With O as a surfactant, the initial growth of Co (<1 ML) results in a flat monolayer structure. When the Co is thicker than 1 ML, three-dimensional clusters begin to form. These clusters become ordered islands at 3 ML Co and coalesce at ~5 ML Co. Above 5 ML Co, layer-by-layer growth resumes. No significant Cu segregation is observed. SMOKE studies at room temperature show that the Co film is magnetic above ~5 ML Co, with the magnetization easy axis along the [001] direction. On the other hand, without using oxygen as a surfactant, Co grows three-dimensionally on Cu(110). The Co overlayer has its easy magnetization axis along the [001] direction, but the onset of the magnetization was observed at 11 ML Co at room temperature.

Ling, W. L.; Qiu, Z. Q.; Takeuchi, O.; Ogletree, D. F.; Salmeron, M.

2001-01-01

27

L-Methionine adsorption on Cu(110), binding and geometry of the amino acid as a function of coverage  

NASA Astrophysics Data System (ADS)

The adsorption of L-methionine on Cu(110) has been characterized by combining in situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) and X-ray Photoelectron Spectroscopy (XPS). Both the chemical state of the molecule, and its anchoring points were determined at various coverage values. Adsorbed methionine is anionic and first interacts with the copper surface via its sulfur and/or oxygen atoms, likely lying flat on the surface; at higher coverage, a stronger interaction of oxygen and nitrogen atoms with copper, evidenced by slight shifts of the XPS peaks, together with an angular dependence of the peak ratios, suggests that the molecule stands up on the surface, interacting with the surface via the N and O atoms but almost not anymore via its S atom. Last but not least, no multilayers were evidenced, and this was explained by the geometry of the molecules which leaves no groups accessible for intermolecular interactions.

Méthivier, Christophe; Humblot, Vincent; Pradier, Claire-Marie

2015-02-01

28

Coadsorption Systems with Electrochemical Relevance: Coadsorption of Water with Oxygen, Bromine and Sodium on Cu(110)  

Microsoft Academic Search

A unique approach of synthesizing the electric double layer at a metal-electrolyte interface under ultra-high vacuum conditions is briefly outlined. Results are presented of a study of water adsorption on clean Cu (110) using ultra-violet photoelectron spectroscopy (UPS), low energy electron diffraction (LEED), thermal desorption spectroscopy (TDS), as well as changes in the work function (? ?) as determined by

D E Grider; K Bange; J K Sass; G Paolucci

1983-01-01

29

DFT study of gas-phase adsorption of benzotriazole on Cu(111), Cu(100), Cu(110), and low coordinated defects thereon.  

PubMed

The adsorption of benzotriazole--an outstanding corrosion inhibitor for copper--on Cu(111), Cu(100), Cu(110), and low coordinated defects thereon has been studied and characterized using density functional theory (DFT) calculations. We find that benzotriazole can either chemisorb in an upright geometry or physisorb with the molecular plane being nearly parallel to the surface. While the magnitude of chemisorption energy increases as passing from densely packed Cu(111) to more open surfaces and low coordinated defects, the physisorption energy is instead rather similar on all three low Miller index surfaces. It is pointed out that due to a large dipole moment of benzotriazole the dipole-dipole interactions are rather important. For perpendicular chemisorption modes the lateral repulsion is very long ranged, extending up to the nearest-neighbor distance of about 60 bohrs, whereas for parallel adsorption modes the lateral interactions are far less pronounced and the molecules experience a weak attraction at distances ?25 bohrs. The chemisorption energies were therefore extrapolated to zero coverage by a recently developed scheme and the resulting values are -0.60, -0.73, and -0.92 eV for Cu(111), Cu(100), and Cu(110), respectively, whereas the zero-coverage physisorption energy is about -0.7 eV irrespective of the surface plane. While the more densely packed surfaces are not reactive enough to interact with the molecular ?-system, the reactivity of Cu(110) appears to be at the onset of such interaction, resulting in a very stable parallel adsorption structure with an adsorption energy of -1.3 eV that is ascribed as an apparent chemisorption+physisorption mode. PMID:21997376

Peljhan, Sebastijan; Kokalj, Anton

2011-12-01

30

Coadsorption Systems with Electrochemical Relevance: Coadsorption of Water with Oxygen, Bromine and Sodium on Cu(110)  

Microsoft Academic Search

A unique approach of synthesizing the electric double layer at a metal-electrolyte interface under ultra-high vacuum conditions is briefly outlined. Results are presented of a study of water adsorption on clean Cu (110) using ultra-violet photoelectron spectroscopy (UPS), low energy electron diffraction (LEED), thermal desorption spectroscopy (TDS), as well as changes in the work function (Delta phi) as determined by

D. E. Grider; K. Bange; J. K. Sass; G. Paolucci

1983-01-01

31

Local chemical reaction of benzene on Cu(110) via STM-induced excitation  

NASA Astrophysics Data System (ADS)

We have investigated the mechanism of the chemical reaction of the benzene molecule adsorbed on Cu(110) surface induced by the injection of tunneling electrons using scanning tunneling microscopy (STM). With the dosing of tunneling electrons of the energy 2-5 eV from the STM tip to the molecule, we have detected the increase of the height of the benzene molecule by 40% in the STM image and the appearance of the vibration feature of the ?(C-H) mode in the inelastic tunneling spectroscopy (IETS) spectrum. It can be understood with a model in which the dissociation of C-H bonds occurs in a benzene molecule that induces a bonding geometry change from flat-lying to up-right configuration, which follows the story of the report of Lauhon and Ho on the STM-induced change of benzene on the Cu(100) surface. [L. J. Lauhon and W. Ho, J. Phys. Chem. A 104, 2463 (2000)]. The reaction probability shows a sharp rise at the sample bias voltage at 2.4 V, which saturates at 3.0 V, which is followed by another sharp rise at the voltage of 4.3 V. No increase of the reaction yield is observed for the negative sample voltage up to 5 eV. In the case of a fully deuterated benzene molecule, it shows the onset at the same energy of 2.4 eV, but the reaction probability is 103 smaller than the case of the normal benzene molecule. We propose a model in which the dehydrogenation of the benzene molecule is induced by the formation of the temporal negative ion due to the trapping of the electrons at the unoccupied resonant states formed by the ? orbitals. The existence of the resonant level close to the Fermi level (˜2.4 eV) and multiple levels in less than ˜5 eV from the Fermi level, indicates a fairly strong interaction of the Cu-?* state of the benzene molecule. We estimated that the large isotope effect of ˜103 can be accounted for with the Menzel-Gomer-Redhead (MGR) model with an assumption of a shallow potential curve for the excited state.

Komeda, T.; Kim, Y.; Fujita, Y.; Sainoo, Y.; Kawai, Maki

2004-03-01

32

Control of the intermolecular coupling of dibromotetracene on cu(110) by the sequential activation of c?br and c?h bonds.  

PubMed

Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723?K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673?K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions. PMID:25711882

Ferrighi, Lara; Píš, Igor; Nguyen, Thanh Hai; Cattelan, Mattia; Nappini, Silvia; Basagni, Andrea; Parravicini, Matteo; Papagni, Antonio; Sedona, Francesco; Magnano, Elena; Bondino, Federica; Di Valentin, Cristiana; Agnoli, Stefano

2015-04-01

33

Structural and magnetic studies of fcc Fe films with self-organized lateral modulation on striped Cu(110)-O(2x1) substrates.  

SciTech Connect

Fcc Fe wedges of 0-12 monolayer (ML) were grown by means of molecular beam epitaxy onto a novel substrate: flat Cu(110) with an oxygen-induced, long-range ordered striped phase, and studied in-situ with medium energy electron diffraction (MEED) and the surface magneto-optical Kerr effect (SMOKE). In contrast to Fe growth on either clean or oxygen-saturated Cu(110), the films on the striped substrates retain a layer-by-layer growth mode up to 6-7 ML and are fcc at least up to 12 ML. In addition, satellite peaks were observed on both sides of the MEED (0,0) streak, indicating a long-range-ordered lateral modulation of the Fe surface. We postulate that the Fe films grow conformally onto the original striped substrate. SMOKE studies show that these fcc Fe wedges are ferromagnetic with an easy axis along the original stripes for Fe thickness > 4ML and a remnant magnetization that increases linearly with thickness beyond 4 ML.

Li, D.

1998-09-21

34

Adsorption-geometry induced transformation of self-assembled nanostructures of an aldehyde molecule on Cu(110)  

NASA Astrophysics Data System (ADS)

From an interplay of high-resolution STM imaging/manipulation and DFT calculations, we have revealed that different self-assembled nanostructures of BA molecules on Cu(110) are attributable to specific molecular adsorption geometries, and thus the corresponding intermolecular hydrogen bonding patterns. The STM manipulations demonstrate the feasibility of switching such weak-hydrogen-bonding patterns.From an interplay of high-resolution STM imaging/manipulation and DFT calculations, we have revealed that different self-assembled nanostructures of BA molecules on Cu(110) are attributable to specific molecular adsorption geometries, and thus the corresponding intermolecular hydrogen bonding patterns. The STM manipulations demonstrate the feasibility of switching such weak-hydrogen-bonding patterns. Electronic supplementary information (ESI) available: Supplementary STM images and DFT calculation results. See DOI: 10.1039/c4nr03754e

Zhang, Chi; Sun, Qiang; Sheng, Kai; Tan, Qinggang; Xu, Wei

2014-09-01

35

Effect of Surface Oxide Transformation on CO Oxidation  

NASA Astrophysics Data System (ADS)

Under sub-atmospheric conditions, many metal catalyst surfaces for CO oxidation transform to the oxide phase with higher catalytic activity than chemisorbed oxygen. The surface phase transformation from metal to its oxide could be by collective oxidation of the adsorbed oxygen sites as soon as their coverage reaches a global critical threshold, or such oxidation may be restricted to small patches of the surface, which is driven by the local coverage. In this communication, we investigate the effect of the latter on the phase diagram and the CO2 production rate behavior using a kinetic Monte Carlo surface reaction lattice gas model for CO oxidation.

Sinha, I.; Mukherjee, A. K.

2015-02-01

36

Local triboelectricity on oxide surfaces  

NASA Astrophysics Data System (ADS)

In triboelectric phenomena, electric charges are transferred when two materials are touched or rubbed together. We present in this paper a study of this effect performed on metallic oxides at the nanometric scale by an Atomic Force Microscope in the resonant mode. We show that following the electrification processes, positive or negative charges can be deposited. From our experimental data, we conclude that the charge transfer results in an equilibrium final state, the occupied states in the gap being ``surface states'' with large density and spread under the surface along a characteristic distance of about 100 nm.

Saint Jean, M.; Hudlet, S.; Guthmann, C.; Berger, J.

1999-12-01

37

Ultrasonically enhanced persulfate oxidation of polyethylene surfaces  

Microsoft Academic Search

The ultrasonically enhanced oxidation of polyethylene surfaces by potassium and ammonium persulfates is described. The use of ultrasound allows significant levels of surface modification to be achieved using these oxidizing agents under mild conditions. Changes in the water contact angle and attenuated total reflection infra-red spectra were used to follow the changes in surface chemistry. Variation of conditions such as

Fiona Keen

1996-01-01

38

Surface Precipitation of Hydrolyzable Metal Ions on Oxide Surfaces  

E-print Network

Surface Precipitation of Hydrolyzable Metal Ions on Oxide Surfaces S. E. Fendorf Heavy metalO2 and TiO2 near and beyond monolayer coverage. Surface precipitation of Al(III) and La(III) was observed on MnO2, but was not apparent on TiO2 nor in bulk solution. Al(III) formed a surface precipitate

Sparks, Donald L.

39

Surface nitriding and oxidation of nitinol  

NASA Astrophysics Data System (ADS)

Nitinol has been widely employed in biomedical devices due to its unique mechanical properties such as superelasticity, shape memory, and good biocompatibility. However, nickel ion release from the surface of the Nitinol is an issue. Surface nitriding and oxidation was performed on the Nitinol specimens to develop a nickel-free oxide layer on the surface. Nitinol specimens were nitrided in nitrogen + 4% hydrogen at 800--1000°C for 10--30 min and further nitrided in nitrogen + 5% ammonia at 500--675°C for 0--30 min. The thickness and chemical composition, specifically the nickel content of the surface layer, were determined by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The effect of the nitriding time and temperature on the thickness and chemical composition of the nitride layer was evaluated. Nitriding temperature was found to be more effective than nitriding time on the thickness of TiN layer. Titanium nitride, the dominant phase on the surface of the nitrided specimens, was nickel free. The nitrided Nitinol specimens were then oxidized at 675°C and 700°C for 30 and 60 min, respectively. The chemical composition and elemental depth profile showed that oxidizing Nitinol specimens with a 0.4 microm thick nitride layer on the surface did not provide a nickel-free oxide layer on the surface of the Nitinol. However, oxidizing the Nitinol specimens with a surface nitride layer that was thicker than 6 microm resulted in a nickel-free oxide layer.

Bazochaharbakhsh, Edin

40

Surface oxidation of TiNx films  

NASA Astrophysics Data System (ADS)

Thin films of TiNx, with 0.8 < x < 1.2. have been deposited by reactive sputtering in a nitrogen atmosphere. The films were then anodically oxidized. The influence of the anodization potential on the surface oxidation process was also investigated. The characterization of the resultant oxides has been made by Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). The results show that the oxidation reaction proceeds at the TiNx interface, resulting in the formation of an oxygen-enriched TiOxNy overlayer on the underlying TiNx, nitrogen atoms diffusing outwards. In the case of thicker oxides the surface layer is titanium dioxide followed by TiNxOy groups presenting a low level of disolved oxygen. In all cases, a smooth oxide/nitride interface is obtained.

Montero, I.; Jiménez, C.; Perrière, J.

1991-07-01

41

Surface Wrinkling on Polydimethylsiloxane Microspheres via Wet Surface Chemical Oxidation  

NASA Astrophysics Data System (ADS)

Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties.

Yin, Jian; Han, Xue; Cao, Yanping; Lu, Conghua

2014-07-01

42

Surface Wrinkling on Polydimethylsiloxane Microspheres via Wet Surface Chemical Oxidation  

PubMed Central

Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties. PMID:25028198

Yin, Jian; Han, Xue; Cao, Yanping; Lu, Conghua

2014-01-01

43

Local triboelectricity on oxide surfaces  

Microsoft Academic Search

:   In triboelectric phenomena, electric charges are transferred when two materials are touched or rubbed together. We present\\u000a in this paper a study of this effect performed on metallic oxides at the nanometric scale by an Atomic Force Microscope in\\u000a the resonant mode. We show that following the electrification processes, positive or negative charges can be deposited. From\\u000a our experimental

M. Saint Jean; S. Hudlet; C. Guthmann; J. Berger

1999-01-01

44

Vanadium oxide surfaces and supported vanadium oxide nanoparticles  

Microsoft Academic Search

The information obtained from the characterization of vanadium oxide single crystal surfaces is related to the study of vanadia\\u000a nanoparticles supported on silica and alumina thin films, model systems for the so-called “supported monolayer vanadia catalysts”.\\u000a It is found that these particles have properties similar to V2O3 surfaces, where the topmost V ions are involved in vanadyl groups and have

S. Guimond; M. Abu Haija; S. Kaya; J. Lu; J. Weissenrieder; S. Shaikhutdinova; H. Kuhlenbeck; H.-J. Freund; J. Döbler; J. Sauer

2006-01-01

45

Water Oxidation on GaN Surface  

Microsoft Academic Search

Efficient solar water-splitting requires a good catalyst to oxidize water into O2 with the photo-holes. Efficient water oxidation catalysts are hard to find. The solid solution of wurtzite GaN\\/ZnO is a water-splitting photocatalyst which works in visible light, while pure GaN is a water-splitting photocatalyst which works in UV. Unlike other semiconductors, the surfaces of both materials exhibit high efficiencies

Xiao Shen; Jue Wang; Y. A. Small; P. B. Allen; M. V. Fernandez-Serra; M. S. Hybertsen; J. T. Muckerman

2010-01-01

46

Geometrical Characterization of Adenine And Guanine on Cu(110) By NEXAFS, XPS, And DFT Calculation  

SciTech Connect

Adsorption of purine DNA bases (guanine and adenine) on Cu(1 1 0) was studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine-structure spectroscopy (NEXAFS), and density-functional theory (DFT) calculation. At coverages near 0.2 monolayers, Angular-resolved NEXAFS analysis revealed that adenine adsorbates lie almost flat and that guanine adsorbates are tilted up on the surface with the purine ring parallel to the atom rows of Cu(1 1 0). Referring to the previous studies on pyrimidine DNA bases [M. Furukawa, H. Fujisawa, S. Katano, H. Ogasawara, Y. Kim, T. Komeda, A. Nilsson, M. Kawai, Surf. Sci. 532-535 (2003) 261], the isomerization of DNA bases on Cu(1 1 0) was found to play an important role in the adsorption geometry. Guanine, thymine and cytosine adsorption have an amine-type nitrogen next to a carbonyl group, which is dehydrogenated into imine nitrogen on Cu(1 1 0). These bases are bonded by the inherent portion of - NH-CO - altered by conversion into enolic form and dehydrogenation. Adenine contains no CO group and is bonded to Cu(1 1 0) by participation of the inherent amine parts, resulting in nearly flatly-lying position.

Furukawa, M.; Yamada, T.; /Wako, RIKEN; Katano, S.; /tohoku U.; Kawai, M.; /Wako, RIKEN /Tokyo U.; Ogasawara, H.; /SLAC, SSRL; Nilsson, A.; /SLAC, SSRL /Stockholm U.

2009-04-30

47

SURFACE REACTIONS OF OXIDES OF SULFUR  

EPA Science Inventory

Surface reactions of several sulfur-containing molecules have been studied in order to understand the mechanism by which sulfate ions are formed on atmospheric aerosols. At 25C the heterogeneous oxidation of SO2 by NO2 to sulfuric acid and sulfate ions occurred on hydrated silica...

48

The Properties of Alkali Metal and Alkali-Coadsorbate Overlayers on Metal Surfaces  

Microsoft Academic Search

I have investigated properties of alkalis on metal surfaces and coadsorbate-alkali interactions. The systems in this investigation are Na\\/Cu(111) Na\\/Ni(111), Cs\\/Ni(111), Na\\/Cu(110), O_{2}\\/Cu(110),O _{2}\\/Na\\/Cu(110), O _{2}\\/Na\\/Ni(111), CO\\/Na\\/Ni(111), and O_{2}\\/Na\\/Cu(111). The experiments were all performed in ultra high vacuum. Thermal Desorption Spectroscopy, Low Energy Electron Diffraction, and work function change measurements have been carried out to study the adsorption of sodium

Daixing Tang

1993-01-01

49

Oxidation enthalpies for reduction of ceria surfaces  

NASA Astrophysics Data System (ADS)

The thermodynamic properties of surface ceria were investigated through equilibrium isotherms determined by flow titration and coulometric titration measurements on high-surface-area ceria and ceria supported on La-modified alumina (LA). While the surface area of pure ceria was found to be unstable under redox conditions, the extent of reduction at 873 K and a P(O 2) of 1.6 × 10 -26 atm increased with surface area. Because ceria/LA samples were stable, equilibrium isotherms were determined between 873 and 973 K on a 30-wt% ceria sample. Oxidation enthalpies on ceria/LA were found to vary with the extent of reduction, ranging from -500 kJ/mol O 2 at low extents of reduction to near the bulk value of -760 kJ/mol O 2 at higher extents. To determine whether +3 dopants could affect the oxidation enthalpies for ceria, isotherms were measured for Sm +3-doped ceria (SDC) and Y +3-doped ceria. These dopants were found to remove the phase transition observed in pure ceria below 973 K but appeared to have minimal effect on the oxidation enthalpies. Implications of these results for catalytic applications of ceria are discussed.

Zhou, Gong; Shah, Parag R.; Montini, Tiziano; Fornasiero, Paolo; Gorte, Raymond J.

2007-06-01

50

Patterning pentacene surfaces by local oxidation nanolithography.  

PubMed

Sequential and parallel local oxidation nanolithographies have been applied to pattern pentacene samples by creating a variety of nanostructures. The sequential local oxidation process is performed with an atomic force microscope and requires the application of a sequence of voltage pulses of 36V for 1ms. The parallel local oxidation process is performed by using a conductive and patterned stamp. Then, a voltage pulse is applied between the stamp and the pentacene surface. Patterns formed by arrays of parallel lines covering 1mm(2) regions and with a periodicity of less than 1microm have been generated in a few seconds. We also show that the patterns can be used as templates for the deposition of antibodies. PMID:20226594

Losilla, N S; Martinez, J; Bystrenova, E; Greco, P; Biscarini, F; García, R

2010-05-01

51

Surface Structure of Aerobically Oxidized Diamond Nanocrystals.  

PubMed

We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5-50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (?excit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core-hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed. PMID:25436035

Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E; Chen, Edward H; Nordlund, Dennis; Diaz, Rosa E; Gaathon, Ophir; Englund, Dirk; Owen, Jonathan S

2014-11-20

52

Surface wettability of macroporous anodized aluminum oxide.  

PubMed

The correlation between the structural characteristics and the wetting of anodized aluminum oxide (AAO) surfaces with large pore sizes (>100 nm) is discussed. The roughness-induced wettability is systematically examined for oxide films grown by a two-step, high-field anodization in phosphoric acid of three different concentrations using a commercial aluminum alloy. This is done for the as-synthesized AAO layers, after various degrees of pore widening by a wet chemical etching in phosphoric acid solution, and upon surface modification by either Lauric acid or a silane. The as-grown AAO films feature structurally disordered pore architectures with average pore openings in the range 140-190 nm but with similar interpore distances of about 405 nm. The formation of such AAO structures induces a transition from slightly hydrophilic to moderately hydrophobic surfaces up to film thicknesses of about 6 ?m. Increased hydrophobicity is obtained by pore opening and a maximum value of the water contact angle (WCA) of about 128° is measured for AAO arrays with a surface porosity close to 60%. Higher surface porosity by prolonged wet chemical etching leads to a rapid decrease in the WCA as a result of the limited pore wall thickness and partial collapse of the dead-end pore structures. Modification of the AAO surfaces by Lauric acid results in 5-30° higher WCA's, whereas near-superhydrophobicity (WCA ~146°) is realized through silane coating. The "rose petal effect" of strongly hydrophobic wetting with high adhesive force on the produced AAO surfaces is explained by a partial penetration of water through capillary action into the dead-end pore cavities which leads to a wetting state in-between the Wenzel and Cassie states. Moreover, practical guidelines for the synthesis of rough, highly porous AAO structures with controlled wettability are provided and the possibility of forming superhydrophobic surfaces is evaluated. PMID:23506401

Buijnsters, Josephus G; Zhong, Rui; Tsyntsaru, Natalia; Celis, Jean-Pierre

2013-04-24

53

Excitation and quenching mechanisms in the near-UV photodissociation of CH3Br and CH3Cl adsorbed on D2O or CH3OH on Cu(110).  

PubMed

Photochemical processes for CH3X (X = Cl, Br, I) adsorbed on top of thin films of D2O or CH3OH on a Cu(110) substrate is studied by time-of-flight mass spectrometry for a range of UV wavelengths (351-193 nm). Photodissociation via dissociative electron attachment by photoelectrons and by neutral photodissociation is identified and quantified based on the observed dynamics of the desorbing CH3 fragments. Photoelectron-driven dissociation of CH3X is found to be a maximum for monolayer quantities of the D2O or CH3OH on Cu(110), but with differing kinetic energy release on the two substrates. The dynamics of CH3Br and CH3Cl photodissociation qualitatively differ on CH3OH/Cu(110) as compared to D2O/Cu(110), which is ascribed to differing molecular structures for these systems. Evidence is presented for an efficient inter-molecular quenching mechanism for neutral photoexcitation of CH3Cl and CH3Br on the CH3OH/Cu(110) substrate. PMID:25757378

Jensen, E T

2015-04-14

54

Acceleration of Biochar Surface Oxidation during Composting?  

PubMed

Biochar composting experiments were performed to determine whether composting is a suitable method to accelerate biochar surface oxidation for increasing its reactivity. To assess the results, surface properties of Terra Preta (Brazil) and ancient charcoal pit (Northern Italy) biochars were additionally investigated. Calculation of O/C ratios by energy-dispersive X-ray spectroscopy demonstrated the anticipated increasing values from fresh biochars (0.13) to composted biochars (0.40), and finally charcoal pit biochars (0.54) and ancient Terra Preta biochars (0.64). By means of Fourier transformation infrared microscopy, formation of carboxylic and phenolic groups on biochars surface could be detected. Carboxylic acids of three composted biochars increased up to 14%, whereas one composted biochar showed a 21% lower proportion of carboxylic acids compared to the corresponding fresh biochar. Phenolic groups increased by 23% for the last mentioned biochar, and on all other biochars phenolic groups decreased up to 22%. Results showed that biochar surface oxidation can be accelerated through composting but still far away from ancient biochars. PMID:25802948

Wiedner, Katja; Fischer, Daniel; Walther, Sabine; Criscuoli, Irene; Favilli, Filippo; Nelle, Oliver; Glaser, Bruno

2015-04-22

55

Surface Stabilization Mechanisms in Metal Oxides  

NASA Astrophysics Data System (ADS)

Metal oxide surfaces play a central role in modern applications, ranging from heterogeneous catalysis to electronic devices, yet little is known about the processes determining their structural stabilization. Several such stabilization mechanisms are explored via a combination of theoretical and experimental methods. The processes of periodic reconstruction, adsorption and segregation are studied through case studies of model material systems. The evaluation of structural models of periodic SrTiO3(001) reconstructions via bonding analysis and simulated scanning tunneling microscopy images supports the family of "DL" models terminating in two consecutive layers of TiO2 composition, and discards alternative proposals such as the models based on periodic Sr adatoms. Experimental and simulated scanning tunneling microscopy images and complementary spectroscopic data are used to determine the structure of linear Ti-rich SrTiO 3(001) nanostructures. The structural solution exemplifies the recurrence of locally stable motifs across numerous surfaces. In particular, the arrangement of edge-sharing TiO5 surface polyhedra is a trait is shared by (001) nanostructures and DL reconstructions. This is a flexible framework which allows for optimal bonding in surface atoms. Modeling of water adsorption on reconstructed SrTiO3(001) surfaces reveals that water plays two major roles in the stabilization of oxide surfaces: it may mediate the formation of certain ordered structures, or it may be part of the ultimately stable structures themselves. This can be understood in terms of the inevitable presence of chemisorbed water on defective surfaces. Since the surface mobility of cationic species is relatively low, the kinetics associated to water diffusion and desorption dominate the surface ordering process. High-temperature annealing of SrLaAlO4 single crystals leads to the segregation of SrO to the surfaces, in the form of islands. This process is in fact a bulk stabilization mechanism, due initially to the increasing number of bulk Sr-O vacancy pairs. This material enables a second accommodation mechanism for further surface segregation and increasing bulk non-stoichiometry, consisting of the formation of low-energy stacking faults. In spite of previous speculation of a similar fault-based compensation process taking place in SrTiO3, this is found to be decidedly unviable in perovskite systems.

Becerra Toledo, Andres Enrique

2011-07-01

56

Surface oxidation kinetics of sputtering targets  

NASA Astrophysics Data System (ADS)

Films of compounds can be deposited by sputtering a metal or alloy target in an atmosphere containing a suitable reactive gas. Both Al and 90 : 10 In : Sn targets have been sputtered in argon/oxygen mixtures to obtain Al 2O 3 and indium tin oxide films. The experiments were carried out in a planar magnetron sputtering system with both dc and rf excitation. To investigate the kinetics of the reactive sputtering process, the time dependence of the total gas pressure was measured after a change in oxygen flow rate or sputtering power; a capacitance manometer gave accurate and reproducible results. There were simultaneous changes in the rf matching conditions when rf excitation was used. These changes can be attributed to the formation of an oxide on the target surface. The time dependence of the oxygen pressure measured for the Al and In : Sn targets have been used to compare various models of the reactive sputtering process. Fitting of the experimental values to these models yields values of the equilibrium oxide thickness on the target and these have been compared with measured values. For rf sputtering of an Al target at 500 W with flow rates of 3 {ml}/{min} and 2.2 {ml}/{min} for argon and oxygen respectively, both the calculated and the measured value of the oxide thickness is 100 nm.

Maniv, S.; Westwood, W. D.

1980-10-01

57

Oxidation-driven surface dynamics on NiAl(100)  

PubMed Central

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling up of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). By comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps. PMID:25548155

Qin, Hailang; Chen, Xidong; Li, Liang; Sutter, Peter W.; Zhou, Guangwen

2015-01-01

58

Oxidation-driven surface dynamics on NiAl(100).  

PubMed

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling up of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). By comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps. PMID:25548155

Qin, Hailang; Chen, Xidong; Li, Liang; Sutter, Peter W; Zhou, Guangwen

2015-01-13

59

Perfluorodiethoxymethane on nickel and nickel oxide surfaces  

SciTech Connect

The interaction of perfluorodiethoxymethane with a nickel single crystal, Ni(100); a nickel crystal with chemisorbed oxygen, Ni(100)-c(2x2)O; and a nickel crystal with nickel oxide crystallites, NiO(100) is investigated in an ultra high vacuum environment using thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. Nickel, a component of hard disk drives and stainless steel, is used to represent metal surfaces in these {open_quotes}real{close_quotes} systems. Perfluorodiethoxymethane is used in this study as a model compound of industrial perfluoropolyether lubricants. These lubricants are known for their exceptional stability, except in the presence of metals. Perfluorodiethoxymethane contains the acetal group (-OCF{sub 2}O-), believed to be particularly vulnerable to attack in the presence of Lewis acids. Since the surfaces studied show increasing Lewis acidity at the nickel atom sites, one might expect to see increasing decomposition of perfluorodiethoxymethane due to acidic attack of the acetal group. No decomposition of perfluorodiethoxymethane is observed on the clean Ni(100) surface, while more research is needed to determine whether a small decomposition pathway is observed on the oxygenated surfaces, or whether sample impurities are interfering with results. The strength of the bonding of perfluorodiethoxymethane to the surface is found to increase as the nickel atoms sites become more acidic in moving from Ni(100) to Ni (100)-c(2x2)O to NiO (100).

Jacobson, J.

1994-03-03

60

Oxide modified air electrode surface for high temperature electrochemical cells  

DOEpatents

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

Singh, Prabhakar (Export, PA); Ruka, Roswell J. (Churchill Boro, Allegheny County, PA)

1992-01-01

61

Shape-selective sieving layers on an oxide catalyst surface  

E-print Network

- allel, mesostructured oxides are available with high surfaces area and 2­50 nm pores that are ableShape-selective sieving layers on an oxide catalyst surface Christian P. Canlas1 , Junling Lu2 such as zeolites, metal­organic frameworks and mesostructured oxides are of immense practical utility for gas

Mohseni, Hooman

62

Energetics of nanoparticle oxides: interplay between surface energy and polymorphism†  

PubMed Central

Many oxides tend to form different structures (polymorphs) for small particles. High temperature oxide melt solution calorimetry has been used to measure the enthalpy as a function of polymorphism and surface area for oxides of Al, Ti, and Zr. The results confirm crossovers in polymorph stability at the nanoscale. The energies of internal and external surfaces of zeolitic silicas with open framework structures are an order of magnitude smaller than those of oxides of normal density.

Navrotsky, Alexandra

2003-01-01

63

Electron spectroscopic studies of perfect and defect metal oxide surfaces  

NASA Astrophysics Data System (ADS)

A number of surface sensitive electron spectroscopic techniques have been used during the last few years to study the geometric and electronic structure of well characterized surfaces of metal oxide single crystals. For rocksalt monoxides, the (100) surface has been found to be very nearly a truncation of the bulk lattice; only qualitative low energy electron diffraction (LEED) measurements have been performed on other oxide crystal structures. The electronic structure of nearly perfect oxide surfaces is generally very similar to that of the bulk, although excitonic surface states have been found on some rocksalt oxides. However, the presence of O-vacancy point defects on transition metal oxide surfaces changes their electronic structure drastically, increasing the d-orbital population of the cations adjacent to the defect. These surface defects are generally the active sites for chemisorption, with nearly perfect surfaces being relatively inert with respect to most of the molecules that have been studied.

Henrich, Victor E.

1987-09-01

64

Pretreatment of lubricated surfaces with sputtered cadmium oxide  

NASA Technical Reports Server (NTRS)

Cadmium oxide is used with a dry solid lubricant on a surface to improve wear resistance. The surface topography is first altered by photochemical etching to a predetermined pattern. The cadmium oxide is then sputtered onto the altered surface to form an intermediate layer to more tightly hold the dry lubricant, such as graphite.

Fusaro, Robert L. (inventor)

1991-01-01

65

Step-Edge-Induced Oxide Growth During the Oxidation of Cu Surfaces  

NASA Astrophysics Data System (ADS)

Using in situ atomic-resolution electron microscopy observations, we report observations of the oxide growth during the oxidation of stepped Cu surfaces. Oxidation occurs via direct growth of Cu2O on flat terraces with Cu adatoms detaching from steps and diffusing across the terraces. This process involves neither reconstructive oxygen adsorption nor oxygen subsurface incorporation and is rather different from the mechanism of solid-solid transformation of bulk oxidation that is most commonly postulated. These results demonstrate that the presence of surface steps can promote the development of a flat metal-oxide interface by kinetically suppressing subsurface oxide formation at the metal-oxide interface.

Zhou, Guangwen; Luo, Langli; Li, Liang; Ciston, Jim; Stach, Eric A.; Yang, Judith C.

2012-12-01

66

Oxidation of heated diamond C(100):H surfaces  

NASA Astrophysics Data System (ADS)

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O ?2). In this paper, the oxidation is performed at substrate temperatures from Tsub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED). The oxygen coverage ( ?) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage ( ?) was lower at higher temperatures. For example, ? plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to Tsub=600°C, lost ˜60% of their adsorbed oxygen. ELS revealed few C?C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C-H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.

Pehrsson, Pehr E.; Mercer, Thomas W.

2000-07-01

67

Influence of the Side Group Aromaticity on the Organic Molecule Adsorption on Cu(110) E. Rauls* and W. G. Schmidt  

E-print Network

is of pharmaceutical importance is tartaric acid, being one of the few molecules for which heterogeneous catalytic of an otherwise nonchiral metal surface.11,12 A similar example are the inves- tigations of methyl pyruvate of the 2-[1-(aminomethyl)cyclohexyl]acetic acid (C9H17NO2) molecule on a copper (110) surface

Schmidt, Wolf Gero

68

Surface Science Letters CO oxidation on ruthenium: The nature of the active catalytic surface  

E-print Network

in automotive catalytic converters, the reaction proceeds via the Langmuir­Hin- shelwood (L­H) mechanism betweenSurface Science Letters CO oxidation on ruthenium: The nature of the active catalytic surface D(110) The oxidation of CO, i.e. CO + 1=2O2 ! CO2, over metal surfaces is one of the most studied catalytic reactions

Goodman, Wayne

69

Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies  

PubMed Central

Surface functionalized magnetic iron oxide nanoparticles (NPs) are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed. PMID:21749733

2008-01-01

70

High-Temperature Oxide Regrowth on Mechanically-Damaged Surfaces  

SciTech Connect

Here we report the effects of mechanical damage from a sharp stylus on the regrowth of oxide layers on a Ni-based superalloy known as Pyromet 80A . It was found that the oxide that reformed on the damaged portion of a pre-oxidized surface differed from that which formed on undamaged areas after the equal exposures to elevated temperature in air. These findings have broad implications for modeling the processes of material degradation in applications such as exhaust valves in internal combustion engines because they imply that static oxidation data for candidate materials may not adequately reflect their reaction to operating environments that involve both mechanical contact and oxidation.

Blau, Peter Julian [ORNL; Lowe, Tracie M [ORNL

2008-01-01

71

Design and construction of rigs for studying surface condensation and creating anodized metal oxide surfaces  

E-print Network

This thesis details the design and construction of a rig for studying surface condensation and a rig for creating anodized metal oxides (AMOs). The condensation rig characterizes condensation for different surfaces; this ...

Sun, Wei-Yang

2011-01-01

72

Surface Oxidation and Dissolution of Metal Nanocatalysts in Acid Medium  

E-print Network

medium and the oxidation of the surface reduce the activity and durability of the alloy catalyst through changes in its local composition and structure. Molecular simulation techniques are applied to characterize the thermodynamics and dynamic evolution...

Callejas-Tovar, Juan

2012-10-19

73

Oxidative dissolution of pyrite surfaces by hexavalent chromium: Surface site saturation and surface renewal  

NASA Astrophysics Data System (ADS)

In-situ reduction of toxic Cr(VI) to nontoxic Cr(III) represents an important natural attenuation process for Cr(VI)-impacted environments. This study investigates the stoichiometry and kinetics of Cr(VI) reduction by pyrite, a reduced iron-sulfur mineral ubiquitous in recent estuarine and marine sediments. Pyrite suspensions at surface loadings of 0.28-2.10 m2/L (typical of estuarine or marine sediments) were capable of completely reducing 7-120 ?M Cr(VI) on the timescale of minutes to days, with the time to reaction completion decreasing with increasing pyrite loading, decreasing initial Cr(VI) concentration, and decreasing suspension pH. Analysis of metal species (Cr and Fe) and sulfur species in solution and at the mineral surface indicated that Cr(VI) oxidatively dissolved the pyrite surface, releasing ferrous iron and sulfate into solution as the reaction progressed. Surface disulfide groups were postulated as the Cr(VI)-reactive surface entity. Net production or consumption of aqueous Fe(II) was shown to depend upon the relative rates of proton-promoted Fe(II) release, Fe(II) release due to oxidative dissolution of pyrite in the presence of Cr(VI), and Fe(II) consumption due to homogeneous reaction with Cr(VI). Kinetics of Cr(VI) reduction by pyrite displayed a biphasic pattern, and the time to reaction completion increased dramatically with increasing initial Cr(VI) concentration. Rapid Cr(VI) removal occurred early in the reaction progress, attributable to Cr(VI) loss under an adsorption-limited regime. Slow, approximately zero-order, Cr(VI) removal occurred over the bulk of the time courses, and corresponded to Cr(VI) removal under surface site saturation conditions. Stoichiometric Cr(VI) reduction was able to proceed under surface site limited conditions owing to regeneration of reactive surface sites following desorption/dissolution of oxidized surface products, as demonstrated in repeat Cr(VI)-spiking experiments. The role of surface passivation was evaluated by comparing rates of Cr(VI) reduction in the presence and absence of the Cr(III)-complexing agent citrate. While citrate addition significantly enhanced Cr(III) solubility, rates of Cr(VI) reduction were only marginally accelerated, suggesting that Cr(OH)3(s) coatings did not completely block access of Cr(VI) to reactive surface sites on pyrite. Given the rapid rates of Cr(VI) reduction with pyrite under pH and surface coverage conditions typical of natural environments, we propose that Cr(VI) reduction by pyrite be considered in fate and transport models for Cr in contaminated sediments.

Graham, Andrew M.; Bouwer, Edward J.

2012-04-01

74

Bacterial adhesion to glass and metal-oxide surfaces  

Microsoft Academic Search

Metal oxides can increase the adhesion of negatively-charged bacteria to surfaces primarily due to their positive charge. However, the hydrophobicity of a metal-oxide surface can also increase adhesion of bacteria. In order to understand the relative contribution of charge and hydrophobicity to bacterial adhesion, we measured the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength

Baikun Li; Bruce E. Logan

2004-01-01

75

The nature of transition-metal-oxide surfaces  

NASA Astrophysics Data System (ADS)

The surfaces of the 3d-transition-metal oxides form a rich and important system in which to study the effects of atomic geometry, ligand coordination and d-orbital population on surface electronic structure and chemisorption. This article considers the properties of those surfaces in terms of the types of surface structures that can exist, including steps and point defects, and their relation to the experimental data that is available for well characterized, single-crystal surfaces. The electronic structure of nearly perfect surfaces is very similar to that of the bulk for many of the oxides that have been studied; atoms at step sites also appear to have properties similar to those of atoms on terraces. Point defects are often associated with surfaces 0 vacancies and attendant transfer of electrons to adjacent metal cations. Those cations are poorly screened from each other, and the excess charge is presumably shared between two or more cations having reduced ligand coordination. Point defects are generally more active for chemisorption than are perfect surfaces, however for Ti 2O 3 and V 2O 3, whose cations have 3d 1 and 3d 2 electronic configurations respectively, the cleaved (047) surface is more active than are surfaces having a high density of defects. The chemisorption behavior of both nearly perfect and defect surfaces of 3d-transition-metal oxides varies widely from one material to another, and it is suggestive to correlate this with cation d-orbital population. However, too few oxides have yet been studied to draw any firm conclusions. Additional theoretical work on perfect surfaces, defects and chemisorption is also necessary in order to gain a more complete understanding of transition-metal-oxide surfaces.

Henrich, V. E.

76

MOISTURE AND SURFACE AREA MEASUREMENTS OF PLUTONIUM-BEARING OXIDES  

SciTech Connect

To ensure safe storage, plutonium-bearing oxides are stabilized at 950 C for at least two hours in an oxidizing atmosphere. Stabilization conditions are expected to decompose organic impurities, convert metals to oxides, and result in moisture content below 0.5 wt%. During stabilization, the specific surface area is reduced, which minimizes readsorption of water onto the oxide surface. Plutonium oxides stabilized according to these criteria were sampled and analyzed to determine moisture content and surface area. In addition, samples were leached in water to identify water-soluble chloride impurity content. Results of these analyses for seven samples showed that the stabilization process produced low moisture materials (< 0.2 wt %) with low surface area ({le} 1 m{sup 2}/g). For relatively pure materials, the amount of water per unit surface area corresponded to 1.5 to 3.5 molecular layers of water. For materials with chloride content > 360 ppm, the calculated amount of water per unit surface area increased with chloride content, indicating hydration of hygroscopic salts present in the impure PuO{sub 2}-containing materials. The low moisture, low surface area materials in this study did not generate detectable hydrogen during storage of four or more years.

Crowder, M.; Duffey, J.; Livingston, R.; Scogin, J.; Kessinger, G.; Almond, P.

2009-09-28

77

Comparison of thermal oxidation and plasma oxidation of 4H-SiC (0001) for surface flattening  

NASA Astrophysics Data System (ADS)

The thermal oxidation and water vapor plasma oxidation of 4H-SiC (0001) were investigated. The initial oxidation rate of helium-based atmospheric-pressure plasma oxidation was six times higher than that of thermal oxidation. The oxide-SiC interface generated by plasma oxidation became flatter with increasing thickness of the oxide, whereas the interface generated by thermal oxidation was atomically flat regardless of the oxide thickness. Many pits were generated on the thermally oxidized surface, whereas few pits were observed on the surface oxidized by plasma. After the oxide layer generated plasma oxidation was removed, an atomically flat and pit-free SiC surface was obtained.

Deng, Hui; Endo, Katsuyoshi; Yamamura, Kazuya

2014-03-01

78

Comparison of thermal oxidation and plasma oxidation of 4H-SiC (0001) for surface flattening  

SciTech Connect

The thermal oxidation and water vapor plasma oxidation of 4H-SiC (0001) were investigated. The initial oxidation rate of helium-based atmospheric-pressure plasma oxidation was six times higher than that of thermal oxidation. The oxide-SiC interface generated by plasma oxidation became flatter with increasing thickness of the oxide, whereas the interface generated by thermal oxidation was atomically flat regardless of the oxide thickness. Many pits were generated on the thermally oxidized surface, whereas few pits were observed on the surface oxidized by plasma. After the oxide layer generated plasma oxidation was removed, an atomically flat and pit-free SiC surface was obtained.

Deng, Hui; Endo, Katsuyoshi; Yamamura, Kazuya, E-mail: yamamura@upst.eng.osaka-u.ac.jp [Research Center for Ultra-precision Science and Technology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)] [Research Center for Ultra-precision Science and Technology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

2014-03-10

79

Oxidation of pyrite surfaces: a photoelectron spectroscopic study  

NASA Astrophysics Data System (ADS)

Surfaces of pyrite (FeS 2) differently prepared in situ and ex situ have been studied before and after contact to air and air-saturated aqueous solutions of 4?pH?10 by means of photoelectron spectroscopy. Pyrite surfaces fractured or scraped in situ revealed FeS-like species concentrated in the surface region. Preparation (polishing, grinding, powdering) and prolonged oxidation in air mainly resulted in basic iron sulphate and iron oxide/hydroxide. A promoting effect of an increased surface roughness due to the preparation was observed for the formation of iron oxide/hydroxide compared with sulphate in contrast to the natural oxidation process. Oxidation in air also led to sulphur-rich species identified as iron-deficient regions below monolayer coverage. Similar regions were present at ground surfaces exposed to air-saturated solution of pH4 and pH5. In near-neutral to alkaline solution mainly iron hydroxy-oxide is formed the layer thickness of which was estimated in the range of 0.5 nm (pH5) to 1.7 nm (pH10).

Karthe, S.; Szargan, R.; Suoninen, E.

1993-10-01

80

New perspectives on thermal and hyperthermal oxidation of silicon surfaces  

NASA Astrophysics Data System (ADS)

The growth of (ultra)thin silica (SiO2) layers on crystalline silicon (c-Si) and controlling the thickness of SiO2 is an important issue in the fabrication of microelectronics and photovoltaic devices (e.g., MOSFETs, solar cells, optical fibers etc.). Such ultrathin oxide can be grown and tuned even at low temperature (including room temperature), by hyperthermal oxidation or when performed on non-planar Si surfaces (e.g., Si nanowires or spheres). However, hyperthermal silica growth as well as small Si-NW oxidation in general and the initial stages in particular have not yet been investigated in full detail. This work is therefore devoted to controlling ultrathin silica thickness on planar and non-planar Si surfaces, which can open new perspectives in nanodevice fabrication. The simulation of hyperthermal (1-100 eV) Si oxidation demonstrate that at low impact energy (<10 eV), oxygen does not damage the Si surface and this energy region could thus beneficially be used for Si oxidation. In contrast to thermal oxidation, 10 eV species can directly oxidize Si subsurface layers. A transition temperature of about 700 K was found: below this temperature, the oxide thickness only depends on the impact energy of the impinging species. Above this temperature, the oxide thickness depends on the impact energy, type of oxidant and the surface temperature. The results show that control over the ultrathin oxide (a-SiO2) thickness is possible by hyperthermal oxidation of silicon surfaces at temperatures below the transition temperature. In small Si-NWs, oxidation is a self-limiting process that occurs at low temperature, resulting in small Si core - SiO2 shell (semiconductor + dielectric) or c-Si|SiOx| a-SiO2 nanowire, which has also being envisaged to be used as nanowire field-effect transistors and photovoltaic devices in near-future nanotechnology. Above the transition temperature such core-shell nanowires are completely converted to a-SiO2 nanowires. It can be concluded that an accurate control over the interfacial stress by choosing a suitable oxidation temperature and Si-NW diameter can lead to precise nanoscale control over the Si-core radius. All investigations were carried out by applying molecular dynamics calculations using the ReaxFF potential, allowing a accurately study of the underpinning physical and chemical processes.

Khalilov, Umedjon

81

A molecular catalyst for water oxidation that binds to metal oxide surfaces.  

PubMed

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

Sheehan, Stafford W; Thomsen, Julianne M; Hintermair, Ulrich; Crabtree, Robert H; Brudvig, Gary W; Schmuttenmaer, Charles A

2015-01-01

82

A molecular catalyst for water oxidation that binds to metal oxide surfaces  

PubMed Central

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

2015-01-01

83

OXYANION SORPTION TO HIGH SURFACE AREA IRON AND ALUMINUM OXIDES  

Technology Transfer Automated Retrieval System (TEKTRAN)

Sorption of selected oxyanions (Mo, As, and P) to high surface area iron and aluminum oxides was investigated using in situ Raman and ATR-FTIR spectroscopy, batch sorption methods, electrophoretic mobility measurements, and surface complexation modeling. In situ ATR-FTIR and Raman spectra were coup...

84

The Protonation Behavior of Metal Oxide Surfaces to Hydrothermal Conditions  

SciTech Connect

Metal oxide surface protonation under hydrothermal conditions is summarized. Important concepts and definitions are introduced first, followed by a brief overview of experimental methods and presentation of representative results. Finally, the modeling methods that are most useful in predicting surface protonation behavior between 0 and 300oC are presented and compared.

Machesky, Michael L. [Illinois State Water Survey, Champaign, IL; Wesolowski, David J [ORNL; Ridley, Mora K. [Texas Tech University, Lubbock; Palmer, Donald [ORNL; Rosenqvist, Jorgen K [ORNL; Lvov, Serguei N. [Pennsylvania State University; Predota, M. [University of South Bohemia, Czech Republic; Vlcek, L. [Vanderbilt University

2008-01-01

85

Method of producing adherent metal oxide coatings on metallic surfaces  

DOEpatents

Provided is a process of producing an adherent synthetic corrosion product (sludge) coating on metallic surfaces. The method involves a chemical reaction between a dry solid powder mixture of at least one reactive metal oxide with orthophosphoric acid to produce a coating in which the particles are bound together and the matrix is adherent to the metallic surface.

Lane, Michael H. (Clifton Park, NY); Varrin, Jr., Robert D. (McLean, VA)

2001-01-01

86

Heterogeneous nucleation of calcium oxalate on native oxide surfaces  

SciTech Connect

The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation.

Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

1994-04-01

87

Adsorption Mechanism(s) of Poly(Ethylene Oxide) on Oxide Surfaces  

Microsoft Academic Search

Adsorption of poly(ethylene oxide) (PEO) on various oxides and the flocculation behavior of PEO-coated particles was investigated to elucidate the polymer adsorption mechanism(s). It was determined that strong Bronsted acid sites on the surface interact with the ether oxygen of PEO, a Lewis base, to induce adsorption and subsequent flocculation of the substrate particles. In general highly acidic oxides of

Sharad Mathur; Brij Mohan Moudgil

1997-01-01

88

Microbial reduction of crystalline iron(III) oxides: Influence of oxide surface area and potential for cell growth  

Microsoft Academic Search

Quantitative aspects of microbial crystalline iron(III) oxide reduction were examined using a dissimilatory iron(III) oxide-reducing bacterium (Shewanella alga strain BrY). The initial rate and long-term extent of reduction of a range of synthetic iron(III) oxides were linearly correlated with oxide surface area. Oxide reduction rates reached an asymptote at cell concentrations in excess of =1 x 10⁹\\/m² of oxide surface.

Eric E. Roden; John M. Zachara

1996-01-01

89

Oxidation of silicon surface with atomic oxygen radical anions  

NASA Astrophysics Data System (ADS)

The surface oxidation of silicon (Si) wafers by atomic oxygen radical anions (O- anions) and the preparation of metal-oxide-semiconductor (MOS) capacitors on the O- -oxidized Si substrates have been examined for the first time. The O- anions are generated from a recently developed O- storage-emission material of [Ca24Al28O64]4+.4O-(C12A7-O- for short). After it has been irradiated by an O- anion beam (0.5 ?A/cm2) at 300°C for 1-10 hours, the Si wafer achieves an oxide layer with a thickness ranging from 8 to 32 nm. X-ray photoelectron spectroscopy (XPS) results reveal that the oxide layer is of a mixture of SiO2, Si2O3, and Si2O distributed in different oxidation depths. The features of the MOS capacitor of < Al electrode/SiOx/SI > are investigated by measuring capacitance-voltage (C — V) and current-voltage (I — V) curves. The oxide charge density is about 6.0 × 1011 cm-2 derived from the C — V curves. The leakage current density is in the order of 10-6A/cm2 below 4MV/cm, obtained from the I — V curves. The O- anions formed by present method would have potential applications to the oxidation and the surface-modification of materials together with the preparation of semiconductor devices.

Wang, Lian; Song, Chong-Fu; Sun, Jian-Qiu; Hou, Ying; Li, Xiao-Guang; Li, Quan-Xin

2008-06-01

90

A characterization study of a hydroxylated polycrystalline tin oxide surface  

NASA Technical Reports Server (NTRS)

In this study Auger electron spectroscopy, electron spectroscopy for chemical analysis (ESCA) and electron-stimulated desorption (ESD) have been used to examine a polycrystalline tin oxide surface before and after annealing in vacuum at 500 C. Features due to surface hydroxyl groups are present in both the ESCA and ESD spectra, and ESD shows that several chemical states of hydrogen are present. Annealing at 500 C causes a large reduction in the surface hydrogen concentration but not complete removal.

Hoflund, Gar B.; Grogan, Austin L., Jr.; Asbury, Douglas A.; Schryer, David R.

1989-01-01

91

Evidence of nitric-oxide-induced surface band bending of indium tin oxide  

NASA Astrophysics Data System (ADS)

The interaction of indium tin oxide (ITO) film with nitric oxide (NO) has been investigated in situ by a four-point probe and x-ray photoelectron spectroscopy (XPS). The XPS N 1s peak emerged at a high binding energy of 404 eV indicating that NO was molecularly adsorbed on ITO surface. The adsorption of NO on ITO surface also induced a 0.2 eV shift in its valence band maximum to the low binding energy side leading to an upward surface band bending. We have shown that the increase in the ITO sheet resistance was attributed to its surface band bending.

Hu, Jianqiao; Pan, Jisheng; Zhu, Furong; Gong, Hao

2004-06-01

92

Oxidation-Resistant Surfaces For Solar Reflectors  

NASA Technical Reports Server (NTRS)

Thin films on silver provide highly-reflective, corrosion-resistant mirrors. Study evaluated variety of oxidation-resistant reflective materials for use in solar dynamic power system, one that generates electricity by focusing Sunlight onto reciever of heat engine. Thin films of platinum and rhodium deposited by ion-beam sputtering on various substrate materials. Solar reflectances measured as function of time of exposure to radio-frequency-generated air plasma. Several protective coating materials deposited on silver-coated substrates and exposed to plasma. Analyzed before and after exposure by electon spectroscopy for chemical analysis and by Auger spectroscopy.

Gulino, Daniel A.; Egger, Robert A.; Banholzer, William F.

1988-01-01

93

High-efficiency surface-induced dissociation on a rhenium oxide surface.  

PubMed

We report on the high-efficiency surface-induced dissociation of benzene and cyclohexane polyatomic ions after scattering from a rhenium oxide surface with a kinetic energy of 5-290 eV. Rhenium oxide was prepared by directly heating a rhenium metal foil, under 10(-5) mbar partial oxygen pressure, at about 1000 K.Rhenium oxide is characterized by a very high work function of 6.4 eV and thus minimizes ion reneutralization probabilities. The catalytic combustion of surface organic impurities with oxygen ensures good long-term stability.We found that the surface-induced dissociation ion current is 70 times larger on rhenium oxide than on bare rhenium or stainless steel. Absolute scattered ion yields of about 50% were measured. The implications of surface-induced dissociation on mass spectrometry in supersonic molecular beams are mentioned. PMID:24227530

Dagan, S; Amirav, A

1993-11-01

94

Tribological interaction between polytetrafluoroethylene and silicon oxide surfaces  

SciTech Connect

We investigated the tribological interaction between polytetrafluoroethylene (PTFE) and silicon oxide surfaces. A simple rig was designed to bring about a friction between the surfaces via sliding a piece of PTFE on a thermally oxidized silicon wafer specimen. A very mild inclination (?0.5°) along the sliding motion was also employed in order to monitor the tribological interaction in a gradual manner as a function of increasing contact force. Additionally, some patterns were sketched on the silicon oxide surface using the PTFE tip to investigate changes produced in the hydrophobicity of the surface, where the approximate water contact angle was 45° before the transfer. The nature of the transferred materials was characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS results revealed that PTFE was faithfully transferred onto the silicon oxide surface upon even at the slightest contact and SEM images demonstrated that stable morphological changes could be imparted onto the surface. The minimum apparent contact pressure to realize the PTFE transfer is estimated as 5 kPa, much lower than reported previously. Stability of the patterns imparted towards many chemical washing processes lead us to postulate that the interaction is most likely to be chemical. Contact angle measurements, which were carried out to characterize and monitor the hydrophobicity of the silicon oxide surface, showed that upon PTFE transfer the hydrophobicity of the SiO{sub 2} surface could be significantly enhanced, which might also depend upon the pattern sketched onto the surface. Contact angle values above 100° were obtained.

Uçar, A.; Çopuro?lu, M.; Suzer, S., E-mail: suzer@fen.bilkent.edu.tr [Department of Chemistry, Bilkent University, 06800 Ankara (Turkey); Baykara, M. Z. [Department of Mechanical Engineering, Bilkent University, 06800 Ankara (Turkey); Ar?kan, O. [Department of Electrical and Electronics Engineering, Bilkent University, 06800 Ankara (Turkey)

2014-10-28

95

Reporting central tendencies of chamber measured surface emission and oxidation  

SciTech Connect

Methane emissions, concentrations, and oxidation were measured on eleven MSW landfills in eleven states spanning from California to Pennsylvania during the three year study. The flux measurements were performed using a static chamber technique. Initial concentration samples were collected immediately after placement of the flux chamber. Oxidation of the emitted methane was evaluated using stable isotope techniques. When reporting overall surface emissions and percent oxidation for a landfill cover, central tendencies are typically used to report 'averages' of the collected data. The objective of this study was to determine the best way to determine and report central tendencies. Results showed that 89% of the data sets of collected surface flux have lognormal distributions, 83% of the surface concentration data sets are also lognormal. Sixty seven percent (67%) of the isotope measured percent oxidation data sets are normally distributed. The distribution of data for all eleven landfills provides insight of the central tendencies of emissions, concentrations, and percent oxidation. When reporting the 'average' measurement for both flux and concentration data collected at the surface of a landfill, statistical analyses provided insight supporting the use of the geometric mean. But the arithmetic mean can accurately represent the percent oxidation, as measured with the stable isotope technique. We examined correlations between surface CH{sub 4} emissions and surface air CH{sub 4} concentrations. Correlation of the concentration and flux values using the geometric mean proved to be a good fit (R{sup 2} = 0.86), indicating that surface scans are a good way of identifying locations of high emissions.

Abichou, Tarek, E-mail: abichou@eng.fsu.edu [Department of Civil and Environmental Engineering, FAMU-FSU College of Engineering, 2525 Pottsdamer Street, Tallahassee, FL 32310 (United States); Clark, Jeremy [Department of Civil and Environmental Engineering, FAMU-FSU College of Engineering, 2525 Pottsdamer Street, Tallahassee, FL 32310 (United States); Chanton, Jeffery, E-mail: jchanton@fsu.edu [Department of Earth, Ocean and Atmospheric Science, Florida State University, Tallahassee, FL 32306-4327 (United States)

2011-05-15

96

Nickel surface anodic oxidation and electrocatalysis of oxygen evolution  

Microsoft Academic Search

The processes of nickel surface anodic oxidation taking place within the range of potentials preceding oxygen evolution reaction\\u000a (OER) in the solutions of 1 M KOH, 0.5 M K2SO4, and 0.5 M H2SO4 have been analyzed in the present paper. Metallic nickel, thermally oxidized nickel, and black nickel coating were used as\\u000a Ni electrodes. The methods of cyclic voltammetry and X-ray photoelectron spectroscopy

K. Juodkazis; J. Juodkazyt?; R. Vilkauskait?; V. Jasulaitien?

2008-01-01

97

Surface Properties of Photo-Oxidized Bituminous Coals: Final report  

SciTech Connect

Natural weathering has a detrimental effect on the hydrophobic nature of coal, which in turn can influence clean-coal recovery during flotation. Few techniques are available that can establish the quality of coal surfaces and that have a short analysis time to provide input for process control. Luminescence emissions which can be quantified with an optical microscope and photometer system, are measurably influenced by degree of weathering as well as by mild storage deterioration. In addition, it has been shown that when vitrinite is irradiated with a relatively high intensity flux of violet- or ultraviolet- light in the presence of air, photo-oxidation of the surface occurs. The combination of measuring the change in luminescence emission intensity with degree of surface oxidation provided the impetus for the current investigation. The principal aim of this research was to determine whether clear correlations could be established among surface oxygen functionality, hydrophobicity induced by photo-oxidation, and measurements of luminescence intensity and alteration. If successful, the project would result in quantitative luminescence techniques based on optical microscopy that would provide a measure of the changes in surface properties as a function of oxidation and relate them to coal cleanability. Two analytical techniques were designed to achieve these goals. Polished surfaces of vitrain bands or a narrow size fraction of powdered vitrain concentrates were photo-oxidized using violet or ultraviolet light fluxes and then changes in surface properties and chemistry were measured using a variety of near-surface analytical techniques. Results from this investigation demonstrate that quantitative luminescence intensity measurements can be performed on fracture surfaces of bituminous rank coals (vitrains) and that the data obtained do reveal significant variations depending upon the level of surface oxidation. Photo-oxidation induced by violet or ultraviolet light fluxes does result in a progressive and significant increase in the amount of near-surface oxygen concentration at about the same level regardless of bituminous coal rank. These incremental changes in oxygen concentration appear to lower the hydrophobicity as shown by contact angle measurements on polished surfaces. Although this influence diminished as coal rank increased, the level of oxygen uptake was about the same, suggesting that the type of oxygen functionality formed during oxidation may be of great importance in modifying surface hydrophobicity. Changes in functional-group chemistry, measured by a variety of near-surface techniques, showed a general increase in the concentration of carbonyl-containing groups while those of CH{sub 2} groups decreased. All of these observations follow the trends observed in previous investigations of naturally weathered coals. The photo-oxidation technique also resulted in the development of phenolic, ester and anhydride moieties instead of the expected emplacement of carboxylic acid groups which are normally associated with naturally weathered coals. The importance of this observation is that esters and anhydrides would result in a more hydrophobic surface in comparison to the more hydrophilic surface resulting from acid functionality. This observation is consistent with the results of film flotation of UV-irradiated powdered vitrain in which floatability was generally observed to increase with increasing photo- oxidation.

NONE

1998-09-01

98

The oxidation state of the surface of Venus. [Abstract only  

NASA Technical Reports Server (NTRS)

We present experimental results showing that basalt is oxidized in CO-CO2 gas mixtures having CO number densities close to those (approximately 2 times higher) at the surface of Venus. The results suggest that the red color observed by Pieters et al at the Venera 9 and 10 landing sites is due to subaerial oxidation of Fe(2+)-bearing basalt on the surface of Venus, and that hematite, instead of magnetite, is present on the surface of Venus. Well-characterized basalt powder was iosthermally heated in 1000 ppm CO-CO2 gas mixtures at atmospheric pressure for several days. The starting material and reacted samples were analyzed by Mossbauer spectroscopy to determine the amount of Fe(2+) and Fe(3+) in the samples. X-ray diffraction and optical microscopy were also used to characterize samples. The basalt oxidation occurs because the CO and CO2 do not equilibrate in the gas mixture at the low temperatures used. Thus, the basalt reacts with the more abundant CO2 and is oxidized. We propose that the red color of the surface of Venus is due to failure of CO and CO2 to equilibrate with one another in the near-surface atmosphere of Venus, leading to subaerial oxidation of erupted Fe(2+)-bearing basalts. Our interpretation is supported by our studies of magnetite oxidation, which show that synthetic magnetite powders are oxidized to hematite in CO-CO2 gas mixtures inside the magnetite stability field, by our studies of pyrite decomposition, and by independent work on CO-CO2 equilibration in furnace gases.

Fegley, B., Jr.; Klingelhofer, G.; Brackett, R. A.; Izenberg, N.

1994-01-01

99

STRUCTURE AND SURFACE CHEMISTRY OF THORIUM OXIDE  

Microsoft Academic Search

The structure and surface properties of thorium dioxide were studied ; from the viewpoints of electron microscopy, electron diffraction, x-ray ; diffraction, and water vapor adsorption isotherms in an attempt to obtain a ; better understanding of the caking tendencies exhibited by some aqueous thoria ; slurries when circulated in loop experiments at elevated temperatures. In water ; vapor adsorption

A. L. Draper; W. O. Milligan

1959-01-01

100

Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles  

NASA Astrophysics Data System (ADS)

A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al2O3 and Fe3O4, on various substrates followed by treatment with polydimethylsiloxane (PDMS) via chemical vapor deposition (CVD) method. Using ZnO nanoparticles as a model, the changes in the surface chemical composition and crystalline structures of the metal oxide nanoparticles by PDMS treatment were investigated by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The results show that the combination of the improved surface roughness generated from of the nanoparticles aggregation with the low surface-energy of silicon-coating originated from the thermal pyrolysis of PDMS would be responsible for the surface superhydrophobicity. By a simple dip-coating method, we show that the metal oxide nanoparticles can be easily coated onto the surfaces of various textural and dimensional substrates, including glass slide, paper, fabric or sponge, for preparation of superhydrophobic surfaces for different purpose. The present strategy may provide an inexpensive and new route to surperhydrophobic surfaces, which would be of technological significance for various practical applications especially for separation of oils or organic contaminates from water.

Bao, Xue-Mei; Cui, Jin-Feng; Sun, Han-Xue; Liang, Wei-Dong; Zhu, Zhao-Qi; An, Jin; Yang, Bao-Ping; La, Pei-Qing; Li, An

2014-06-01

101

Process of forming catalytic surfaces for wet oxidation reactions  

NASA Technical Reports Server (NTRS)

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Jagow, R. B. (inventor)

1977-01-01

102

Surface activity of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers  

Microsoft Academic Search

The surface tension of aqueous solutions of seven poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) Pluronic copolymers, covering a wide range of molecular weights (3400-14600) and PPO\\/PEO ratios (0.19-1.79), was determined over the 10[sup [minus]5]-10% w\\/v concentration range, at two temperatures (25 and 35[degree]C). Two breaks (changes in slope) were observed in the surface tension vs log concentration curve for most of

Paschalis Alexandridis; Vassiliki Athanassiou; Shinya Fukuda; T. Alan Hatton

1994-01-01

103

Atomic probes of surface structure and dynamics. Technical progress report, September 15, 1991--September 14, 1992  

SciTech Connect

The following were studied: New semiclassical method for scattering calculations, He atom scattering from defective Pt surfaces, He atom scattering from Xe overlayers, thermal dissociation of H{sub 2} on Cu(110), spin flip scattering of atoms from surfaces, and Car-Parrinello simulations of surface processes.

Heller, E.J.; Jonsson, H.

1992-12-31

104

Cr(OH)3(s) Oxidation Induced by Surface Catalyzed Mn(II) Oxidation  

SciTech Connect

This study examined the feasibility of Cr(OH)3(s) oxidation mediated by surface catalyzed Mn(II) oxidation under common groundwater pH conditions as a potential pathway of natural Cr(VI) contaminations. Dissolved Mn(II) (50 ?M) was reacted with or without synthesized Cr(OH)3(s) (1.0 g/L) at pH 7 – 9 under oxic or anoxic conditions. In the absence of Cr(OH)3(s), homogeneous Mn(II) oxidation by dissolved O2 was not observed at pH ? 8.0 for 50 d. At pH 9.0, by contrast, dissolved Mn(II) was completely removed within 8 d and precipitated as hausmannite. When Cr(OH)3(s) was present, this solid was oxidized and released substantial amounts of Cr(VI) as dissolved Mn(II) was added into the suspension at pH ? 8.0 under oxic conditions. Our results suggest that Cr(OH)3(s) was readily oxidized by a newly formed Mn oxide as a result of Mn(II) oxidation catalyzed on Cr(OH)3(s) surface. XANES analysis of the residual solids after the reaction between 1.0 g/L Cr(OH)3(s) and 204 ?M Mn(II) at pH 9.0 for 22 d revealed that the product of surface catalyzed Mn(II) oxidation resembled birnessite. The rate and extent of Cr(OH)3(s) oxidation was likely controlled by those of surface catalyzed Mn(II) oxidation as the production of Cr(VI) increased with increasing pH and initial Mn(II) concentrations. This study evokes the potential environmental hazard of sparingly soluble Cr(OH)3(s) that can be a source of Cr(VI) in the presence of dissolved Mn(II).

Namgung, Seonyi; Kwon, M.; Qafoku, Nikolla; Lee, Gie Hyeon

2014-09-16

105

Tunable localized surface plasmon resonances in tungsten oxide nanocrystals.  

PubMed

Transition-metal oxide nanocrystals are interesting candidates for localized surface plasmon resonance hosts because they exhibit fascinating properties arising from the unique character of their outer-d valence electrons. WO(3-?) nanoparticles are known to have intense visible and near-IR absorption, but the origin of the optical absorption has remained unclear. Here we demonstrate that metallic phases of WO(3-?) nanoparticles exhibit a strong and tunable localized surface plasmon resonance, which opens up the possibility of rationally designing plasmonic tungsten oxide nanoparticles for light harvesting, bioimaging, and sensing. PMID:22332881

Manthiram, Karthish; Alivisatos, A Paul

2012-03-01

106

Interactions of Graphene Oxide Nanomaterials with Natural Organic Matter and Metal Oxide Surfaces  

EPA Science Inventory

Interactions of graphene oxide (GO) with silica surfaces were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Both GO deposition and release were monitored on silica- and poly-l-lysine (PLL) coated surfaces as a function of GO concentration a...

107

Surface binding vs. sequestration; the uptake of benzohydroxamic acid at iron(III) oxide surfaces   

E-print Network

Benzohydroxamic acid is shown to be an unexpectedly good ligand for iron(III) oxides, favouring surface attachment to the formation of trisbenzohydroxamato complexes, which are known to have very high thermodynamic stability ...

Tasker, Peter; Harris, S.G.; Brechin, E.K.; White, Fraser J; Rio-Echevarria I.M.

2008-01-01

108

Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid  

NASA Astrophysics Data System (ADS)

Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ? Ep ? 1.50 V), polarization time (tp, 100 ? tp ? 104 s), and temperature (T, 278 ? T ? 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt?+-O?- surface dipole (?PtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

2014-10-01

109

Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid.  

PubMed

Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (E(p), 1.10 ? E(p) ? 1.50 V), polarization time (t(p), 10(0) ? t(p) ? 10(4) s), and temperature (T, 278 ? T ? 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (d(ox)). Because X1 > d(ox) for the entire range of E(p), t(p), and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt(?+)-O(?-) surface dipole (?(PtO)), and the potential drop (V(ox)) and electric field (E(ox)) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide. PMID:25362330

Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

2014-10-28

110

Oxidative nanopatterning of titanium generates mesoporous surfaces with antimicrobial properties  

PubMed Central

Mesoporous surfaces generated by oxidative nanopatterning have the capacity to selectively regulate cell behavior, but their impact on microorganisms has not yet been explored. The main objective of this study was to test the effects of such surfaces on the adherence of two common bacteria and one yeast strain that are responsible for nosocomial infections in clinical settings and biomedical applications. In addition, because surface characteristics are known to affect bacterial adhesion, we further characterized the physicochemical properties of the mesoporous surfaces. Focused ion beam (FIB) was used to generate ultrathin sections for elemental analysis by energy-dispersive X-ray spectroscopy (EDS), nanobeam electron diffraction (NBED), and high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) imaging. The adherence of Staphylococcus aureus, Escherichia coli and Candida albicans onto titanium disks with mesoporous and polished surfaces was compared. Disks with the two surfaces side-by-side were also used for direct visual comparison. Qualitative and quantitative results from this study indicate that bacterial adhesion is significantly hindered by the mesoporous surface. In addition, we provide evidence that it alters structural parameters of C. albicans that determine its invasiveness potential, suggesting that microorganisms can sense and respond to the mesoporous surface. Our findings demonstrate the efficiency of a simple chemical oxidative treatment in generating nanotextured surfaces with antimicrobial capacity with potential applications in the implant manufacturing industry and hospital setting. PMID:24872694

Variola, Fabio; Zalzal, Sylvia Francis; Leduc, Annie; Barbeau, Jean; Nanci, Antonio

2014-01-01

111

Octadecanethiol Island Formation on Single Crystal Zinc Oxide Surfaces  

NASA Astrophysics Data System (ADS)

Organic photovoltaic devices, comprised of zinc oxide (ZnO) nanorod electron acceptor arrays intercalated with organic polymers, could lead to low-cost renewable energy generation. Surface modifications of ZnO with octadecanethiol (ODT) monolayers can help to improve charge transfer in such devices. In the present work, single crystals of ZnO provided well-defined oxygen-terminated and zinc-terminated surfaces on which to learn fundamentally about the attachment and growth of ODT. Both bare zinc oxide and ODT-functionalized surfaces were characterized with atomic force microscopy, Fourier transform infrared spectroscopy, x-ray photoemission spectroscopy, and contact angle analysis. ODT seemed to form islands of multilayers on zinc-terminated surfaces, while it formed islands of monolayers on oxygen-terminated surfaces. While ODT was expected to preferentially bond along defects and terraces on oxygen-terminated surfaces, this was not observed. ODT was also expected to more effectively bond to the zinc-terminated surface, which was observed. Finally, surface preparation treatments designed to leave atomically-flat oxygen terminated surfaces were developed. This work was made possible by the National Science Foundation Division of Materials Research and the Renewable Energy Materials Research Science and Engineering Center at the Colorado School of Mines.

Yocom, Andrea

2009-10-01

112

Superhydrophobic zinc oxide surface by differential etching and hydrophobic modification  

Microsoft Academic Search

A superhydrophobic ZnO nanorod films on zinc substrate were fabricated by natural oxidation of zinc metal and subsequent modification with a monolayer of n-octadecyl thiol (ODT). The surface morphology and composition were studied using SEM, XRD, and XPS, respectively. The surface of ZnO films directly grown on zinc substrate was hydrophilic with a water contact angle (CA) of 40±2°, whereas

Xianming Hou; Feng Zhou; Bo Yu; Weimin Liu

2007-01-01

113

Long-Term Oxidation Behaviour of Lead Sulfide Surfaces  

NASA Astrophysics Data System (ADS)

We have applied nanospectroscopy to examine the surface oxidation of the prototypic mineral lead sulfide in two states: `oxidised' (oxidised in air for one year); and `clean' (cleaved in air and inserted into the vacuum system within about 10 minutes). The elements detected on the surfaces were Pb, S, O, Cl (a natural impurity) and C (adventitious or natural, carbonate). Images showed strong topographic contrast and weak chemical contrast for the oxygen 1s maps. Near defects such as st eps, there is a higher concentration of oxygen, indicating a higher oxidation rate in this zone. From the O 1s and Pb 4f binding energies, it is concluded that the oxidation products present are Pb3O4, PbCO3 and Pb(OH)2, while PbO, PbSO4 and PbO2 were excluded. Sulfur is present on the oxidised sample in two chemical states: one with the same binding energy as for the clean sample, due to the native PbS below the oxide film; and another of hi gher binding energy. The binding energy is assigned to S present as polysulfide and/or sulfur located at the oxide/sulfide interface. Spectra taken at different points on the surface show energy shifts up to about 0.5 eV, due to band bending and pinning of the Fermi level by defects or impurities.

Prince, K. C.; Heun, S.; Gregoratti, L.; Barinov, A.; Kiskinova, M.

114

Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface  

NASA Technical Reports Server (NTRS)

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

Miyoshi, K.; Shigaki, H.; Buckley, D. H.

1982-01-01

115

Effects of ionizing radiation on oxidized silicon surfaces and planar devices  

Microsoft Academic Search

This paper examines in detail the effects of high and low energy electron, X-ray, and ultraviolet radiation on oxidized silicon surfaces and planar devices. Two permanent effects of ionizing radiation on oxidized silicon surfaces are distinguished: 1) The buildup of a positive space charge within the oxide, and 2) The creation of fast surface states at the oxide-silicon interface resulting

E. H. Snow; A. S. Grove; D. J. Fitzgerald

1967-01-01

116

Emerging applications of liquid metals featuring surface oxides.  

PubMed

Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide "skin" enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects. PMID:25283244

Dickey, Michael D

2014-11-12

117

Emerging Applications of Liquid Metals Featuring Surface Oxides  

PubMed Central

Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide “skin” enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects. PMID:25283244

2014-01-01

118

Oxidation of silicon surfaces by CO2 lasers  

NASA Astrophysics Data System (ADS)

We report for the first time, the use of a focussed CO2 laser beam and a controlled oxygen atmosphere to induce localized oxidation on the surface of a silicon wafer. These thin oxide films have been compared by infrared spectrometry with thin furnace-grown layers. We conclude that the laser-grown oxides are compositionally similar to conventional layers, and can be described by the formula SiO2. In contrast the half-width of the Si-O stretching vibration at 1070 cm-1 was found to be consistently less than for furnace-grown oxides. By fabricating simple Al-SiO2-Si-Al diodes, the dielectric properties of the films have been studied.

Boyd, I. W.; Wilson, J. I. B.

1982-07-01

119

Faraday Discussion # 114 The Surface Science of Metal Oxides  

E-print Network

-1- Faraday Discussion # 114 The Surface Science of Metal Oxides Ultrathin Alumina Film Al ____________________________________________________________________________ First principles density-functional slab calculations have produced the following results: 1) For 5 Ã? (two O-layer) alumina films on Al(111) and Ru(0001), with larger unit cells than in recent work

Jennison, Dwight R.

120

Viewpoint Paper Surface oxide effects on failure of polysilicon MEMS  

E-print Network

fatigue cycles, excluding stress corrosion of the surface oxide as a cause of fatigue failure. Possible in the fatigue cycle), but no dependence on the testing environment using either air or low vacuum (10 Pa) [3 layer leads to continued crack growth until a critical length is reached (``reaction layer fatigue" [10

Ballarini, Roberto

121

Transmission electron microscopy studies of surface phenomena in polar oxides  

NASA Astrophysics Data System (ADS)

Atomic scale processes at surfaces dictate the macroscopic properties of solid surfaces and have been the subject of numerous theoretical and experimental studies. Polar surfaces, due to their non-vanishing dipole moment along the surface normal, are unstable from classic electrostatics arguments. The ionic model often used to describe this class of materials falls short in explaining the experimental observations of stable polar surfaces. A change in the electronic structure of the surface has been proposed as a stabilization mechanism, but until this study has not been experimentally verified. The research approach described in this manuscript involves a combination of computational (Direct Methods) and experimental (TEM) methods for investigation of polar oxide surface structures. The results from the studies of the surfaces of three different polar oxides, namely MgO (111), NiO (111) and SrTiO3 (110), are presented in this dissertation. The atomic structure and charge density of the MgO (111)- 3 x 3 R30° reconstruction has been experimentally measured and verified by ab initio calculations. The structure and densities of two other reconstructions on the NiO (111) surface, namely the ( 3 x 3 R30°) and (2 x 2), are also presented. The phase transition between these two surface phases of NiO is accompanied by a novel step ordering pheneomenon and is documented using TEM and SEM. Finally, the results from the studies of the atomic structure of the SrTiO3 (110)-3 x 4 surface reveal similarities with another surface structure (SrTiO3 (100)-c(6 x 2)).

Subramanian, Arun Kumar

122

Isopropanol oxidation by pure metal oxide catalysts: number of active surface sites and turnover frequencies  

Microsoft Academic Search

The objective of the present study was to determine the number of active surface sites and their nature, redox or acidic, for bulk metal oxide catalysts using isopropanol as a chemical probe molecule. Isopropanol oxidation activity on the following metal oxides was investigated: MgO, CaO, SrO, BaO, Y2O3, La2O3, CeO2, TiO2, ZrO2, HfO2, V2O5, Nb2O5, Ta2O5, Cr2O3, MoO3, WO3, Mn2O3,

Deepak Kulkarni; Israel E. Wachs

2002-01-01

123

Modeling of surface oxidation and oxidation induced damage in metal matrix composites  

E-print Network

. LITERATURE REVIEW 2. 1. Oxidation Mechanism of Titanium Alloys 4 2. 2. Stress and Effective Properties Analysis in MMC with Surface Oxidation. . . . 9 3. MODELING OF OXIDATION BY FICKIAN DIFFUSION PROBLEM . . . . 10 3. 1. Diffusion Equations 3. 2... of the applied loading is evaluated for a SiC/Ti-15-3 four-ply laminate loaded in tension. In the temperature range considered in this study (500'C to 800'C), the titanium is susceptible to oxygen diffusion which chemically forms a brittle thermodynainically...

Ma, Xinzheng

1995-01-01

124

Giant and switchable surface activity of liquid metal via surface oxidation.  

PubMed

We present a method to control the interfacial tension of a liquid alloy of gallium via electrochemical deposition (or removal) of the oxide layer on its surface. In sharp contrast with conventional surfactants, this method provides unprecedented lowering of surface tension (? 500 mJ/m(2) to near zero) using very low voltage, and the change is completely reversible. This dramatic change in the interfacial tension enables a variety of electrohydrodynamic phenomena. The ability to manipulate the interfacial properties of the metal promises rich opportunities in shape-reconfigurable metallic components in electronic, electromagnetic, and microfluidic devices without the use of toxic mercury. This work suggests that the wetting properties of surface oxides--which are ubiquitous on most metals and semiconductors--are intrinsic "surfactants." The inherent asymmetric nature of the surface coupled with the ability to actively manipulate its energetics is expected to have important applications in electrohydrodynamics, composites, and melt processing of oxide-forming materials. PMID:25228767

Khan, Mohammad Rashed; Eaker, Collin B; Bowden, Edmond F; Dickey, Michael D

2014-09-30

125

Giant and switchable surface activity of liquid metal via surface oxidation  

PubMed Central

We present a method to control the interfacial tension of a liquid alloy of gallium via electrochemical deposition (or removal) of the oxide layer on its surface. In sharp contrast with conventional surfactants, this method provides unprecedented lowering of surface tension (?500 mJ/m2 to near zero) using very low voltage, and the change is completely reversible. This dramatic change in the interfacial tension enables a variety of electrohydrodynamic phenomena. The ability to manipulate the interfacial properties of the metal promises rich opportunities in shape-reconfigurable metallic components in electronic, electromagnetic, and microfluidic devices without the use of toxic mercury. This work suggests that the wetting properties of surface oxides—which are ubiquitous on most metals and semiconductors—are intrinsic “surfactants.” The inherent asymmetric nature of the surface coupled with the ability to actively manipulate its energetics is expected to have important applications in electrohydrodynamics, composites, and melt processing of oxide-forming materials. PMID:25228767

Khan, Mohammad Rashed; Eaker, Collin B.; Bowden, Edmond F.; Dickey, Michael D.

2014-01-01

126

Electrochemically-Controlled Compositional Oscillations of Oxide Surfaces  

SciTech Connect

Perovskite oxides can exhibit a wide range of interesting characteristics such as being catalytically active and electronically and/or ionically conducting, and thus they have been used in a number of solid-state devices such as solid oxide fuel cells and sensors. As the surface compositions of perovskites can greatly influence the catalytic properties, knowing and controlling their surface chemistries is crucial to enhance device performance. In this study, we demonstrate that the surface strontium (Sr) and cobalt (Co) concentrations of perovskite-based thin films can be controlled reversibly at elevated temperatures by applying small electrical potential biases. The surface chemistry changes of La0.8Sr0.2CoO3 (LSC113), LaSrCoO4 (LSC214), and LSC214-decorated LSC113 films (LSC113/214) were investigated in situ by utilizing synchrotron-based X-ray photoelectron spectroscopy (XPS), where the largest changes of surface Sr was found for the LSC113/214 surface. These findings offer the potential of reversibly controlling the surface functionality of perovskites.

Mutoro, Eva [Massachusetts Institute of Technology (MIT); Crumlin, Ethan [Massachusetts Institute of Technology (MIT); Pöpke, Hendrik [Institute of Physical Chemistry, Justus-Liebig-University Giessen; Luerssen, Bjoern [Institute of Physical Chemistry, Justus-Liebig-University Giessen; Amati, Matteo [Sincrotrone Trieste Elettra; Abyaneh, Majid [Sincrotrone Trieste, Basovizza, Italy; Biegalski, Michael D [ORNL; Christen, Hans M [ORNL; Gregoratti, Luca [Sincrotrone Trieste, Basovizza, Italy; Janek, Jürgen [Institute of Physical Chemistry, Justus-Liebig-University Giessen; Shao-Horn, Yang [Massachusetts Institute of Technology (MIT)

2012-01-01

127

Bacterial adhesion to glass and metal-oxide surfaces.  

PubMed

Metal oxides can increase the adhesion of negatively-charged bacteria to surfaces primarily due to their positive charge. However, the hydrophobicity of a metal-oxide surface can also increase adhesion of bacteria. In order to understand the relative contribution of charge and hydrophobicity to bacterial adhesion, we measured the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength (1 and 100 mM, respectively) to 11 different surfaces and examined adhesion as a function of charge, hydrophobicity (water contact angle) and surface energy. Inorganic surfaces included three uncoated glass surfaces and eight metal-oxide thin films prepared on the upper (non-tin-exposed) side of float glass by chemical vapor deposition. The Gram-negative bacteria differed in lengths of lipopolysaccharides on their outer surface (three Escherichia coli strains), the amounts of exopolysaccharides (two Pseudomonas aeruginosa strains), and their known relative adhesion to sand grains (two Burkholderia cepacia strains). One Gram positive bacterium was also used that had a lower adhesion to glass than these other bacteria (Bacillus subtilis). For all eight bacteria, there was a consistent increase in adhesion between with the type of inorganic surface in the order: float glass exposed to tin (coded here as Si-Sn), glass microscope slide (Si-m), uncoated air-side float glass surface (Si-a), followed by thin films of (Co(1-y-z)Fe(y)Cr(z))3O4, Ti/Fe/O, TiO2, SnO2, SnO2:F, SnO2:Sb, A1(2)O3, and Fe2O3 (the colon indicates metal doping, a slash indicates that the metal is a major component, while the dash is used to distinguish surfaces). Increasing the ionic strength from 1 to 100 mM increased adhesion by a factor of 2.0 +/- 0.6 (73% of the sample results were within the 95% CI) showing electrostatic charge was important in adhesion. However, adhesion was not significantly correlated with bacterial charge and contact angle. Adhesion (A) of the eight strains was significantly (P < 10(-25)) correlated with total adhesion free energy (U) between the bacteria and surface (A = 2162e(-1.8U)). Although the correlation was significant, agreement between the model and data was poor for the low energy surfaces (R2 = 0.68), indicating that better models or additional methods to characterize bacteria and surfaces are still needed to more accurately describe initial bacterial adhesion to inorganic surfaces. PMID:15261011

Li, Baikun; Logan, Bruce E

2004-07-15

128

Effects of dielectric barrier discharges on silicon surfaces: Surface roughness, cleaning, and oxidation  

NASA Astrophysics Data System (ADS)

Silicon wafers were exposed to a dielectric barrier discharge (DBD) at atmospheric pressure, which was ignited by applying a high voltage (>12 kV peak voltage) to a small gap (dg=300 ?m) above the wafer surface in an oxygen process gas atmosphere. The effect of the DBD on H-terminated silicon and native silicon oxide surfaces was investigated in situ and ex situ by means of Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy (XPS). The influence of the treatment on surface roughness was studied by atomic force microscopy. In order to determine the thickness of the newly formed oxide under DBD influence, the method of calculating the oxide thickness from the Si 2p peak ratio in the XPS spectrum, which has so far been described for thermal oxides only, was adopted with x-ray reflectometry calibration samples. Additionally, infrared spectroscopy and spectroscopic ellipsometry were used to verify the XPS measurements. The calculated thickness values can be fitted with the growth law d =d0 ln[(t /?)+k], with d being the oxide thickness, grown during DBD exposure time t. Oxide thicknesses of more than 3 nm could be achieved within 350 s DBD exposure time. Our analysis of infrared spectra, XPS, and ellipsometry leads us to conclude that the newly formed oxide is porous with a pore fraction of roughly 10%.

Michel, B.; Giza, M.; Krumrey, M.; Eichler, M.; Grundmeier, G.; Klages, C.-P.

2009-04-01

129

Radiation Induced Surface Activity Phenomenon: 1. Report - Surface Wettability on Metal Oxides  

SciTech Connect

Improving the limit of boiling heat transfer or critical heat flux requires that the cooling liquid can contact the heating surface, or a high-wettability, highly hydrophilic heating surface, even if a vapor bubble layer is generated on the surface. We investigated surface wettability using metal oxides irradiated by gamma rays in room condition. Contact angle, an indicator of macroscopic wettability, was measured by image processing of the images obtained by a CCD video camera. The results showed that the surface wettability on oxide metal pieces of titanium, zircaloy No. 4, SUS-304 and copper improved significantly by Radiation Induced Surface Activity (RISA) phenomenon. Highly hydrophilic conditions on the test pieces were achieved after 500 kGy irradiation of {sup 60}Co gamma ray. (authors)

Yasuyuki Imai; Tatsuya Koga; Tomoji Takamasa [Tokyo University of Mercantile Marine, 2-1-6 Etchu-jima, Koto-Ku, Tokyo 135-8533 (Japan); Koji Okamoto [University of Tokyo (Japan); Susumu Uematsu [Advanced Maritime Transport Technology Department, National Maritime Research Institute, Mitaka, Tokyo 181-0004 (Japan)

2002-07-01

130

Adsorption of phosphonic and ethylphosphonic acid on aluminum oxide surfaces  

NASA Astrophysics Data System (ADS)

Phosphonic acid and ethylphosphonic acid chemisorbed on aluminum oxide surfaces have been investigated using a density-functional based tight-binding method. We have in particular focused on hydroxylated surface models based on corundum ?-AlO (0 0 0 1), bayerite ?-Al(OH) (0 0 1) and boehmite ?-AlOOH (0 1 0). On these we have studied monodentate, bidentate and tridentate adsorption of the acids on all possible adsorption sites on the surfaces considering different surface coverages. By comparing the energies of the adsorption complexes we determined the favored adsorption sites for each coordination mode and surface structure. We found that the preference of an adsorption site is strongly influenced by its geometry and the regioselectivity increases when going from mono- to tridentate adsorption complexes. Moreover, the ethyl chain has no influence on the selection of the preferred adsorption sites.

Luschtinetz, Regina; Oliveira, Augusto F.; Frenzel, Johannes; Joswig, Jan-Ole; Seifert, Gotthard; Duarte, Helio A.

2008-04-01

131

Optimum conditions for fabricating superhydrophobic surface on copper plates via controlled surface oxidation and dehydration processes  

NASA Astrophysics Data System (ADS)

The superhydrophobic surfaces on copper substrate were fabricated by direct oxidation and dehydration processes, and the reaction and modification conditions were optimized. Firstly, the oxidation conditions including the concentrations of K2S2O8 and NaOH, the oxidation time were studied. It is found that the superhydrophobicity would be better if the copper plates were oxidized in 0.06 M K2S2O8 and 3.0 M NaOH solution at 65 °C for 35 min. Then, the modification conditions including modifier concentration and modification time were investigated. The results showed that 5 wt% lauric acid and 1 h modification time were suitable modification conditions for preparing copper-based superhydrophobic surfaces. The surface fabricated under optimized conditions displayed excellent superhydrophobicity of high water contact angle of 161.1° and a low contact angle hysteresis of 2.5°. The surface microstructure and composition of the superhydrophobic surfaces were also characterized by SEM and FT-IR. It is found that the highly concentrated micro/nanostructured sheets and the low surface energy materials on the surface should be responsible for the high superhydrophobicity.

Zhang, Yan; Li, Wen; Ma, Fumin; Yu, Zhanlong; Ruan, Min; Ding, Yigang; Deng, Xiangyi

2013-09-01

132

Molecularly imprinted Ru complex catalysts integrated on oxide surfaces.  

PubMed

Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such as the imprinting of a transition state structure or the addition of multiple binding sites could lead to systems that can achieve 100% selective catalysis. PMID:23030829

Muratsugu, Satoshi; Tada, Mizuki

2013-02-19

133

Comparison Between Crystalline and Amorphous Surfaces of Transition Metal Oxide Water Oxidation Catalysts: a Theoretical Perspective  

NASA Astrophysics Data System (ADS)

Amorphous films of transition-metal oxide water oxidation catalysts (WOCs) often show an enhanced catalytic activity compared to their crystalline counterparts [1-4]. In particular, in the case of cobalt-oxide based WOCs the observed similarity in their electrochemical properties and catalytic activity, under oxidative conditions, has been correlated with the formation of similar amorphous surface morphologies, suggesting the presence of a common, catalytically active amorphous structural motif [3,4]. We present ab initio calculations of cobalt oxide based material surfaces and we compare the electronic properties of crystalline and amorphous surfaces, with the aim of identifying differences related to their different catalytic activity.[4pt] [1] Blakemore, J. D., Schley, N. D., Kushner-Lenhoff, M. N., Winter, A. M., D'Souza, F., Crabtree, R. H., and Brudvig, G. W. Inorg. Chem. 51, 7749 (2012); [2] Tsuji, E., Imanishi, A., Fukui, K.-I. and Nakato, Y. Electrochimica Acta 56, 2009 (2011); [3] Jia, H., Stark, J., Zhou, L. Q., Ling, C., Takeshi, S., and Markin, Z. RSC Advances 2, 10874 (2012); [4] Lee, S. W., Carlton, C., Risch, M., Surendranath, Y., Chen, S., Furutsuki, S., Yamada, A., Nocera, D. G., and Shao-Horn, Y. J. Am. Chem. Soc. 134, 16959 (2012).

Skone, Jonathan H.; Galli, Giulia

2013-03-01

134

Electrocatalytic oxygen evolution at surface-oxidized multiwall carbon nanotubes.  

PubMed

Large-scale storage of renewable energy in the form of hydrogen (H2) fuel via electrolytic water splitting requires the development of water oxidation catalysts that are efficient and abundant. Carbon-based nanomaterials such as carbon nanotubes have attracted significant applications for use as substrates for anchoring metal-based nanoparticles. We show that, upon mild surface oxidation, hydrothermal annealing and electrochemical activation, multiwall carbon nanotubes (MWCNTs) themselves are effective water oxidation catalysts, which can initiate the oxygen evolution reaction (OER) at overpotentials of 0.3 V in alkaline media. Oxygen-containing functional groups such as ketonic C?O generated on the outer wall of MWCNTs are found to play crucial roles in catalyzing OER by altering the electronic structures of the adjacent carbon atoms and facilitates the adsorption of OER intermediates. The well-preserved microscopic structures and highly conductive inner walls of MWCNTs enable efficient transport of the electrons generated during OER. PMID:25658670

Lu, Xunyu; Yim, Wai-Leung; Suryanto, Bryan H R; Zhao, Chuan

2015-03-01

135

Study of tin oxide: Surface properties and palladium adsorption  

NASA Astrophysics Data System (ADS)

Surface properties of various single-crystalline SnO2 surfaces were studied and the growth of palladium was investigated in the low-coverage regime. Metal - oxide structures play an important role in microelectronics and nanotechnology. They are also widely used in catalysis. Small catalytically-active metal particles on metal oxide substrates are key features in the gas sensing mechanism: they dramatically increase the sensitivity and selectivity of solid-state gas sensors towards target gases. Tin Oxide is widely used in solid-state gas sensors for detection of combustible and toxic gases. Its sensitivity and selectivity strongly depends on catalytic dopants, such as Pd or Pt, on the surface of the material. Thus, the characterization of Pd growth on tin oxide may give new insights into the catalytic and gas sensing mechanisms, and also help to understand fundamental steps that lead to various metal-on-oxide growth modes. Upon deposition of Pd onto the reduced (101) surface of a SnO2 single crystal, 1D cluster growth was observed. Starting from very low coverages, one-dimensional Pd clusters grow on the terraces, which indicates that the Pd wets the reduced tin oxide surface. Pd deposition on the oxidized surface results in randomly distributed three-dimensional Pd clusters. The clusters are distributed at step edges and on terraces without any apparent preferential adsorption sites. The one-dimensional clusters are imaged in scanning tunneling microscopy (STM) as straight, parallel nanostructures oriented along the [-101] direction, all with the same characteristic width of 0.5 nm and a height of 1 monolayer (ML). X-ray photoelectron spectroscopy (XPS) experiments show no sign of Pd oxidation; i.e. Pd grows as a metal. There is a 0.5 eV shift in the Pd 3d 5/2 core level peak position to lower binding energy that occurs during the initial stages of the growth on the reduced surface. This is an indication of charge transfer from the Pd clusters to the substrate. Coverage-dependent Ultraviolet Photoelectron Spectroscopy (UPS) spectra show that, at submonolayer Pd coverages, a Pd 4d-derived peak appears at the same position (3eV from Fermi edge) in the band gap as the Sn surface state and shifts towards the Fermi edge as coverage increases. Angular resolved photoemission data of the valence band of the clean reduced SnO2 surface and the Pd dosed reduced surface shows a strong correlation between the Sn 5s derived surface state and the Pd 4d state. The position, as well as the shape of Pd 4d peak closely follows the position and the shape of the 5s derived Sn peak in both low-index directions. This is a sign of a strong electronic interaction, hybridization between Pd 4d and Sn 5s derived states. Scanning tunneling microscopy experiments on a clean, reduced SnO 2 (100)-(1x1) surface reveal surface defects with zero, one, and two dimensions. Point defects consist of missing SnO/SnO2 units. Line defects are probably crystallographic shear planes that extend to the surface and manifest themselves as rows of atoms, shifted half a unit cell along the [010] direction. Their ends act as preferential nucleation sites for the formation of Pd clusters upon vapor-deposition. Submonolayer coverages of Pd deposited on the reduced surface at room temperature by vapour deposition result in the formation of three-dimensional clusters nucleating on the terraces. Areas of a more reduced surface phase, i.e. elongated "holes", observed at the surface after annealing to higher temperatures, still with a (1x1) structure and a half-unit-cell deep, form at [001]-oriented step edges. Recently, the use of nanobelts and nanoribbons has been suggested as novel materials for gas sensing applications. The large surface-to-volume ratio of the semiconducting metal oxide nanobelts and the congruence of the carrier screening length with their lateral dimensions make them highly sensitive and efficient transducers of surface chemical processes into electrical signal. The surface morphology of an individual nanobelts (NB) was studied with STM. Atom

Katsiev, Khabiboulakh

136

Effects of surface oxide formation on germanium nanowire band-edge photoluminescence  

SciTech Connect

The effect of intentional surface oxide formation on band-edge photoluminescence (PL) of Ge nanowires was investigated. Thermal oxidation in molecular O{sub 2} was used to produce a surface oxide layer on assemblies of single crystal nanowires grown by the vapor-liquid-solid method. With increasing oxidation of the wires, the band-edge PL associated with the indirect gap transition becomes more intense. X-ray photoelectron spectroscopy confirms the formation of an increasingly GeO{sub 2}-like surface oxide under annealing conditions that enhance the indirect-gap PL, consistent with surface oxide passivation of nonradiative recombination centers initially present on the nanowire surface.

Minaye Hashemi, Fatemeh Sadat [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States) [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Laboratoire des Materiaux Semiconducteurs, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland); Thombare, Shruti; Brongersma, Mark L. [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States)] [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Morral, Anna Fontcuberta i [Laboratoire des Materiaux Semiconducteurs, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland)] [Laboratoire des Materiaux Semiconducteurs, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland); McIntyre, Paul C. [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States) [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Geballe Laboratory for Advanced Materials, Stanford University, Stanford, California 94305 (United States)

2013-06-24

137

Water-Mediated Proton Hopping on an Iron Oxide Surface  

SciTech Connect

The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H3O+-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO2(110), where water dissociation is a key step in proton diffusion.

Merte, L. R.; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A.; Grabow, Lars C.; Kudernatsch, Wilhelmine; Wendt, Stefen; Laegsgaard, E.; Mavrikakis, Manos; Besenbacher, Fleming

2012-05-18

138

Huge steric effects in surface oxidation of Si(100)  

NASA Astrophysics Data System (ADS)

We report an experimental evidence that the initial sticking probability (S0) of O2 on a clean Si(100) surface depends strongly on the alignment of O2 molecules. S0 was measured with a single spin-rotational state [(J,M)=(2,2)] selected O2 (3?g-) beam. The temperature and translational energy dependence of S0 indicate that oxidation via the direct process gives a sticking probability ratio of 1.7 between “helicopter” and “cartwheel” geometries, while the indirect process dominant at low temperatures and translational energies exhibits no appreciable steric effects. The present experiment reveals that oxidation via the direct process occurs only when the molecular axis is nearly parallel to the surface.

Kurahashi, Mitsunori; Yamauchi, Yasushi

2012-04-01

139

Optical measurements of surface oxide layer formation on metal films  

SciTech Connect

We have employed two optical techniques which give complementary indications of the formation of monolayers of oxide on freshly evaporated aluminum and silicon thin films. Visible ellipsometry is utilized to observe the growth of the initial monolayer of oxide on these films. From these data, we deduce the pressure and coverage dependence as well as the growth rate for the initial monolayer arising from these surface reactions. In addition, extreme ultraviolet (xuv) reflectance vs angle of incidence measurements at 58.4 nm wavelength clearly indicate the growth of oxide on the surface of our freshly deposited aluminum and silicon films as well. We have utilized this reflectance data to deduce the optical constants of aluminum and silicon at 58.4 nm. We find that previous xuv measurements of these optical constants were hampered by the presence of oxides. We also determined that the xuv reflectivity performance of aluminum films freshly deposited in our uhv system does not degrade appreciably when stored for four weeks in a helium atmosphere of 2 x 10/sup -9/ Torr. 11 refs., 7 figs., 1 tab.

Scott, M.L.

1987-01-01

140

Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides  

NASA Astrophysics Data System (ADS)

The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is discussed for TiO 2, ?-AlOOH (boehmite), ?-FeOOH (lepidocrocite), ?-FeOOH (goethite) and HFO (ferrihydrite) in relation to the surface structure and surface sites. One type of surface complex is formed at TiO 2 and ?-AlOOH, i.e. a surface-coordinated Fe 2+ ion. At the TiO 2 (Degussa) surface, the Fe 2+ ion is probably bound as a quattro-dentate surface complex. The CD value of Fe 2+ adsorbed to ?-AlOOH points to the formation of a tridentate complex, which might be a double edge surface complex. The adsorption of Fe(II) to ferric (hydr)oxides differs. The charge distribution points to the transfer of electron charge from the adsorbed Fe(II) to the solid and the subsequent hydrolysis of the ligands that coordinate to the adsorbed ion, formerly present as Fe(II). Analysis shows that the hydrolysis corresponds to the hydrolysis of adsorbed Al(III) for ?-FeOOH and ?-FeOOH. In both cases, an adsorbed M(III)(OH)2+ is found in agreement with structural considerations. For lepidocrocite, the experimental data point to a process with a complete surface oxidation while for goethite and also HFO, data can be explained assuming a combination of Fe(II) adsorption with and without electron transfer. Surface oxidation (electron transfer), leading to adsorbed tbnd Fe(III)(OH) 2, is favored at high pH (pH > ˜7.5) promoting the deprotonation of two Fe III-OH 2 ligands. For goethite, the interaction of Fe(II) with As(III) and vice versa has been modeled too. To explain Fe(II)-As(III) dual-sorbate systems, formation of a ternary type of surface complex is included, which is supposed to be a monodentate As(III) surface complex that interacts with an Fe(II) ion, resulting in a binuclear bidentate As(III) surface complex.

Hiemstra, Tjisse; van Riemsdijk, Willem H.

2007-12-01

141

Optical Anisotropy of Oxidized Si(001) Surfaces and Its Oscillation in the Layer-By-Layer Oxidation Process  

SciTech Connect

Reflectance-difference (RD) measurements for the oxidation of single-domain (2 x 1) -reconstructed Si(001) surfaces show that the polarity of the interface-induced optical anisotropy is reversed repeatedly with increasing oxide thickness. The oscillation of the RD amplitude, which we show is due to layer-by-layer progression of the oxidation, has allowed us to count the number of oxidized Si layers in situ during oxidation. The origins of the observed spectral line shape are discussed.

Yasuda, T.; Yamasaki, S.; Nishizawa, M.; Miyata, N.; Shklyaev, A.; Ichikawa, M.; Matsudo, T.; Ohta, T.

2001-07-16

142

SURFACE COMPLEXATION OF ACTINIDES WITH IRON OXIDES: IMPLICATIONS FOR RADIONUCLIDE TRANSPORT IN NEAR-SURFACE AQUIFERS  

SciTech Connect

The surface complexation of actinides with iron oxides plays a key role in actinide transport and retardation in geosphere-biosphere systems. The development of accurate actinide transport models therefore requires a mechanistic understanding of surface complexation reactions (i.e. knowledge of chemical speciation at mineral/fluid interfaces). Iron oxides are particularly important actinide sorbents due to their pH dependent surface charges, relatively high surface areas and ubiquity in oxic and suboxic near-surface systems. In this paper we present results from field and laboratory investigations that elucidate the mechanisms involved in binding uranium and neptunium to iron oxide mineral substrates in near neutral groundwaters. The field study involved sampling and characterizing uranium-bearing groundwaters and solids from a saprolite aquifer overlying an unmined uranium deposit in the Virginia Piedmont. The groundwaters were analyzed by inductively coupled mass spectrometry and ion chromatography and the aquifer solids were analyzed by electron microprobe. The laboratory study involved a series of batch sorption tests in which U(VI) and Np(V) were reacted with goethite, hematite and magnetite in simulated groundwaters. The pH, ionic strength, aging time, and sorbent/sorbate ratios were varied in these experiments. The oxidation state and coordination environment of neptunium in solutions and sorbents from the batch tests were characterized by X-ray absorption spectroscopy (XAS) at the Advanced Photon Source, Argonne National Laboratory. Results from this work indicate that, in oxidizing near-surface aquifers, the dissolved concentration of uranium may be limited to less than 30 parts per billion due to uptake by iron oxide mineral coatings and the precipitation of sparingly soluble U(VI) phosphate minerals. Results from the batch adsorption tests showed that, in near neutral groundwaters, a significant fraction of the uranium and neptunium adsorbed as strongly bound surface complexes that were not removed (desorbed) when the sorbents were resuspended in dilute groundwater. The XAS results indicate that at pH 7.0-8.0 neptunium adsorbs to goethite as a neptunyl(V) complex and to magnetite as an inner-sphere Np(lV) complex with a Np-Fe distance of approximately 3.5 angstroms. These findings demonstrate that the presence of iron oxides in oxidizing near-surface aquifers may significantly retard actinide transport and that future reactive-transport models for actinides should therefore account for irreversible sorption processes.

J.L. Jerden Jr.; A.J. Kropf; Y. Tsai

2005-08-25

143

Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch  

NASA Astrophysics Data System (ADS)

Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to 13 mg L-1 and reduced Cu and Mn from 8 and 3 mg L-1 to below the detection limits, respectively. The experimental results suggested that the amendment of surface coating agents can be a promising alternative for inhibition of sulfide oxidation at AMD sites.

Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

2012-04-01

144

Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces  

Microsoft Academic Search

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon

Jagdeep Singh

2010-01-01

145

Surface activity of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers  

SciTech Connect

The surface tension of aqueous solutions of seven poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) Pluronic copolymers, covering a wide range of molecular weights (3400-14600) and PPO/PEO ratios (0.19-1.79), was determined over the 10[sup [minus]5]-10% w/v concentration range, at two temperatures (25 and 35[degree]C). Two breaks (changes in slope) were observed in the surface tension vs log concentration curve for most of the copolymers. The low-concentration break, occurring at bulk copolymer concentrations of approximately 10[sup [minus]3]%, is believed to originate from rearrangement of the copolymer molecules on the surface at complete coverage of the air/water interface. The breaks at the high-concentration part of the surface tension curve occurred at concentrations that correspond to the critical micellization concentration values as determined by a dye solubilization technique. The surface area per copolymer molecule, A, increased as a function of the number of EO segments, N[sub EO], obeying a scaling law (A [approx] N[sub EO][sup 1/2]) similar to that of lower molecular weight C[sub i]E[sub j] nonionic surfactants. 56 refs., 6 figs., 2 tabs.

Alexandridis, P.; Athanassiou, V.; Fukuda, Shinya; Hatton, T.A. (Massachusetts Inst. of Technology, Cambridge, MA (United States))

1994-08-01

146

Physical properties of spin-valve films grown on naturally oxidized metal nano-oxide surfaces  

NASA Astrophysics Data System (ADS)

The physical properties of spin-valve films NiFe 25 Å/CoFe 10 Å/Cu(tCu)/CoFe 30 Å/IrMn 70 Å/Ta 20 Å with graded Cu layer thickness (tCu=18-45 Å) grown on the surface of metal nano-oxide layers (NOLs) were studied. The NOLs were formed from ultrathin Al, Cr, Cu, Nb, Ta, CoFe, NiFe, and NiFeCr layers by natural oxidation. The growth of the spin-valve films on NOLs has led to an enhancement in giant magnetoresistance value by up to 48%. A corresponding reduction in minimum film resistance by over 10% confirms that this enhancement originates from an increase in the mean free path of spin-polarized electrons due to the resultant specular reflection at the nano-oxide surfaces. A wide spectrum of oscillatory interlayer exchange coupling dependence on tCu for these NOL-bearing films suggests that a specular nano-oxide surface does not necessarily result in a smoother multilayer structure. The observation of an enhanced exchange biasing among these spin-valve films appears in contradiction to the observed deterioration of their crystallographic quality. As an important application, TaOx, CrOx, and NbOx could be employed as an alternative to AlOx as the barrier layer for magnetic tunnel junctions.

Mao, Ming; Cerjan, Charlie; Kools, Jacques

2002-05-01

147

Enhanced biogenic emissions of nitric oxide and nitrous oxide following surface biomass burning  

NASA Technical Reports Server (NTRS)

Recent measurements indicate significantly enhanced biogenic soil emissions of both nitric oxide (NO) and nitrous oxide (N2O) following surface burning. These enhanced fluxes persisted for at least six months following the burn. Simultaneous measurements indicate enhanced levels of exchangeable ammonium in the soil following the burn. Biomass burning is known to be an instantaneous source of NO and N2O resulting from high-temperature combustion. Now it is found that biomass burning also results in significantly enhanced biogenic emissions of these gases, which persist for months following the burn.

Anderson, Iris C.; Levine, Joel S.; Poth, Mark A.; Riggan, Philip J.

1988-01-01

148

Structure and thermodynamics of model catalytic oxide surfaces  

NASA Astrophysics Data System (ADS)

The atomic scale structure of crystalline surfaces plays an important role in the overall properties of materials systems, especially those relating to heterogeneous catalysis, thin film growth, and the increasingly miniaturized world of micro electrical mechanical systems (MEMS). Nanoscale engineering of materials has become commonplace and as technologies begin to emerge on smaller and smaller length scales, surface properties become increasingly more important relative to those of the bulk. Only through knowledge of the surface structure of materials can one truly understand the nature of the processes that play out on them. The research described in this manuscript involves a combination of computational (Direct Methods) and experimental (TEM) methods for the investigation of the surface structure and thermodynamics of two model heterogeneous catalytic oxides, alpha-Fe2O 3 (the mineral hematite) and SrTiO3. A new flux system has been developed for the growth of single crystal alpha-Fe 2O3. The effect of ion bombardment and annealing on the (0001) surface of hematite was investigated, and the differences between pure and impure samples are presented. Finally, methodologies are discussed for obtaining the "biphase" surface structure on a TEM-ready sample. Several new reconstructions were observed on the (111) surface of SrTiO 3, including (3x3), (9/5x9/5), (6x6), and (4x4) unit cells. The structure of the (3x3) surface has been solved and it is proposed that all of the herein observed reconstruct ions will be scalable structures from a general motif, with the different unit cell sizes being accommodated by differences in the occupancy of surface sites. The regions of phase stability have been accurately determined for the reconstructions in time, temperature and oxygen partial pressure, and a metastable surface phase diagram has been constructed. A region of metastable three-phase coexistence has been observed over a wide range of temperatures and oxygen partial pressures.

Chiaramonti, Ann Norina

149

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces  

NASA Technical Reports Server (NTRS)

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

150

Attachment of Pathogenic Prion Protein to Model Oxide Surfaces  

PubMed Central

Prions are the infectious agents in the class of fatal neurodegenerative diseases known as transmissible spongiform encephalopathies, which affect humans, deer, sheep, and cattle. Prion diseases of deer and sheep can be transmitted via environmental routes, and soil is has been implicated in the transmission of these diseases. Interaction with soil particles is expected to govern the transport, bioavailability and persistence of prions in soil environments. A mechanistic understanding of prion interaction with soil components is critical for understanding the behavior of these proteins in the environment. Here, we report results of a study to investigate the interactions of prions with model oxide surfaces (Al2O3, SiO2) using quartz crystal microbalance with dissipation monitoring and optical waveguide light mode spectroscopy. The efficiency of prion attachment to Al2O3 and SiO2 depended strongly on pH and ionic strength in a manner consistent with electrostatic forces dominating interaction with these oxides. The N-terminal portion of the protein appeared to facilitate attachment to Al2O3 under globally electrostatically repulsive conditions. We evaluated the utility of recombinant prion protein as a surrogate for prions in attachment experiments and found that its behavior differed markedly from that of the infectious agent. Our findings suggest that prions preferentially associate with positively charged mineral surfaces in soils (e.g., iron and aluminum oxides). PMID:23611152

Jacobson, Kurt H.; Kuech, Thomas R.; Pedersen, Joel A.

2014-01-01

151

How strain affects the reactivity of surface metal oxide catalysts.  

PubMed

Highly dispersed molybdenum oxide supported on mesoporous silica SBA-15 has been prepared by anion exchange resulting in a series of catalysts with changing Mo densities (0.2-2.5?Mo atoms?nm(-2) ). X-ray absorption, UV/Vis, Raman, and IR spectroscopy indicate that doubly anchored tetrahedral dioxo MoO4 units are the major surface species at all loadings. Higher reducibility at loadings close to the monolayer measured by temperature-programmed reduction and a steep increase in the catalytic activity observed in metathesis of propene and oxidative dehydrogenation of propane at 8?% of Mo loading are attributed to frustration of Mo oxide surface species and lateral interactions. Based on DFT calculations, NEXAFS spectra at the O-K-edge at high Mo loadings are explained by distorted MoO4 complexes. Limited availability of anchor silanol groups at high loadings forces the MoO4 groups to form more strained configurations. The occurrence of strain is linked to the increase in reactivity. PMID:24259425

Amakawa, Kazuhiko; Sun, Lili; Guo, Chunsheng; Hävecker, Michael; Kube, Pierre; Wachs, Israel E; Lwin, Soe; Frenkel, Anatoly I; Patlolla, Anitha; Hermann, Klaus; Schlögl, Robert; Trunschke, Annette

2013-12-16

152

Depth profile analysis of native oxide layer on GaAs (100) surface  

NASA Astrophysics Data System (ADS)

Ar+ ion etching and X-ray photoelectron spectroscopy (XPS)depth profile analysis have been performed on the native oxide layerof GaAs(100) surface. The composition of the native oxide layer,that isthe oxide phases of gallium and arsenic, was characterized precisely. It is indicated that native oxide phases on extreme surface of GaAs(100) consist of a mixture of Ga2O3, As2O3 and As2O5. Furthermore, the respective distribution of oxide phases of gallium and arsenic along the depthwere compared and analyzed.A seemingly contradictory phenomenon was found, that is As enrichment exist in total oxide layer, but the content of Ga oxide was greater than that of As oxide in the oxide layer except for the outmost surface layer.Based on the comprehensive influence of oxidation process, etching, segregation and growth process, the intrinsic mechanism of the change of oxides along etching depth was discussed. According to the analyzed results, the oxide layer of GaAs (100) surface should be divided to two layers,that is the outmost layer containing oxides of Ga and As and the intermediate layer including only oxide of Ga.The concentration of As oxides in the outmost layer and the enrichment of As in total oxide layer are derived from surface structure inhomogeneity. The throughout total oxide layer of Ga oxide is attributed to its stronger oxidability.In the present work, the system study for native oxide layer of GaAs surface provides the powerful foundation for understanding surface state of GaAs and surface treatment.

Cheng, Xing; Shi, Feng; Cheng, Hongchang; Niu, Sen; Wang, Long; Miao, Zhuang; Chen, Chang

2014-12-01

153

Reflection spectra and magnetochemistry of iron oxides and natural surfaces  

NASA Technical Reports Server (NTRS)

The magnetic properties and spectral characteristics of iron oxides are distinctive. Diagnostic features in reflectance spectra (0.5 to 2.4 micron) for alpha Fe2O3, gamma Fe2O3, and FeOOH include location of Fe3(+) absorption features, intensity ratios at various wavelengths, and the curve shape between 1.2 micron and 2.4 micron. The reflection spectrum of natural rock surfaces are seldom those of the bulk rock because of weathering effects. Coatings are found to be dominated by iron oxides and clay. A simple macroscopic model of rock spectra (based on concepts of stains and coatings) is considered adequate for interpretation of LANDSAT data. The magnetic properties of materials associated with specific spectral types and systematic changes in both spectra and magnetic properties are considered.

Wasilewski, P.

1978-01-01

154

Oxide surfaces in practical and model catalytic systems  

NASA Astrophysics Data System (ADS)

Oxide surface structures play a key role in many technological processes, including catalysis, thin film growth, and layered structures, and a thorough understanding of surface structures and surface structure dynamics is required in order to better engineer materials systems for these processes. This research works towards understanding these fundamental principles through an investigation of practical and model catalytic systems. In this work, the surface structures and dynamics of Mg3(VO4)2, LaAlO3, SrTiO3, and alpha-Fe2O3/Fe3O 4 are investigated under a variety of conditions and by a range of experimental and computational techniques. The structure and morphology of LaAlO3 has been investigated over a range of annealing temperatures, and the ( 5x5 )R26.6° reconstruction of LaAlO3 (001) has been determined using transmission electron diffraction combined with direct methods. The structure is relatively simple, consisting of a lanthanum oxide termination with one lanthanum cation vacancy per surface unit cell. The electronic structure is unusual since a fractional number of holes or atomic occupancies per surface unit cell are required to achieve charge neutrality. The reconstruction can be understood in terms of expulsion of the more electropositive cation from the surface followed by an increased covalency between the remaining surface lanthanum atoms and adjacent oxygen atoms. The c(6x2) is a reconstruction of the SrTiO3 (001) surface that is formed between 1050-1100°C in oxidizing annealing conditions. This work proposes a model for the atomic structure for the c(6x2) obtained through a combination of results from transmission electron diffraction, surface x-ray diffraction, direct methods analysis, computational combinational screening, and density functional theory. As it is formed at high temperatures, the surface is complex and can be described as a short-range ordered phase featuring microscopic domains composed of four main structural motifs. Additionally, non-periodic TiO2 units are present on the surface. The surface and bulk of oriented single crystal Mg3(VO 4)2 have been characterized after treatment in a reducing environment. Annealing in a flow of 7% H2 in N2 causes the reduction of Mg3(VO4)2 to Mg3V 2O6, which is shown to be single-crystal to single-crystal and occurs in such a way that the oxygen framework of the crystal is preserved. Transmission electron microscopy images of crystals at the early stages of reduction show low angle grain boundaries and the formation of channels approximately 50nm in diameter. A model for reduction of Mg3(VO4) 2 to Mg3V2O6 based on the experimental observations and derived from classic nucleation theory is proposed. The so-called Biphase structure on alpha-Fe2O3 has been previously reported and described as islands of Fe1-xO and alpha-Fe2O3 arranged in a 40A periodic unit cell. Based on thermodynamic arguments and experimental evidence, including transmission electron diffraction, we find that the previous structure model was incorrect. Rather, it is found that the Biphase structure is, in fact, related to the reduction of alpha-Fe2O3 to Fe 3O4, is a layered structure, and does not contain islands of Fe1-xO. A model for the Biphase termination consisting of bulk alpha-Fe 2O3 with an Fe3O4 -derived overlayer is developed and is consistent with all current and previously reported experimental findings.

Lanier, Courtney H.

155

Work function measurements on nano-crystalline zinc oxide surfaces  

NASA Astrophysics Data System (ADS)

The work function of nano-crystalline zinc oxide (ZnO) thin films was examined using photoemission spectroscopy (PES). Colloidally dispersed ZnO nano-particles were electrospray-deposited in vacuum to form nano-crystalline thin films. The samples showed an immediate work function reduction by 0.35 eV during ultraviolet photoemission spectroscopy (UPS) measurements. This artifact was detected and quantified through low intensity x-ray photoemission spectroscopy (LIXPS) measurements, which use a very low photon flux. This prevented significant photochemical changes on the measured surface, i.e. the true work function unaffected by the UPS artifact can be measured. Annealing of an identical sample removed all ambient contamination from the ZnO surface with the effect to prevent the work function lowering artifact. This allowed the conclusion that ambient contamination is essential for the artifact to occur, similar to what was observed earlier on indium tin oxide and TiO2 surfaces. In an additional experiment, exposure of the annealed sample to the ambient resulted in a sample that again showed the artifact further demonstrating the necessity of water to be present. This experiment also demonstrated that the solubility enhancing surfactant shell of the nano-crystals does not play a significant role in the artifact, since it was removed during the annealing process.

Gutmann, S.; Conrad, M.; Wolak, M. A.; Beerbom, M. M.; Schlaf, R.

2012-06-01

156

Porphyrins bearing arylphosphonic acid tethers for attachment to oxide surfaces.  

PubMed

Synthetic molecules bearing phosphonic acid groups can be readily attached to oxide surfaces. As part of a program in molecular-based information storage, we have developed routes for the synthesis of diverse porphyrinic compounds bearing phenylphosphonic acid tethers. The routes enable (1) incorporation of masked phosphonic acid groups in precursors for use in the rational synthesis of porphyrinic compounds and (2) derivatization of porphyrins with masked phosphonic acid groups. The precursors include dipyrromethanes, monoacyldipyrromethanes, and diacyldipyrromethanes. The tert-butyl group has been used to mask the dihydroxyphosphoryl substituent. The di-tert-butyloxyphosphoryl unit is stable to the range of conditions employed in syntheses of porphyrins and multiporphyrin arrays yet can be deprotected under mild conditions (TMS-Cl/TEA or TMS-Br/TEA in refluxing CHCl(3)) that do not cause demetalation of zinc or magnesium porphyrins. The porphyrinic compounds that have been prepared include (1) A(3)B-, trans-AB(2)C-, and ABCD-porphyrins that bear a single phenylphosphonic acid group, (2) a trans-A(2)B(2)-porphyrin bearing two phenylphosphonic acid groups, (3) a chlorin that bears a single phenylphosphonic acid group, and (4) a porphyrin dyad bearing a single phenylphosphonic acid group. For selected porphyrin-phosphonic acids, the electrochemical characteristics have been investigated for molecules tethered to SiO(2) surfaces grown on doped Si. The voltammetric behavior indicates that the porphyrin-phosphonic acids form robust, electrically well-behaved monolayers on the oxide surface. PMID:14986995

Muthukumaran, Kannan; Loewe, Robert S; Ambroise, Arounaguiry; Tamaru, Shun-ichi; Li, Qiliang; Mathur, Guru; Bocian, David F; Misra, Veena; Lindsey, Jonathan S

2004-03-01

157

Atomistic modeling of ultra-thin surface oxide growth on a ternary alloy : oxidation of Al-Ni-Fe  

Microsoft Academic Search

By employing variable-charge molecular dynamics, surface oxide film growth on aluminum-nickel-iron alloys has been studied at 300 and 600 K. The dynamics of oxidation and oxide growth is strongly dependent on the composition of the initial alloy and the ambient temperature. Higher content of Ni and Fe in Al alloys is found to reduce the oxide growth kinetics; 15% Ni

J. Byoungseon; S. K. R. S. Sankaranarayanan; S. Ramanathan

2011-01-01

158

Surface x-ray diffraction study on polar oxide surface and interface  

NASA Astrophysics Data System (ADS)

An atomic scale study of surface/interface structure is required to properly understand physical and chemical phenomena such as crystal growth, lubrication and electrochemistry. The stability of polar oxide surface has long been an interesting question. A bulk-terminated polar oxide surface comprises alternating layers of opposite charges, thus resulting in diverging surface energies. In order to reduce the surface energy, various reconstruction-stabilized MgO (111) surfaces have been reported experimentally. However, the atomic structure of the MgO (111)rt3xrt3R30° reconstructed surface remains unclear. Using a third-generation X-ray source is one of the feasible methodologies to probe such a system due to its increase of sensitivity on the interface layer. Surface X-ray diraction (SXRD) experiments were performed for the MgO(111) rt3xrt3R30° reconstructed surface at Advanced Photon Source, Argonne National Laboratory. The sample surface was prepared at home laboratory by annealing in a tube furnace for 36hrs at 1050°C, with N2 blowing at rate 1 to 2 scft. Crystal truncation rod (CTR) and super structure rod (SSR) measurements were acquired in both the absence and presence of a thin layer of water, obtained by compressing the bulk water layer with a thin Kapton sheet. A differential evolution algorithm, GenX, was used to search for the appropriate atomic model of reconstructed structure. Some reasonable models are presented and discussed with quantitative calculation of optimizing parameters (R factor and chi square). Preliminary SXRD results of the dry surface and solid-liquid interface are compared. This determination will shed light on whether physical (as opposed to chemical) factors are operant in the formation of ice-like layers.

Han, Wei

159

Covalent attachment of 1-alkenes to oxidized platinum surfaces.  

PubMed

We report the formation of covalently bound alkyl layers onto oxidized Pt (PtOx) substrates by reaction with 1-alkenes as a novel way to bind organic molecules to metal surfaces. The organic layers were characterized by static contact angle, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The grafted alkyl layers display a hydrolytic stability that is comparable to that of alkyl thiols on Au. PtOx-alkene attachment is compatible with terminal ester moieties enabling further anchoring of functional groups, such as redox-active ferrocene, and thus has great potential to extend monolayer chemistry on noble metals. PMID:25710809

Alonso, Jose Maria; Fabre, Bruno; Trilling, Anke K; Scheres, Luc; Franssen, Maurice C R; Zuilhof, Han

2015-03-10

160

Surface and interfacial reaction study of InAs(100)-crystalline oxide interface  

SciTech Connect

A crystalline oxide film on InAs(100) is investigated with in situ monochromatic x-ray photoelectron spectroscopy and low energy electron diffraction before and after in situ deposition of Al{sub 2}O{sub 3} by atomic layer deposition (ALD) as well as upon air exposure. The oxidation process leads to arsenic and indium trivalent oxidation state formation. The grown epitaxial oxide-InAs interface is stable upon ALD reactor exposure; however, trimethyl aluminum decreases oxidation states resulting in an unreconstructed surface. An increase in oxide concentration is also observed upon air exposure suggesting the crystalline oxide surface is unstable.

Zhernokletov, D. M. [Department of Physics, University of Texas at Dallas, Richardson, Texas 75080 (United States)] [Department of Physics, University of Texas at Dallas, Richardson, Texas 75080 (United States); Laukkanen, P. [Department of Physics and Astronomy, University of Turku, Turku FI-20014 (Finland)] [Department of Physics and Astronomy, University of Turku, Turku FI-20014 (Finland); Dong, H.; Brennan, B.; Kim, J. [Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080 (United States)] [Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080 (United States); Galatage, R. V. [Department of Electrical Engineering, University of Texas at Dallas, Richardson, Texas 75080 (United States)] [Department of Electrical Engineering, University of Texas at Dallas, Richardson, Texas 75080 (United States); Yakimov, M.; Tokranov, V.; Oktyabrsky, S. [College of Nanoscale Science and Engineering, University at Albany-SUNY, Albany, New York 12203 (United States)] [College of Nanoscale Science and Engineering, University at Albany-SUNY, Albany, New York 12203 (United States); Wallace, R. M. [Department of Physics, University of Texas at Dallas, Richardson, Texas 75080 (United States) [Department of Physics, University of Texas at Dallas, Richardson, Texas 75080 (United States); Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080 (United States)

2013-05-27

161

Methane oxidation and methane fluxes in the ocean surface layer and deep anoxic waters  

NASA Technical Reports Server (NTRS)

Measured biological oxidation rates of methane in near-surface waters of the Cariaco Basin are compared with the diffusional fluxes computed from concentration gradients of methane in the surface layer. Methane fluxes and oxidation rates were investigated in surface waters, at the oxic/anoxic interface, and in deep anoxic waters. It is shown that the surface-waters oxidation of methane is a mechanism which modulates the flux of methane from marine waters to the atmosphere.

Ward, B. B.; Kilpatrick, K. A.; Novelli, P. C.; Scranton, M. I.

1987-01-01

162

Investigating phosphonate monolayer stability on ALD oxide surfaces  

NASA Astrophysics Data System (ADS)

We report a series of studies aimed at investigating the stability of phosphonate self-assembled monolayers (SAMs) made from octadecylphosphonic acid (ODPA) or a perfluorinated phosphonic acid (PFPA) on hafnium and aluminum oxide surfaces deposited by atomic layer deposition (ALD). The monolayers were deposited by a series of techniques including self-assembly from solution, tethering by aggregation and growth, and the Langmuir-Blodgett (LB) method. SAMs prepared by LB method were primarily used in our stability investigations because they were found to be the most uniform and reproducible. All films deposited on ALD oxide-coated substrates were characterized by means of water contact angle measurements, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS data conclusively showed covalent phosphonate formation on both substrates. SAMs formed on both Al2O3 and HfO2 were stable upon exposure to water. PFPA SAMs on HfO2 were found to be the most stable SAMs studied here in either water or phosphate buffer (PBS) at room temperature. We also show that similar silane-based SAMs made from octadecyltrichlorosilane (OTS) on silicon oxide (SiO2) are less stable in PBS than phosphonate SAMs on atomic layer deposited HfO2 substrates. These data suggest that phosphonate SAMs should be considered for use in (bio)molecular sensing and actuator devices that utilize ALD and require longer-term stability under aqueous conditions.

Branch, Brittany; Dubey, Manish; Anderson, Aaron S.; Artyushkova, Kateryna; Baldwin, J. Kevin; Petsev, Dimiter; Dattelbaum, Andrew M.

2014-01-01

163

Soil bacterial strains able to grow on the surface of oxidized polyethylene film containing prooxidant additives  

E-print Network

Soil bacterial strains able to grow on the surface of oxidized polyethylene film containing low-density polyethylene film containing prooxidant additives were isolated from three forest soils of adhering to the surface of oxidized polyethylene, growing there and possibly biodegrading its oxidation

Boyer, Edmond

164

A predictive model (ETLM) for arsenate adsorption and surface speciation on oxides consistent with spectroscopic  

E-print Network

with high values of the dielectric constant relative to aluminum oxides such as gibbsite with much lowerA predictive model (ETLM) for arsenate adsorption and surface speciation on oxides consistent iron and aluminum oxides. However, integration of the results of these studies with surface

Sverjensky, Dimitri A.

165

Surface Science Letters Synthesis of well-ordered ultra-thin titanium oxide films  

E-print Network

Surface Science Letters Synthesis of well-ordered ultra-thin titanium oxide films on Mo(112) M microscopy (STM); X-ray photoelectron spectroscopy (XPS); Titanium oxide; Surface structure, morphology oxide systems, titanium dioxide has served as the prototypical reducible 0039-6028/$ - see front matter

Goodman, Wayne

166

Electrodeposited ruthenium oxide thin films for supercapacitor: Effect of surface treatments  

E-print Network

Electrodeposited ruthenium oxide thin films for supercapacitor: Effect of surface treatments V,2]. The examples include transition metal oxides and conducting polymers [3­6]. Ruthenium oxide (RuO2ÁxH2O films [10]. Several studies are reported to improve the specific capacitance of ruthenium oxide

Chow, Lee

167

Role of Surface Precipitation in Copper Sorption by the Hydrous Oxides of Iron and Aluminum  

E-print Network

Role of Surface Precipitation in Copper Sorption by the Hydrous Oxides of Iron and Aluminum K. G precipitation; sorption; isotherms; X-ray diffraction; hydrous iron oxide; hydrous aluminum oxide; copper. INTRODUCTION Hydrous oxides of iron (HFO) and aluminum (HAO) are important mineral components of natural

Chorover, Jon

168

The electrochemisty of surface modified <10 nm metal oxide nanoparticles  

NASA Astrophysics Data System (ADS)

Chapter One provides a general introduction of the research on metal oxide nanoparticles (MOx), highlighting their synthesis, surface modification, and functionalization. Emphasis is given to the different synthetic route for producing small (<10 nm) MOx nanoparticles with narrow size distributions. Different methods for modifying their surface with small organic molecules are discussed with focus given to silanes and phosphates. Furthermore, functionalizing surface modified nanoparticles for specific functions is addressed, with markers for analytically relevant nanoscale quantification being the primary focus. Chapter Two describes in detail the thermal degradation synthesis used for the generation of small MOx nanoparticles. It demonstrates the versatile of the synthesis by successfully synthesizing ZrO 2 and IrO2 nanoparticles. Preliminary work involving the formation of Bi2S3, Bi2O3, and RuO2 nanomaterials is also addressed. The solvothermal synthesis of indium tin oxide (ITO) is also shown for comparison to ITO produced by thermal degradation. Chapter Three details the surface modification of ITO nanoparticles and subsequent electrochemical tagging with a ferrocene moiety. ITO nanoparticles were synthesized via thermal degradation. These nanoparticles underwent a ligand exchange with a covalently binding mondentate silane terminated with a primary amine. Acyl chloride coupling between the amine and chlorocarbonylferrocene provided an electrochemical tag to quantify the level of surface modification. Electrochemisty of the quasi-diffusing nanoparticles was evaluated via cyclic voltammetry (CV), chronoamperometry (CA), and mircodisk electrode (microE) experiments. Chapter Four investigates spectroscopic tagging of ITO and ZrO2 nanoparticles as well as electrochemical tagging of ZrO 2 and IrO2 nanoparticles. An unbound azo-dye was synthesized and attempts were made to attach the dye to the surface of ITO nanoparticles. Imine couple between a spectroscopic tag and ZrO2 nanoparticles was also explored, but resulted in very low surface coverages. ZrO2 nanoparticles were also ferrocene tagged using previously discussed siloxane chemistry as well as a new route using click chemistry with an azo-phosphate ligand. A similar approach was taken with hydrolytically synthesized IrO 2 and is included for comparison. Chapter Five studies the multivalent electrochemistry of 4 nm magnetite nanoparticles. These nanoparticles are synthesized via thermal degradation and capped with citric acid to make them water soluble. pH dependent electrochemistry was discovered and characterized using cyclic voltammetry, chronoamperometry, and rotating disk electrode experiments. Two separate electrochemical species are present and undergo two irreversible, but separate electrochemical reactions; Fe(II) ? Fe (III) and Fe(III) ? Fe(II).

Roberts, Joseph J. P.

169

Surface complexation of organic arsenic on nanocrystalline titanium oxide.  

PubMed

The adsorption mechanisms of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) on nanocrystalline titanium oxide (TiO2) were investigated with X-ray absorption spectroscopy (XAS), surface charge and zeta potential measurements, adsorption edge, and surface complexation modeling. XAS data demonstrated that MMA and DMA formed bidentate and monodentate inner sphere complexes with the TiO2 surface, respectively. The charge and zeta potential behaviors of TiO2 as a function of ionic strength suggested that the point of zero charge (PZC) and isoelectric point (IEP) of TiO2 were identical at pH 5.8. Adsorption of MMA and DMA on TiO2 shifted the IEP to pH 4.1 and 4.8, respectively, indicating the formation of negatively charged surface complexes. A satisfactory interpretation of the experimental data was provided by the charge distribution (CD) multi-site complexation (MUSIC) model with the triple plane option under the constraint of the XAS evidence. PMID:16122542

Jing, Chuanyong; Meng, Xiaoguang; Liu, Suqin; Baidas, Salem; Patraju, Ravi; Christodoulatos, Christos; Korfiatis, George P

2005-10-01

170

Crystalline oxide tunnel barriers formed by thermal oxidation of aluminum overlayers on superconductor surfaces  

NASA Astrophysics Data System (ADS)

Crystalline oxide tunnel barriers were formed by thermal oxidation of thin Al overlayers on single-crystal and polycrystalline films of four refractory superconductors: Nb, Mo-Re, Nb3Sn, and NbN. Tunnel junctions were fabricated mostly with Pb-Bi and also with Nb, Mo-Re, and NbN counterelectrodes. Differences in the base electrode crystallinity, surface roughness, oxygen affinity, and native oxide properties influenced the average barrier height, the subgap and normal (above-gap) conductance and the occurrence of microshorts. An effect of the overlayer deposition method (evaporation versus sputtering) was also noticed. The comparison of properties of barriers obtained on different base electrodes and of those amorphized by ion milling lead to the observation that amorphous barriers are more uniform and representative of Al2O3 than the crystalline and epitaxial barriers. The properties of the latter are defined, in part, by the shunting native oxide channels which result from a nonuniform coverage of the base electrode.

Braginski, A. I.; Talvacchio, J.; Janocko, M. A.; Gavaler, J. R.

1986-09-01

171

THE ATOMIC-SCALE CHARACTERIZATION OF DEFECTS ON CLEAVED VANADIUM AND MOLYBDENUM OXIDE SURFACES USING STM  

E-print Network

THE ATOMIC-SCALE CHARACTERIZATION OF DEFECTS ON CLEAVED VANADIUM AND MOLYBDENUM OXIDE SURFACES of experimental evidence supporting the idea that the oxidation reactions catalyzed by molybdenum and vanadium

Rohrer, Gregory S.

172

Probing and mapping electrode surfaces in solid oxide fuel cells.  

PubMed

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen (1-7). The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion(2). Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation(8-12). It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition(8, 10, 13, 14) ("coking") and sulfur poisoning(11, 15) and the manner in which surface modifications stave off this degradation(16). The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated(17-22). In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode. PMID:23023264

Blinn, Kevin S; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A; Liu, Meilin

2012-01-01

173

Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells  

PubMed Central

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated17-22. In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode. PMID:23023264

Blinn, Kevin S.; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A.; Liu, Meilin

2012-01-01

174

Molecular Assembly of Rubrene on a Metal/Metal Oxide Nanotemplate Fabio Cicoira, Jill A. Miwa, Dmitrii F. Perepichka, and Federico Rosei*,  

E-print Network

that the reaction between chemisorbed oxygen and surface Cu atoms leads to the formation of O-Cu strings running, namely the clean and the oxygen-passivated Cu(110). Rubrene (5,6,11,12-tetraphenyltetracene, C42H28 of the backbone (Figure 1a). It is being widely studied for applications in organic electronics, including light

175

Iron carbide on titania surface modified with group VA oxides as Fisher-Tropsch catalysts  

Microsoft Academic Search

Catalysts comprising iron carbide on a surface modified titania support wherein said support comprises a surface modifying oxide of tantalum, niobium, vanadium and mixtures thereof supported on said titania wherein at least a portion of said surface modifying oxide is in a non-crystalline form. These catalysts are useful for Fischer-Tropsch hydrocarbon synthesis reactions. Preferably, at least about 25 wt. %

I. E. Wachs; C. C. Cherisch; R. A. Fiato

1985-01-01

176

Morphology of the Cu2O surface oxide phase formed on Cu,,100... at high temperature  

E-print Network

Morphology of the Cu2O surface oxide phase formed on Cu,,100... at high temperature C. L. H. Devlin June 2009 We have observed the nucleation and growth of the Cu2O surface oxide on a Cu 100 surface-terraced step bunches to broad, deeply curved terraces with more highly bunched steps. Using x-ray photoelectron

Chiang, Shirley

177

The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid  

PubMed Central

The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation. PMID:24229051

2013-01-01

178

Oxide treatments of Al 2024 for adhesive bonding- surface characterization  

NASA Astrophysics Data System (ADS)

A study was made to characterize the surface of oxides formed on Al 2024 in comparison to those formed on Al 1100, using Auger, ESCA, SIMS, FTIR and SEM/EDAX techniques. The pretreatments studied were chromate conversion coating, chromic acid anodizing and sulfuric acid anodizing. The specimens were evaluated as treated and after exposure to laboratory conditions ( T=25?3°C and relative humidity of 60?10%) for 6 months. In addition, a new surface pretreatment was studied, which was based on McDonnell Douglas P.S. 13201 specification. Adhesive bond strength of silicone rubbers and epoxy adhesives to pretreated Al 2024 was determined, using single lap joint specimens. It was shown that the main difference between the anodic coatings on Al 1100 and Al 2024 was the presence of copper on the surface in the latter. The presence of copper led us to postulate the mechanism of polymerization inhibition of 2 parts polysiloxane adhesive. The most suitable treatments for adhesive joining were found to be chromic acid sealed or unsealed anodizing for both Al 2024 and Al 1100. Our standard chromic acid anodizing gave higher bond strength for aluminum-adhesive joints than the "Douglas" process. as determined with several epoxy adhesives. Correlation between microscopic and macroscopic phenomena was established.

Fin, N.; Dodiuk, H.; Yaniv, A. E.; Drori, L.

1987-03-01

179

The surface composition and initial oxidation of zirconium-nickel intermetallic compounds at room temperature  

NASA Astrophysics Data System (ADS)

The surface compositions of five sputter-cleaned zirconium-nickel intermetallic compounds (ZrNi 5, Zr 2Ni 7, ZrNi 3, ZrNi, and Zr 2Ni) have been estimated by quantitative Auger analysis. The quantitative analysis was calibrated using Auger intensities measured on UHV fracture exposed alloy surfaces. The five sputter-cleaned alloys are slightly enriched in surface Zr relative to their bulk compositions. Their initial oxidation at room temperature is accompanied by the preferential surface accumulation of oxidized Zr. We have previously shown that the oxidation of Zr 2Ni 7, ZrNi 3, and ZrNi at 673 K results in the preferential surface accumulation of oxidized Ni. This variation with temperature of the surface compositional stratification and preferential oxidation characteristics of Zr-Ni alloys can have a significant influence on their stability in oxidizing environments.

Deibert, Max C.; Wright, Randy B.

1988-10-01

180

High surface area, electrically conductive nanocarbon-supported metal oxide  

DOEpatents

A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

Worsley, Marcus A; Han, Thomas Yong-Jin; Kuntz, Joshua D; Cervanted, Octavio; Gash, Alexander E; Baumann, Theodore F; Satcher, Jr., Joe H

2014-03-04

181

Transition metal oxides deposited on rhodium and platinum: Surface chemistry and catalysis  

SciTech Connect

The surface chemistry and catalytic reactivity of transition metal oxides deposited on Rh and Pt substrates has been examined in order to establish the role of oxide-metal interactions in influencing catalytic activity. The oxides investigated included titanium oxide (TiOx), vanadium oxide (VOx), iron oxide (FeOx), zirconium oxide (ZrOx), niobium oxide (NbOx), tantalum oxide (TaOx), and tungsten oxide (WOx). The techniques used to characterize the sample included AES, XPS, LEED, TPD, ISS, and STM. After characterization of the surface in UHV, the sample was enclosed in an atmospheric reaction cell to measure the influence of the oxide deposits on the catalytic activity of the pure metal for CO and CO{sub 2} hydrogenation. The oxide deposits were found to strongly enhance the reactivity of the Rh foil. The rates of methane formation were promoted by up to 15 fold with the maximum in rate enhancement occurring at oxide coverages of approximately 0.5 ML. TiOx TaOx, and NbOx were the most effective promoters and were stable in the highest oxidation states during both reactions (compared to VOx, WOx, and FeOx). The trend in promoter effectiveness was attributed to the direct relationship between oxidation state and Lewis acidity. Bonding at the metal oxide/metal interface between the oxygen end of adsorbed CO and the Lewis acidic oxide was postulated to facilitate C-O bond dissociation and subsequent hydrogenation. 192 refs.

Boffa, A.B. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Materials Sciences Div.

1994-07-01

182

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation  

NASA Astrophysics Data System (ADS)

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu +/Cu 2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified.

Hoppe, E. W.; Seifert, A.; Aalseth, C. E.; Bachelor, P. P.; Day, A. R.; Edwards, D. J.; Hossbach, T. W.; Litke, K. E.; McIntyre, J. I.; Miley, H. S.; Schulte, S. M.; Smart, J. E.; Warren, G. A.

2007-08-01

183

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation  

SciTech Connect

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu+/Cu2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified. © 2001 Elsevier Science. All rights reserved

Hoppe, Eric W.; Seifert, Allen; Aalseth, Craig E.; Bachelor, Paula P.; Day, Anthony R.; Edwards, Danny J.; Hossbach, Todd W.; Litke, Kevin E.; McIntyre, Justin I.; Miley, Harry S.; Schulte, Shannon M.; Smart, John E.; Warren, Glen A.

2007-08-21

184

Frequency-selective surface coupled metal-oxide-metal diodes  

NASA Astrophysics Data System (ADS)

Metal-Oxide-Metal diodes offer the possibility of directly rectifying infrared radiation. To be effective for sensing or energy harvesting they must be coupled to an antenna which produces intense fields at the diode. While antennas significantly increase the effective capture area of the MOM diode, it is still limited and maximizing the captured energy is still a challenging goal. In this work we investigate integrating MOM diodes with a slot antenna Frequency Selective Surface (FSS). This maximizes the electromagnetic capture area while minimizing the transmission line length which helps reduce losses because metal losses are much lower at DC than at infrared frequencies. Our design takes advantage of a single self-aligned patterning step using shadow evaporation. The structure is optimized at 10.6 µm to have less than 2% reflection (polarization sensitive) and simulations predict that 70% of the incident energy is dissipated into the oxide layer. Initial experimental results fabricated with e-beam lithography are presented and the diode coupled FSS is shown to produce a polarization sensitive unbiased DC short circuit current. This work is promising for both infrared sensing and imaging as well as direct conversion of thermal energy.

Kinzel, Edward C.; Brown, Robert L.; Ginn, James C.; Lail, Brian A.; Slovick, Brian A.; Boreman, Glenn D.

2013-06-01

185

Characterization of the thrombogenic potential of surface oxides on stainless steel for implant purposes  

NASA Astrophysics Data System (ADS)

Marketed stents are manufactured from various metals and passivated with different degrees of surface oxidation. The functional surface oxides on the degree of antithrombotic potential were explored through a canine femoral extracorporeal circuit model. Related properties of these oxide films were studied by open-circuit potential, current density detected at open-circuit potential, the electrochemical impedance spectroscopy, transmission electron microscopy, Auger spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. Experimental evidences showed that blood clot weight after a 30-min follow-up was significantly lower for the stainless steel wire passivated with amorphous oxide (AO) compared to the wire passivated with polycrystalline oxide (PO) or commercial as-received wire coils (AS). Surface characterizations showed that a stable negative current density at open-circuit potential and a significant lower potential were found for the wire surface passivated with AO than for the surface passivated with PO. Time constant of AO is about 25 times larger than that of polycrystalline oxide. Significant difference in oxide grain sizes was found between PO and AO. Surface chemistries revealed by the AES and XPS spectra indicated the presence of a Cr- and oxygen-rich surface oxide for AO, and a Fe-rich and oxygen-lean surface oxide for PO. These remarkable characteristics of AO surface film might have a potential to provide for excellent antithrombotic characteristics for the 316L stainless steel stents.

Shih, Chun-Che; Shih, Chun-Ming; Su, Yea-Yang; Chang, Mau-Song; Lin, Shing-Jong

2003-12-01

186

Decontamination of U-metal Surface by an Oxidation Etching System  

SciTech Connect

A surface oxidation treatment is described to remove surface contamination from uranium (U) metal and/or hydrides of uranium and heavy metals (HM) from U-metal parts. In the case of heavy metal atomic contamination on a surface, and potentially several atomic layers beneath, the surface oxidation treatment combines both chemical and chemically driven mechanical processes. The chemical process is a controlled temperature-time oxidization process that creates a thin film of uranium oxide (UO{sub 2} and higher oxides) on the U-metal surface. The chemically driven mechanical process is strain induced by the volume increase as the U-metal surface transforms to a UO{sub 2} surface film. These volume strains are sufficiently large to cause surface failure spalling/scale formation and thus, removal of a U-oxide film that contains the HM-contaminated surface. The case of a HM-hydride surface contamination layer can be treated similarly by using inert hot gas to decompose the U-hydrides and/or HM-hydrides that are contiguous with the surface. A preliminary analysis to design and to plan for a sequence of tests is developed. The tests will provide necessary and sufficient data to evaluate the effective implementation and operational characteristics of a safe and reliable system. The following description is limited to only a surface oxidation process for HM-decontamination.

Stout, R B; Kansa, E J; Shaffer, R J; Weed, H C

2000-12-18

187

Effects of surface oxidation during HVOF processing on the primary stage oxidation of a CoNiCrAlY coating  

Microsoft Academic Search

Nanostructured CoNiCrAlY coating specimens, prepared from cryomilled powder, were deposited using HVOF thermal spraying. During the thermal spraying process some of the particles oxidized, resulting in a surface oxide on the coatings. In order to investigate the effects of this surface oxide on the subsequent oxidation behavior of the CoNiCrAlY coating, the surface oxide on some of the coating specimens

Feng Tang; Leonardo Ajdelsztajn; George E Kim; Virgil Provenzano; Julie M Schoenung

2004-01-01

188

Monday, November 5, 2007 -9:30 AM Real-Time Surface-Chemistry of Arsenite Oxidation by Hydrous Manganese Oxide.  

E-print Network

by Hydrous Manganese Oxide. Matthew Ginder-Vogel and Donald L. Sparks. University of Delaware, 152 Townsend(V)) by manganese(IV) oxide is an important reaction impacting the natural cycling of As. The aresenite species(III) on the surface of manganese oxides has been well characterized; however, the surface chemistry of the oxidation

Sparks, Donald L.

189

Surface induced disorder of nematic MBBA near silica with grafted poly(ethylene oxide)  

E-print Network

909 Surface induced disorder of nematic MBBA near silica with grafted poly(ethylene oxide) H. Ben with grafted polymers poly(ethylene oxide) 2000, has been investigated by the electron paramagnetic resonance different. This paper describes the effect of macromolecules, namely poly- (ethylene oxide), grafted i

Paris-Sud XI, Université de

190

Correlation and surface effects in vanadium oxides S. Schwieger, M. Potthoff, and W. Nolting  

E-print Network

Correlation and surface effects in vanadium oxides S. Schwieger, M. Potthoff, and W. Nolting modifications in the spectra from vanadium oxides such as (V,Cr)2O3 or (Sr,Ca)VO3. The effective mass transitions are caused by correlations. Typical ma- terials that show such behavior are vanadium oxides

Potthoff, Michael

191

External noise-induced phenomena in CO oxidation on single crystal surfaces  

E-print Network

External noise-induced phenomena in CO oxidation on single crystal surfaces M. Pinedaa and R. Toral of external noise on minimalistic models for the catalytic CO oxidation on Ir 111 and Pt 111 is studied the interplay between external noise and the kinetic bistability of CO oxidation. We report the phenomena

Toral, Raúl

192

Oxidation rate of iron sulfides as affected by surface area, morphology, oxygen concentration and autotrophic bacteria  

Microsoft Academic Search

The relationship between surface area and rate of oxidation of Fe sulphides (pyrite and marcasite) separated from Texas lignite was studied. The reaction kinetics with respect to Fe sulphide morphology and particle size were evaluated. The oxygen concentration and the presence of autotrophic Fe and S-oxidizing bacteria (thiobacillus ferro-oxidans) on the rate of oxidation were also evaluated. The formation of

C. E. PUGH; L. R. HOSSNER; J. B. DIXON

1984-01-01

193

Author's personal copy Highly active surfaces for CO oxidation on Rh, Pd, and Pt  

E-print Network

Author's personal copy Highly active surfaces for CO oxidation on Rh, Pd, and Pt M.S. Chen, Y. Cai oxidation on Pt-group metals at temperatures between 450 and 600 K and pressures between 1 and 300 Torr of oxygen, the heats of formation of the bulk oxides, and the metal particle sizes. Auger spectroscopy and X

Goodman, Wayne

194

Advanced Surface Modification of Indium Tin Oxide for Improved Charge Injection in Organic Devices  

E-print Network

Advanced Surface Modification of Indium Tin Oxide for Improved Charge Injection in Organic Devices and involves sequential formation of a monolayer of a -conjugated organic semiconductor on the indium tin oxide, indium tin oxide, ITO) and cathode of organic light emitting diodes (OLEDs), or at electrodes in other

Schwartz, Jeffrey

195

Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix I  

NASA Technical Reports Server (NTRS)

Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.

Xu, F.; El-Leathy, A. M.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2003-01-01

196

Microstructure of oxide layers formed on zirconium alloy by air oxidation, uniform corrosion and fresh-green surface modification  

NASA Astrophysics Data System (ADS)

Cladding materials with superior corrosion resistance and anti-hydrogen pickup have been developed for high burnup nuclear fuel. We have suggested a surface modification of the cladding materials for this purpose and invented a new surface modification method "Fresh-Green". The Fresh-Green treatment oxidizes and carbonizes a material surface in the same process. Zircaloy-2 with the Fresh-Green treatment showed the improvement of corrosion resistance in autoclave tests. In order to investigate the effect of surface modifications on the corrosion resistance, a synchrotron radiation experiment and a TEM observation were performed on different oxide layers formed on Zircaloy-2. The oxide layers were formed by air-oxidation, an autoclave test and the Fresh-Green treatment. Crystal structures of all the samples were transformed as Zr > Zr 3O > tetragonal ZrO 2 > monoclinic ZrO 2 from the matrix to the surface. Columnar grains of monoclinic zirconia were arranged unidirectionally in the Fresh-Green oxide layer treated at a low temperature. Diffusing capacity for oxygen influenced the crystal structure of the oxide layers.

Sawabe, Takashi; Sonoda, Takeshi; Furuya, Masahiro; Kitajima, Shoichi; Kinoshita, Motoyasu; Tokiwai, Moriyasu

2011-12-01

197

Surface reconstruction evolution and anatase formation in the process of oxidation of titanium nitride film  

NASA Astrophysics Data System (ADS)

Titanium nitride film was grown on MgO(001) substrate by plasma-assisted molecular beam epitaxy and then oxidized by oxygen plasma. Reflection high-energy electron diffraction (RHEED) was employed to in situ monitor the process of growth and oxidation. After the TiN film was oxidized for a moment, spots among main streaks were observed in RHEED pattern, which should be attributed to the isolated surface reconstruction domains disorderedly distributing on flat surface. Subsequently, the spots gradually evolved to streaks so that more clear RHEED patterns of (2×1) surface reconstruction were observed. It was argued that the disordered and isolated reconstruction domains congregated to large domains or even perfect reconstruction surface with oxidation time evolving. After oxidation, a series of characterization methods were applied to study the TiO2 phase, which consistently confirmed that the phase of oxidized titanium nitride is anatase but not rutile.

Wu, S. X.; Liu, Y. J.; Xing, X. J.; Yu, X. L.; Xu, L. M.; Yu, Y. P.; Li, S. W.

2008-03-01

198

Oxidation state of surface tin in an industrially produced float glass  

Microsoft Academic Search

The stoichiometry of tin oxide incorporated in the bottom surfaces of float glasses has been studied by CEMS. Our results indicate the predominance in the investigated surfaces of the Sn(II) oxidation state, which is higher in the outer layer (some tens of nm) as compared to the inner one.

G. Principi; A. Maddalena; A. Gupta; F. Geotti-Bianchini; S. Hreglich; M. Veritá

1993-01-01

199

Generation of active oxygen species on solid surfaces. Opportunity for novel oxidation technologies over zeolites  

Microsoft Academic Search

Generation of surface oxygen species and their role in partial oxidation reactions catalyzed by metal oxides are discussed. Main attention is paid to a new concept related to a recent discovery of remarkable ability of Fe complexes stabilized in a ZSM-5 matrix to generate a new form of surface oxygen (?-oxygen) from N2O. At room temperature, ?-oxygen exhibits a high

Gennady I. Panov; Anthony K. Uriarte; Mikhail A. Rodkin; Vladimir I. Sobolev

1998-01-01

200

Superhydrophilicity and antibacterial property of a Cu-dotted oxide coating surface  

PubMed Central

Background Aluminum-made settings are widely used in healthcare, schools, public facilities and transit systems. Frequently-touched surfaces of those settings are likely to harbour bacteria and be a potential source of infection. One method to utilize the effectiveness of copper (Cu) in eliminating pathogens for these surfaces would be to coat the aluminum (Al) items with a Cu coating. However, such a combination of Cu and Al metals is susceptible to galvanic corrosion because of their different electrochemical potentials. Methods In this work, a new approach was proposed in which electrolytic plasma oxidation (EPO) of Al was used to form an oxide surface layer followed by electroplating of Cu metal on the top of the oxide layer. The oxide was designed to function as a corrosion protective and biocompatible layer, and the Cu in the form of dots was utilized as an antibacterial material. The antibacterial property enhanced by superhydrophilicity of the Cu-dotted oxide coating was evaluated. Results A superhydrophilic surface was successfully prepared using electrolytic plasma oxidation of aluminum (Al) followed by electroplating of copper (Cu) in a Cu-dotted form. Both Cu plate and Cu-dotted oxide surfaces had excellent antimicrobial activities against E. coli ATCC 25922, methicillin-resistant Staphylococcus aureus (MRSA) ATCC 43300 and vancomycin-resistant Enterococcus faecium (VRE) ATCC 51299. However, its Cu-dotted surface morphology allowed the Cu-dotted oxide surface to be more antibacterial than the smooth Cu plate surface. The enhanced antibacterial property was attributed to the superhydrophilic behaviour of the Cu-dotted oxide surface that allowed the bacteria to have a more effective killing contact with Cu due to spreading of the bacterial suspension media. Conclusion The superhydrophilic Cu-dotted oxide coating surface provided an effective method of controlling bacterial growth and survival on contact surfaces and thus reduces the risk of infection and spread of bacteria-related diseases particularly in moist or wet environments. PMID:20843373

2010-01-01

201

Deep oxidation of pollutants using gold deposited on a high surface area cobalt oxide prepared by a nanocasting route.  

PubMed

Gold deposited on a cobalt oxide with high surface area (138 m(2)g(-1)), obtained through a nanocasting route using a siliceous KIT-6 mesoporous material as a hard template, has demonstrated high activity for the total oxidation of propane and toluene, and ambient temperature CO oxidation. The addition of gold promotes the activity when compared to a gold-free Co(3)O(4) catalyst prepared using the same nanocasting technique. The enhanced catalytic activity when gold is present has been explained for the deep oxidation of propane and toluene in terms of the improved reducibility of cobalt oxide when gold is added, rather than to the intrinsic activity of metallic gold particles. The improved behaviour for CO oxidation has been linked to the simultaneous presence of Au(?+) and Au°. PMID:21315508

Solsona, Benjamín; Aylón, Elvira; Murillo, Ramón; Mastral, Ana M; Monzonís, Alejandro; Agouram, Said; Davies, Thomas E; Taylor, Stuart H; Garcia, Tomás

2011-03-15

202

Surface Catalysis and Oxidation on Stagnation Point Heat Flux Measurements in High Enthalpy Arc Jets  

NASA Technical Reports Server (NTRS)

Heat flux sensors are routinely used in arc jet facilities to determine heat transfer rates from plasma plume. The goal of this study is to assess the impact of surface composition changes on these heat flux sensors. Surface compositions can change due to oxidation and material deposition from the arc jet. Systematic surface analyses of the sensors were conducted before and after exposure to plasma. Currently copper is commonly used as surface material. Other surface materials were studied including nickel, constantan gold, platinum and silicon dioxide. The surfaces were exposed to plasma between 0.3 seconds and 3 seconds. Surface changes due to oxidation as well as copper deposition from the arc jets were observed. Results from changes in measured heat flux as a function of surface catalycity is given, along with a first assessment of enthalpy for these measurements. The use of cupric oxide is recommended for future heat flux measurements, due to its consistent surface composition arc jets.

Nawaz, Anuscheh; Driver, David M.; Terrazas-Salinas

2013-01-01

203

Creation of Exotic Features in Metal Oxides by Surface Treatment for Enhanced Gas Sensing  

E-print Network

Creation of Exotic Features in Metal Oxides by Surface Treatment for Enhanced Gas Sensing Majed of ceramics are predominantly surface-dominated, benign surface features in terms of small grain size, large surface area and, open and connected porosity, are required to realize a successful device. In the case

Azad, Abdul-Majeed

204

Surface characterisation of dextran-coated iron oxide nanoparticles prepared by laser pyrolysis and coprecipitation  

NASA Astrophysics Data System (ADS)

The favoured mechanism of adsorption of dextran on the surface of maghemite nanoparticles (5 nm) prepared by laser pyrolysis seems to be the collective hydrogen bonding between dextran hydroxyl groups and iron oxide particle surface. After heating, the formation of a surface complex between the polysaccharide oxygen atoms and the surface iron atoms gave rise to a stronger bonding.

Carmen Bautista, M.; Bomati-Miguel, Oscar; del Puerto Morales, María; Serna, Carlos J.; Veintemillas-Verdaguer, Sabino

2005-05-01

205

Surface behaviour in deuterium permeation through erbium oxide coatings  

NASA Astrophysics Data System (ADS)

Suppression of tritium permeation through structural materials is essential in order to mitigate fuel loss and radioactivity concerns. Ceramic coatings have been investigated for over three decades as tritium permeation barriers (TPBs); however, a very limited number of investigations on the mechanism of hydrogen-isotope permeation through the coatings have been reported. In this study, deuterium permeation behaviour of erbium oxide coatings fabricated by filtered arc deposition on reduced activation ferritic/martensitic steels has been investigated. The samples coated on both sides of the substrates showed remarkably lower permeability than those coated on one side, and the maximum reduction efficiency indicated a factor of 105 compared with the substrate. The different permeation behaviour between the coatings facing the high and low deuterium pressure sides has been found by the crystal structure analysis and the evaluation of the energy barriers. It is suggested that the permeation processes on the front and back surfaces are independent, and the TPB efficiency of the samples coated on both sides can be expressed by a multiplication of that of each side.

Chikada, T.; Suzuki, A.; Adelhelm, C.; Terai, T.; Muroga, T.

2011-06-01

206

Electrogenerated Chemiluminescence of Partially Oxidized Highly Oriented Pyrolytic Graphite Surfaces and of Graphene Oxide Nanoparticles  

E-print Network

Electrogenerated Chemiluminescence of Partially Oxidized Highly Oriented Pyrolytic Graphite electrochemically oxidized highly oriented pyrolytic graphite (HOPG) and from a suspension of graphene oxide, and electrical devices. For example, graphene, a one-atom thick sheet of carbon, and its oxidized form, graphene

207

Oxidative removal of Mn(II) from solution catalysed by the ?-FeOOH (lepidocrocite) surface  

NASA Astrophysics Data System (ADS)

A laboratory study was undertaken to ascertain the role of surface catalysis in Mn(II) oxidative removal. ?-FeOOH, a ferric oxyhydroxide formed by O2 oxidation of ferrous iron in solution, was studied in the following ways: surface charge characteristics by acid base titration, adsorption of Mn(II) and surface oxidation of Mn(II). A rate law was formulated to account for the effects of pH and the amount of surface on the surface oxidation rate of Mn(II). The presence of milli-molar levels of ?-FeOOH was shown to reduce significantly the half-life of Mn(II) in 0.7 M NaCl from hundreds of hours to hours. The numerical values of the surface rate constants for the ?-FeOOH and that reported for colloidal MnO2 are comparable in order of magnitude.

Sung, Windsor; Morgan, James J.

1981-12-01

208

An STM study of the initial oxidation of single-crystalline zirconium surfaces  

NASA Astrophysics Data System (ADS)

The microstructural development of thin (thickness < 10 nm) oxide layers grown on Zr surfaces by thermal oxidation was investigated by in-vacuo STM and XPS. To this end, single-crystalline Zr(0001) and Zr(101¯0) surfaces were prepared under UHV conditions by a cyclic treatment of ion-sputtering and in-vacuo annealing steps and then exposed to dry O2(g) in the temperature range of 300-450 K (at pO2 = 1×10- 4 Pa). Oxidation proceeds by the fast formation of a dense arrangement of tiny oxide nuclei, which cover the entire Zr surface. The initial oxide cluster size is about 1.2 ± 0.1 nm. The transport processes on the oxidizing surface become promoted with increasing temperature and thereby the oxide clusters rearrange into bigger agglomerates with increasing oxidation time. At the same time, a long-range atomic order develops in the oxide overgrowths, as evidenced from the emergence of a bonding/non-bonding fine structure in the resolved oxide-film upper valence band, as measured in-situ by XPS.

Bakradze, Georgijs; Jeurgens, Lars P. H.; Mittemeijer, Eric J.

2012-05-01

209

Aqueous stabilization of carbon nanotubes: effects of surface oxidization and solution chemistry.  

PubMed

Surface oxygen functional groups can affect the morphological characteristics, aggregation kinetics, and adsorption capacity of multi-walled carbon nanotubes (MWCNTs). However, little is known about the quantitative relationship between oxygen content and the dispersion stability of MWCNTs. To investigate the effects of surface oxidization, MWCNTs were oxidized using concentrated H2SO4/HNO3 acids for 0, 1, 2, 4, and 8 h, respectively. Experimental results showed that the oxygen content of MWCNTs increased with surface oxidization time. Linear correlations were found to exist between the oxygen content, critical coagulation concentration (CCC) for NaCl, and critical coagulation pH values of MWCNTs detected by optical density at 800 nm. The CCC values for CaCl2 increased with oxygen contents for unmodified MWCNTs and lowly oxidized MWCNTs, while which decreased after further increasing the surface oxidization. CCC ratios in the presence of Ca(2+) to Na(+) were consistent with the empirical Schulze-Hardy rule for unmodified MWCNTs and lowly oxidized MWCNTs; however, which were much lower than the expected values for highly oxidized MWCNTs. Fulvic acid can clearly increase the stability of MWCNT suspension with unmodified MWCNTs and lowly oxidized MWCNTs, while it cannot affect the dispersion of highly oxidized MWCNTs. This study implied that the oxidation and presence of fulvic acid will possibly increase the mobility, exposure, bioavailability, and toxicity of MWCNTs. PMID:24323322

Bai, Yingchen; Wu, Fengchang; Lin, Daohui; Xing, Baoshan

2014-03-01

210

Oxidation characteristics of the electron beam surface-treated Alloy 617 in high temperature helium environments  

NASA Astrophysics Data System (ADS)

The oxidation characteristics of the electron beam surface-treated Alloy 617, which has an Al-rich surface layer, were evaluated in high temperature helium environments. Isothermal oxidation tests were performed in helium (99.999% purity) and VHTR-helium (helium of prototypical VHTR chemistry containing impurities like CO, CO2, CH4, and H2) environments at 900 °C for up to 1000 h. The surface-treated Alloy 617 showed an initial transient oxidation stage followed by the steady-state oxidation in all test environments. In addition, the steady-state oxidation kinetics of the surface-treated Alloy 617 was 2-order of magnitude lower than that of the as-received Alloy 617 in both helium environments as well as in air. The improvement in oxidation resistance was primarily due to the formation of the protective Al2O3 layer on the surface. The weight gain was larger in the order of air, helium, and VHTR-helium, while the parabolic rate constants (kp) at steady-state were similar for all test environments. In both helium environments, the oxide structure consisted of the outer transition Al2O3 with a small amount of Cr2O3 and inner columnar structured Al2O3 without an internal oxide. In the VHTR-helium environment, where the impurities were added to helium, the initial transient oxidation increased but the steady state kinetics was not affected.

Lee, Ho Jung; Sah, Injin; Kim, Donghoon; Kim, Hyunmyung; Jang, Changheui

2015-01-01

211

Structures and unexpected dynamic properties of phosphine oxides adsorbed on silica surfaces.  

PubMed

Solid-state NMR spectroscopy of selected phosphine oxides adsorbed on silica surfaces establishes the surface mobilities, even of phosphine oxides with high melting points. Crystal structures of the adducts Ph3 PO?HOSiPh3 and Cy3 PO?H2 O indicate that the interactions with silica involve hydrogen bonding of the P=O group to adsorbed water and surface silanol groups. PMID:25394806

Hilliard, Casie R; Kharel, Sugam; Cluff, Kyle J; Bhuvanesh, Nattamai; Gladysz, John A; Blümel, Janet

2014-12-22

212

TEMPO-mediated surface oxidation of cellulose whiskers  

Microsoft Academic Search

Cellulose whiskers resulting from HCl acid hydrolysis of tunicin were subjected to TEMPO-mediated oxidation under various conditions and the extent of the resulting oxidation was characterized by Fourier-transform infrared spectroscopy (FT-IR), conductimetry, X-Ray diffraction analysis and transmission electron microscopy (TEM). With degree of oxidation of up to 0.1 the samples kept their initial morphological integrity and native crystallinity, but at

Youssef Habibi; Henri Chanzy; Michel R. Vignon

2006-01-01

213

Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces  

Microsoft Academic Search

Valence band photoemission (XPS), valence band electron energy loss spectroscopy (EELS), Ce3d and 4d XPS, O1s XPS and O1s X-ray absorption (XAS) have been investigated for oxidized and sputtered single crystal CeO2 films and for oxidized Ce foil. Features were identified that distinguish between the Ce4+ or Ce3+ oxidation states. Ce4+ was identified by the highest binding energy peaks in

D. R Mullins; S. H Overbury; D. R Huntley

1998-01-01

214

Ab initio atomistic thermodynamics study on the oxidation mechanism of binary and ternary alloy surfaces  

NASA Astrophysics Data System (ADS)

Utilizing a combination of ab initio density-functional theory and thermodynamics formalism, we have established the microscopic mechanisms for oxidation of the binary and ternary alloy surfaces and provided a clear explanation for the experimental results of the oxidation. We construct three-dimensional surface phase diagrams (SPDs) for oxygen adsorption on three different Nb-X(110) (X = Ti, Al or Si) binary alloy surfaces. On the basis of the obtained SPDs, we conclude a general microscopic mechanism for the thermodynamic oxidation, that is, under O-rich conditions, a uniform single-phase SPD (type I) and a nonuniform double-phase SPD (type II) correspond to the sustained complete selective oxidation and the non-sustained partial selective oxidation by adding the X element, respectively. Furthermore, by revealing the framework of thermodynamics for the oxidation mechanism of ternary alloys through the comparison of the surface energies of two separated binary alloys, we provide an understanding for the selective oxidation behavior of the Nb ternary alloy surfaces. Using these general microscopic mechanisms, one could predict the oxidation behavior of any binary and multi-component alloy surfaces based on thermodynamics considerations.

Liu, Shi-Yu; Liu, Shiyang; Li, De-Jun; Wang, Sanwu; Guo, Jing; Shen, Yaogen

2015-02-01

215

Process for growing a film epitaxially upon an oxide surface and structures formed with the process  

DOEpatents

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

McKee, Rodney Allen (Kingston, TN); Walker, Frederick Joseph (Oak Ridge, TN)

1998-01-01

216

Process for growing a film epitaxially upon an oxide surface and structures formed with the process  

DOEpatents

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

McKee, Rodney A. (Kingston, TN); Walker, Frederick J. (Oak Ridge, TN)

1995-01-01

217

Surface-oxide stress induced band-structure modulation in two-dimensional Si layers  

NASA Astrophysics Data System (ADS)

We experimentally studied an impact of the surface oxide layer on quantum confinement effects (QCE) in Si quantum well (SQW) structures (surface-oxide/two-dimensional-Si/buried-oxide) with various surface oxide layer thickness TOX on silicon-on-insulator (SOI) substrate, by UV-Raman spectroscopy, photoluminescence (PL) method, and two-dimensional (2D) stress simulator. UV-Raman data show that tensile strain ? of SQW, stressed by a thermal expansion mismatch between surface oxide and Si layers, decreases with decreasing the TOX. According to the strain behavior in the SQW and strained-Si on strained-SOI, PL results show that bandgap EG of the SQW rapidly expands with decreasing TOX. As a result, we can estimate the EG of the fully relaxed SQW. However, QCE in SQW keep thermally stable, in spite of carrying out a high temperature N2 annealing process.

Mizuno, Tomohisa; Suzuki, Yuhya; Nagamine, Yoshiki; Nakahara, Yuhta; Nagata, Yuhsuke; Aoki, Takashi; Maeda, Tatsuro

2015-04-01

218

A mass-spectrometry study of the surface chemical activities of thorium oxide and cerium-doped thorium oxide  

Microsoft Academic Search

The capacity for thorium oxide and cerium doped thorium oxide for Fischer-Tropsch catalytic activity in the 0-20 Torr pressure regime was evaluated by Quadrupole Mass Spectrometry. High surface area catalysts were prepared and characterized by adsorption isotherm measurements, scanning electron microscopy, energy dispersive x-ray spectrometry and by gas-solid oxygen isotope exchange kinetics. The oxygen exchange mechanisms were found to follow

Grabbe

1989-01-01

219

Probing the electronic structure of early transition metal oxide clusters: Molecular models towards mechanistic insights into oxide surfaces and catalysis  

Microsoft Academic Search

Selected recent works from the authors’ laboratory on the intrinsic electronic and structural properties of early transition metal oxide clusters are reviewed. These clusters provide well-defined molecular models pertinent to mechanistic understandings of complex oxide surface chemistry and catalysis. The energy gap evolution with cluster size was probed for the stoichiometric (TiO2)n?, (V2O5)n?, and (CrO3)n? clusters, and each system was

Hua-Jin Zhai; Lai-Sheng Wang

2010-01-01

220

Surface effects and phase stability in metal oxides nanoparticles under visible irradiation  

NASA Astrophysics Data System (ADS)

The light induced phase transformation between stable phases of metal oxides nanoparticles is analyzed. The surrounding atmosphere as well as the defect density at the surface play a fundamental role. It has been found that in oxygen poor chamber atmosphere the phase transformation is favored, while the phase transition cannot be achieved if the defects at the surface are properly passivated. The phase transition is activated by intragap irradiation, able to activate the F- center at the surface connected to oxygen vacancies, and promoting the activation of the surface and the nucleation of neighboring crystallites. The phase transition was studied in Titanium oxide (TiO2) and in Iron oxide (Fe2O3): Maghemite is subjected to a phase transformation to ?-Fe2O3 (hematite), Anatase nanoparticles converts to Rutile. The general mechanism of the phase transition and, more in general, the possibility to optically control the surface activity of metal oxides is discussed.

Ricci, Pier Carlo; Carbonaro, C. M.; Corpino, R.; Chiriu, D.; Stagi, L.

2014-10-01

221

Effect of SiO2 surface chemistry on the oxidation of silicon  

NASA Astrophysics Data System (ADS)

We show that the retardation in the silicon oxidation rate associated with an ammonium hydroxide-hydrogen peroxide preclean is due to trace amounts of aluminum in the region of the SiO2 surface. This aluminum and the retarding effect can be eliminated by removing less than 50 Å of thermal oxide in a HF:H2O etch. Depositing thin films of aluminum with thicknesses between 0.05 and 1 monolayers (ML) on HF cleaned surfaces produced the same retardation as the NH4OH based cleans. These results indicate the importance of the SiO2 surface in silicon oxidation.

deLarios, J. M.; Kao, D. B.; Helms, C. R.; Deal, B. E.

1989-02-01

222

Structure of adsorption layers and conformation transformations of ethylhydroxyethylcellulose on surfaces of titanium and iron oxides  

NASA Astrophysics Data System (ADS)

Regularities of the adsorption of ethylhydroxyethylcellulose (EHEC) hydrophilic polymer on a surface of inorganic pigments of TiO2 and Fe2O3 were investigated by infrared spectroscopy. It was found that the adsorption interaction between EHEC and a surface of oxides is accompanied by conformation transformations of the adsorbed molecules of EHEC. The means by which macromolecules bind with active centers on a surface of metal oxides and the influence of the oxides' nature on the EHEC macromolecule conformation transformations determining the structure of the adsorption layer upon adsorption were established.

Bulychev, N. A.; Fomin, V. N.; Malyukova, E. B.; Ur'ev, N. B.

2011-01-01

223

Vacancy segregation in the initial oxidation stages of the TiN(100) surface.  

PubMed

The well-known corrosion resistance and biocompatibility of TiN depend on the structural and chemical properties of the stable oxide film that forms spontaneously on its surface after exposure to air. In the present work, we focus on the atomistic structure and stability of the TiN(100) surface in contact with an oxidizing atmosphere. The early oxidation stages of TiN(100) are investigated by means of first-principles molecular dynamics (FPMD). We observe selective oxidation of Ti atoms and formation of an ultrathin Ti oxide layer, while Ti vacancies are left behind at the metal/oxide interface. Within the formalism of ab initio thermodynamics we compute the segregation energies of vacancies and vacancy clusters at the metal/oxide interface, comparing the stability of the system obtained by FPMD simulations with ideally reconstructed models. We find that the localization of Ti vacancies in the thin oxide layer and at the TiN/oxide interface is thermodynamically stable and may account for the early removal of N atoms from the interface by segregation of N vacancies from the bulk reservoir. We suggest that superficial oxidation may proceed along two distinct possible pathways: a thermodynamically stable path along the potential energy minimum surface and a metastable, kinetically driven path that results from the high heat release during the dissociation of O(2). PMID:19355771

Zimmermann, Janina; Finnis, Mike W; Ciacchi, Lucio Colombi

2009-04-01

224

Surface modification of polymeric biomaterials with poly(ethylene oxide), albumin, and heparin for reduced thrombogenicity  

Microsoft Academic Search

Appropriate surface modification has significantly improved the blood compatibility of polymeric biomaterials. This article reviews methods of surface modification with water-soluble polymers, such as polyethylene oxide (PEO), albumin, and heparin. PEO is a synthetic, neutral, watersoluble polymer, while albumin and heparin are a natural globular protein and an anionic polysaccharide, respectively. When grafted onto the surface, all three macromolecules share

Mansoor Amiji

1993-01-01

225

Quantitative surface structure determination using in situ high-energy SXRD: Surface oxide formation on Pd(100) during catalytic CO oxidation  

NASA Astrophysics Data System (ADS)

We have performed a quantitative structure determination of the ?{5}×?{5}R27° surface oxide, formed on Pd(100) under semi-realistic conditions for catalytic CO oxidation, using in situ high-energy surface X-ray diffraction. We describe the experiment and the extraction of quantitative data in detail. The structural results are in agreement with previous reports of a system consisting of a single layer of PdO(101) formed in pure O2 on top of Pd(100) and studied under ultra-high vacuum conditions.

Shipilin, Mikhail; Hejral, Uta; Lundgren, Edvin; Merte, Lindsay R.; Zhang, Chu; Stierle, Andreas; Ruett, Uta; Gutowski, Olof; Skoglundh, Magnus; Carlsson, Per-Anders; Gustafson, Johan

2014-12-01

226

Polymeric heterogeneous catalysts of transition-metal oxides: surface characterization, physicomechanical properties, and catalytic activity.  

PubMed

We investigate the physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, specifically, the specific surface area, elongation at break, breaking strength, specific electrical resistance, and volume resistivity. Digital microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. The experimental results show that polymeric heterogeneous catalysts of transition-metal oxides exhibit high stability and can maintain their catalytic activity under extreme reaction conditions for long-term use. The oxidation mechanism of sulfur-containing compounds in the presence of polymeric heterogeneous catalysts of transition-metal oxides is confirmed. Microstructural characterization of the catalysts is performed by using X-ray computed tomography. The activity of various catalysts in the oxidation of sulfur-containing compounds is determined. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment. PMID:24243767

Nhi, Bui Dinh; Akhmadullin, Renat Maratovich; Akhmadullina, Alfiya Garipovna; Samuilov, Yakov Dmitrievich; Aghajanian, Svetlana Ivanova

2013-12-16

227

Effects of additives on volume change on melting, surface tension, and viscosity of liquid aluminum oxide  

NASA Technical Reports Server (NTRS)

The effects of various oxide additives on the volume change on melting, the surface tension, and the viscosity of liquid Al2O3 were studied. Additives of Sm2O3, MgO, and Y2O3 which form solid solutions, compounds, and multiphase solids with Al2O3 were studied. A review of the property data for Al2O3 and Al2O3 containing oxide additives is presented. Oxide additives to Al2O3 reduce the volume change on melting and with the exception of SiO2 lower the viscosity; surface tensions change with oxide additives, but changes vary with different container material. Viscosity and volume change on melting appeared to be significantly more important for studying the properties of liquid oxides than surface tension. Supercooling of 270 K of yttrium aluminum garnet was observed.

Bates, J. L.; Rasmussen, J. J.

1972-01-01

228

Surface kinetics modeling of silicon oxide etching in fluorocarbon plasmas  

E-print Network

Fluorocarbon plasma for silicon oxide etching is a complicated system involving many ion and neutral species. Depending on the plasma condition, many difficulties arise such as RIE lag, etch stop, and low selectivity to ...

Kwon, Ohseung, 1969-

2004-01-01

229

Surface modifications of iron oxide nanoparticles for biological applications  

E-print Network

Iron oxides magnetic nanoparticles (MPs) of high crystallinity, high magnetization, and size-monodispersity were synthesized with oleic acid as their native ligands. These hydrophobic and non-functionalized MPs have magnetic ...

Insin, Numpon

2011-01-01

230

Solid State, Surface and Catalytic Studies of Oxides  

SciTech Connect

This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

Kung, H. H.

2004-11-23

231

Influence of a Cerium surface treatment on the oxidation behavior of type 347 stainless steel  

SciTech Connect

A surface treatment was applied to the surface of Type 347 stainless steel to enhance oxidation resistance. The treatment consisted of dip coating coupons in a CeO2 and halide activator slurry, followed by a thermal treatment at 900C in an inert atmosphere for 12 hours. Cyclical oxidation tests were conducted at 800C in either dry air or air+3%H2O. In dry air, the treatment reduced the oxidation rate (reduced the magnitude of weight gain) of the alloy by a factor of three. Protective chromium based oxide and spinel ((Mn,Cr)3O4 and (Cr,Fe)2O3) phases formed on the surface of the untreated and treated alloy. More significantly, the treatment suppressed the oxide scale spallation that occurred upon cyclical exposure of this alloy to moist air. In moist air, less protective chromite (FeCr2O4), magnetite (Fe+2Fe2+3O4), and hematite (Fe2O3) formed as oxide products on the surface of the base alloy. The treated alloy did not spall during exposure to moist air, and interestingly, the treated alloy possessed similar oxidation rates (magnitude of weight gain) in both moist and dry air. The same protective chromium based oxide and spinel ((Mn,Cr)3O4 and (Cr,Fe)2O3) phases formed on the surface of the treated alloy exposed to both moist and dry air. In the aggressive moist environment, the Ce surface treatment suppressed the formation of less protective iron-oxides, and concomitant oxide scale spallation during thermal cycling.

Alman, D.E.; Jablonski, P.D.

2007-04-01

232

The effect of surface oxides on multi-walled carbon nanotube aqueous colloidal properties  

NASA Astrophysics Data System (ADS)

Carbonaceous nanomaterials are being produced and integrated into consumer products and specialized applications at an accelerating rate. Recently, however, concerns have increased about the environmental, health and safety risks of these nanomaterials, particularly those chemically functionalized to enhance their aqueous colloidal stability and biocompatibility. In this dissertation research, I have investigated the role that surface-oxide concentration plays in the aqueous colloidal stability of multi-walled carbon nanotubes (MWCNTs), a prominent class of engineered nanomaterials. To vary the concentration of surface oxides on the MWCNTs' surface, pristine (unmodified) tubes were treated with a wet-chemical oxidant (e.g., HNO3, H2SO4 /HNO3, KMnO4); the concentration of surface oxides imparted was measured by x-ray photoelectron spectroscopy (XPS). In conjunction with XPS, previously developed chemical derivatization techniques were used to determine the distribution of hydroxyl, carboxyl, and carbonyl functional groups present on the MWCNTs' surface. The length distribution and structural integrity of pristine and oxidized MWCNTs were characterized using atomic force microscopy and transmission electron microscopy, respectively. To examine the aqueous colloidal stability and aggregation properties of oxidized MWCNTs, sedimentation and time-resolved dynamic light scattering (TR-DLS) experiments were conducted on neat (i.e., ideal) suspensions prepared by prolonged sonication of MWCNTs in Milli-Q water. Over a range of environmentally relevant pH values (4--9) and electrolyte (NaCL, CaCl2) concentrations (0.001--1.000 M), the aggregation and colloidal properties of MWCNTs were found to agree with the basic tenants of DLVO theory, in that ( i) more highly oxidized, negatively charged MWCNTs remained stable over a wider range of solution conditions than lowly oxidized tubes, ( ii) oxidized MWCNTs adhered to the empirical Schulze-Hardy rule, and (iii) in early-time aggregation experiments, MWCNTs exhibited reaction- and diffusion-limited aggregation regimes. Structure-property relationships developed during this dissertation research showed that linear correlations existed between MWCNT colloidal stability, XPS measured surface oxidation, and the solution pH. Comparisons between surface charge titrations and electrophoretic mobility (EM) measurements showed that MWCNT colloidal stability was more strongly correlated with surface charge than EM. Analysis of chemical derivatization results indicated that carboxylic functionalities on the MWCNT's surface played a dominate role regulating colloidal stability; however, stronger correlations were observed when colloidal stability was compared to the overall level of surface oxidation. To complement the investigations conducted under ideal solution conditions, the effect that natural organic matter (NOM---an ubiquitous environmental macromolecule) had on the MWCNT's colloidal properties were examined. Before conducting aggregation experiments, a series of NOM adsorption studies were performed. In the first study, NOM adsorption as a function of MWCNT surface oxide concentration was evaluated. Results showed a systematic decrease in NOM adsorption with increasing surface oxidation. In parallel, the sorption of NOM by pristine MWCNTs and a set of highly oxidized tubes was examined under different solution conditions (i.e., pH and ionic strength). NOM adsorption onto pristine MWCNTs was negligibly affected by the solution conditions while NOM sorption by the oxidized MWCNTs increased with increasing ionic strength and decreasing pH. The colloidal stability of MWCNTs was greatly enhanced in the presence of NOM due to steric stabilization, as expected. However, bench top sedimentation and TR-DLS studies indicated that the colloidal stability of lowly oxidized MWCNTs could exceed that of oxidized MWCNTs at environmentally relevant NOM concentrations (˜3 mg/L). Sorption data was used to rationalize these results, in that, because lowly oxidized MWCNTs adsorb more NOM than highly oxidize

Smith, Billy

233

Understanding Surface Processes on Mars Through Study of Iron Oxides/Oxyhydroxides: Clues to Surface Alteration and Aqueous Processes  

NASA Technical Reports Server (NTRS)

We are performing oxidation and reduction reactions on hydrated ferric oxide minerals in order to investigate how these might alter under a variety of conditions on the surface of Mars. Preliminary experiments on ferrihydrite and goethite showed that heating these minerals in a dry oxidizing environment produces fine-grained hematite, while heating these minerals in a reducing environment produces fine-grained magnetite. Under Mars-like oxidation levels this magnetite then oxidizes to maghemite. These reactions are dependent on the presence of water and organic material that can act as a reductant. We are using reflectance and Mossbauer spectroscopy to characterize the reaction products and TEM to analyze the sample texture. Our preliminary results indicate that magnetite and maghemite could be formed in the soil on Mars from ferrihydrite and goethite if organics were present on early Mars.

Bishop, J. L.; Mancinelli, R. L.; Dyar, M. D.; Parente, M.; Drief, A.; Lane, M. D.; Murad, E.

2006-01-01

234

Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides  

E-print Network

As the oxygen reduction reaction (ORR) becomes more critical for development of solid oxide fuel cells (SOFCs) that operate at 500-700 °C, the correlation between the surface chemistry and electrochemical performance is ...

Lee, Wonyoung

235

Diphosphine Dioxide Cages and Hydrogen Peroxide Adducts of Phosphine Oxides: Syntheses and Applications in Surface Science  

E-print Network

and in HRMAS NMR spectra the reduction of the originally large CSA, the residual halfwidth, as well as the downfield shift of the signals when adsorbing phosphine oxides on silica surfaces are most indicative. This research provides new insights regarding...

Hilliard, Casie Renee

2013-12-09

236

Electronic structure of perovskite oxide surfaces at elevated temperatures and its correlation with oxygen reduction reactivity  

E-print Network

The objective is to understand the origin of the local oxygen reduction reaction (ORR) activity on the basis of the local electronic structure at the surface of transition metal oxides at elevated temperatures and in oxygen ...

Chen, Yan, Ph. D. Massachusetts Institute of Technology

2014-01-01

237

Intrinsic stress evolution during amorphous oxide film growth on Al surfaces  

SciTech Connect

The intrinsic stress evolution during formation of ultrathin amorphous oxide films on Al(111) and Al(100) surfaces by thermal oxidation at room temperature was investigated in real-time by in-situ substrate curvature measurements and detailed atomic-scale microstructural analyses. During thickening of the oxide a considerable amount of growth stresses is generated in, remarkably even amorphous, ultrathin Al{sub 2}O{sub 3} films. The surface orientation-dependent stress evolutions during O adsorption on the bare Al surfaces and during subsequent oxide-film growth can be interpreted as a result of (i) adsorption-induced surface stress changes and (ii) competing processes of free volume generation and structural relaxation, respectively.

Flötotto, D., E-mail: d.floetotto@is.mpg.de; Wang, Z. M.; Jeurgens, L. P. H. [Max Planck Institute for Intelligent Systems (former Max Planck Institute for Metals Research), Heisenbergstraße 3, D-70569 Stuttgart (Germany); Mittemeijer, E. J. [Max Planck Institute for Intelligent Systems (former Max Planck Institute for Metals Research), Heisenbergstraße 3, D-70569 Stuttgart (Germany); Institute for Materials Science, University of Stuttgart (Germany)

2014-03-03

238

DOI: 10.1002/cctc.201000006 The Role of Surface Oxides in NOx Storage Reduction Catalysts  

E-print Network

with the increase in fuel efficiency, an increase in the air to fuel ratio also results in heightened pro- duction operation scheme, whereby thermodynamics may not be a controlling factor, it is not clear if the formation pre- vent transformation of a monolayer surface oxide film to the bulk oxide on time scales in excess

239

Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts  

Microsoft Academic Search

A catalyst is described comprising iron carbide supported on a surface modified titania wherein the support comprises an oxide of a metal selected form the group consisting of niobium, vanadium, tantalum or mixture thereof supported on the titania wherein at least a portion of the supported oxide of niobium, vanandium, tantalum or mixture is in a non-crystalline form. The amount

I. E. Wachs; R. A. Fiato; C. C. Chersich

1986-01-01

240

Chemical modification of carbon fiber surfaces by nitric acid oxidation followed by reaction with tetraethylenepentamine  

Microsoft Academic Search

Amino groups react rapidly with both isocyanates and epoxides. Thus, to prepare carbon fibers which might exhibit enhanced adhesion to both polyurethanes and epoxy resin matrices, attempts were made to introduce a high surface amine concentration onto high-strength carbon fibers (derived from PAN) by nitric acid oxidation followed by reaction with excess tetraethylenepentamine (TEPA). Fibers were oxidized with concentrated (70%)

C. U. Pittman; G.-R. He; B. Wu; S. D. Gardner

1997-01-01

241

Effects of moisture and temperature ageing on reliability of interfacial adhesion with black copper oxide surface  

Microsoft Academic Search

This paper reports the recent studies on adhesion performance of copper alloy substrate with bare surface, black oxide coating and black oxide with debleeding treatment. The interfacial adhesion of substrate with polyimide tape and glob top resin were measured after autoclave test (or pressure cooker test, PCT), temperature ageing and thermal cycles based on the button shear and tape peel

Mohamed Lebbai; O. Y. M. Lam; Jang-Kyo Kim

2002-01-01

242

PHYSICAL REVIEW B 83, 035410 (2011) Atomic and electronic surface structures of dopants in oxides  

E-print Network

PHYSICAL REVIEW B 83, 035410 (2011) Atomic and electronic surface structures of dopants in oxides Road, Oxford OX1 3QR, United Kingdom (Received 9 September 2010; published 20 January 2011) High stimulated by its photocatalytic properties,1 use as an anode in solid oxide fuel cells2­4 and in oxygen

Castell, Martin

243

Radiation-induced processes at oxide surfaces and interfaces relevant to spent nuclear fuel storage  

SciTech Connect

Gas generation, oxidation, corrosion, and other important phenomena accompanying the long-term storage of spent nuclear fuel (SNF) are highly affected by radiation-induced processes at oxide surfaces and interfaces. Oxides covering fuel rods and other surfaces, as well as oxide particles dispersed in the aqueous phase, can promote water radiolysis and decomposition. Surface-enhanced water radiolysis may accelerate oxidation, corrosion, and hydriding of Zircaloy, uranium, and other materials and may affect the amount of H{sub 2} and O{sub 2} produced during SNF storage. Mechanisms of surface-enhanced radiolysis are not well understood. Some proposed mechanisms are based on the transfer of energy initially deposited in the bulk of the oxide phase to the interface. This process depends on the oxide electronic structure and on the energetics and geometric structures of the adsorbed molecules. Typically, mobile electrons, holes, and excitons contribute to the enhancement. Their effective range is directly related to carrier mean free paths and excited state lifetimes. These parameters can be studied with a technique known as laser-stimulated luminescence (LSL). The authors present data on the gamma radiation-induced degradation of water at oxide particle/water interfaces and on time-resolved LSL measurements of ZrO{sub 2} recombination luminescence.

Petrik, N.G.; Alexandrov, A.B.; Orlando, T.M.; Vall, A.I.

1999-07-01

244

Vertical Gradient of Net Oxidant near the Ground Surface at Barrow Alaska  

Microsoft Academic Search

surface were investigated. This investigation was corollary to a general long-term ozone program [Kelley, 1967] at a field site near Barrow, Alaska. The measurements, performed by microcoulombmetric analysis, may have been biased by oxides of nitrogen and reductants such as SO2, which are generally found in urban and industrial atmospheres, and by oxidation products produced within the plant canopy. Contamination

J. J. Kelley Jr.; J. D. McTaggart-Cowan

1968-01-01

245

Further studies of the effects of oxidation on the surface properties of coal and coal pyrite  

SciTech Connect

The objective of this research was to investigate the oxidation behavior of coal and coal pyrite and to correlate the changes in the surface properties induced by oxidation, along with the intrinsic physical and chemical properties of these organic and inorganic materials, with the behavior in physical coal cleaning processes. This provide more fundamental knowledge for understanding the way in which different factors interact in a medium as heterogeneous as coal. Fourteen coal samples of different ranks ranging from high to medium sulfur content were studied by dry oxidation tests at different temperatures and humidities, and by wet oxidation tests using different oxidizing agents. The concentration of surface oxygen functional groups was determined by ion-exchange methods. The changes in the coal composition with oxidation were analyzed by spectroscopic techniques. The wettability of as-received and oxidized coal and coal pyrite samples was assessed by film flotation tests. The electrokinetic behavior of different coals and coal pyrite samples was studied by electrokinetic tests using electrophoresis. Possible oxidation mechanisms have been proposed to explain the changes on the coal surface induced by different oxidation treatments.

Herrera, M.N.

1994-12-31

246

Dynamic oxidation behavior of TD-NiCr alloy with different surface pretreatments  

NASA Technical Reports Server (NTRS)

Oxidation tests of TD-NiCr alloy with different surface pretreatments were conducted in a Mach-5 arc-jet at 1200 C and 0.002 lb/sec flowing air environment. The mechanisms responsible for the observed oxidation behavior are examined. The presence of atomic oxygen in the air stream plays a significant role in determining the oxidation characteristic of the alloy. The rate of Cr2O3 vaporization by formation of volatile CrO3 is greatly enhanced by the flowing conditions. The typical microstructure of oxides formed in the dynamic tests consists of an external layer of NiO with a porous mushroom-type morphology, an intermediate layer of NiO and Cr2O3 oxide mixture, and a continuous inner layer of Cr2O3 in contact with the Cr-depleted alloy substrate. Three basic processes underlying the formation of mushroom-type NiO are identified and discussed. The oxidation rate is determined by the rate of vaporization of NiO. Surface pretreatment has a significant effect on the oxidation behavior of the alloy in the early stage of oxidation, but becomes less important as exposure time increases. Mechanical polishing induces surface recrystallization, but promotes the concurrence of external growth of NiO and internal oxidation of the alloy in the dynamic atmosphere.

Young, C. T.; Tenney, D. R.; Herring, H. W.

1975-01-01

247

Evaluation of springtime nitrogen oxide and oxidant data from a suburban\\/rural northeast USA surface site. [PRECP  

Microsoft Academic Search

Full characterization of the air chemistry (gases, particles and meteorology) was accomplished for a rural site in Bucks County, PA during April 1985, in connection with PRECP field experiments. Data from continuous monitoring of nitrogen oxides (NO\\/sub y\\/), nitric acid, ozone and SOâ are used in this evaluation along with PAN analyses every 30 min, meteorological data from surface observations

R. L. Tanner; J. M. Roberts; J. S. Gaffney; D. L. Sisterson

1988-01-01

248

Start | Author Index 699-28 Impact of Mineral Surface Modification on As(III) Oxidation by Mn(IV) Oxides.  

E-print Network

Start | Author Index 699-28 Impact of Mineral Surface Modification on As(III) Oxidation by Mn, and the oxidation and retention of As on the HMO mineral surface is followed in real-time, using quick-scanning X-ray absorption spectroscopy (Q-XAS). We found that initially, only As(V) is retained on the mineral surface

Sparks, Donald L.

249

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces  

NASA Astrophysics Data System (ADS)

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

McBriarty, Martin E.

250

A new advanced surface modification technique--titanium oxide ceramic surface implants: the background and long-term results.  

PubMed

This paper discusses the background of advanced surface modification technologies and presents a new technique that forms a titanium oxide ceramic coating with relatively long-term clinical use. Three general techniques are used to modify surfaces: adding or removing material, or changing material already present. Surface properties can also be changed through laser or electron beam thermal treatment without adding or removing material. The new technique outlined in this paper describes producing a corrosion-resistant, 2000 A to 2500 A thick, coherent crystalline oxide ceramic layer on the surface of titanium implants. The layer is grown electrochemically from the bulk of the metal and modified by heat treatment. Compared with implants covered with other coatings, the improved properties of such oxide ceramic-coated implants include the advantages of higher external hardness and greater adherence between the titanium and the ceramic oxide coating. The virtually perfect insulation between the tissue and the metal prevents metal allergy. The coated implants were subjected to various physical and chemical tests and electron microscopy for a qualitative characterization. Finally, these implants (plates, screws for maxillofacial osteosynthesis, and dental root implants) were followed in surgical practice for 10 years. Tests demonstrated and the acquired experience confirmed the good properties of the titanium oxide ceramic-coated implants. PMID:10847966

Szabó, G; Kovács, L; Vargha, K; Barabás, J; Németh, Z

1999-01-01

251

The design, synthesis, and use of phosphonic acids for the surface modification of metal oxides  

NASA Astrophysics Data System (ADS)

The design and synthesis of a large variety of novel phosphonic acids has been described. Phosphonic acids are known to bind strongly to the surface of a number of metal oxides. The phosphonic acids designed and synthesized herein were used to modify the surface of both planar and nanoparticle metal oxides for use in a variety of applications. Indium tin oxide (ITO) substrates were modified with different fluorinated phosphonic acids in order to tune both the work function and the surface energy of the material. These changes in surface properties resulted in increased performance when the surface-modified ITO was incorporated into organic electronic devices. Additionally, the binding of phosphonic acids to a number of metal oxide species was studied. It has been shown that phosphonic acids bind strongly (bi- and tridentate) to ITO, zinc oxide (ZnO), and barium titanate (BaTiO3). Phosphonic acids bind to a variety of other metal oxides via at least a monodentate binding. More generally, the roles of monolayers in surface science and the properties they can tune are discussed.

Hotchkiss, Peter J.

252

Origin of complex impact craters on native oxide coated silicon surfaces  

SciTech Connect

Crater structures induced by impact of keV-energy Ar{sub n}{sup +} cluster ions on silicon surfaces are measured with atomic force microscopy. Complex crater structures consisting of a central hillock and outer rim are observed more often on targets covered with a native silicon oxide layer than on targets without the oxide layer. To explain the formation of these complex crater structures, classical molecular dynamics simulations of Ar cluster impacts on oxide coated silicon surfaces, as well as on bulk amorphous silica, amorphous Si, and crystalline Si substrates, are carried out. The diameter of the simulated hillock structures in the silicon oxide layer is in agreement with the experimental results, but the simulations cannot directly explain the height of hillocks and the outer rim structures when the oxide coated silicon substrate is free of defects. However, in simulations of 5 keV/atom Ar{sub 12} cluster impacts, transient displacements of the amorphous silicon or silicon oxide substrate surfaces are induced in an approximately 50 nm wide area surrounding the impact point. In silicon oxide, the transient displacements induce small topographical changes on the surface in the vicinity of the central hillock. The comparison of cluster stopping mechanisms in the various silicon oxide and silicon structures shows that the largest lateral momentum is induced in the silicon oxide layer during the impact; thus, the transient displacements on the surface are stronger than in the other substrates. This can be a reason for the higher frequency of occurrence of the complex craters on oxide coated silicon.

Samela, Juha; Nordlund, Kai; Popok, Vladimir N.; Campbell, Eleanor E. B. [Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 Espoo (Finland); Department of Physics, Gothenburg University, 41296 Gothenburg (Sweden); Department of Physics, Gothenburg University, 41296 Gothenburg, Sweden and School of Chemistry, Edinburgh University, West Mains Road, Edinburgh EH9 3JJ, Scotland (United Kingdom)

2008-02-15

253

Outer Cell Surface Components Essential for Fe(III) Oxide Reduction by Geobacter metallireducens  

PubMed Central

Geobacter species are important Fe(III) reducers in a diversity of soils and sediments. Mechanisms for Fe(III) oxide reduction have been studied in detail in Geobacter sulfurreducens, but a number of the most thoroughly studied outer surface components of G. sulfurreducens, particularly c-type cytochromes, are not well conserved among Geobacter species. In order to identify cellular components potentially important for Fe(III) oxide reduction in Geobacter metallireducens, gene transcript abundance was compared in cells grown on Fe(III) oxide or soluble Fe(III) citrate with whole-genome microarrays. Outer-surface cytochromes were also identified. Deletion of genes for c-type cytochromes that had higher transcript abundance during growth on Fe(III) oxides and/or were detected in the outer-surface protein fraction identified six c-type cytochrome genes, that when deleted removed the capacity for Fe(III) oxide reduction. Several of the c-type cytochromes which were essential for Fe(III) oxide reduction in G. metallireducens have homologs in G. sulfurreducens that are not important for Fe(III) oxide reduction. Other genes essential for Fe(III) oxide reduction included a gene predicted to encode an NHL (Ncl-1–HT2A–Lin-41) repeat-containing protein and a gene potentially involved in pili glycosylation. Genes associated with flagellum-based motility, chemotaxis, and pili had higher transcript abundance during growth on Fe(III) oxide, consistent with the previously proposed importance of these components in Fe(III) oxide reduction. These results demonstrate that there are similarities in extracellular electron transfer between G. metallireducens and G. sulfurreducens but the outer-surface c-type cytochromes involved in Fe(III) oxide reduction are different. PMID:23183974

Smith, Jessica A.; Lovley, Derek R.

2013-01-01

254

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface  

SciTech Connect

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

Fazleev, N. G. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States) and Institute of Physics, Kazan Federal University, Kremlevskaya18, Kazan 420008 (Russian Federation); Weiss, A. H. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States)

2013-04-19

255

Facile surface PEGylation via tyrosinase-catalyzed oxidative reaction for the preparation of non-fouling surfaces.  

PubMed

The control of biological interactions that occur at material-cell/blood interfaces is of great importance to help maximize in vitro and in vivo performance of biomedical devices. PEGylation has been extensively used as an effective surface modification tool that can alter biological responses on device surfaces. Herein, we report a new surface PEGylation method using a tyrosinase-catalyzed oxidative reaction. Tyramine (TA), an enzymatically active phenolic compound, was chemically conjugated to methoxy poly(ethylene glycol) (mPEG). Surface immobilization of mPEG-TA onto various substrates was accomplished simply and rapidly by adding tyrosinase under mild conditions. It was shown that the water contact angles on all surfaces modified with mPEG-TA were decreased, indicating successful introduction of hydrophilic PEG. In addition, the X-ray photoelectron spectroscopy (XPS) spectra demonstrated the differences in the atomic composition on the TiO(2) surface after treatment with mPEG-TA. Non-fouling surfaces prevent non-specific interactions with proteins and cells; consistently, the PEGylated TiO(2) surface clearly showed a decrease in both levels of bovine serum albumin (BSA) adsorption and NIH3T3 cell attachment. Therefore, the facile surface PEGylation using a tyrosinase-catalyzed oxidative reaction should be useful for designing non-fouling surfaces of biomedical devices. PMID:23104029

Lee, Yunki; Park, Kyung Min; Bae, Jin Woo; Park, Ki Dong

2013-02-01

256

Role of surface complexed iron in oxidant generation and lung inflammation induced by silicates  

SciTech Connect

The hypothesis was tested that silica and silicate dusts complex iron on their surface and that this iron increases (1) in vitro oxidant generation, and mediator release by alveolar macrophages, and (2) acute inflammatory lung injury. Silica and silicates were found to complex more than ten times the Fe(3+) onto their surfaces than did a biologically inactive dust, titanium dioxide. In vivo generation of oxidants by alveolar macrophages measured after exposure to dusts was increased by surface complexed iron. Also, acute inflammatory lung injury after intratracheal injection of silica dusts was made more severe by surface iron. The authors conclude that silica and silicate surfaces complex Fe(3+) to increase oxidant generation and mediator release by alveolar macrophages, and to increase acute lung injury in the rat.

Ghio, A.J.; Kennedy, T.P.; Whorton, A.R.; Crumbliss, A.L.; Hatch, G.E.

1993-01-01

257

In?situ observation of surface species on iridium oxide nanoparticles during the oxygen evolution reaction.  

PubMed

An iridium oxide nanoparticle electrocatalyst under oxygen evolution reaction conditions was probed in?situ by ambient-pressure X-ray photoelectron spectroscopy. Under OER conditions, iridium undergoes a change in oxidation state from Ir(IV) to Ir(V) that takes place predominantly at the surface of the catalyst. The chemical change in iridium is coupled to a decrease in surface hydroxide, providing experimental evidence which strongly suggests that the oxygen evolution reaction on iridium oxide occurs through an OOH-mediated deprotonation mechanism. PMID:24889896

Sanchez Casalongue, Hernan G; Ng, May Ling; Kaya, Sarp; Friebel, Daniel; Ogasawara, Hirohito; Nilsson, Anders

2014-07-01

258

Oxygen desorption from molybdenum oxide by synchrotron radiation and its surface-cleaning applications  

NASA Astrophysics Data System (ADS)

The effects of synchrotron radiation (SR) irradiation on molybdenum oxide are studied. Removal of native molybdenum oxide by SR irradiation is observed by reflection high-energy electron diffraction and Auger-electron spectroscopy measurements. SR irradiation changes MoO3 thin films to MoO2. Indications are that SR-stimulated oxygen desorption is the cause. Those SR-irradiated molybdenum surfaces which are originally covered with native oxide are found to be highly reactive with disilane gas, while nonirradiated surfaces are not.

Nagase, Masao; Utsumi, Yuichi; Akawaza, Housei; Urisu, Tsuneo

1993-01-01

259

Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics  

SciTech Connect

during the seventh quarter, electrokinetic, humic acid extraction and film flotation tests were done on oxidized samples of Upper Freeport coal from the Troutville {number sign} 2 Mine, Clearfield County, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis was done to characterize the morphology and composition of the surface of as-received coal, oxidized coal, oxidized coal after extraction of humic acids and humic acid extracted from oxidized coal. In addition, electrochemical studies were done on electrodes prepared from coal pyrite samples.

Doyle, F.M.

1992-06-30

260

High-Resolution Electron Energy Loss Studies of Oxygen, Hydrogen, Nitrogen, Nitric Oxide, and Nitrous Oxide Adsorption on Germanium Surfaces.  

NASA Astrophysics Data System (ADS)

The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting compounds Mg _2Sn, Mg_2Ge and Mg _2Si were detected at 29, 32, and 40 meV, respectively. The native oxide of all three show a dominant Mg-O mode at 80 meV. Probable Sn-O, Ge-O, and Si-O modes are also identified. Complete removal of the oxide layer was accomplished only on the Mg_2 Si surface but resulted in no noticeable change in the energy of the surface phonon. Results are compared to the known bulk optical properties of these compounds.

Entringer, Anthony G.

261

Modification on surface oxide layer structure and surface morphology of niobium by gas cluster ion beam treatments  

SciTech Connect

Recently, it was demonstrated that significant reductions in field emission on Nb surfaces could be achieved by means of a new surface treatment technique called gas cluster ion beam (GCIB). Further study as shown in this paper revealed that GCIB treatments could modify surface irregularities and remove surface asperities leading to a smoother surface finish as demonstrated through measurements using a 3D profilometer, an atomic force microscope, and a scanning electron microscope. These experimental observations were supported by computer simulation via atomistic molecular dynamics and a phenomenological surface dynamics. Measurements employing a secondary ion mass spectrometry found that GCIB could also alter Nb surface oxide layer structure. Possible implications of the experimental results on the performance of Nb superconducting radio frequency cavities treated by GCIB will be discussed. First experimental results on Nb single cell superconducting radio frequency cavities treated by GCIB will be reported.

A. T. Wu, D. R. Swenson, Z. Insepov

2010-09-01

262

Fe(VI) as a Possible Oxidant on the Martian Surface  

NASA Technical Reports Server (NTRS)

The essential findings of the three biological experiments (Gas Exchange, Labeled Released, and Pyrolitic Release) aboard the Viking Mars landers were the discovery of the presence of one or more strong oxidants on the Martian surface. The Gas Exchange experiments showed that wetting Martian soil leads to the evolution of oxygen, while in the Labeled Release experiment addition of a nutrient solution containing C-14-labeled formate, glycine, lactate, alanine, and glycolic acid induced CO2 evolution. A general consensus was reached that all data taken together pointed to the presence on Martian surface of a strong oxidant, or most probably several different types of oxidants. Several candidates have been proposed as oxidants, including superoxides, hydrogen peroxide, and iron oxides (possibly gamma-Fe2O3). Additional information is contained in the original extended abstract.

Tsapin, A. I.; Goldfeld, M. G.; McDonald, G. D.; Nealson, K. H.

1999-01-01

263

Characterization of bioactive surface oxidation layer on NiTi alloy  

NASA Astrophysics Data System (ADS)

To enhance the bioactivity of NiTi alloy, the surface oxidation layers were synthesized by heat treatment in air in the temperature range of 300-800 °C. The surface oxidation layer on NiTi alloy was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The heat treated sample was soaked in simulated body fluid (SBF) to study the bioactivity of the thermally grown oxide layer. Results showed that a protective layer of TiO 2 was formed on the surface of NiTi alloy at heat treatment temperatures of 600 °C or higher with varying degree of anatase and rutile. Small amount of nickel oxide was found on the surface of 300 and 400 °C treated samples by X-ray photoelectron spectroscopy. With further increase in the heat treatment temperature, the nickel concentration on the surface decreased and there was almost no nickel species on the surface after heat treatment at 600 °C or 800 °C. Depth profiling revealed that the amount of TiO 2 (Ti 4+) decreased with depth with a concomitant increase of metallic Ti. In addition, both TiO (Ti 2+) and Ti 2O 3 (Ti 3+) increased initially and then decreased gradually with depth. Ni existed mainly in the oxidized state on the surface of heat treated samples and it changed to metallic state with increasing depth. In vitro test revealed that the titanium oxide layer formed on the 600 and 800 °C heat treated samples was bioactive, and a layer of apatite was formed on the surface of the titanium oxide layer after soaking in simulated body fluid.

Gu, Y. W.; Tay, B. Y.; Lim, C. S.; Yong, M. S.

2005-12-01

264

Rates of oxidative weathering on the surface of Mars  

NASA Technical Reports Server (NTRS)

A model of acid weathering is proposed for the iron-rich basalts on Mars. Aqueous oxidation of iron sulfides released SO4(2-) and H(+) ions that initiated the dissolution of basaltic ferromagnesian silicates and released Fe(2+) ions. The Fe(2+) ions eventually underwent ferrolysis reactions and produced insoluble hydrous ferric oxide phases. Measurements of the time-dependence of acid weathering reactions show that pyrrhotite is rapidly converted to pyrite plus dissolved ferrous iron, the rate of pyrite formation decreasing with rising pH and lower temperatures. On Mars, oxidation rates of dissolved Fe(2+) ions in equatorial melt-waters in contact with the atmosphere are estimated to lie in the range 0.3-3.0 ppb Fe/yr over the pH range 2 to 6. Oxidation of Fe(2+) ions is estimated to be extremely slow in brine eutectic solutions that might be present on Mars and to be negligible in the frozen regolith.

Burns, Roger G.; Fisher, Duncan S.

1993-01-01

265

Large area nanoscale patterning of silicon surfaces by parallel local oxidation.  

PubMed

The homogeneity and the reproducibility of parallel local oxidation have been improved by introducing a thin film of polymethylmethacrylate (PMMA) between the stamp and the silicon surface. The flexibility of the polymer film enables a homogeneous contact of the stamp with the silicon surface to be achieved. The oxides obtained yield better aspect ratios compared with the ones created with no PMMA layer. The pattern is formed when a bias voltage is applied between the stamp and the silicon surface for 1 min. The patterning can be done by a step and repeat technique and is reproducible across a centimetre length scale. Once the oxide nanostructures have been created, the polymer is removed by etching in acetone. Finally, parallel local oxidation is applied to fabricate silicon nanostructures and templates for the growth of organic molecules. PMID:19875876

Losilla, N S; Martínez, J; García, R

2009-11-25

266

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes  

NASA Astrophysics Data System (ADS)

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

267

Apatite deposition on thermally and anodically oxidized titanium surfaces in a simulated body fluid.  

PubMed

By application of a special specimen set-up, thermally oxidized titanium specimen pairs were found able to deposit apatite on the contact surfaces after soaking for 7 days in the simulated body fluid (SBF) of Kokubo's recipe. The specimens oxidized at 400 degrees C and 500 degrees C showed the highest ability of apatite deposition. Both increase and decrease in oxidation temperature from this range caused the apatite deposition ability to decrease. The specimen without treatment failed to deposit any apatite. Specimens anodically oxidized in electrolytes of H(3)PO(4), H(2)SO(4) and acetic acid exhibited very low ability of apatite deposition. Furthermore, the specimen thermally oxidized at 400 degrees C was even able to help the surfaces of PTFE and silicone deposit apatite in the PTFE-Ti and silicone-Ti pairs. This in vitro experimental results indicated that the difference in apatite deposition among various titanium oxides does exist and can be distinguished by applying the present specimen set-up. The mechanism of the apatite deposition on the contact surfaces was discussed in relation to the passive dissolution of titanium in SBF. The release of titanium hydroxide and OH(-) ions from the titanium surfaces and their accumulation inside the confined space between the two contact surfaces were suggested to be responsible for the apatite deposition. PMID:12951006

Wang, Xiao-Xiang; Yan, Wei; Hayakawa, Satoshi; Tsuru, Kanji; Osaka, Akiyoshi

2003-11-01

268

Electrically polarized micro-arc oxidized TiO2 coatings with enhanced surface hydrophilicity.  

PubMed

The use of micro-arc oxidation titania (MAO TiO2) coatings to modify titanium surfaces improves the biocompatibility of implant surfaces. To obtain hydrophilic MAO TiO2 coating surfaces electric polarization, which induces surface electric fields in the materials and produces surface charges, was performed in this study. Electric polarization of the MAO TiO2 coatings was confirmed by measuring the thermally stimulated depolarization current. After electric polarization treatment the MAO TiO2 coatings did not exhibit any obvious changes in surface roughness, morphology, or phase components. X-ray photoelectron spectroscopy results indicated that electric polarization resulted in oxidation of the cathodic-faced surfaces and reduction of the anodic-faced surfaces. This result suggests that the existence of a concentration gradient of oxide ions/oxygen vacancies produced the stored space charge in the coatings. Reduction of the deionized water contact angle on the polarized MAO TiO2 surfaces was maintained for longer periods compared with the non-polarized surface. Our study demonstrated that metastable electric fields across the MAO TiO2 coating produced by electric polarization made it durably wettable by reducing the interfacial surface tension between the material and water. PMID:21971419

Ma, Chufan; Nagai, Akiko; Yamazaki, Yuko; Toyama, Takeshi; Tsutsumi, Yusuke; Hanawa, Takao; Wang, Wei; Yamashita, Kimihiro

2012-02-01

269

Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces  

NASA Astrophysics Data System (ADS)

Sulfate and phosphate, oxoanions common in natural systems, affect iron oxide growth and dissolution processes, the adsorption behavior of divalent cations, and iron oxide phase transformations. These oxoanions may thus influence Fe(II) adsorption behavior and subsequently alter the mechanisms and products of Fe(II)-catalyzed Fe(III) oxide recrystallization processes, such as trace metal repartitioning. In this study, the macroscopic and molecular-scale effects of the coadsorption of Fe(II) and sulfate or phosphate onto Fe(III) oxide surfaces were investigated. Macroscopic adsorption edges show that both sulfate and phosphate increase Fe(II) adsorption and that Fe(II) increases sulfate and phosphate adsorption. Attenuated total reflectance Fourier transform infrared spectroscopy shows that the cooperative adsorption behavior of oxoanions and aqueous Fe(II) likely results from a combination of ternary complexation and electrostatic interactions. Surface complexation modeling requires the inclusion of ternary complexes to simulate all conditions of the macroscopic data, further suggesting that these oxoanions and Fe(II) form ternary complexes on Fe(III) oxide surfaces. Despite clear evidence in previous research for Fe(II) oxidation upon adsorption on iron oxide surfaces, this work shows that Fe(II) also displays macroscopic and molecular-scale behaviors associated with divalent (i.e., non-oxidative) cation adsorption. Prior work has shown that metal release from iron oxides caused by ET-AE reactions is directly proportional to the macroscopically-determined Fe(II) surface coverage. Predicting the effects of sulfate and phosphate on processes controlled by ET-AE reactions at redox interfaces, such as mineral phase transformations and trace element repartitioning, may thus not require the explicit consideration of electron transfer processes.

Hinkle, Margaret A. G.; Wang, Zimeng; Giammar, Daniel E.; Catalano, Jeffrey G.

2015-06-01

270

Ferrous iron oxidation under acidic conditions - The effect of ferric oxide surfaces  

NASA Astrophysics Data System (ADS)

In this study, the kinetics of Fe(II) oxidation in the presence of the iron oxyhydroxides ferrihydrite, Si-ferrihydrite, schwertmannite, lepidocrocite and goethite are investigated over the pH range 4-5.5. Despite limited sorption of Fe(II), the rate of Fe(II) oxidation is up to 70-fold faster than in the absence of any Fe oxyhydroxide phase over pH 4.5-5.5. Enhanced Fe(II) oxidation was minor or negligible at pH 4 with undetectable amounts of Fe(II) adsorbed to the iron oxyhydroxides at this pH. Heterogeneous rate constants derived from kinetic modeling were normalized to the concentration of adsorbed Fe(II) and deviated by no more than 13.8% at pH 4.5, 5 and 5.5, indicating that oxidation is proportional to the concentration of adsorbed Fe(II). Average rate constants were found to be: 2.12 ± 0.20, 1.30 ± 0.09, 1.69 ± 0.22, 1.20 ± 0.08 and 0.68 ± 0.09 M-1 s-1 for ferrihydrite, goethite, lepidocrocite, schwertmannite and Si-ferrihydrite, respectively. The role of reactive oxygen species, such as hydrogen peroxide, the hydroxyl radical and superoxide, towards the overall oxidation of Fe(II) was examined but found to have only a minor impact on Fe(II) oxidation when compared to the effect of heterogeneous oxidation.

Jones, Adele M.; Griffin, Phillipa J.; Collins, Richard N.; Waite, T. David

2014-11-01

271

Geochemical modelling of arsenic adsorption to oxide surfaces  

Microsoft Academic Search

In natural environments, arsenic chemistry is dominated by the reactions of its two predominant soluble forms, arsenate and arsenite. To predict the fate of As in the environment, it is necessary to consider processes that act to restrict its mobility. The mobility of As is strongly influenced by adsorption reactions to particle surfaces. Arsenate and arsenite may form surface complexes

J. P. Gustafsson; P. Bhattacharya

2007-01-01

272

Development of a classical force field for the oxidized Si surface: Application to hydrophilic wafer bonding  

NASA Astrophysics Data System (ADS)

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO2 polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90mJ /m2, respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166mJ/m2), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account.

Cole, Daniel J.; Payne, Mike C.; Csányi, Gábor; Mark Spearing, S.; Colombi Ciacchi, Lucio

2007-11-01

273

Development of a classical force field for the oxidized Si surface: application to hydrophilic wafer bonding.  

PubMed

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO(2) polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90 mJm(2), respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166 mJm(2)), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account. PMID:18052443

Cole, Daniel J; Payne, Mike C; Csányi, Gábor; Spearing, S Mark; Colombi Ciacchi, Lucio

2007-11-28

274

Surface spectroscopic characterization of oxide thin films and bimetallic model catalysts  

E-print Network

of the surface morphology and electronic/geometric structure of the following catalysts: SiO2/Mo(112), Ag/SiO2/Mo(112), Au–Pd/Mo(110), Au–Pd/SiO2/Mo(110), and Pd– Sn/Rh(100). Specifically, different types of oxide surface defects were directly identified by MIES...

Wei, Tao

2009-05-15

275

Surfactant Organic Molecules Restore Magnetism in Metal-Oxide Nanoparticle Surfaces  

E-print Network

Surfactant Organic Molecules Restore Magnetism in Metal-Oxide Nanoparticle Surfaces Juan Salafranca, Nashville, Tennessee 37235, United States *S Supporting Information ABSTRACT: The properties of magnetic nanoparticles tend to be depressed by the unavoidable presence of a magnetically inactive surface layer. However

Pennycook, Steve

276

CO Oxidation on the Pd(111) Surface Zhiyao Duan and Graeme Henkelman*  

E-print Network

. INTRODUCTION Pd is a widely used catalyst in catalytic converters for the oxidation of CO and unburnt fuel catalytically relevant gas-phase conditions. Three-fold oxygen atoms in the surface are found to react with gas, will dramatically influence the catalytic reaction mechanism. Due to the complex nature of the catalyst surface

Henkelman, Graeme

277

Wet etching of InSb surfaces in aqueous solutions: Controlled oxide formation  

NASA Astrophysics Data System (ADS)

This paper investigates the wet etching of InSb surfaces by two different oxidant agents: Br2 and H2O2 and the consecutive oxides generation onto the surfaces. The strong dependence between the chemical composition of the etching baths and the nature of the final surface chemistry of this low band-gap III-V semiconductor will be especially highlighted. One aqueous etching solution combined hydrobromic acid and Bromine (HBr-Br2:H2O) with adjusted concentrations. The other solution combines orthophosphoric and citric acids with hydrogen peroxide (H3PO4-H2O2:H2O). Depending on its composition, each formulation gave rise to variable etching rate. The dosage of Indium traces in the etching solution by atomic absorption spectroscopy (AAS) gives the kinetic variation of the dissolution process. The variations on etching rates are associated to the properties and the nature of the formed oxides on InSb surfaces. Surface characterization is specifically performed by X-ray photoelectron spectroscopy (XPS). A clear evidence of the differences between the formed oxides is highlighted. Atomic force microscopy is used to monitor the surface morphology and pointed out that very different final morphologies can be reached. This paper presents new results on the strong variability of the InSb oxides in relation with the InSb reactivity toward environment interaction.

Aureau, D.; Chaghi, R.; Gerard, I.; Sik, H.; Fleury, J.; Etcheberry, A.

2013-07-01

278

Colloids and Surfaces B: Biointerfaces 36 (2004) 8190 Bacterial adhesion to glass and metal-oxide surfaces  

E-print Network

metal-oxide thin films prepared on the upper (non-tin-exposed) side of float glass by chemical vaporColloids and Surfaces B: Biointerfaces 36 (2004) 81­90 Bacterial adhesion to glass and metal the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength (1 and 100 m

279

Vanadium surface oxides on Pd(111): A structural analysis  

Microsoft Academic Search

Scanning tunneling microscopy studies of vanadium oxides grown on Pd(111) show interesting structures especially in the low-coverage region. Evaporation of V in an oxygen background at elevated sample temperature (250 °C) results in the formation of a nonperiodic honeycomb-like structure growing from the steps, which starts to transform into an ordered phase at a vanadium coverage of ≈0.2 ML (monolayer).

C. Klein; G. Kresse; S. Surnev; F. P. Netzer; M. Schmid; P. Varga

2003-01-01

280

Structure of peptides on metal oxide surfaces probed by NMR.  

PubMed

Peptides that bind inorganic surfaces and template the formation of nanometer-sized inorganic particles are of great interest for the self- or directed assembly of nanomaterials for sensors and diagnostic applications. These surface-recognizing peptides can be identified from combinatorial phage-display peptide libraries, but little experimental information is available for understanding the relationship between the peptide sequence, structure at the nanoparticle surface, and function. We have developed NMR methods to determine the structures of peptides bound to inorganic nanoparticles and report on the structure of three peptides bound to silica and titania surfaces. Samples were prepared under conditions leading to rapid peptide exchange at the surface such that solution-based nuclear Overhauser experiments can be used to determine the three-dimensional structure of the bound peptide. The binding motif is defined by a compact "C"-shaped structure for the first six amino acids in the 12-mer. The orientation of the peptide on the nanoparticle surface was determined by magnetization transfer from the nanoparticle surface to the nearby peptide protons. These methods can be applied to a wide variety of abiotic interfaces to provide an insight into the relationship between the primary sequence of peptides and their functionality at the interface. PMID:21981074

Mirau, Peter A; Naik, Rajesh R; Gehring, Patricia

2011-11-16

281

Octadecanethiol Island Formation on Single Crystal Zinc Oxide Surfaces  

NASA Astrophysics Data System (ADS)

Organic photovoltaic devices, containing ZnO nanorod electron acceptor arrays intercalated with organic polymers, could lead to low-cost solar cells. Surface modifications of ZnO with octadecanethiol (ODT) monolayers have been shown to improve charge transfer in such devices. The present work is an effort to understand these monolayers through studies of ODT on single crystals of ZnO with well-defined oxygen-terminated or zinc-terminated surfaces. Both bare and ODT- functionalized surfaces were characterized with atomic force microscopy, Fourier transform infrared spectroscopy, x-ray photoemission spectroscopy, and water contact angle measurements. ODT seemed to form islands of multilayers on zinc-terminated surfaces and islands of monolayers on oxygen- terminated surfaces. While ODT was expected to preferentially bond along defects and terraces on oxygen-terminated surfaces, this was not observed. ODT was also expected to more effectively bond to the zinc-terminated surface, which was observed. This work was supported by the National Science Foundation Division of Materials Research DMR-0606054, DMR-0907409, and the Renewable Energy Materials Research Science and Engineering Center at the Colorado School of Mines.

Yocom, Andrea; Collins, Reuben; Furtak, Thomas; Baker, Darick; Ohno, Timothy

2010-03-01

282

Study of water adsorption on activated carbons with different degrees of surface oxidation  

SciTech Connect

A carbon of wood origin was oxidized with different oxidizing agents (nitric acid, hydrogen peroxide, and ammonium persulfate). The microstructural properties of the starting material and the oxidized samples were characterized using sorption of nitrogen. The surface acidity was determined using Boehm titration and potentiometric titration. The changes in the surface chemistry were also studied by diffuse reflectance FTIR. Water adsorption isotherms were measured at three different temperatures close to ambient (relative pressure from 0.001 to 0.3). From the isotherms the heats of adsorption were calculated using a virial equation. The results indicated that the isosteric heats of water adsorption are affected by the surface heterogeneity only at low surface coverage. In all cases the limiting heat of adsorption was equal to the heat of water condensation (45 kJ/mol).

Salame, I.I.; Bandosz, T.J. [City Coll. of New York, NY (United States). Dept. of Chemistry] [City Coll. of New York, NY (United States). Dept. of Chemistry; [City Univ. of New York, NY (United States). Graduate School

1999-02-15

283

Surface Engineering of Core/Shell Iron/Iron Oxide Nanoparticles from Microemulsions for Hyperthermia  

PubMed Central

This paper describes the synthesis and surface engineering of core/shell-type iron/iron oxide nanoparticles for magnetic hyperthermia cancer therapy. Iron/iron oxide nanoparticles were synthesized from microemulsions of NaBH4 and FeCl3, followed by surface modification in which a thin hydrophobic hexamethyldisilazane layer - used to protect the iron core - replaced the CTAB coating on the particles. Phosphatidylcholine was then assembled on the nanoparticle surface. The resulting nanocomposite particles have a biocompatible surface and show good stability in both air and aqueous solution. Compared to iron oxide nanoparticles, the nanocomposites show much better heating in an alternating magnetic field. They are good candidates for both hyperthermia and magnetic resonance imaging applications. PMID:21833157

Zhang, Guandong; Liao, Yifeng; Baker, Ian

2011-01-01

284

Intermolecular potential energy surface and thermophysical properties of ethylene oxide.  

PubMed

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide. PMID:25362314

Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

2014-10-28

285

Intermolecular potential energy surface and thermophysical properties of ethylene oxide  

SciTech Connect

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

Crusius, Johann-Philipp, E-mail: johann-philipp.crusius@uni-rostock.de; Hassel, Egon [Lehrstuhl für Technische Thermodynamik, Universität Rostock, 18059 Rostock (Germany); Hellmann, Robert; Bich, Eckard [Institut für Chemie, Universität Rostock, 18059 Rostock (Germany)

2014-10-28

286

Intermolecular potential energy surface and thermophysical properties of ethylene oxide  

NASA Astrophysics Data System (ADS)

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

2014-10-01

287

Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.  

PubMed

TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery. PMID:24291076

Carlsson, Daniel O; Hua, Kai; Forsgren, Johan; Mihranyan, Albert

2014-01-30

288

Effects of different surfaces on the transport and deposition of ruthenium oxides in high temperature air  

NASA Astrophysics Data System (ADS)

In order to understand the behaviour of ruthenium oxides in the reactor coolant system during an air ingress accident, new tests were performed in the frame of the RUSET (RUthenium Separate Effect Test) experimental program. These aimed to ascertain the effects of different surfaces (quartz, stainless steel (SS), zirconium alloy, alumina, oxidised metal, and surfaces with Mo or Cs deposits) on the transport and decomposition of ruthenium oxides in air stream along the temperature gradient zone (1100-100 °C). The results demonstrated that the heterogeneous phase decomposition of RuO 3 and RuO 4 to RuO 2 is catalysed more efficiently by the quartz surface than by the SS or alumina surfaces. The presence of MoO 3 layers decreased the RuO x precipitation extent on all investigated surfaces. The trapping effect of Cs deposit on Ru in the temperature gradient zone was proved in the case of the SS surface. On the contrary, presence of Cs precipitate on alumina and especially on quartz surfaces was found to decrease their catalytic effect on the decomposition of ruthenium oxides, and thus increased the RuO 4 concentration in the outlet air. Similarly to the effect observed for Cs deposition, the presence of other fission products in the evaporation area (at 1100 °C) decreased the partial pressure of RuO 4 in the outlet air at the SS surface and increased it at quartz and alumina surfaces. When zirconium (E110) cladding material was placed in the temperature gradient zone, no Ru transmittance occurred until the high temperature end of the zirconium tube was completely oxidised. After the intense oxidation of E110, Ru release occurred only in the presence of other fission product species. Pre-oxidation of SS surfaces in steam had no significant effect on the Ru passage.

Vér, N.; Matus, L.; Pintér, A.; Osán, J.; Hózer, Z.

2012-01-01

289

SPECTROSCOPIC STUDY OF SURFACE REDOX REACTIONS WITH MANGANESE OXIDES  

EPA Science Inventory

Redox reactions involving soil minerals and materials are important processes in environmental chemistry, but unfortunately they only have been characterized in the solution phase. he lack of a suitable method has prevented investigations of the mineral surface component of redox...

290

[A method of temperature measurement for hot forging with surface oxide based on infrared spectroscopy].  

PubMed

High temperature large forging is covered with a thick oxide during forging. It leads to a big measurement data error. In this paper, a method of measuring temperature based on infrared spectroscopy is presented. It can effectively eliminate the influence of surface oxide on the measurement of temperature. The method can measure the surface temperature and emissivity of the oxide directly using the infrared spectrum. The infrared spectrum is radiated from surface oxide of forging. Then it can derive the real temperature of hot forging covered with the oxide using the heat exchange equation. In order to greatly restrain interference spectroscopy through included in the received infrared radiation spectrum, three interference filter system was proposed, and a group of optimal gap parameter values using spectral simulation were obtained. The precision of temperature measurement was improved. The experimental results show that the method can accurately measure the surface temperature of high temperature forging covered with oxide. It meets the requirements of measurement accuracy, and the temperature measurement method is feasible according to the experiment result. PMID:22827063

Zhang, Yu-cun; Qi, Yan-de; Fu, Xian-bin

2012-05-01

291

Water oxidation surface mechanisms replicated by a totally inorganic tetraruthenium–oxo molecular complex  

PubMed Central

Solar-to-fuel energy conversion relies on the invention of efficient catalysts enabling water oxidation through low-energy pathways. Our aerobic life is based on this strategy, mastered by the natural Photosystem II enzyme, using a tetranuclear Mn–oxo complex as oxygen evolving center. Within artificial devices, water can be oxidized efficiently on tailored metal-oxide surfaces such as RuO2. The quest for catalyst optimization in vitro is plagued by the elusive description of the active sites on bulk oxides. Although molecular mimics of the natural catalyst have been proposed, they generally suffer from oxidative degradation under multiturnover regime. Here we investigate a nano-sized Ru4–polyoxometalate standing as an efficient artificial catalyst featuring a totally inorganic molecular structure with enhanced stability. Experimental and computational evidence reported herein indicates that this is a unique molecular species mimicking oxygenic RuO2 surfaces. Ru4–polyoxometalate bridges the gap between homogeneous and heterogeneous water oxidation catalysis, leading to a breakthrough system. Density functional theory calculations show that the catalytic efficiency stems from the optimal distribution of the free energy cost to form reaction intermediates, in analogy with metal-oxide catalysts, thus providing a unifying picture for the two realms of water oxidation catalysis. These correlations among the mechanism of reaction, thermodynamic efficiency, and local structure of the active sites provide the key guidelines for the rational design of superior molecular catalysts and composite materials designed with a bottom–up approach and atomic control. PMID:23479603

Piccinin, Simone; Sartorel, Andrea; Aquilanti, Giuliana; Goldoni, Andrea; Bonchio, Marcella; Fabris, Stefano

2013-01-01

292

Raman and surface-enhanced Raman spectroscopy of adsorbed phthalic acid on oxidized aluminum foil  

Microsoft Academic Search

Adsorption of phthalic acid on anodically oxidized aluminum has been investigated at different pHs and ionic strengths by means of FT-Raman and surface-enhanced FT-Raman spectroscopy (SERS). The surface-enhancement was achieved by deposition of silver sol after adsorption. The spectra of the surface species obtained by the two techniques were significantly different. Raman spectra of the adsorbed phthalic compounds were pH

O. Klug; Gy. Parlagh; W. Forsling

1998-01-01

293

Evidence of alloy formation during reduction of platinized tin oxide surfaces  

NASA Technical Reports Server (NTRS)

Ion scattering spectroscopy, Auger electron spectroscopy, and electron spectroscopy for chemical analysis have been used to examine a platinized tin oxide catalyst surface before, during, and after reduction by annealing under vacuum at 250 to 450 C. These techniques were then used to examine the reduced surface after a room-temperature, low-pressure oxygen exposure. The spectral results and the behavior of the reduced surface toward oxygen exposure both indicate that a Pt/Sn alloy is produced during reduction.

Gardner, Steven D.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

1989-01-01

294

Zinc (hydr)oxide/graphite oxide/AuNPs composites: role of surface features in H?S reactive adsorption.  

PubMed

Zinc hydroxide/graphite oxide/AuNPs composites with various levels of complexity were synthesized using an in situ precipitation method. Then they were used as H2S adsorbents in visible light. The materials' surfaces were characterized before and after H2S adsorption by various physical and chemical methods (XRD, FTIR, thermal analysis, potentiometric titration, adsorption of nitrogen and SEM/EDX). Significant differences in surface features and synergistic effects were found depending on the materials' composition. Addition of graphite oxide and the deposition of gold nanoparticles resulted in a marked increase in the adsorption capacity in comparison with that on the zinc hydroxide and zinc hydroxide/AuNP. Addition of AuNPs to zinc hydroxide led to a crystalline ZnO/AuNP composite while the zinc hydroxide/graphite oxide/AuNP composite was amorphous. The ZnOH/GO/AuNPs composite exhibited the greatest H2S adsorption capacity due to the increased number of OH terminal groups and the conductive properties of GO that facilitated the electron transfer and consequently the formation of superoxide ions promoting oxidation of hydrogen sulfide. AuNPs present in the composite increased the conductivity, helped with electron transfer to oxygen, and prevented the fast recombination of the electrons and holes. PMID:25306297

Giannakoudakis, Dimitrios A; Bandosz, Teresa J

2014-12-15

295

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water  

NASA Astrophysics Data System (ADS)

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-11-01

296

Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. [Coal pyrite electrodes  

SciTech Connect

The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the eighth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville [number sign]2 Mine, Clearfield County, Pennsylvania. In addition electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania.

Doyle, F.M.

1992-01-01

297

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces  

NASA Technical Reports Server (NTRS)

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.; Stair, Peter C.

1992-01-01

298

Oxygen18 incorporation in NICI mass spectrometry: the role of O 2, H 2O and rhenium oxides in surface-assisted oxidation reactions  

Microsoft Academic Search

Surface-assisted oxidation reactions in the chemical ionization (CI) source have been studied using oxidation yield determinations and oxygen-18 incorporation measurements with 18O2 or H218O added to the negative ion chemical ionization buffer gas (N2 or Ar). Oxidation yield measurements show that O2, but not H2O, affects the oxidation yield. Using 18O2, 18O incorporation was found to be consistently lower in

Elizabeth A. Stemmler

1995-01-01

299

Oxygen18 incorporation in NICI mass spectrometry: the role of O2, H2O and rhenium oxides in surface-assisted oxidation reactions  

Microsoft Academic Search

Surface-assisted oxidation reactions in the chemical ionization (CI) source have been studied using oxidation yield determinations and oxygen-18 incorporation measurements with 18O2 or H218O added to the negative ion chemical ionization buffer gas (N2 or Ar). Oxidation yield measurements show that O2, but not H2O, affects the oxidation yield. Using 18O2, 18O incorporation was found to be consistently lower in

Elizabeth A. Stemmler

1995-01-01

300

Oxidized GaN(0001) Surfaces studied by Scanning Tunneling Microscopy and Spectroscopy and by First-Principles Theory  

E-print Network

1 Oxidized GaN(0001) Surfaces studied by Scanning Tunneling Microscopy and Spectroscopy Abstract Oxidized Ga-polar GaN surfaces have been studied both experimentally and theoretically. For in tunneling spectroscopy revealed a surface band gap with size close to that of GaN, indicating that any

Feenstra, Randall

301

Stability and Degradation Processes of Pentaerythritol Tetranitrate (PETN) on Metal Oxide Surfaces  

Microsoft Academic Search

The chemical stability of pentaerythritol tetranitrate (PETN) when placed in physical contact with metal oxides is investigated. In this study, PETN was placed on the surfaces of a range of microcrystalline metal oxides including MnO2, CuO, MoO3, WO3, Bi2O3, SnO2, and Fe2O3 in coverages of 1–3.5 monolayers by a wet impregnation technique. Samples were then placed in a controlled temperature

Melissa Mileham; Jonathan Burk; Preya Bhavsar; A. E. Stiegman; Michael P. Kramer

2008-01-01

302

Optimization of photo-Fenton oxidation of sulfidic spent caustic by using response surface methodology  

Microsoft Academic Search

This paper investigated the degradation of sulfidic spent caustic by using photo-Fenton oxidation process. Response surface methodology was employed to study the interaction effect between process parameters namely ferrous ion and H2O2 dosage towards the oxidation efficiency of sulfidic spent caustic. Hence, the best conditions for photo-Fenton process were determine based on the developed empirical model. By comprehensive studies, the

S. H. Y. Sayid Abdulah; M. A. Abu Hassan; Z. Zainon Noor; A. Aris

2011-01-01

303

Oxidation behavior of surface-modified titanium for titanium-ceramic restorations  

Microsoft Academic Search

Statement of problem. Titanium-ceramic bonding is an unsolved problem for the current use of titanium-ceramic restorations.Purpose. The purpose of the study was to characterize oxide formation on titanium surfaces at porcelain sintering temperatures and to determine the effect of chromium coating methods on titanium oxide formation.Material and methods. Sputter coating and electroplating methods of chromium application were compared and combined.Results.

Russell R. Wang; Kon K. Fung

1997-01-01

304

Characterization study of native oxides on GaAs(100) surface by XPS  

NASA Astrophysics Data System (ADS)

In order to know more about the surface state of GaAs(100) epitaxial wafer during a storage period of two years, the XPS analysis was carried out four times on the surface, respectively polished by chemical etching, stored in desiccator for half a year, one year and two years. The results indicated that even after cleaned by proper etchant solutions, the fresh surface was slightly oxidized with Ga2O3, As2O3 and organic contaminant. The epi-wafer was always exposed to air during the storage period, so more and more oxides turned out. The mixed oxide layer comprised of C-OR, COOR, Ga2O3, As2O3 and As2O5 appeared after only half a year. In the ageing process of two years, the oxide types of gallium or arsenic did not change with stable content of Ga2O3 and remarkably fluctuating relative contents of As2O3 and As2O5. Based on the intensity ratio of Ga 3d-Ga2O3 to Ga 3d-GaAs, the thickness of oxide layer was estimated. The oxide layer generated after chemical polishing was very thin, just only 0.435nm thick, and then it grew rapidly, approximately 1.822nm after one year while almost no change any more subsequently. It was indicated that after the epi-wafer was stored for one year, because of volatile As2O3 or As2O5, there remained a large amount of Ga2O3 in oxide layer, which prevented the reactions between bulk material and oxide layer with oxygen. So native oxide layer plays a role as passive film to protect epi-wafer against the environment during a long storage period.

Feng, Liu; Zhang, Lian-dong; Liu, Hui; Gao, Xiang; Miao, Zhuang; Cheng, Hong-chang; Wang, Long; Niu, Sen

2013-08-01

305

Stabilization of catalytically active Cu? surface sites on titanium-copper mixed-oxide films.  

PubMed

The oxidation of CO is the archetypal heterogeneous catalytic reaction and plays a central role in the advancement of fundamental studies, the control of automobile emissions, and industrial oxidation reactions. Copper-based catalysts were the first catalysts that were reported to enable the oxidation of CO at room temperature, but a lack of stability at the elevated reaction temperatures that are used in automobile catalytic converters, in particular the loss of the most reactive Cu(+) cations, leads to their deactivation. Using a combined experimental and theoretical approach, it is shown how the incorporation of titanium cations in a Cu2O film leads to the formation of a stable mixed-metal oxide with a Cu(+) terminated surface that is highly active for CO oxidation. PMID:24719231

Baber, Ashleigh E; Yang, Xiaofang; Kim, Hyun You; Mudiyanselage, Kumudu; Soldemo, Markus; Weissenrieder, Jonas; Senanayake, Sanjaya D; Al-Mahboob, Abdullah; Sadowski, Jerzy T; Evans, Jaime; Rodriguez, José A; Liu, Ping; Hoffmann, Friedrich M; Chen, Jingguang G; Stacchiola, Darío J

2014-05-19

306

An unusual surface peroxiredoxin protects invasive Entamoeba histolyticafrom oxidant attack  

Microsoft Academic Search

Peroxiredoxins are an important class of antioxidant enzymes found from Archaea to humans, which reduce and thereby detoxify peroxides and peroxynitrites. The major thiol-containing surface antigen of the invasive ameba, Entamoeba histolytica, is a peroxiredoxin and is likely to be important during the transition from the anaerobic environment of the large intestine to human tissues. The closely related species, Entamoeba

Min-Ho Choia; Dana Sajed; Leslie Poole; Ken Hirata; Scott Herdman; Bruce E. Torian; Sharon L. Reed

2005-01-01

307

A theoretical investigation on photocatalytic oxidation on the TiO{sub 2} surface  

SciTech Connect

The TiO{sub 2} photocatalytic oxidation mechanism was theoretically investigated by using long-range corrected time-dependent density functional theory (LC-TDDFT) with a cluster model of the anatase TiO{sub 2}(001) surface. We found that LC-TDDFT with the cluster model quantitatively reproduces the photoexcitations of the TiO{sub 2} surface by calculating the electronic spectra of a clean TiO{sub 2} surface and one with oxygen defects. We calculated the electronic spectra of a molecularly adsorbed TiO{sub 2} surface for the adsorptions of phenol, methanol, and methane molecules as typical organic molecules. We obtained the surprising result that the main peak of the phenol-adsorbed TiO{sub 2} surface, which overlaps with the main peak of the clean TiO{sub 2} surface, corresponds to charge transfers from the phenol molecule to the TiO{sub 2} surface. This indicates that the TiO{sub 2} photocatalytic oxidation proceeds through direct charge transfer excitation from the substrate molecules to the TiO{sub 2} surface. In contrast, we found slight and no charge transfer for methanol and methane adsorption, respectively, in agreement with the experimental findings for their reactivities. In light of these results, we propose a new mechanism for heterogeneous TiO{sub 2} photocatalytic oxidations.

Suzuki, Satoshi [Department of Applied Chemistry, School of Engineering, University of Tokyo, Tokyo 113-8656 (Japan); Tsuneda, Takao; Hirao, Kimihiko [Advanced Science Institute, RIKEN, Wako, Saitama 351-0198 (Japan); CREST, Japan Science and Technology Agency (JST), Tokyo 113-8656 (Japan)

2012-01-14

308

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water  

NASA Astrophysics Data System (ADS)

The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-06-01

309

Influence of a controlled oxidation at moderate temperatures on the surface chemistry of nitinol wire  

NASA Astrophysics Data System (ADS)

Commercial nitinol wire is oxidised at 480-530 °C/10 min in air. Surface morphology and chemistry is studied in detail using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, Raman spectrometry and X-ray photoelectron spectroscopy. It is found that the main oxidation product at both temperatures is rutile containing a few at.% Ni. Beneath the rutile layer, there are titanium sub-oxides, showing characteristic maxima in depth profiles. Nickel in an oxidised state is present on the surface, whereas in a sub-surface region of scales, there is only metallic nickel. Thickness of the total oxide layers is 70 and 140 nm after oxidation at 480 and 530 °C, respectively. The preferential oxidation of titanium causes the formation of a Ni-enriched and Ti-depleted zone, suggesting the presence of Ni 3Ti phase. XRD reveals that the presence of cubic B2 NiTi phase in the base alloy is not affected by oxidation at 480-530 °C/10 min.

Vojtech, D.; Joska, L.; Leitner, J.

2008-07-01

310

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride  

PubMed Central

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

311

Effects of trace surface oxidation in low temperature epitaxy grown from dichlorosilane  

SciTech Connect

The hydrogen carrier gas in an atmospheric pressure epitaxial growth reactor is found to suppress the oxidation of Si surface intentionally exposed to trace oxygen before epitaxial growth. After an initial delay the oxidation proceeds rapidly to form nanometer size oxide islands at surface coverages in the range of 0.001 to 1 monolayers. A small fraction of the oxide islands nucleate visible pyramidal-shaped defects in the subsequently grown epitaxial layer which enables the interfacial oxidation process to be easily studied. Replacement of the hydrogen ambience with argon leads to more than an order of magnitude increase in initial oxidation rate and a many order of magnitude increase in density of pyramidal defects for the same trace oxygen exposure. The pyramid density is proportional to the square of the interfacial oxygen density over a wide range of surface oxygen density, 5 {times} 10{sup 11} cm{sup {minus}2} to 10{sup 15} cm{sup {minus}2}, and for samples prepared over a wide range of experimental conditions.

Sedgwick, T.O.; Agnello, P.D.; Gruetzmacher, D.A. [IBM T.J. Watson Research Center, Yorktown Heights, NY (United States)

1993-12-01

312

Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces.  

PubMed

Understanding the interaction of small metal clusters and isolated atoms with oxide surfaces is crucial in order to rationalize the properties of heterogeneous catalysts composed of sub-nanometer metal particles dispersed on an oxide support. The interaction with the oxide surface can significantly alter the original properties of the metal deposit. In particular, the occurrence and the direction of charge transfer at the metal/oxide interface determine the chemical activity of the supported catalyst. The charge transfer depends on a number of factors like the nature of the oxide (reducible or non-reducible), the surface exposed, the presence of defects, the nature of the supported metal, etc. In this article we describe the most important conceptual aspects of the electronic metal-support interaction, a phenomenon related to the direct modification of the metal nano-particle determined by the formation of chemical bonds at the interface with the oxide. For metal nano-particles with a size of about 1 nm or below these effects become dominant although difficult to identify experimentally. PMID:23287900

Pacchioni, Gianfranco

2013-02-14

313

Dependence of cryogenic strength of hydroxide catalysis bonded silicon on type of surface oxide  

NASA Astrophysics Data System (ADS)

Hydroxide catalysis bonding is a joining technique used in the construction of highly stable opto-mechanical systems including quasi-monolithic silica suspensions for first and second generation gravitational wave detectors. Future generations of detector are likely to operate at cryogenic temperatures necessitating a change in testmass/suspension material. A promising candidate material is silicon, which requires an oxide surface layer for hydroxide catalysis bonding to be reliable. Here, we present first results showing the influence of the type of oxide layer applied on bond strength, measured at room temperature and 77 K, and identify preferred oxide deposition methods.

Beveridge, N. L.; van Veggel, A. A.; Cunningham, L.; Hough, J.; Martin, I. W.; Nawrodt, R.; Reid, S.; Rowan, S.

2013-01-01

314

Highly water repellent but highly adhesive surface with segregation of poly(ethylene oxide) side chains.  

PubMed

Polymer surfaces were modified using methacrylate terpolymers containing both perfluoroalkyl (Rf) groups and poly(ethylene oxide) (PEO) as side chains in the same molecule. The structure and properties of the modified surfaces were evaluated using X-ray photoelectron spectroscopy and by measuring the dynamic contact angles and 90° peel strength. It was found that not only Rf groups but also PEO side chains were segregated on the surface being against the order of the surface free energy. The terpolymer modified surface is hydrophobic in air because Rf groups are predominant, but it becomes hydrophilic in water because the surface is covered with PEO side chains. This response to the environment is rapid and reversible. The modified surface showed high water repellency because of the surface Rf groups and high adhesive strength because of the side chains. PMID:25511288

Tokuda, Kaya; Kawasaki, Motoko; Kotera, Masaru; Nishino, Takashi

2015-01-13

315

Increased reactivity and in vitro cell response of titanium based implant surfaces after anodic oxidation.  

PubMed

In the quest for improved bone growth and attachment around dental implants, chemical surface modifications are one possibility for future developments. The biological properties of titanium based materials can be further enhanced with methods like anodic polarization to produce an active rather than a passive titanium oxide surface. Here we investigate the formation of hydroxide groups on sand blasted and acid etched titanium and titanium-zirconium alloy surfaces after anodic polarization in an alkaline solution. X-ray photoelectron spectroscopy shows that the activated surfaces had increased reactivity. Furthermore the activated surfaces show up to threefold increase in OH(-) concentration in comparison to the original surface. The surface parameters Sa, Sku, Sdr and Ssk were more closely correlated to time and current density for titanium than for titanium-zirconium. Studies with MC3T3-E1 osteoblastic cells showed that OH(-) activated surfaces increased mRNA levels of osteocalcin and collagen-I. PMID:23912792

Walter, M S; Frank, M J; Sunding, M F; Gómez-Florit, M; Monjo, M; Bucko, M M; Pamula, E; Lyngstadaas, S P; Haugen, H J

2013-12-01

316

Structure and the catalysis mechanism of oxidative chlorination in nanostructural layers of a surface of alumina  

PubMed Central

On the basis of X-ray diffraction and mass spectrometric analysis of carrier ?-Al2O3 and catalysts CuCl2/CuCl on its surface, the chemical structure of the active centers of two types oxidative chlorination catalysts applied and permeated type of industrial brands “Harshow” and “MED?-B” was investigated. On the basis of quantum-mechanical theory of the crystal, field complexes were detected by the presence of CuCl2 cation stoichiometry and structure of the proposed model crystal quasichemical industrial catalyst permeated type MED?-B for oxidative chlorination of ethylene. On the basis of quantum-mechanical calculations, we propose a new mechanism of catalysis crystal quasichemical oxidative chlorination of ethylene reaction for the catalysts of this type (MED?-B) and confirmed the possibility of such a mechanism after the analysis of mass spectrometric studies of the active phase (H2 [CuCl4]) catalyst oxidative chlorination of ethylene. The possibility of the formation of atomic and molecular chlorine on the oxidative chlorination of ethylene catalyst surface during Deacon reaction was displaying, which may react with ethylene to produce 1,2-dichloroethane. For the active phase (H [CuCl2]), catalyst offered another model of the metal complex catalyst oxidative chlorination of ethylene deposited type (firm ‘Harshow,’ USA) and the mechanism of catalysis of oxidative chlorination of ethylene with this catalyst. PMID:25258594

2014-01-01

317

Correlation between the surface electronic structure and CO-oxidation activity of Pt alloys.  

PubMed

The surface electronic structure and CO-oxidation activity of Pt and Pt alloys, Pt3T (T = Ti, Hf, Ta, Pt), were investigated. At temperatures below 538 K, the CO-oxidation activities of Pt and Pt3T increased in the order Pt < Pt3Ti < Pt3hHf < Pt3Ta. The center-of-gravity of the Pt d-band (the d-band center) of Pt and Pt3T was theoretically calculated to follow the trend Pt3Ti < Pt3Ta < Pt3Hf < Pt. The CO-oxidation activity showed a volcano-type dependence on the d-band center, where Pt3Ta exhibited a maximum in activity. Theoretical calculations demonstrated that the adsorption energy of CO on the catalyst surface monotonically decreases with the lowering of the d-band center because of diminished hybridization of the surface d-band and the lowest-unoccupied molecular orbital (LUMO) of CO. The observed volcano-type correlation between the d-band center and the CO oxidation activity is rationalized in terms of the CO adsorption energy, which counterbalances the surface coverage by CO and the rate of CO oxidation. PMID:25271906

Abe, Hideki; Yoshikawa, Hideki; Umezawa, Naoto; Xu, Ya; Saravanan, Govindachetty; Ramesh, Gubbala V; Tanabe, Toyokazu; Kodiyath, Rajesh; Ueda, Shigenori; Sekido, Nobuaki; Yamabe-Mitarai, Yoko; Shimoda, Masahiko; Ohno, Takahisa; Matsumoto, Futoshi; Komatsu, Takayuki

2015-02-21

318

Ion Adsorption on Metal Oxide Surfaces to Hydrothermal Conditions  

SciTech Connect

In this article, we review the sorption of multivalent cations on rutile ({alpha}-TiO{sub 2}) powder surfaces in aqueous 1:1 electrolyte media from room temperature to 250 C. All cations are shown to occupy 'inner sphere' sorption sites in contact with surface oxygens and hydroxyl groups, as well as the diffuse portion of the electrical double layer (EDL). Sorption is shown to increase strongly with increasing temperature, and the sorption affinity is strongly-related to cation radius and charge. Macroscopic powder pH-titration results obtained with ORNL's high temperature hydrogen electrode concentration cells can be rationalized with Gouy-Chapman-Stern models of the EDL, augmented by atomic-scale structural and proton affinity data from synchrotron X-ray studies and computational modeling approaches.

Wesolowski, David J [ORNL; Machesky, Michael L. [Illinois State Water Survey, Champaign, IL; Ridley, Mora K. [Texas Tech University, Lubbock; Palmer, Donald [ORNL; Zhang, Zhan [Argonne National Laboratory (ANL); Fenter, Paul [Argonne National Laboratory (ANL); Predota, M. [University of South Bohemia, Czech Republic; Cummings, Peter T [ORNL

2004-01-01

319

Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface  

NASA Astrophysics Data System (ADS)

Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone, with Fe(II) oxidation taking place in the soil surrounding the ditch during summer and in the surface water during winter. The dynamics in Fe(II) oxidation did not affect the dissolved P concentrations. The dissolved P concentrations of the in-stream reservoirs water were an order of magnitude lower than observed in the groundwater and have no seasonal trend. Our data showed preferential binding of P during initial stage of the Fe(II) oxidation process, indicating the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at the groundwater-surface water interface is an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and therefore a major control on the P retention in natural waters that drain anaerobic aquifers.

van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

2014-05-01

320

Formation of nitrogen oxides via NO + O2 gas-solid reaction on cold surfaces  

NASA Astrophysics Data System (ADS)

The oxidation of nitrogen monoxide has implications for the complex atmospheric chemistry of Antarctica, as well as for planetary atmospheres. In this study we unveil that O2 adsorbed on a cold surface reacts with a very high efficiency with NO coming from the gas phase to form NO2. Via two molecular beams, O2 and NO molecules are aimed at a cold (10 K) sample held in a UHV chamber. NO2 is formed independently of the surface composition and morphology. We show that the NO + O2 reaction occurs mainly through the direct Eley Rideal mechanism to form nitrogen oxides (NO2, N2O3, N2O4).

Minissale, M.; Congiu, E.; Baouche, S.; Chaabouni, H.; Moudens, A.; Dulieu, F.; Manicó, G.; Pirronello, V.

2013-04-01

321

Speciation of adsorbed yttrium and rare earth elements on oxide surfaces  

NASA Astrophysics Data System (ADS)

The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y 3+ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species 4>SOH+M+2HO=(>SOH)2_M(OH)2++4H was found to account for a significant fraction of the adsorbed Y 3+, La 3+, Nd 3+, Gd 3+, and Yb 3+ on rutile, hematite, alumina and silica over wide ranges of pH and ionic strength. Where adsorption data were available as a function of surface coverage for hematite and silica, an additional reaction involving a mononuclear species could be used to account for the higher surface coverages. However, it is also possible that some of the higher surface coverage data refer to surface precipitation rather than adsorption. The results of the present study provide an internally consistent basis for describing YREE adsorption which could be used to investigate more complex systems in which YREE compete both in aqueous solution and on mineral surfaces with alkaline earths and ligands such as carbonate, sulfate, chloride and organic species, in order to build a predictive adsorption model applicable to natural waters.

Piasecki, Wojciech; Sverjensky, Dimitri A.

2008-08-01

322

Photoemission and LEED study of the Sn/Rh(111) surface—early oxidation steps and thermal stability  

NASA Astrophysics Data System (ADS)

We have deposited two monolayers of Sn onto Rh(111) single crystal. After the deposition, no ordered structure was revealed by low energy electron diffraction (LEED). We oxidized the obtained system in a low-pressure oxygen atmosphere at 420 K. The oxidized sample was then gradually heated to study the thermal stability of the oxide layer. We characterized the system by synchrotron radiation stimulated photoelectron spectroscopy and LEED. Valence band and core level photoelectron spectra of rhodium, tin and oxygen were used to study the oxidation of the Sn-Rh(111) surface and its behaviour upon annealing. A low stoichiometric oxide of Sn was created on the surface. The oxidation process did not continue towards creation of SnO2 with higher oxygen dose. The annealing at 970 K caused decomposition of the surface oxide of Sn and creation of an ordered (?3 × ?3)R30° Sn-Rh(111) surface alloy.

Hanyš, Petr; Píš, Igor; Mašek, Karel; Šutara, František; Matolín, Vladimír; Nehasil, Václav

2012-01-01

323

Microstructure and biocompatibility of titanium oxides produced on nitrided surface layer under glow discharge conditions.  

PubMed

The disadvantages of titanium implants are their low wear resistance and the release of titanium elements into surrounding tissue. These can be eliminated by modifying the surface by surface engineering methods, among them nitriding under glow discharge conditions which allow to produce diffusive surface layers. Their combining with an oxide layer might be valuable for biological events occurring at the bone implant interface. The aim of this study was to enhance the titanium biomaterial performance via combining nitriding and oxidizing treatments in one process under glow discharge conditions. The oxynitrided surface layers were produced at 680 degrees C. The obtained layer was TiO + TiN + Ti2N + alphaTi(N) type and about 4-microm thick and was of diffusive character. This layer significantly increased wear resistance and slightly corrosion resistance compared to that of the reference titanium alloy. The produced titanium oxide was about 400-nm thick and built from fine crystallites. This oxide exhibits bioactivity in SBF (simulated body fluid). Osteoblasts of Saos-2 line incubated on this surface exhibited good adhesion and proliferation and ALP release comparable with cells cultured on the reference titanium alloy and TiN + Ti2N + alphaTi(N) surface layers. A quantitative analysis of blood platelets adhering to this layer revealed their highest amount in comparison to that on both the nitrided surface layer and titanium alloy. The presented study provided a simple and reproducible method of combining oxidizing and nitriding under glow discharge in one process. Experimental data in vitro suggests that titanium alloy oxynitriding under low temperatures at glow discharge conditions improves titanium alloy properties and biocompatibility and tissue healing. Therefore, the layer of TiO + TiN +Ti2N + alphaTi(N) type could be valuable for long-term bone implants. PMID:22400281

Czarnowska, E; Morgiel, J; Ossowski, M; Major, R; Sowinska, A; Wierzchon, T

2011-10-01

324

Fabrication of condensate microdrop self-propelling porous films of cerium oxide nanoparticles on copper surfaces.  

PubMed

Condensate microdrop self-propelling (CMDSP) surfaces have attracted intensive interest. However, it is still challenging to form metal-based CMDSP surfaces. We design and fabricate a type of copper-based CMDSP porous nanoparticle film. An electrodeposition method based on control over the preferential crystal growth of isotropic nanoparticles and synergistic utilization of tiny hydrogen bubbles as pore-making templates is adopted for the in?situ growth of cerium oxide porous nanoparticle films on copper surfaces. After characterizing their microscopic morphology, crystal structure and surface chemistry, we explore their CMDSP properties. The nanostructure can realize the efficient ejection of condensate microdrops with sizes below 50??m. PMID:25693502

Luo, Yuting; Li, Juan; Zhu, Jie; Zhao, Ye; Gao, Xuefeng

2015-04-13

325

Effects of the Thickness of Niobium Surface Oxide Layers on Field Emission  

SciTech Connect

Field emission on the inner surfaces of niobium superconducting radio frequency cavities is still one of the major obstacles for reaching high accelerating gradients for SRF community. Our previous experimental results* seemed to imply that the threshold of field emission was related to the thickness of Nb surface oxide layers. In this contribution, a more detailed study on the influences of the surface oxide layers on the field emission on Nb surfaces will be reported. By anodization technique, the thickness of the surface pentoxide layer was artificially fabricated from 3 nm up to 460 nm. A home-made scanning field emission microscope was employed to perform the scans on the surfaces. Emitters were characterized using a scanning electron microscope together with an energy dispersive x-ray analyzer. The SFEM experimental results were analyzed in terms of surface morphology and oxide thickness of Nb samples and chemical composition and geographic shape of the emitters. A model based on the classic electromagnetic theory was developed trying to understand the experimental results. Possibly implications for Nb SRF cavity applications from this study will be discussed.

A.T. Wu, S. Jin, J.D. Mammosser, R.A. Rimmer, X.Y. Lu, K. Zhao

2011-09-01

326

Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.  

PubMed

Surface redox-active centres in transition-metal oxides play a key role in determining the efficacy of electrocatalysts. The extreme sensitivity of surface redox states to temperatures, to gas pressures and to electrochemical reaction conditions renders them difficult to investigate by conventional surface-science techniques. Here we report the direct observation of surface redox processes by surface-sensitive, operando X-ray absorption spectroscopy using thin-film iron and cobalt perovskite oxides as model electrodes for elevated-temperature oxygen incorporation and evolution reactions. In contrast to the conventional view that the transition metal cations are the dominant redox-active centres, we find that the oxygen anions near the surface are a significant redox partner to molecular oxygen due to the strong hybridization between oxygen 2p and transition metal 3d electronic states. We propose that a narrow electronic state of significant oxygen 2p character near the Fermi level exchanges electrons with the oxygen adsorbates. This result highlights the importance of surface anion-redox chemistry in oxygen-deficient transition-metal oxides. PMID:25598003

Mueller, David N; Machala, Michael L; Bluhm, Hendrik; Chueh, William C

2015-01-01

327

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides  

USGS Publications Warehouse

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

White, A.F.; Peterson, M.L.

1996-01-01

328

Modifications of oxidized Zircaloy-4 surface in contact with radiolysed wet air  

NASA Astrophysics Data System (ADS)

In the framework of radioactive waste geological disposal, the long term evolution of the nuclear wastes packages and the release of the radionuclides from the wastes have to be studied. Regarding compacted wastes (cladding tubes) coming from reprocessing of spent fuel, the Zircaloy-4 (zirconium alloy) cladding tubes have been activated and oxidized in reactors. In the disposal, the radioactive waste is exposed to humid air in a first phase and to water after the resaturation phase. In order to better assess the degradation process of these nuclear waste package, the influence of wet air proton radiolysis on the behavior of surface oxidized Zircaloy-4 has been investigated. Radiolysis experiments were performed using an irradiation cell which is associated to an extracted beam. Samples are exposed to wet air, under and without radiolysis, during 12 and 24 h. The water partial pressure has been fixed at 6 and 50 mbar in order to have, respectively, localized adsorbed water molecules and a thin film of adsorbed water. Before and after each treatment, sample surfaces were characterized by X-ray Photoelectron Spectroscopy (XPS) in order to identify the elements at the topmost surface of the solid. The wet air radiolysis causes changes at the surface of oxidized Zircaloy-4 and influences the corrosion phenomenon. Indeed, an enrichment of tin and the presence of nitrogen species were observed. It could be due to the formation of tritin(II) tetrahydroxide dinitrate and a Zr 4+ tetramer on the topmost oxide surface.

Guipponi, C.; Millard-Pinard, N.; Bérerd, N.; Serris, E.; Pijolat, M.; Peres, V.; Wasselin-Trupin, V.

2012-02-01

329

Density functional theory study of Fe(II) adsorption and oxidation on goethite surfaces  

NASA Astrophysics Data System (ADS)

We study the interactions between Fe(II) aqua complexes and surfaces of goethite (?-FeOOH) by means of density functional theory calculations including the so-called Hubbard U correction to the exchange-correlation functional. Using a thermodynamic approach, we find that (110) and (021) surfaces in contact with aqueous solutions are almost equally stable, despite the evident needlelike shape of goethite crystals indicating substantially different reactivity of the two faces. We thus suggest that crystal anisotropy may result from different growth rates due to virtually barrierless adsorption of hydrated ions on the (021) but not on the (110) surface. No clear evidence is found for spontaneous electron transfer from an adsorbed Fe(II) hex-aqua complex to a defect-free goethite substrate. Crystal defects are thus inferred to play an important role in assisting such electron transfer processes observed in a recent experimental study. Finally, goethite surfaces are observed to enhance the partial oxidation of adsorbed aqueous Fe(II) upon reaction with molecular oxygen. We propose that this catalytic oxidation effect arises from donation of electronic charge from the bulk oxide to the oxidizing agent through shared hydroxyl ligands anchoring the Fe(II) complexes on the surface.

Russell, Benedict; Payne, Mike; Ciacchi, Lucio Colombi

2009-04-01

330

Surface effects and phase stability in metal oxides nanoparticles under visible irradiation  

SciTech Connect

The light induced phase transformation between stable phases of metal oxides nanoparticles is analyzed. The surrounding atmosphere as well as the defect density at the surface play a fundamental role. It has been found that in oxygen poor chamber atmosphere the phase transformation is favored, while the phase transition cannot be achieved if the defects at the surface are properly passivated. The phase transition is activated by intragap irradiation, able to activate the F- center at the surface connected to oxygen vacancies, and promoting the activation of the surface and the nucleation of neighboring crystallites. The phase transition was studied in Titanium oxide (TiO{sub 2}) and in Iron oxide (Fe{sub 2}O{sub 3}): Maghemite is subjected to a phase transformation to ??Fe{sub 2}O{sub 3} (hematite), Anatase nanoparticles converts to Rutile. The general mechanism of the phase transition and, more in general, the possibility to optically control the surface activity of metal oxides is discussed.

Ricci, Pier Carlo, E-mail: carlo.ricci@dsf.unica.it; Carbonaro, C. M., E-mail: carlo.ricci@dsf.unica.it; Corpino, R., E-mail: carlo.ricci@dsf.unica.it; Chiriu, D., E-mail: carlo.ricci@dsf.unica.it; Stagi, L., E-mail: carlo.ricci@dsf.unica.it [Dipartimento di Fisica, Universitá degli Studi di Cagliari, S.P. Monserrato-Sestu Km 0,700, 09042 Monserrato (Canada) (Italy)

2014-10-21

331

Surface Analysis of Micro-Arc Oxidized Coatings Deposited on cp-Ti  

NASA Astrophysics Data System (ADS)

The surface of commercially pure titanium (grade 4) was modified by micro-arc oxidation treatment. A porous TiO2 coating layer was formed on the Ti surface and its crystal structure was analyzed as rutile phase. Both the thickness of the TiO2 layer and the pore size on the surface were strongly dependent on the applied current density as well as the micro-arc oxidizing time during the oxidation treatment. When a current density of 50 mA/cm2 had been applied for 10 minutes, the thickness and the pore size of the oxide layer were 1.2 µm and 230 nm, respectively. The thickness and the pore size of the layer continued to increase with increasing the applied current density. The TiO2 passive layer of the titanium surface can attribute to the excellent biocompatibility and the formation of nano-sized pores may maximize the interlocking between mineralized bone and the surface of the Ti implant.

Kim, Yeon-Wook; Nam, Tae-Hyun

332

Efficient modification of metal oxide surfaces with phosphonic acids by spray coating.  

PubMed

We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time. The data show that the work function shifts and surface coverage by the phosphonic acid were similar to or greater than those obtained by the dip-coating method. When the deposition temperature was increased, the magnitude of the surface coverage and work function shift was also found to increase. The rapid exposure of the spray coating was found to result in less etching of zinc-containing oxides than the dip-coating method. Bulk heterojunction solar cells made of polyhexylthiophene (P3HT) and bis-indene-C60 (ICBA) were tested with PFBPA dip and spray-modified ITO substrates as well as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-modified ITO. The spray-modified ITO solar cells showed a similar open circuit voltage (VOC) and fill factor (FF) and a less than 5% lower short circuit current density (JSC) and power conversion efficiency (PCE) than the dip- and PEDOT:PSS-modified ITO. These results demonstrate a potential path to a scalable method to deposit phosphonic acid surface modifiers on metal oxides while overcoming the limitations of other techniques that require long exposure and post-processing times. PMID:23421597

Bulusu, Anuradha; Paniagua, Sergio A; MacLeod, Bradley A; Sigdel, Ajaya K; Berry, Joseph J; Olson, Dana C; Marder, Seth R; Graham, Samuel

2013-03-26

333

Probing the electronic structure of early transition metal oxide clusters: Molecular models towards mechanistic insights into oxide surfaces and catalysis  

NASA Astrophysics Data System (ADS)

Selected recent works from the authors' laboratory on the intrinsic electronic and structural properties of early transition metal oxide clusters are reviewed. These clusters provide well-defined molecular models pertinent to mechanistic understandings of complex oxide surface chemistry and catalysis. The energy gap evolution with cluster size was probed for the stoichiometric (TiO 2) n-, (V 2O 5) n-, and (CrO 3) n- clusters, and each system was shown to approach the band gap of bulk oxides in a unique way. A variety of other model clusters have been characterized, such as the oxygen radical or diradical on a single W 6+ site in WO 4-/WO 4, the superoxide (WO 3) n(O 2-) complexes for dioxygen activation, and terminal versus bridging oxygen in M 3O 2- (M = Nb, Ta) clusters. Novel chemical bonding has been observed in a number of oxide clusters. The W 3O 9- and W 3O 92- clusters were found to possess d-orbital aromaticity, whereas ?-aromaticity was discovered in the Ta 3O 3- cluster.

Zhai, Hua-Jin; Wang, Lai-Sheng

2010-11-01

334

Plasma surface oxidation of 316L stainless steel for improving adhesion strength of silicone rubber coating to metal substrate  

NASA Astrophysics Data System (ADS)

Stainless steel 316L is one of the most widely used materials for fabricating of biomedical devices hence, improving its surface properties is still of great interest and challenging in biomaterial sciences. Plasma oxidation, in comparison to the conventional chemical or mechanical methods, is one of the most efficient methods recently used for surface treatment of biomaterials. Here, stainless steel specimens were surface oxidized by radio-frequency plasma irradiation operating at 34 MHz under pure oxygen atmosphere. Surface chemical composition of the samples was significantly changed after plasma oxidation by appearance of the chromium and iron oxides on the plasma-oxidized surface. A wettable surface, possessing high surface energy (83.19 mN m-1), was observed after plasma oxidation. Upon completion of the surface modification process, silicone rubber was spray coated on the plasma-treated stainless steel surface. Morphology of the silicone rubber coating was investigated by scanning electron microscopy (SEM). A uniform coating was formed on the oxidized surface with no delamination at polymer-metal interface. Pull-off tests showed the lowest adhesion strength of coating to substrate (0.12 MPa) for untreated specimens and the highest (0.89 MPa) for plasma-oxidized ones.

Latifi, Afrooz; Imani, Mohammad; Khorasani, Mohammad Taghi; Daliri Joupari, Morteza

2014-11-01

335

Unveiling and controlling the electronic structure of oxidized semiconductor surfaces: Crystalline oxidized InSb(100)(1 Ã-- 2)-O  

NASA Astrophysics Data System (ADS)

The exothermic nature of oxidation causes nearly all semiconductor applications in various fields like electronics, medicine, photonics, and sensor technology to acquire an oxidized semiconductor surface part during the application manufacturing. The significance of understanding and controlling the atomic scale properties of oxidized semiconductor surfaces is expected to increase even further with the development of nanoscale semiconductor crystals. The nature of oxidized semiconductor layers is, however, hard to predict and characterize as they are usually buried and amorphous. To shed light on these issues, we pursue a different approach based on oxidized III-V semiconductor layers that are crystalline. We present a comprehensive characterization of oxidized crystalline InSb(100)(1×2)-O layers by ab initio calculations, photoelectron spectroscopy, scanning tunneling microscopy, and spectroscopy, and demonstrate the electronic band structures of different oxidized phases of the semiconductor, which elucidate the previous contradictory semiconductor-oxidation effects. At 0.5 monolayer (ML) oxidation, oxygen atoms tend to occupy subsurface Sb sites, leading to metallic states in the semiconductor band gap, which arise from top dimers. When the oxidation is increased to the 1.0-2.0 ML concentration, oxygen occupies also interstitial sites, and the insulating band structure without gap states is stabilized with unusual occupied In dangling bonds. In contrast, the 2.5-3.0 ML oxide phases undergo significant changes toward a less ordered structure. The findings suggest a methodology for manipulating the electronic structure of oxidized semiconductor layers.

Lâng, J. J. K.; Punkkinen, M. P. J.; Tuominen, M.; Hedman, H.-P.; Vähä-Heikkilä, M.; Polojärvi, V.; Salmi, J.; Korpijärvi, V.-M.; Schulte, K.; Kuzmin, M.; Punkkinen, R.; Laukkanen, P.; Guina, M.; Kokko, K.

2014-07-01

336

Chemistry of sulfur oxides on transition metal surfaces: BOC-MP analysis  

Microsoft Academic Search

The bond order conservation-Morse potential (BOC-MP) method proved to be versatile and useful in analyzing chemisorption and reactivity on transition metal surfaces [1–3]. Most recently, we have applied the BOC-MP method to analyze surface chemistry of sulfur oxides on the Cu and Ni group metals [4,5]. We have calculated the reaction energetics (heats of adsorption, reaction enthalpies and intrinsic activation

Harrell Sellers; Evgeny Shustorovich

1997-01-01

337

Role of surface precipitation in copper sorption by the hydrous oxides of iron and aluminum  

SciTech Connect

Isotherms were developed at pH 6.9 for adsorption (ADS) and coprecipitation (CPT) of Cu by hydrous oxides of Fe (HFO) and Al (HAO) to study the role of sorbate/sorbent ratio in metal cation removal. For low sorbate/sorbent conditions, HFO had a higher Cu retention capacity than HAO regardless of contact methodology. For either oxide, CPT was consistently more effective than ADS in removing Cu from solution. At high sorbate/sorbent ratios, surface precipitation dominates and the oxide`s net cation retention capacity depends on the nature and solubility of the precipitate formed at the oxide-water interface. X-ray diffraction patterns and isotherms of HAO for both ADS and CPT suggest formation of a solid solution [e.g., CuAl{sub 2}O{sub 4}(s)] with dramatically loser solubility than Cu(OH){sub 2}(s) precipitated in bulk solution. In contrast, Cu precipitated on the HFO surface exhibited a solubility comparable to the bulk precipitated Cu(OH){sub 2}(s). Therefore, at high sorbate/sorbent ratios, HAO has a higher Cu apparent sorption capacity than HFO. The relative utility of these oxides as metal scavengers thus depends markedly on sorbate/sorbent conditions.

Karthikeyan, K.G.; Elliott, H.A.; Chorover, J. [Pennsylvania State Univ., University Park, PA (United States)] [Pennsylvania State Univ., University Park, PA (United States)

1999-01-01

338

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide  

SciTech Connect

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al{sub 2}O{sub 3} gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge. These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001)

Kerr, A. J. [Department of Electrical and Computer Engineering, University of California, San Diego, La Jolla, California 92093 (United States); Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 (United States); Chagarov, E.; Kaufman-Osborn, T.; Kummel, A. C., E-mail: akummel@ucsd.edu [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 (United States); Gu, S.; Wu, J.; Asbeck, P. M. [Department of Electrical and Computer Engineering, University of California, San Diego, La Jolla, California 92093 (United States); Madisetti, S.; Oktyabrsky, S. [Department of Nanoscale Science and Engineering, University at Albany–State University of New York, Albany, New York 12222 (United States)

2014-09-14

339

Zinc Oxide on Silicon Surface Acoustic Wave Devices.  

NASA Astrophysics Data System (ADS)

Results will be presented describing the operational behavior of a metal-ZnO-SiO(,2)-Si (MZOS) surface acoustic wave (SAW) device with a new transducer configuration. In the new configuration the transducer is positioned at the ZnO-SiO(,2) interface; there is a metal overlay above the transducer at the outer ZnO surface. The transduction in a SAW delay line is observed to vary by 30 dB when a dc voltage is applied to the interface transducer. Also the lowest measured insertion loss is 20 dB, a value comparable to that obtained from conventional MZOS devices. A new transducer configuration, the separate comb transducer, will also be introduced, which enables one to double the possible operating frequency for a given photolithographic capability. The increase is due to the metal widths and spacings being one-half of the wavelength for the separate comb transducer while the metal widths and spacings for the conventional interdigital transducer are a quarter of the wavelength. The separate comb transducer structure also has yield advantages compared to the interdigital transducer structure. The separate comb transducer has been utilized in the fabrication of higher frequency MZOS convolvers than previously reported (285 MHz synchronous frequency Rayleigh and 355 MHz synchronous frequency Sezawa devices). The occurrence of conversion from the Sezawa mode to the Rayleigh mode due to periodic gratings in the MZOS device structure is demonstrated. In order to avoid unwanted stopbands, the occurrence of such a conversion must be considered in the design of grating structures, such as the multistrip coupler, in layered monolithic configurations. Recently the elimination of the bias instability in the MZOS structure has been achieved by use of a low temperature nitrogen anneal. This technique has been utilized in the fabrication of a bias stable MZOS Rayleigh mode convolver.

Melloch, Michael Raymond

340

Intrinsic activity and poisoning rate for HCOOH oxidation on platinum stepped surfaces.  

PubMed

Pulsed voltammetry has been used to study formic acid oxidation on platinum stepped surfaces to determine the kinetics of the reaction and the role of the surface structure in the reactivity. From the current transients at different potentials, the intrinsic activity of the electrode through the active intermediate reaction path (j(theta = 0)), as well as the rate constant for the CO formation (k(ads)) have been calculated. The kinetics for formic acid oxidation through the active intermediate reaction path is strongly dependent on the surface structure of the electrode, with the highest activity found for the Pt(100) surface. The presence of steps, both on (100) and (111) terraces, does not increase the activity of these surfaces. CO formation only takes place in a narrow potential window very close to the local potential of zero total charge. The extrapolation of the results obtained with stepped surfaces with (111) terraces to zero step density indicates that CO formation should not occur on an ideal Pt(111) electrode. Additionally, the analysis of the Tafel slopes obtained for the different electrodes suggests that the oxidation of formic acid is strongly affected by the presence of adsorbed anions, hydrogen and water. PMID:20539876

Grozovski, Vitali; Climent, Víctor; Herrero, Enrique; Feliu, Juan M

2010-08-21

341

Oxidation processes of surface hydrogenated silicon nanocrystallites prepared by pulsed laser ablation and their effects on the photoluminescence wavelength  

NASA Astrophysics Data System (ADS)

Natural oxidation processes of surface hydrogenated silicon nanocrystallites prepared by pulsed laser ablation under various hydrogen gas pressures are discussed by measuring the vibrational frequency of Si-Hn units on the surface and intensity of Si-O-Si stretching vibration. The surfaces of nanocrystallites are predominantly composed of Si-H bonds and oxidation starts from backbonds of these bonds. The deposited nanocrystal films have a porous secondary structure which depends on the background gas pressure. The oxidation rate observed by infrared absorption measurements depended on this porous secondary structure. The oxidation process is discussed by the correlation between oxidation rate and porous structure of nanocrystal film. We found that Si-O bond density increases with covering the surface of the nanocrystallites during the diffusion of oxygen-related molecules through the void spaces in the porous structure. The surface oxidation of each nanocrystallite is not homogeneous; after the coverage of easy-to-oxidize sites, oxidation continues to gradually progress at the post-coverage stage. We point out that the oxidation process at coverage and post-coverage stages result in different photoluminescence (PL) wavelengths. Adsorption of the water molecule before oxidation also affects the PL wavelength. Defect PL centers which have light emission around 600 and 400 nm are generated during the coverage and post-coverage oxidation processes, respectively.

Umezu, Ikurou; Sugimura, Akira; Makino, Toshiharu; Inada, Mitsuru; Matsumoto, Kimihisa

2008-01-01

342

Manganese Peroxidase Degrades Pristine but Not Surface-Oxidized (Carboxylated) Single-Walled Carbon Nanotubes  

E-print Network

Manganese Peroxidase Degrades Pristine but Not Surface-Oxidized (Carboxylated) Single-Walled Carbon ligninolytic enzymes: lignin perox- idase, manganese peroxidase (MnP), and laccase. Only MnP was capable peroxidase (HRP) in the presence of 40 M H2O2 and proposed that the reactive oxygen species (ROS) generated

Alvarez, Pedro J.

343

Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications  

Microsoft Academic Search

Superparamagnetic iron oxide nanoparticles (SPION) with appropriate surface chemistry have been widely used experimentally for numerous in vivo applications such as magnetic resonance imaging contrast enhancement, tissue repair, immunoassay, detoxification of biological fluids, hyperthermia, drug delivery and in cell separation, etc. All these biomedical and bioengineering applications require that these nanoparticles have high magnetization values and size smaller than 100nm

Ajay Kumar Gupta; Mona Gupta

2005-01-01

344

Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides Wonyoung Lee and Bilge Yildiz  

E-print Network

for efficient and durable operation of SOFCs at intermediate temperatures. Cation segregation on the perovskiteFactors that Influence Cation Segregation at the Surfaces of Perovskite Oxides Wonyoung Lee transforms to different chemical phases, including the perovskite-termination structure with the Sr replacing

Yildiz, Bilge

345

Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems  

DOEpatents

The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed. 2 figs.

Sugama, Toshifumi.

1990-05-22

346

Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems  

DOEpatents

The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed.

Sugama, Toshifumi (Mastic Beach, NY)

1990-01-01

347

Nitric Oxide Production from Surface Recombination of Oxygen and Nitrogen Atoms  

E-print Network

1 Nitric Oxide Production from Surface Recombination of Oxygen and Nitrogen Atoms Dusan A. Pejakovi from the recombination of oxygen and nitrogen atoms on quartz. The experiments employ two-photon laser induced fluorescence detection of atomic oxygen and atomic nitrogen to characterize changes in gas

Martín, Pino

348

INFLUENCE OF TEMPERATURE ON NICKEL SORPTION ON CLAY MINERAL AND OXIDE SURFACES. K. G. Scheckel1  

E-print Network

INFLUENCE OF TEMPERATURE ON NICKEL SORPTION ON CLAY MINERAL AND OXIDE SURFACES. K. G. Scheckel1- mation of metal precipitates. However, the influence of temperature on the kinetic formation of these metal pre- cipitates has not been studied. The effect of temperature on reaction rates is well known

Sparks, Donald L.

349

Role of oxide surface in coordination chemistry of transition metal ions in catalytic systems  

Microsoft Academic Search

On going from the solution into the bulk of an oxide through the fluid-solid interface, it is possible to encounter four types of coordina- tion chemistry (CC) for a transition metal ion (TMI) : solution coordina- tion chemistry, extraframework ion CC, surface framework ion CC and solid state CC. In each case, the reactivity of the TMI is discussed on

L. Bonneviot; M. Curie

1988-01-01

350

Speciation of adsorbed yttrium and rare earth elements on oxide surfaces  

E-print Network

Speciation of adsorbed yttrium and rare earth elements on oxide surfaces Wojciech Piasecki, Dimitri 10 June 2008 Abstract The distribution of yttrium and the rare earth elements (YREE) between natural. INTRODUCTION The relative abundances of yttrium and the rare earth elements (YREE) are widely used tracers

Sverjensky, Dimitri A.

351

Temperature effects of pad conditioning process on oxide CMP: Polishing pad, slurry characteristics, and surface reactions  

Microsoft Academic Search

Temperature effects were investigated on the improvement of silicon dioxide (oxide) chemical mechanical polishing performances including removal rate and surface morphology by controlling the pad conditioning temperature. The characteristics of silica slurry including potential of hydrogen (pH), conductivity, particle size, and zeta potential were changed by the frictional heat of the polishing process and the remaining heat after a high-temperature

Nam-Hoon Kim; Yong-Jin Seo; Woo-Sun Lee

2006-01-01

352

In situ XPS studies of perovskite oxide surfaces under electrochemical polarization.  

PubMed

An in situ XPS study of oxidation-reduction processes on three perovskite oxide electrode surfaces was carried out by incorporating the materials in an electrochemical cell mounted on a heated sample stage in an ultrahigh vacuum (UHV) chamber. Electrodes made of powdered LaCr(1-x)Ni(x)O(3-delta) (x = 0.4, 1) showed changes in the XPS features of all elements upon redox cycling between formal Ni3+ and Ni2+ oxidation stoichiometries, indicating the delocalized nature of the electronic states involved and strong mixing of O 2p to Ni 3d levels to form band states. The surface also showed changes in adsorption capacity for CO2 upon reduction as a result of increased nucleophilicity of surface oxygen. Another perovskite oxide, La(0.5)Sr(0.5)CoO(3-delta), laser deposited as highly oriented thin films on (100) oriented yttria-stabilized zirconia (YSZ), also showed evidence of both local and nonlocal effects in the XPS features upon redox cycling. In contrast to LaCr(1-x)Ni(x)O(3-delta), redox cycling mainly affected the XPS features of cobalt with little effect on oxygen. This signifies reduced participation of O 2p states in the conduction band of this material. Small changes in surface cation stoichiometry in this film were observed and attributed to mobility of the A-site Sr dopant under polarization. PMID:16851240

Vovk, Greg; Chen, Xiaohua; Mims, Charles A

2005-02-17

353

ROLE OF SURFACE COMPLEXED IRON IN OXIDANT GENERATION AND LUNG INFLAMMATION INDUCED BY SILICATES  

EPA Science Inventory

The hypothesis was tested that silica and silicate dusts complex iron on their surface and that this iron increases 1) in vitro oxidant generation, and mediator release by alveolar macrophages, and 2) acute inflammatory lung injury. ilica and silicates were found to complex more ...

354

Drift analysis of surface oxygen complexes on soot formed by metal oxides  

SciTech Connect

At the Delft University of Technology a project concerning the catalytic removal of soot from diesel exhaust gases is being carried out. We are interested in a catalyst for the oxidation of soot particulates because: (i) diesel engines can no longer meet the requirements of the particulate (soot) emission standards, and (ii) collection of soot in a monolithic filter and simultaneous oxidation at diesel exhaust gas temperatures (600 K) is considered to be the best option to abate the emission of soot. The mechanism of catalytic oxidation reactions of carbonaceous materials has been the subject of many researchers over the last decades. Although it has been generally exepted that Surface Oxygen Complexes (S.O.C.) play an essential role in these reactions, their chemical nature, and interaction with catalysts and the oxidant (CO{sub 2}, H{sub 2}O or O{sub 2}) have hardly been reported. A powerful tool in analyzing carbonaceous materials is Fourier Transformed Infrared spectroscopy and in particular Diffuse Reflectance Infrared Fourier Transformed (DRIFT) spectroscopy. Several research groups have analyzed coal of several ranks using this technique e.g.. Also in situ studies regarding the oxidation of coal have been performed, as well as DRIFT studies on oxidized soot and PF chars. In this paper DRIFT analyses of partially converted soot by impregnated Fe-, Co-, Cr, K, and Ca-oxides (10 wt%) are presented, which validates a comparison of these analyses with literature data on catalyzed carbon and coal gasification.

Mul, G.; Kapteijn, F.; Moulijn, J.A. [Delft Univ. of Technology (Netherlands)

1996-12-31

355

Activated carbon enhanced ozonation of oxalate attributed to HO oxidation in bulk solution and surface oxidation: effect of activated carbon dosage and pH.  

PubMed

Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon (AC) in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals (HO) in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol (tBA) with low dosages of AC, while it was hardly affected by tBA when the AC dosage was greater than 0.3g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05g/L, but it did not work when the AC dosage was no less than 0.1g/L. These observations indicate that HO in bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HO oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HO oxidation in basic bulk solution. A mechanism involving both HO oxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate. PMID:25288554

Xing, Linlin; Xie, Yongbing; Minakata, Daisuke; Cao, Hongbin; Xiao, Jiadong; Zhang, Yi; Crittenden, John C

2014-10-01

356

Influence of surface mechanical attrition treatment on the oxidation behavior of 316L stainless steel at 750°C  

NASA Astrophysics Data System (ADS)

In this paper, the effects of Surface Mechanical Attrition Treatment on the high- temperature oxidation of AISI 316L austenitic stainless steel are investigated. Samples treated with different conditions were oxidized at 750°C in order to study the effect of this type of nanocrystallisation on the oxidation resistance of the alloy concerned. X-ray diffraction and in- situ Raman spectroscopy were used to identify the oxides formed at the surface. The results indicate the presence of hematite, magnetite and chromium oxides. Experimental results obtained by Raman spectroscopy were also used to study the stress evolution in Cr2O3 films during isothermal conditions.

Benafia, S.; Retraint, D.; Panicaud, B.; Grosseau Poussard, J. L.

2014-08-01

357

Aqueous aggregation and surface deposition processes of engineered superparamagnetic iron oxide nanoparticles for environmental applications.  

PubMed

Engineered, superparamagnetic, iron oxide nanoparticles (IONPs) have significant potential as platform materials for environmental sensing, imaging and remediation due to their unique size, physicochemical and magnetic properties. To this end, controlling the size and surface chemistry of the materials is crucial for such applications in the aqueous phase, and in particular, for porous matrixes with particle-surface interaction considerations. In this study, superparamagnetic, highly monodispersed 8 nm IONPs were synthesized and transferred into water as stable suspensions (remaining monodispersed) by way of an interfacial oleic acid bilayer surface. Once stabilized and characterized, particle-particle and model surface interactions (deposition and release) were quantitatively investigated and described systematically as a function of ionic strength (IS) and type with time-resolved dynamic light scattering (DLS), zeta potential, and real-time quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The critical coagulation concentration (CCC) for oleic acid bilayer coated iron oxide nanoparticles (OA-IONPs) were determined to be 710 mM for NaCl (matching DLVO predictions) and 10.6 mM for CaCl2, respectively. For all conditions tested, surface deposition kinetics showed stronger, more favorable interactions between OA-IONPs and polystyrene surfaces compared to silica, which is hypothesized to be due to increased particle-surface hydrophobic interactions (when compared to silica surfaces). PMID:25222070

Li, Wenlu; Liu, Di; Wu, Jiewei; Kim, Changwoo; Fortner, John D

2014-10-21

358

Decorating metal oxide surfaces with fluorescent chlorosulfonated corroles.  

PubMed

We have prepared 2,17-bis(chlorosulfonyl)-5,10,15-tris(pentafluorophenyl)corrole (1), 2,17-bis(chlorosulfonyl)-5,10,15-tris(pentafluorophenyl)corrolatoaluminum(III) (1-Al), and 2,17-bis(chlorosulfonyl)-5,10,15-tris(pentafluorophenyl)corrolatogallium(III) (1-Ga). The metal complexes 1-Al and 1-Ga were isolated and characterized by electronic absorption and NMR spectroscopies, as well as by mass spectrometry. Relative emission quantum yields for 1, 1-Al, and 1-Ga, determined in toluene, are 0.094, 0.127, and 0.099, respectively. Reactions between 1, 1-Al, and 1-Ga and TiO2 nanoparticles (NPs) result in corrole-TiO2 NP conjugates. The functionalized NP surfaces were investigated by solid-state Fourier transform infrared and X-ray photoelectron spectroscopies and by confocal fluorescence imaging. The fluorescence images for 1-Al-TiO2 and 1-Ga-TiO2 suggest a promising application of these NP conjugates as contrast agents for noninvasive optical imaging. PMID:23611256

Blumenfeld, Carl M; Grubbs, Robert H; Moats, Rex A; Gray, Harry B; Sorasaenee, Karn

2013-05-01

359

The Role of Surface Defects in CO Oxidation, Methanol Oxidation, and Oxygen Reduction on Pt,,111...  

E-print Network

of defects in each of these reactions was interpreted in terms of geometric and electronic effects to have a significant effect on reactivity, although in the case of rapid surface diffusion even a low, with different types of defects kink type and step type showing different effects for the different

Kenis, Paul J. A.

360

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics  

PubMed Central

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in size associated with a decrease in density with further annealing. PMID:18534025

Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM

2008-01-01

361

Characterization study of polycrystalline tin oxide surfaces before and after reduction in CO  

NASA Technical Reports Server (NTRS)

Polycrystalline tin oxide surfaces have been examined before and after reduction in 40 Torr of CO at 100 and 175 C using Auger electron spectroscopy (AES), electron spectroscopy for chemical analysis (ESCA), ion scattering spectroscopy (ISS) and electron stimulated desorption (ESD). The changes in the surface composition and chemical states of the surface species generally are subtle for the reductive conditions used. However, significant changes do occur with regard to the amounts and the chemical forms of the hydrogen-containing species remaining after both the 100 and 175 C reductions.

Drawdy, Jean E.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

1990-01-01

362

Natural and pyrogenic humic acids at goethite and natural oxide surfaces interacting with phosphate.  

PubMed

Fulvic and humic acids have a large variability in binding to metal (hydr) oxide surfaces and interact differently with oxyanions, as examined here experimentally. Pyrogenic humic acid has been included in our study since it will be released to the environment in the case of large-scale application of biochar, potentially creating Darks Earths or Terra Preta soils. A surface complexation approach has been developed that aims to describe the competitive behavior of natural organic matter (NOM) in soil as well as model systems. Modeling points unexpectedly to a strong change of the molecular conformation of humic acid (HA) with a predominant adsorption in the Stern layer domain at low NOM loading. In soil, mineral oxide surfaces remain efficiently loaded by mineral-protected organic carbon (OC), equivalent with a layer thickness of ? ~0.5 nm that represents at least 0.1-1.0% OC, while surface-associated OC may be even three times higher. In natural systems, surface complexation modeling should account for this pervasive NOM coverage. With our charge distribution model for NOM (NOM-CD), the pH-dependent oxyanion competition of the organo-mineral oxide fraction can be described. For pyrogenic HA, a more than 10-fold increase in dissolved phosphate is predicted at long-term applications of biochar or black carbon. PMID:23875678

Hiemstra, Tjisse; Mia, Shamim; Duhaut, Pierre-Benoît; Molleman, Bastiaan

2013-08-20

363

Sputtered cadmium oxide as a surface pretreatment for graphite solid lubricant films  

NASA Technical Reports Server (NTRS)

Sputtered films of cadmium oxide were applied to sand blasted AISI 440C HT stainless steel disks as a surface pretreatment for the application of rubbed graphite films. Mixtures of cadmium oxide and graphite were applied to the nonpretreated sandblasted metal and evaluated. The results were compared to graphite films applied to other commercially available surface pretreatments. It is found that sputtered CdO pretreated surfaces increase the endurance lives of the graphite films and decrease the counterface steady state wear rate of the pins almost an order of magnitude compared to commercially available pretreatments. The CdO additions in general improved the tribological properties of graphite. The greatest benefit occurred when it was applied to the substrate rather than mixing it with the graphite and that sputtered films of CdO perform much better than rubbed CdO films.

Fusaro, R. L.

1986-01-01

364

Ag-Cu alloy surfaces in an oxidizing environment: A first-principles study  

NASA Astrophysics Data System (ADS)

Recent experiments on model catalysts have shown that Ag-Cu alloys have improved selectivity with respect to pure silver for ethylene epoxidation. In this paper, we review our first-principles investigations on the (1 1 1) surface of this alloy and present new findings on other low index surfaces. We find that, for every surface orientation, the presence of oxygen leads to copper segregation to the surface. Considering the alloy to be in equilibrium with an oxygen atmosphere and accounting for the effect of temperature and pressure, we compute the surface free energy and study the stability of several surface structures. Investigating the dependence of the surface free energy on the surface composition, we construct the phase diagram of the alloy for every surface orientation. Around the temperature, pressure and composition of interest for practical applications, we find that a limited number of structures can be present, including a thin layer of copper oxide on top of the silver surface and copper-free structures. Different surface orientations show a very similar behavior and in particular a single layer with CuO stoichiometry, significantly distorted when compared to a layer of bulk CuO, has a wide range of stability for all orientations. Our results are consistent with, and help explain, recent experimental measurements.

Piccinin, Simone; Stampfl, Catherine; Scheffler, Matthias

2009-06-01

365

Structure and growth kinetics of the oxidation process of Fe(001) whisker surfaces over a 10-decade pressure range  

NASA Astrophysics Data System (ADS)

Fe(001) surfaces of whiskers of good crystalline quality were oxidized in a pressure range from 10 - 7 mbar to 1 bar at different temperatures. Epitaxial Fe 3O 4 and FeO thin films with negligible strain were grown depending on the oxidation temperatures. The kinetics of the oxide thickness growth was measured and compared with the predictions of the Fromhold-Cook theory for oxidation of metals. Some discrepancies were found and a possible explanation is presented.

Ferrer, Salvador; Robach, Odile; Balmes, Olivier; Isern, Helena; Popa, Iona; Ackerman, Marcelo

2010-10-01

366

Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model  

NASA Astrophysics Data System (ADS)

Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

Baltrusaitis, Jonas; Mendoza-Sanchez, Beatriz; Fernandez, Vincent; Veenstra, Rick; Dukstiene, Nijole; Roberts, Adam; Fairley, Neal

2015-01-01

367

Characterization of the oxidized beta-Si3N4 whisker surface layer using XPS and TOF-SIMS.  

PubMed

The change in composition of the surface layer of beta-Si3N4 whiskers was examined after heat treatment in atmosphere. At 873 K, the beta-Si3N4 whisker was barely oxidized. At 1273 K, the oxidation of the surface layers of the whisker occurred easily. With the beta-Si3N4 oxidation, the Si-N bond gradually changed into the Si-N-O bond, and finally became the oxidized layer (amorphous layer) of the whisker surface. It was assumed that the whisker surface has a gradient interface structure which gradually changes from the oxide layer of the whisker's outer surface to the nitride crystal of the inside layer. It was confirmed that impurity elements such as Y and Ca existed mainly in the amorphous region near the interface between the amorphous layer and the crystal layer. PMID:11990541

Tokuse, M; Oyama, R; Nakagawa, H; Nakabayashi, I

2001-02-01

368

Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways  

SciTech Connect

Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger

2004-10-22

369

Surface oxide effect on optical sensing and photoelectric conversion of ?-In2Se3 hexagonal microplates.  

PubMed

The surface formation oxide assists of visible to ultraviolet photoelectric conversion in ?-In2Se3 hexagonal microplates has been explored. Hexagonal ?-In2Se3 microplates with the sizes of 10s to 100s of micrometers were synthesized and prepared by the chemical vapor transport method using ICl3 as a transport agent. Many vacancies and surface imperfection states have been found in the bulk and on the surface of the microplate because of the intrinsic defect nature of ?-In2Se3. To discover physical and chemical properties and finding technological uses of ?-In2Se3, several experiments including transmission electron miscopy (TEM), X-ray photoelectron spectroscopy (XPS), surface photovoltage (SPV), photoluminescence (PL), surface photoresponse (SPR), photoconductivity (PC), and thermoreflectance (TR) measurements have been carried out. Experimental results of TEM, XPS, SPV, PL, and SPR measurements show that a surface oxidation layer ?-In2Se3-3xO3x (0 ? x ? 1) has formed on the crystal face of ?-In2Se3 in environmental air with the inner layer content close to In2Se3 but the outermost layer content approaching In2O3. The near band edge transitions of ?-In2Se3 microplates have been probed experimentally by TR and PC measurements. The direct band gap of ?-In2Se3 has been determined to be 1.453 eV. The SPV result shows a maximum quantum efficiency of the surface oxide ?-In2Se3-3xO3x (0 ? x ? 1) that presents a peak photoresponse near 2.18 eV. The analyses of SPV, SPR, PL, TR, and PC measurements revealed that the surface oxide layer facilitates the conversion of the ultraviolet to the visible range while the native defects (Se and In vacancies) sustain photoconductivity in the near-infrared region. On the basis of the experimental results a wide-energy-range photodetector that combines PC- and SPR-mode operations for ?-In2Se3 microplate has been made. The testing results show a well-behaved function of photoelectric conversion in the near-infrared to ultraviolet region via the auxiliary forming of surface oxide on the crystalline face of the ?-In2Se3 microplates. PMID:23452408

Ho, Ching-Hwa; Lin, Chien-Hao; Wang, Yi-Ping; Chen, Ying-Cen; Chen, Shin-Hong; Huang, Ying-Sheng

2013-03-01

370

First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment  

NASA Astrophysics Data System (ADS)

By means of density-functional theory, together with concepts from atomistic thermodynamics, we present a theoretical procedure for describing the structure and stoichiometry of a binary alloy in contact with a surrounding gas phase environment. We apply the approach to the Ag-Cu alloy in an oxygen atmosphere, for which recent results report a superior selectivity for ethylene epoxidation compared to pure silver, the predominant catalyst for this reaction. We first show that the presence of oxygen leads to copper segregation to the surface. Then, considering the surface free energy as a function of the surface Cu composition, we construct the ``convex hull''. By including the dependence of the surface free energy of the oxygen chemical potential, we determine the phase diagram of the alloy as a function of temperature, pressure, and Cu surface content. We predict that for conditions typical of the epoxidation reaction, a number of structures can be present on the surface of the alloy including the clean silver surface, thin copper-oxide-like structures, and thick copper oxides. These findings are consistent with, and help explain the recent experimental results. We envisage this approach will be useful and generally applicable for the study of other alloys in contact with a gas or liquid phase.

Piccinin, Simone; Stampfl, Catherine; Scheffler, Matthias

2008-03-01

371

Early bone formation adjacent to oxidized and machined implant surfaces: a histologic study.  

PubMed

Various designs of dental implants representing different geometries and surface technologies are commercially available for patient treatment. However, data with regard to the biologic events that occur immediately after implant placement, regardless of the surface characteristic, are scarce. It has become a common procedure to perform immediate/early prosthetic loading rather than delayed loading. The goal of this study was to observe the early biologic events of peri-implant healing to understand the role of surface modifications in relation to the early phases of bone integration. The secondary goal was to observe the possible differences in the healing pattern at two oral implant surfaces differing in morphology and roughness (Ra, with Ra values ranging from 0.5 ?m (machined surface; MS) to 1.5 ?m (oxidized surface; OS). A total of 36 implants were placed in six foxhound dogs, equally divided between machined and oxidized surfaces. Three implants were positioned per hemimandible following a randomization scheme. Each animal was euthanized at a specific time point for histologic observation and histomorphometry: immediately after implant insertion and after 24 hours, 7 days, 15 days, 30 days, and 90 days. The study demonstrated an extremely low bone-implant contact (BIC) for both OS and MS implant surfaces during the first 15 days after implant placement (ranging from 12.9% to 26.9% independent of the implant surface). Increased BIC values were observed only in the 30- and 90-day specimens. The presence and the degradation of residual bone particles acted as centers for new bone formation, with osteoblasts lining osteoid tissue and subsequently woven bone independent of the implant surface characteristics. The bone-forming activity appeared strongly reduced after 30 days of healing and seemed to be complete only in the 90-day specimens, where abundant lamellar bone was evident. There is a continuing effort to develop improved titanium surfaces to achieve more rapid osseointegration and improve BIC, with the ultimate goal of applying occlusal load as early as possible. Since immediate or early implant loading is applied during and not after the first 15 days, the findings in the present study of an extremely low BIC and limited mineralized bone formation for both implant surfaces during the first 15 days after implant placement suggest that the surface roughness may not be a key factor for successful osseointegration of immediately or early loaded implants. Within the limits of this study, it can be stated that osseointegration follows a similar healing pattern with machined and oxidized implant surfaces. PMID:25734702

Simion, Massimo; Benigni, Marco; Al-Hezaimi, Khalid; Kim, David M

2015-01-01

372

Interaction and reactivity of nitric oxide and carbon monoxide on ruthenium surfaces  

SciTech Connect

A multifaceted investigation of the reduction of nitric oxide by carbon monoxide using a ruthenium (102) single crystal catalyst in the pressure range 10/sup -3/ to 10 Torr and temperature range of 300 to 475/sup 0/C has been undertaken. Kinetic and isotopic results indicate that the reaction products CO/sub 2/ and N/sub 2/ were produced via two reaction mechanisms. Using a reducing gas mixture (low P/sub NO//P/sub CO/ ratio) a two site mechanism was operative involving NO dissociation. The carbon monoxide kinetic order varied from +1 to -3 and the nitric oxide order varied from +1 to 0. The catalyst under these conditions was determined to be metallic ruthenium with oxygen bonded within the first surface layer. The oxygen was unreactive and formed a (1 x 3)-0 LEED pattern. Under oxidizing conditions (high P/sub NO//P/sub CO/ ratio) the catalyst was ruthenium dioxide and the functional mechanism under these reaction conditions yielded a nitric oxide order of +2 to -4. Inclusion of a site poisoning mechanism under reducing conditions and an RuO/sub 2/ growth mechanism involving ruthenium cation transfer under oxidizing conditions into the kinetic rate laws led to an overall rate law which could be fit to the carbon monoxide and nitric oxide order plots. Using isotopically oxygen labelled reactants, it was observed that the three possible isotopes of carbon dioxide were produced. A ..gamma..-CO surface species is postulated as an intermediate in the exchange process. The reaction was observed to be initially surface structure insensitive and the reaction kinetics were derived using a Langmuir-Hinshelwood formalism.

Quick, E.E.

1980-03-01

373

Production of hydroxyapatite layers on the plasma electrolytically oxidized surface of titanium alloys.  

PubMed

Hydroxyapatite (HA) is a bioactive material that is widely used for improving the osseointegration of titanium dental implants. Titanium can be coated with HA by various methods, such as chemical vapor deposition (CVD), thermal spray, or plasma spray. HA coatings can also be grown on titanium surfaces by hydrothermal, chemical, and electrochemical methods. Plasma electrolytic oxidation (PEO), or microarc oxidation (MAO), is an electrochemical method that enables the production of a thick porous oxide layer on the surface of a titanium implant. If the electrolyte in which PEO is performed contains calcium and phosphate ions, the oxide layer produced may contain hydroxyapatite. The HA content can then be increased by subsequent hydrothermal treatment. The HA thus produced on titanium surfaces has attractive properties, such as a high porosity, a controllable thickness, and a considerable density, which favor its use in dental and bone surgery. This review summarizes the state of the art and possible further development of PEO for the production of HA on Ti implants. PMID:25175246

Lugovskoy, Alex; Lugovskoy, Svetlana

2014-10-01

374

Association of uranium with iron oxides typically formed on corroding steel surfaces.  

PubMed

Decontamination of metal surfaces contaminated with low levels of radionuclides is a major concern at Department of Energy facilities. The development of an environmentally friendly and cost-effective decontamination process requires an understanding of their association with the corroding surfaces. We investigated the association of uranium with the amorphous and crystalline forms of iron oxides commonly formed on corroding steel surfaces. Uranium was incorporated with the oxide by addition during the formation of ferrihydrite, goethite, green rust II, lepidocrocite, maghemite, and magnetite. X-ray diffraction confirmed the mineralogical form of the oxide. EXAFS analysis at the U L(III) edge showed that uranium was present in hexavalent form as a uranyl oxyhydroxide species with goethite, maghemite, and magnetite and as a bidentate inner-sphere complex with ferrihydrite and lepidocrocite. Iron was present in the ferric form with ferrihydrite, goethite, lepidocrocite, and maghemite; whereas with magnetite and green rust II, both ferrous and ferric forms were present with characteristic ferrous:total iron ratios of 0.65 and 0.73, respectively. In the presence of the uranyl ion, green rust II was converted to magnetite with concomitantreduction of uranium to its tetravalent form. The rate and extent of uranium dissolution in dilute HCl depended on its association with the oxide: uranium present as oxyhydroxide species underwent rapid dissolution followed by a slow dissolution of iron; whereas uranium present as an inner-sphere complex with iron resulted in concomitant dissolution of the uranium and iron. PMID:12214641

Dodge, C J; Francis, A J; Gillow, J B; Halada, G P; Eng, C; Clayton, C R

2002-08-15

375

Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces  

NASA Astrophysics Data System (ADS)

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups. UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure. Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shorte

Singh, Jagdeep

376

Fabricating nanostructures through a combination of nano-oxidation and wet etching on silicon wafers with different surface conditions.  

PubMed

This study investigates the surface conditions of silicon wafers with native oxide layers (NOL) or hydrogen passivated layers (HPL) and how they influence the processes of nano-oxidation and wet etching. We also explore the combination of nano-oxidation and wet etching processes to produce nanostructures. Experimental results reveal that the surface conditions of silicon wafers have a considerable impact on the results of nano-oxidation when combined with wet etching. The height and width of oxides on NOL samples exceeded the dimensions of oxides on HPL samples, and this difference became increasingly evident with an increase in applied bias voltage. The height of oxidized nanolines on the HPL sample increased after wet etching; however, the width of the lines increased only marginally. After wet etching, the height and width of oxides on the NOL were more than two times greater than those on the HPL. Increasing the applied bias voltage during nano-oxidation on NOL samples increased both the height and width of the oxides. After wet etching however, the increase in bias voltage appeared to have little effect on the height of oxidized nanolines, but the width of oxidized lines increased. This study also discovered that the use of higher applied bias voltages on NOL samples followed by wet etching results in nanostructures with a section profile closely resembling a curved surface. The use of this technique enabled researchers to create molds in the shape of a silicon nanolens array and an elegantly shaped nanoscale complex structures mold. PMID:22331692

Huang, Jen-Ching

2012-01-01

377

Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.  

PubMed

A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength. PMID:19176225

Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

2009-04-15

378

Oxidation-Induced Whisker Growth on the Surface of Sn6.6(La, Ce) Alloy  

Microsoft Academic Search

During solidification of rare-earth (RE)-containing Sn-6.6(La, Ce) alloys, (La0.93Ce0.07)Sn3 intermetallic clusters form in the near ?-Sn matrix. These (La0.93Ce0.07)Sn3 intermetallics oxidize predominately after air storage at room temperature for short time periods. Accompanying the oxidation\\u000a reaction, tin sprouts appear on the outer surface of the intermetallic clusters. Increasing the storage time at room temperature\\u000a leads to the formation of thread-like

Tung-Han Chuang; Hsiu-Jen Lin; Chih-Chien Chi

2007-01-01

379

Oxidation-Induced Whisker Growth on the Surface of Sn-6.6(La, Ce) Alloy  

NASA Astrophysics Data System (ADS)

During solidification of rare-earth (RE)-containing Sn-6.6(La, Ce) alloys, (La0.93Ce0.07)Sn3 intermetallic clusters form in the near ?-Sn matrix. These (La0.93Ce0.07)Sn3 intermetallics oxidize predominately after air storage at room temperature for short time periods. Accompanying the oxidation reaction, tin sprouts appear on the outer surface of the intermetallic clusters. Increasing the storage time at room temperature leads to the formation of thread-like tin whiskers. In specimens stored at 150°C in an air furnace, only a small amount of tin sprouts can be found in the interior regions of the oxidized (La0.93Ce0.07)Sn3 intermetallics. However, many coarse tin hillocks formed around the intermetallic clusters. The driving force for whisker growth is the compressive stress induced by the volume expansion of (La0.93 Ce0.07)Sn3, which extrudes the tin atoms released by the oxidation reaction of these RE intermetallics. In addition, the huge compressive stress accumulated by the volume expansion of the drastically oxidized RE intermetallics during 150°C air storage extrudes the Sn-6.6(La, Ce) matrix around the RE oxides to form the coarse hillocks.

Chuang, Tung-Han; Lin, Hsiu-Jen; Chi, Chih-Chien

2007-12-01

380

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation  

Microsoft Academic Search

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited

Eric W. Hoppe; Allen Seifert; Craig E. Aalseth; Paula P. Bachelor; Anthony R. Day; Danny J. Edwards; Todd W. Hossbach; Kevin E. Litke; Justin I. McIntyre; Harry S. Miley; Shannon M. Schulte; John E. Smart; Glen A. Warren

2007-01-01

381

On the correlation between surface morphology and electron work function of indium tin oxide  

NASA Astrophysics Data System (ADS)

The electron work function (EWF) is an important parameter of a semiconductor. The understanding of the correlation between the EWF and surface morphology is of much significance for revealing related photoelectric mechanisms. In this study, the surface of indium tin oxide (ITO) was treated by chemical corrosion or absorption of copper phthalocyanine molecules, and their changes in EWF were systematically investigated using scanning Kelvin probe. The decrease of the EWF with the increase of surface roughness was found. Based on a microcapacitor model, the correlation between the EWF and surface microstructures was built up, which was well consistent with the experimental results. These data are of help for improving the photoelectric behaviors of ITO-based devices by adjusting surface/interface structures.

Xue, Mingshan; Wu, Hainan; Ou, Junfei; Wang, Fajun; Li, Xibao; Li, Wen; Jiang, Zhonghao

2012-06-01

382

Sputtering and native oxide formation on (110) surfaces of Cd(1-x)Mn(x)Te  

NASA Technical Reports Server (NTRS)

Native oxides on the surface of Cd(1-x)Mn(x)Te (X between 0 and 0.7) have been analyzed on the basis of X-ray photoemission spectroscopy measurements. Depth profile analysis revealed a significant increase in the thickness at higher Mn concentrations and a strong Mn segregation to the surface, respectively. Sputter-induced damage on cleaved (110)-oriented surfaces was analyzed by photoreflectance and photoluminescence measurements. The damage was found to be larger on CdTe than on the alloy. Thermal annealing showed nearly complete restoration for the surface of the alloy, while CdTe revealed irreversible modifications in the near-surface regime upon sputtering and post annealing.

Neff, H.; Lay, K. Y.; Abid, B.; Lange, P.; Lucovsky, G.

1986-01-01

383

CO Oxidation Facilitated by Robust Surface States on Au-Covered Topological Insulators  

SciTech Connect

Surface states the electronic states emerging as a solid material terminates at a surface are usually vulnerable to contaminations and defects. The robust topological surface state(s) (TSS) on the three-dimensional topological insulators provide a perfect platform for exploiting surface states in less stringent environments. Employing first-principles density functional theory calculations, we demonstrate that the TSS can play a vital role in facilitating surface reactions by serving as an effective electron bath. We use CO oxidation on gold-covered Bi2Se3 as a prototype example, and show that the robust TSS can significantly enhance the adsorption energy of both CO and O2 molecules, by promoting different directions of electron transfer. The concept of TSS as an electron bath may lead to new design principles beyond the conventional d-band theory of heterogeneous catalysis.

Chen, Hua [University of Tennessee, Knoxville (UTK); Zhu, Wenguang [ORNL; Xiao, Di [ORNL; Zhang, Zhenyu [University of Science and Technology, Beijing, China

2011-01-01

384

Surface Diffusion and Concentration Polarization on Oxide-Supported Metal Electrocatalyst Particles  

SciTech Connect

A common assumption in solid oxide fuel cell models is that the anodic hydrogen-oxygen reaction that produces the electrical current is strictly localized at the triple phase boundary between the metal catalyst particle, the supporting zirconia electrolyte, and the gas atmosphere. This assumption is tested in the present work, and found to lead to the erroneous conclusion that surface diffusion on the catalyst particle is responsible for the anodic concentration polarization that limits the maximum current output of the device. A more detailed analysis that permits oxygen spillover onto the catalyst particle surface indicates that the reactive area simply spreads over the surface as needed to support the current. Hydrogen is readily available for reaction by adsorption over the entire surface. There were no indications in this work that surface diffusion mechanisms can be responsible for anodic concentration polarization.

Williford, Rick E.; Chick, Lawrence A.

2003-12-20

385

Early stages of the oxidation of metal surfaces. [photoelectron spectroscopy of zinc oxide  

NASA Technical Reports Server (NTRS)

Photoemission cross sections were calculated for the ZnO4(-6) cluster using the self consistent-chi alpha- scattered wave theory to display the main features of the ultraviolet and X-ray photoemission data from ZnO. A solid model is suggested for an absolute photoemission intensity comparison resulting in chi alpha intensities which are roughly 70% of the experimental values. Together with the experimental data, the calculations allow a complete determination of the electronic structure of a ZnO surface.

Gatos, H. C.; Johnson, K. H.

1978-01-01

386

TEM studies of the nitrided/oxided Ni-Ti surface layer.  

PubMed

TiN and TiO(2) coatings, which are known from their low chemical reactivity, high hardness and wear and corrosion resistance, are used for protecting the NiTi surface. In the present work, nearly equiatomic NiTi (50.6 at.%) shape memory alloy was covered with the layers obtained by nitriding under glow discharge at 1073 K. Additionally, at the end of the process some amount of oxygen was added. Characterization of the nitrided/oxided layers structure was carried out using transmission and scanning electron microscopy. The investigations were focused on the structure of the multilayer nitrided/oxided NiTi surface. The surface is formed from nanocrystalline and columnar grains of the TiN phase. Between the top layer and beta-NiTi substrate the interface Ti(2)Ni layer was formed. Addition of oxygen at the end of the process created a thin layer of TiO(2) phase nanograins at the surface of the TiN phase. In the same areas, small amount of amorphous phase was identified. The combination of nitriding and oxidation formed layers that reveal relatively high corrosion resistance. PMID:20500413

Lelatko, J; Goryczka, T; Paczkowski, P; Wierzcho?, T; Morawiec, H

2010-03-01

387

Quantitative analysis of chemical interaction and doping of the Si(111) native oxide surface with tetrafluorotetracyanoquinodimethane  

SciTech Connect

The charge-transfer states and the carrier concentration of the native oxide Si(111) surface adsorbed with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F{sub 4}-TCNQ) were investigated by X-ray photoelectron spectroscopy (XPS) and independently driven four-probe electrical conductivity measurements. The XPS results show that F{sub 4}-TCNQ molecules are involved in charge transfer with the SiO{sub 2}/Si(111) surface. The Si 2p XPS spectra and the surface photovoltage shift provide the evidences of (i) change in the oxidation states at the SiO{sub 2}-Si(111) interface region and (ii) formation of a p-type space charge layer (SCL) with a hole concentration of 1.7?×?10{sup 10}?cm{sup ?2}, respectively. The four-probe I–V measurements also support the formation of the p-type SCL, and the estimated hole concentration of 2.0?×?10{sup 10}?cm{sup ?2} agrees well with the XPS results. The estimated SCL hole concentrations were much smaller than the excess charge density in the F{sub 4}-TCNQ layer, of the order of 10{sup 13}?cm{sup ?2}, suggesting that most of charges were localized as the oxidation states at the SiO{sub 2}-Si(111) interface region. The present quantitative methods ensure precise determination of the doping concentration near the surface region.

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Furuhashi, Masayuki; Koitaya, Takanori; Shiozawa, Yuichiro; Fujimaki, Kazutaka; Harada, Yosuke; Mukai, Kozo; Yoshinobu, Jun [The Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan)

2014-04-14

388

Excellent c-Si surface passivation by low-temperature atomic layer deposited titanium oxide  

SciTech Connect

In this work, we demonstrate that thermal atomic layer deposited (ALD) titanium oxide (TiO{sub x}) films are able to provide a—up to now unprecedented—level of surface passivation on undiffused low-resistivity crystalline silicon (c-Si). The surface passivation provided by the ALD TiO{sub x} films is activated by a post-deposition anneal and subsequent light soaking treatment. Ultralow effective surface recombination velocities down to 2.8?cm/s and 8.3?cm/s, respectively, are achieved on n-type and p-type float-zone c-Si wafers. Detailed analysis confirms that the TiO{sub x} films are nearly stoichiometric, have no significant level of contaminants, and are of amorphous nature. The passivation is found to be stable after storage in the dark for eight months. These results demonstrate that TiO{sub x} films are also capable of providing excellent passivation of undiffused c-Si surfaces on a comparable level to thermal silicon oxide, silicon nitride, and aluminum oxide. In addition, it is well known that TiO{sub x} has an optimal refractive index of 2.4 in the visible range for glass encapsulated solar cells, as well as a low extinction coefficient. Thus, the results presented in this work could facilitate the re-emergence of TiO{sub x} in the field of high-efficiency silicon wafer solar cells.

Liao, Baochen, E-mail: liaobaochen@nus.edu.sg [Solar Energy Research Institute of Singapore, National University of Singapore, 7 Engineering Drive 1, Singapore 117574 (Singapore); Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore 117576 (Singapore); A*STAR Institute of Materials Research and Engineering (IMRE), 3 Research Link, Singapore 117602 (Singapore); Hoex, Bram [Solar Energy Research Institute of Singapore, National University of Singapore, 7 Engineering Drive 1, Singapore 117574 (Singapore); Aberle, Armin G.; Bhatia, Charanjit S., E-mail: elebcs@nus.edu.sg [Solar Energy Research Institute of Singapore, National University of Singapore, 7 Engineering Drive 1, Singapore 117574 (Singapore); Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore 117576 (Singapore); Chi, Dongzhi [A*STAR Institute of Materials Research and Engineering (IMRE), 3 Research Link, Singapore 117602 (Singapore)

2014-06-23

389

Quantitative analysis of chemical interaction and doping of the Si(111) native oxide surface with tetrafluorotetracyanoquinodimethane  

NASA Astrophysics Data System (ADS)

The charge-transfer states and the carrier concentration of the native oxide Si(111) surface adsorbed with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) were investigated by X-ray photoelectron spectroscopy (XPS) and independently driven four-probe electrical conductivity measurements. The XPS results show that F4-TCNQ molecules are involved in charge transfer with the SiO2/Si(111) surface. The Si 2p XPS spectra and the surface photovoltage shift provide the evidences of (i) change in the oxidation states at the SiO2-Si(111) interface region and (ii) formation of a p-type space charge layer (SCL) with a hole concentration of 1.7 × 1010 cm-2, respectively. The four-probe I-V measurements also support the formation of the p-type SCL, and the estimated hole concentration of 2.0 × 1010 cm-2 agrees well with the XPS results. The estimated SCL hole concentrations were much smaller than the excess charge density in the F4-TCNQ layer, of the order of 1013 cm-2, suggesting that most of charges were localized as the oxidation states at the SiO2-Si(111) interface region. The present quantitative methods ensure precise determination of the doping concentration near the surface region.

Yoshimoto, Shinya; Furuhashi, Masayuki; Koitaya, Takanori; Shiozawa, Yuichiro; Fujimaki, Kazutaka; Harada, Yosuke; Mukai, Kozo; Yoshinobu, Jun

2014-04-01

390

The growth of cobalt oxides on HOPG and SiO2 surfaces: A comparative study  

NASA Astrophysics Data System (ADS)

The growth of cobalt oxides by reactive thermal evaporation of metallic cobalt on highly oriented pyrolytic graphite (HOPG) and SiO2 (X cut quartz surface), in an oxygen atmosphere at room temperature, has been chemically and morphologically studied by means of X-ray photoelectron spectroscopy and atomic force microscopy. The chemical analysis, which also includes cluster calculations, reveals that for the early deposition stages on both substrates, Co2 + species are stabilized at the surface up to a coverage which depends on the substrate. Further coverages lead to the formation of the spinel oxide Co3O4. The results are discussed in terms of the dependence of the surface energy on the size of the CoO deposited moieties. On the other hand, it has been found that the initial way of growth of cobalt oxides on HOPG is of Stranski-Krastanov mode whereas on SiO2 the growth is of Volmer-Weber mode. The differences in the growth morphology have been discussed in terms of the surface diffusivity of the CoO deposits on the substrates.

Díaz-Fernández, D.; Méndez, J.; Bomatí-Miguel, O.; Yubero, F.; Mossanek, R. J. O.; Abbate, M.; Domínguez-Cañizares, G.; Gutiérrez, A.; Tougaard, S.; Soriano, L.

2014-06-01

391

How surface potential determines the kinetics of the first hole transfer of photocatalytic water oxidation.  

PubMed

Interfacial hole transfer between n-SrTiO3 and OH(-) was investigated by surface sensitive transient optical spectroscopy of an in situ photoelectrochemical cell during water oxidation. The kinetics reveal a single rate constant with an exponential dependence on the surface hole potential, spanning time scales from 3 ns to 8 ps over a ?1 V increase. A voltage- and laser illumination-induced process moves the valence band edge at the n-type semiconductor/water interface to continuously change the surface hole potential. This single step of the water oxidation reaction is assigned to the first hole transfer h(+) + OH(-) ? OH(•). The kinetics quantify how much a change in the free energy difference driving this first hole transfer reduces the activation barrier. They are also used to extrapolate the kinetic rate due to the activation barrier when that free energy difference is zero, or the Nernstian potential. This is the first time transient spectroscopy has enabled the separation of the first hole transfer from the full four hole transfer cycle and a direct determination of these two quantities. The Nernstian potential for OH(-)/OH(•) is also suggested, in rough agreement with gas-phase studies. The observation of a distinct, much longer time scale upon picosecond hole transfer to OH(-) suggests that a dominant, more stable intermediate of the water oxidation reaction, possibly a surface bound oxo, may result. PMID:25029360

Waegele, Matthias M; Chen, Xihan; Herlihy, David M; Cuk, Tanja

2014-07-30

392

Excellent c-Si surface passivation by low-temperature atomic layer deposited titanium oxide  

NASA Astrophysics Data System (ADS)

In this work, we demonstrate that thermal atomic layer deposited (ALD) titanium oxide (TiOx) films are able to provide a—up to now unprecedented—level of surface passivation on undiffused low-resistivity crystalline silicon (c-Si). The surface passivation provided by the ALD TiOx films is activated by a post-deposition anneal and subsequent light soaking treatment. Ultralow effective surface recombination velocities down to 2.8 cm/s and 8.3 cm/s, respectively, are achieved on n-type and p-type float-zone c-Si wafers. Detailed analysis confirms that the TiOx films are nearly stoichiometric, have no significant level of contaminants, and are of amorphous nature. The passivation is found to be stable after storage in the dark for eight months. These results demonstrate that TiOx films are also capable of providing excellent passivation of undiffused c-Si surfaces on a comparable level to thermal silicon oxide, silicon nitride, and aluminum oxide. In addition, it is well known that TiOx has an optimal refractive index of 2.4 in the visible range for glass encapsulated solar cells, as well as a low extinction coefficient. Thus, the results presented in this work could facilitate the re-emergence of TiOx in the field of high-efficiency silicon wafer solar cells.

Liao, Baochen; Hoex, Bram; Aberle, Armin G.; Chi, Dongzhi; Bhatia, Charanjit S.

2014-06-01

393

DESIGN NOTE: A combined unit for viscosity, surface tension and density measurements in oxide melts  

NASA Astrophysics Data System (ADS)

A combined experimental unit for high-temperature viscosity, density and surface-tension measurements in oxide melts (glasses, metallurgical slags and coal ash) is described. The high-temperature viscometer is based on the Brookfield device whereas the density and surface-tension measurements are based on the maximum-bubble-pressure method. A vertical tube furnace is capable of reaching temperatures up to 0957-0233/8/7/020/img1. An inert (argon) atmosphere allows the use of non-standard, molybdenum spindles for viscosity measurements and permits investigation of melts susceptible to oxidation. The ranges for the measured values are 0.1 - 460 Pa s for viscosity, 0957-0233/8/7/020/img2 for surface tension, and 0957-0233/8/7/020/img3 for density. Since the range of the pressure transducer can be changed for measurements of higher surface tension and density, the experimental unit can also be used for density and surface-tension measurements in liquid metals and mattes. These high-temperature measurements are accurate to within 0957-0233/8/7/020/img4 for viscosity, 0957-0233/8/7/020/img5 for surface tension and 0957-0233/8/7/020/img6 for density.

Vaisburd, S.; Brandon, D. G.

1997-07-01

394

Surface oxidation of GaN(0001): Nitrogen plasma-assisted cleaning for ultrahigh vacuum applications  

SciTech Connect

The cleaning of metal-organic vapor-phase epitaxial GaN(0001) template layers grown on sapphire has been investigated. Different procedures, performed under ultrahigh vacuum conditions, including degassing and exposure to active nitrogen from a radio frequency nitrogen plasma source have been compared. For this purpose, x-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and scanning tunneling microscopy have been employed in order to assess chemical as well as structural and morphological surface properties. Initial degassing at 600?°C under ultrahigh vacuum conditions only partially eliminates the surface contaminants. In contrast to plasma assisted nitrogen cleaning at temperatures as low as 300?°C, active-nitrogen exposure at temperatures as high as 700?°C removes the majority of oxide species from the surface. However, extended high-temperature active-nitrogen cleaning leads to severe surface roughening. Optimum results regarding both the removal of surface oxides as well as the surface structural and morphological quality have been achieved for a combination of initial low-temperature plasma-assisted cleaning, followed by a rapid nitrogen plasma-assisted cleaning at high temperature.

Gangopadhyay, Subhashis [Institute of Solid State Physics, University of Bremen, P.O. Box 330440, 28334 Bremen, Germany and Department of Physics, Birla Institute of Technology and Science, Pilani, 333031 Rajasthan (India); Schmidt, Thomas, E-mail: tschmidt@ifp.uni-bremen.de; Kruse, Carsten; Figge, Stephan; Hommel, Detlef; Falta, Jens [Institute of Solid State Physics, University of Bremen, P.O. Box 330440, 28334 Bremen (Germany)

2014-09-01

395

Estimation of equilibrium surface precipitation constants for trivalent metal sorption onto hydrous ferric oxide and calcite  

NASA Astrophysics Data System (ADS)

Equilibrium constants for modeling surface precipitation of trivalent metal cations ( M) onto hydrous ferric oxide and calcite were estimated from linear correlations of standard state Gibbs free energies of formation, ( ?Gf,MvX(ss)0) of the surface precipitates. The surface precipitation reactions were derived from Farley et. al. [K.J. Farley, D.A. Dzombak, F.M.M. Morel, J. Colloid Interface Sci. 106 (1985) 226] surface precipitation model, which are based on surface complexation model coupled with solid solution representation for surface precipitation on the solid surface. The ?Gf,MvX(ss)0 values were correlated through the following linear free energy relations ?Gf,M(OH)3(ss)0-791.70r=0.1587?Gn,M0-1273.07 and ?Gf,M2(CO3)3(ss)0-197.241r=0.278?Gn,M0-1431.27 where 'ss' stands for the end-member solid component of surface precipitate, ?Gf,MvX(ss)0 is in kJ/mol, r is the Shannon-Prewitt radius of M in a given coordination state (nm), and ?Gn,M0 is the non-solvation contribution to the Gibbs free energy of formation of the aqueous M ion. Results indicate that the above surface precipitation correlations are useful tools where experimental data are not available.

Ragavan, Anpalaki J.; Adams, Dean V.

2009-06-01

396

Efficient Chemisorption of Organophosphorous Redox Probes on Indium Tin Oxide Surfaces under Mild Conditions.  

PubMed

We report a mild and straightforward one-step chemical surface functionalization of indium tin oxide (ITO) electrodes by redox-active molecules bearing an organophosphoryl anchoring group (i.e., alkyl phosphate or alkyl phosphonate group). The method takes advantage of simple passive adsorption in an aqueous solution at room temperature. We show that organophosphorus compounds can adsorb much more strongly and stably on an ITO surface than analogous redox-active molecules bearing a carboxylate or a boronate moiety. We provide evidence, through quantitative electrochemical characterization (i.e., by cyclic voltammetry) of the adsorbed organophosphoryl redox-active molecules, of the occurrence of three different adsorbate fractions on ITO, exhibiting different stabilities on the surface. Among these three fractions, one is observed to be strongly chemisorbed, exhibiting high stability and resistance to desorption/hydrolysis in a free-redox probe aqueous buffer. We attribute this remarkable stability to the formation of chemical bonds between the organophosphorus anchoring group and the metal oxide surface, likely occurring through a heterocondensation reaction in water. From XPS analysis, we also demonstrate that the surface coverage of the chemisorbed molecules is highly affected by the degree of surface hydroxylation, a parameter that can be tuned by simply preconditioning the freshly cleaned ITO surfaces in water. The lower the relative surface hydroxide density on ITO, the higher was the surface coverage of the chemisorbed species. This behavior is in line with a chemisorption mechanism involving coordination of a deprotonated phosphoryl oxygen atom to the non-hydroxylated acidic metal sites of ITO. PMID:25611977

Forget, Amélie; Limoges, Benoît; Balland, Véronique

2015-02-17

397

Effects of electrolyzed oxidizing water on reducing Listeria monocytogenes contamination on seafood processing surfaces.  

PubMed

The effects of electrolyzed oxidizing (EO) water on reducing Listeria monocytogenes contamination on seafood processing surfaces were studied. Chips (5 x 5 cm(2)) of stainless steel sheet (SS), ceramic tile (CT), and floor tile (FT) with and without crabmeat residue on the surface were inoculated with L. monocytogenes and soaked in tap or EO water for 5 min. Viable cells of L. monocytogenes were detected on all chip surfaces with or without crabmeat residue after being held at room temperature for 1 h. Soaking contaminated chips in tap water resulted in small-degree reductions of the organism (0.40-0.66 log cfu/chip on clean surfaces and 0.78-1.33 log cfu/chip on dirty surfaces). Treatments of EO water significantly (p<0.05) reduced L. monocytogenes on clean surfaces (3.73 log on SS, 4.24 log on CT, and 5.12 log on FT). Presence of crabmeat residue on chip surfaces reduced the effectiveness of EO water on inactivating Listeria cells. However, treatments of EO water also resulted in significant reductions of L. monocytogenes on dirty surfaces (2.33 log on SS and CT and 1.52 log on FT) when compared with tap water treatments. The antimicrobial activity of EO water was positively correlated with its chlorine content. High oxidation-reduction potential (ORP) of EO water also contributed significantly to its antimicrobial activity against L. monocytogenes. EO water was more effective than chlorine water on inactivating L. monocytogenes on surfaces and could be used as a chlorine alternative for sanitation purpose. Application of EO water following a thorough cleaning process could greatly reduce L. monocytogenes contamination in seafood processing environments. PMID:16219378

Liu, Chengchu; Duan, Jingyun; Su, Yi-Cheng

2006-02-15

398

Surface chemistry of the atomic layer deposition of metals and group III oxides  

NASA Astrophysics Data System (ADS)

Atomic Layer Deposition (ALD) is a thin-film growth technique offering precise control of film thickness and the ability to coat high-aspect-ratio features such as trenches and nanopowders. Unlike other film growth techniques, ALD does not require harsh processing conditions and is not limited by line-of-sight deposition. Emerging applications for ALD materials include semiconductor devices, gas sensors, and water-diffusion barriers. The chemistry behind ALD involves understanding how the precursors interact with surfaces to deposit the desired material. All ALD precursors need to be stable on the substrate to ensure self-limiting behavior yet reactive enough to be easily removed with the second reagent. Recent precursor development has provided many volatile organometallic compounds for most of the periodic table. As the number of precursors increases, proper precursor choice becomes crucial. This is because the film properties, growth rates, and growth temperature vary widely between the precursors. Many of the above traits can be predicted with knowledge of the precursor reaction mechanisms. This thesis aims to link surface reaction mechanisms to observed growth and nucleation trends in metal and oxide ALD systems. The first portion of this thesis explores the mechanisms of two ALD oxide systems. First, I examine the mechanism of ALD alumina with ozone. Ozone is used as an oxidant in the semiconductor industry because the deposited Al 2O3 films possess better insulating properties and ozone is easier to purge from a vacuum system. FT-IR analysis reveals a complicated array of surface intermediates such as formate, carbonate, and methoxy groups that form during Al2O3 growth with ozone. Next, a new method to deposit thin films of Ga2O3 is introduced. Gallium oxide is a transparent conducting oxide that needs expensive solid precursors to be deposited by ALD. I show that trimethylgallium is a good high-temperature ALD precursor that deposits films of Ga2O 3 with low impurities and a good growth rate. The second section of this thesis focuses on two metal ALD systems. One major drawback of metal ALD systems is their inability to nucleate on many oxide surfaces. This greatly limits the applications of metal ALD for interconnects and flexible electrodes. The first emphasis is an on a new palladium ALD system using palladium (II) hexafluoroacetylaceonate (Pd(hfac)2) and formalin. FT-IR studies show that the Pd(hfac)2 dissociatively adsorbs, releasing free hfacH molecules that bind to Lewis acid sites on the alumina. The observed nucleation period of Pd is linked to surface poisoning by hfacH. In a related experiment, I use trimethylaluminum exposures to remove excess hfacH from the surface. Trimethylaluminum is able to ligand exchange an easier to remove methyl group with the surface hfacH, This treatment causes palladium to nucleate much more rapidly and deposit at lower temperatures. Finally, I examine ToRuS, a new precursor solution for Ru ALD. ToRuS, a solution of RuO4 in perfluoroethers, deposits ruthenium faster and at lower temperatures than all other Ru precursors. The mechanism for deposition and role of the perfluoroethers, however, is poorly understood. In the first study, I couple FT-IR spectroscopy with ab-initio calculations to identify the surface species formed when the perfluoroether solvent adsorbs on alumina. These surface species bind strongly to the alumina surface, creating a nonpolar, fluorinated layer. I then use these results to understand how ToRuS deposits Ru films. The fluorinated layer solvates RuO4, stabilizing it near the surface until it can be reduced by H2 gas. FT-IR and XPS analysis shows that the fluorinated layer does not leave carbonaceous impurities on the ruthenium surface or impedes metal deposition.

Goldstein, David Nathan

399

Surface Binding and Organization of Sensitizing Dyes on Metal Oxide Single Crystal Surfaces  

SciTech Connect

Even though investigations of dye-sensitized nanocrystalline semiconductors in solar cells has dominated research on dye-sensitized semiconductors over the past two decades. Single crystal electrodes represent far simpler model systems for studying the sensitization process with a continuing train of studies dating back more than forty years. Even today single crystal surfaces prove to be more controlled experimental models for the study of dye-sensitized semiconductors than the nanocrystalline substrates. We analyzed the scientific advances in the model sensitized single crystal systems that preceded the introduction of nanocrystalline semiconductor electrodes. It then follows the single crystal research to the present, illustrating both their striking simplicity of use and clarity of interpretation relative to nanocrystalline electrodes. Researchers have employed many electrochemical, photochemical and scanning probe techniques for studying monolayer quantities of sensitizing dyes at specific crystallographic faces of different semiconductors. These methods include photochronocoulometry, electronic spectroscopy and flash photolysis of dyes at potential-controlled semiconductor electrodes and the use of total internal reflection methods. In addition, we describe the preparation of surfaces of single crystal SnS2 and TiO2 electrodes to serve as reproducible model systems for charge separation at dye sensitized solar cells. This process involves cleaving the SnS2 electrodes and a photoelectrochemical surface treatment for TiO2 that produces clean surfaces for sensitization (as verified by AFM) resulting in near unity yields for electron transfer from the molecular excited dyes into the conduction band.

Parkinson, Bruce

2010-06-04

400

Surface redox induced bipolar switching of transition metal oxide films examined by scanning probe microscopy  

NASA Astrophysics Data System (ADS)

The bipolar resistive switching mechanisms of a p-type NiO film and n-type TiO2 film were examined using local probe-based measurements. Scanning probe-based current-voltage ( I- V) sweeps and surface potential/current maps obtained after the application of dc bias suggested that resistive switching is caused mainly by the surface redox reactions involving oxygen ions at the tip/oxide interface. This explanation can be applied generally to both p-type and n-type conducting resistive switching films. The contribution of oxygen migration to resistive switching was also observed indirectly, but only in the cases where the tip was in (quasi-) Ohmic contact with the oxide.

Lee, Min Hwan; Kim, Kyung Min; Song, Seul Ji; Rha, Sang Ho; Seok, Jun Yeong; Jung, Ji Sim; Kim, Gun Hwan; Yoon, Jung Ho; Hwang, Cheol Seong

2011-03-01

401

Insulating to metallic transition of an oxidized boron nitride nanosheet coating by tuning surface oxygen adsorption  

NASA Astrophysics Data System (ADS)

Surface modification and functionalization are of fundamental importance in actual application of insulating coating, such as hexagon boron nitride (h-BN) nanosheet. Our first-principles calculations reveal that an oxidized h-BN monolayer supported by a Cu substrate exhibits metallic properties when O adatom vertically bonds with the B atom. This is mainly due to the hybridization of the p orbital of the BN layer and O adatom around the Fermi level. Charge transfer from the Cu substrate to the O atom stabilizes the formation of the vertical O-B bond. Injecting negative charges could trigger the migration of the O adatom from the B-N bond to B atom for metal or insulator-supported h-BN monolayer, which will lead to a metallic transition in the oxidized h-BN nanosheet. Our results provide a viable way to tune the electronic properties of surface h-BN coating through charge injection mediated O adsorption.

Guo, Yufeng; Guo, Wanlin

2014-03-01

402

The Performance of Ce Surface Treated Ferritic Stainless Steels for Solid Oxide Fuel Cell Interconnects  

SciTech Connect

This research deals with the effect of a Ce surface treatment on the behavior of Fe-Cr-Mn ferritic stainless steels which may have application in SOFC technology. This treatment consisted of applying a slurry of CeO2 and a halide activator to the surface of coupons. After the slurry dried the coupons were heated to 900C in a controlled atmosphere furnace for 12 hours. The effectiveness of the treatment on commercial (Type 409 (12Cr), Type 430 (18Cr), Crofer 22APU (22Cr), Type 446(26Cr)) and experimental (NETL F9 (12Cr) and NETL F5 (22Cr)) alloys as a function of Cr content will be presented. The oxidation behavior of the alloys was assessed by exposing coupons (untreated and treated) to moist air at 800C. Area specific resistance (ASR) was measured at 800C. In general, the rare earth treatment effectively reduced the oxidation rate, resulting in thinner oxide scales and less internal oxidation.

Alman, D.E.; Jablonski, P.D.

2007-09-01

403

Oxidation protection of copper surfaces using self-assembled monolayers of octadecanethiol  

NASA Astrophysics Data System (ADS)

Self-assembled monolayers (SAMs) of alkanethiols adsorbed onto clean surfaces of face centred cubic (fcc) metals have been studied extensively for their ability to control the chemical functionality of the surface and as a means of preventing the oxidation and corrosion of the substrate metal. However, in many cases it has been found that on reactive substrates such as copper, it is difficult to prepare SAMs without the incorporation of some oxygen into the structure. In this work, self-assembled monolayers of octadecanethiol (ODT) were formed on copper foil substrates using a series of etching treatments to remove the native oxide layer prior to deposition of the ODT coating from a modified solution. X-ray photoelectron spectroscopy was used to analyse the SAMs and showed that monolayers with no detectable oxygen content could be produced. The effect of exposing the samples to air at different temperatures was monitored to examine the rate of the oxidation process, which was found to vary strongly with temperature. Samples stored at room temperature were found to oxidise relatively quickly, while those kept in a refrigerator were slower. Storing samples in a freezer dramatically reduced the oxidation of the copper, such that samples kept for 10 weeks still did not show any clear evidence of oxygen incorporation.

Hutt, David A.; Liu, Changqing

2005-10-01

404

Preparation of water-dispersible graphene by facile surface modification of graphite oxide.  

PubMed

Water-dispersible graphene was prepared by reacting graphite oxide and 6-amino-4-hydroxy-2-naphthalenesulfonic acid (ANS). X-ray diffraction study showed that the basal reflection (002) peak of graphite oxide was absent in the ANS-functionalized graphene (ANS-G), indicating crystal layer delamination. Ultraviolet-visible spectral data were recorded to assess the solubility of the ANS-G in water. Fourier transform infrared spectral analysis suggested the attachment of ANS molecules to the surface of graphene. Raman and x-ray photoelectron spectroscopy revealed that oxygen functionality in the graphite oxide had been removed during reduction. Atomic force microscopy found that the thickness of ANS-G in water was about 1.8 nm, much higher than that of single layer graphene. Thermal stability measurements also indicated successful removal of oxygen functionality from the graphite oxide and the attachment of thermally unstable ANS to the graphene surfaces. The electrical conductivity of ANS-G, determined by a four-point probe, was 145 S m(-1) at room temperature. PMID:21730750

Kuila, Tapas; Khanra, Partha; Bose, Saswata; Kim, Nam Hoon; Ku, Bon-Cheol; Moon, Bongho; Lee, Joong Hee

2011-07-29