WorldWideScience

Sample records for surface oxidation states

  1. Studies of surface states in zinc oxide nanopowders

    Science.gov (United States)

    Peters, Raul Mugabe

    The surface of ZnO semiconductor nanosystems is a key performance-defining factor in numerous applications. In this work we present experimental results for the surface defect-related properties of ZnO nanoscale systems. Surface photovoltage spectroscopy was used to determine the defect level energies within the band gap, the conduction vs. valence band nature of the defect-related transitions, and to probe key dynamic parameters of the surface on a number of commercially available ZnO nanopowders. In our experimental setup, surface photovoltage characterization is conducted in high vacuum in tandem with in situ oxygen remote plasma treatments. Surface photovoltage investigations of the as-received and plasma-processed samples revealed a number of common spectral features related to surface states. Furthermore, we observed significant plasma-induced changes in the surface defect properties. Ex situ positron annihilation and photoluminescence measurements were performed on the studied samples and correlated with surface photovoltage results. The average positron lifetimes were found to be substantially longer than in a bulk single crystalline sample, which is consistent with the model of grains with defect-rich surface and subsurface layers. Compression of the powders into pellets yielded reduction of the average positron lifetimes. Surface photovoltage, positron annihilation, and photoluminescence spectra consistently showed sample-to-sample differences due to the variation in the overall quality of the nanopowders, which partially obscures observation of the scaling effects. However, the results demonstrated that our approach is efficient in detecting specific surface states in nanoscale ZnO specimens and in elucidating their nature.

  2. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

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

    Energy Technology Data Exchange (ETDEWEB)

    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

    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.

  4. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: 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.

  5. Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

    Directory of Open Access Journals (Sweden)

    Fu-Chien Chiu

    2013-01-01

    Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

  6. Chemical state analysis of oxidation products on steel surface by conversion electron Moessbauer spectrometry

    International Nuclear Information System (INIS)

    Ujihira, Yusuke; Nomura, Kiyoshi

    1978-01-01

    The polished NT-70H steel (Fe: 95.97%, C: 0.56%, diameter: 5 cm, thickness: 0.5 cm) was immersed in deionized water or in solutions containing (0.25 -- 0.5) M of chloride, sulfate and nitrate ions. The chemical states of oxidation products of iron on the surface were identified through the analysis of conversion electron Moessbauer spectra (CEMS). CEMS of the steel surface, which had been dipped in deionized water, revealed that γ-FeOOH was formed on the surface. The thickness of γ-FeOOH layer increased with the increase of the duration of dipping. Dissolved oxygen in the solution played an essential role in the oxidation of iron to γ-FeOOH. Oxidation product of iron dipped in the 0.5 M sodium chloride solution was identified as γ-FeOOH. Amorphous paramagnetic iron (III) compound tended to form in the presence of hydrogen peroxide or ammonium ions in the solutions. The increase of alkalinity of the solution up to pH 12 suppressed the oxidation rate and assisted the formation of green rust, which was confirmed by the appearance of the quadrupole splitting peaks of the green rust. In the 0.25 M sodium sulfate solution, oxidation of the steel surface proceeded slowly and the quadrupole splitting peaks of Fe(OH) 2 were seen in the CEMS. The peak intensity of Fe(OH) 2 gradually decreased and that of γ-FeOOH increased by the extension of immersion of steel in the solution. Magnetite (Fe 3 O 4 ) layer was developed beneath the γ-FeOOH layer, when steel was dipped in 0.5 M sodium nitrate solution. However, the peaks of Fe 3 O 4 were not seen on CEMS of steel surface immersed in 0.5 M ammonium nitrate solution. Thus, applying the feasibility of CEMS for the characterization of oxidated compounds of iron on the steel surface formed by the immersion in solutions, the oxidation mechanism of the steel surface was discussed based upon the results of chemical state analyses. (author)

  7. Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

    Science.gov (United States)

    Zutz, Amelia Marie

    Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

  8. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki

    2014-05-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

  9. Influence of steam generator surface state on corrosion and oxide formation

    International Nuclear Information System (INIS)

    Mazenc, Arnaud; Leclercq, Stephanie; Seyeux, Antoine; Galtayries, Anouk; Marcus, Philippe

    2012-09-01

    The corrosion and release of nickel-based alloy Steam Generator tubes are partly due to their surface state. Among the most important parameters influencing the corrosion, the effect of grain size and the effect of grain crystallographic orientation have been chosen to be studied. The aim of this study is to determine how these parameters have an impact on the corrosion of Steam Generator tubes. Thermal treatments (700 deg. C and 1050 deg. C) have been performed on several samples in Alloy 690 to obtain homogeneous grain sizes, varying from 25 μm to 110 μm. Two samples have been oxidised for four days in a recirculating autoclave, reproducing primary conditions. The changes of oxide composition and thickness were examined by ToF-SIMS on samples exposed to primary water conditions. The intensity profiles versus thicknesses of characteristic oxide anions, such as CrO - , NiO - or FeO - enable us to evaluate the effect of grain size and crystallographic orientation on the formation of an enriched inner chromium layer. As regards to the grain size, there was no effect on the growth, but smaller grains led to a chromium-rich oxide layer. The effect of crystallographic orientation was observed on the oxidation kinetics and the composition of oxide scales. (authors)

  10. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Jihoon [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Moon, Jinok [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Clean/CMP Technology Team, Memory, Samsung Electronics, Hwaseong (Korea, Republic of); Kim, Joo Hyun; Lee, Kangchun [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Hwang, Junha [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Materials R& D Center, K.C.Tech, Anseong (Korea, Republic of); Yoon, Heesung [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Yi, Dong Kee, E-mail: vitalis@mju.ac.kr [Department of Chemistry, Myongji University, Yongin (Korea, Republic of); Paik, Ungyu, E-mail: upaik@hanyang.ac.kr [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of)

    2016-12-15

    Highlights: • We investigated the role of Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for the silicate adsorption. • As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. • The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. - Abstract: In this study, we have investigated the role of the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for silicate adsorption. In aqueous medium, the Ce{sup 3+} sites lead to the formation of −OH groups at the CeO{sub 2} surface through H{sub 2}O dissociation. Silicate ions can adsorb onto the CeO{sub 2} surface through interaction with the −OH groups (−Ce−OH− + −Si−O{sup −} ↔ −Ce−O−Si− + OH{sup −}). As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. To evaluate the adsorption behaviors of silicate ions onto CeO{sub 2} NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surface can have a significant influence on the silicate adsorption.

  11. Defects at oxide surfaces

    CERN Document Server

    Thornton, Geoff

    2015-01-01

    This book presents the basics and characterization of defects at oxide surfaces. It provides a state-of-the-art review of the field, containing information to the various types of surface defects, describes analytical methods to study defects, their chemical activity and the catalytic reactivity of oxides. Numerical simulations of defective structures complete the picture developed. Defects on planar surfaces form the focus of much of the book, although the investigation of powder samples also form an important part. The experimental study of planar surfaces opens the possibility of applying the large armoury of techniques that have been developed over the last half-century to study surfaces in ultra-high vacuum. This enables the acquisition of atomic level data under well-controlled conditions, providing a stringent test of theoretical methods. The latter can then be more reliably applied to systems such as nanoparticles for which accurate methods of characterization of structure and electronic properties ha...

  12. Soluble and immobilized graphene oxide activates complement system differently dependent on surface oxidation state

    DEFF Research Database (Denmark)

    Wibroe, Peter Popp; Petersen, Søren Vermehren; Bovet, Nicolas Emile

    2016-01-01

    on two related elements of innate immunity: the complement system and interleukin-6 (IL-6) release in human blood. In solution, there was a decrease in GO-mediated complement activation with decreasing surface oxygen content (and altered oxygen functionality), whereas with immobilized GO complement...... response were reversed and increased with decreasing oxygen content. GO solutions, at concentrations below complement activating threshold, did not induce IL-6 release from human blood leukocytes, and further dampened lipopolysaccharide-induced IL-6 release in the whole blood. The latter effect became more...... profound with GO's having higher oxygen content. This protective role of GO solutions, however, disappeared at higher concentrations above complement-activating threshold. We discuss these results in relation to GO surface structure and properties, and implications for local administration and development...

  13. Adsorption of CO, CO2, H2, and H2O on titania surfaces with different oxidation states

    International Nuclear Information System (INIS)

    Raupp, G.B.; Dumesic, J.A.

    1985-01-01

    The adsorptive properties of titania surfaces with different oxidation states were proved by temperature-programmed desorption (TPD) of CO, H 2 , CO 2 , and H 2 O. Auger electron spectroscopy and X-ray photoelectron spectroscopy revealed that vacuum annealing an oxidized titanium foil at temperatures from 300 to 800 K was an effective means of systematically varying the average surface oxidation state from Ti 4+ to Ti 2+ . Carbon monoxide weakly adsorbed (desorption energy of 44-49 kJ x mol -1 ) in a carbonyl fashion on coordinatively unsaturated cation sites. Titania surfaces were inert with respect to H 2 adsorption and dissociation. Carbon dioxide adsorbed in a linear molecular fashion. Water adsorbed both molecularly and dissociatively. Results are discussed in terms of the role of titania oxidation state in CO hydrogenation over titania-supported metal catalysts. 74 references, 7 figures

  14. Oxidation state of sulfur, iron and tin at the surface of float glasses

    International Nuclear Information System (INIS)

    Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

    2009-01-01

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  15. Oxidation state of sulfur, iron and tin at the surface of float glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

    2009-11-15

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  16. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    DEFF Research Database (Denmark)

    McMahon, C.A.; Vintró, L.L.; Mitchell, P.I.

    2000-01-01

    (V, VI) (mean, 68 +/- 6%; n = 6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed...... in shelf waters at midlatitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 degrees C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced...... chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean Pu-238/Pu-239,Pu-240 activity ratio in the water column (dissolved phase) at Thule (0.06 +/- 0.02; n = 10) is similar to the global fallout ratio at this latitude...

  17. Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

    Science.gov (United States)

    Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

    2015-05-01

    The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

  18. Iron oxide surfaces

    Science.gov (United States)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  19. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    International Nuclear Information System (INIS)

    McMahon, C.A.; Leon Vintro, L.; Mitchell, P.I.; Dahlgaard, H.

    2000-01-01

    The speciation of plutonium in Arctic waters sampled on the northwest Greenland shelf in August 1997 is discussed in this paper. Specifically, we report the results of analyses carried out on seawater sampled (a) close to the Thule air base where, in 1968, a US military aircraft carrying four nuclear weapons crashed on sea ice, releasing kilogram quantities of plutonium to the snow pack and underlying seabed sediments, and (b) at a reference station (Upernavik) located ∼400 km to the south. The data show that most of the plutonium in the dissolved phase at Thule is in the form of Pu(V, VI) (mean: 68±6%; n=6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed in shelf waters at mid-latitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 deg. C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean 238 Pu/ 239,240 Pu activity ratio in the water column (dissolved phase) at Thule (0.06±0.02; n=10) is similar to the global fallout ratio at this latitude (∼0.04). Thus, there is little evidence of weapons-grade plutonium in the water column at Thule at the present time

  20. Determination of the specific surface energy of oxides and glasses in the solid-state

    International Nuclear Information System (INIS)

    Andryushechkin, S.; Karpman, M.

    2000-01-01

    The production and application of coatings on glasses are used widely in technology. The coatings on glass are used for the regulation of optical, decorative, conducting and other technological and physical properties of glass. In particular, it is important to mention the application of glass fibres for the development of composite materials. However, the specific surface energy of glass and, consequently, its adhesion characteristics are relatively low. The values of these characteristics can be changed by the application of different metallic and nonmetallic coatings is characterised by high surface energy. To produce metallic coatings with the required adhesion strength of glass, it is necessary to have information on the specific surface energy of inorganic glass of different chemical composition. The determination of the relationships between the properties and composition of glass is one of the fundamental problems. At present, a large amount of investigations have been carried out into the investigations of the properties of glass in relation to its composition. However, the problem of establishment of relationships between the properties and composition of glass are especially difficult when examining multicomponent systems (technical glass). It is therefore, in to analyse in each case the properties of not the entire system has a whole but the variation of the properties with temperature of the individual components included in the system, the subsequent application of the additivity principle. The large majority of the glasses represent combinations of oxides of the elements of groups I-III and oxides of the transition metals, forming the mixtures, solid solutions of chemical compounds in the glass production process. Thus, analysis of the characteristics of oxides of the alkali, alkali-earth and transition metals makes it possible to obtain initial data for the evaluation of the surface energy, density, molecular mass of glass containing these oxides

  1. Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

    Science.gov (United States)

    Li, Jingyi; Mao, Jingqiu; Fiore, Arlene M.; Cohen, Ronald C.; Crounse, John D.; Teng, Alex P.; Wennberg, Paul O.; Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Thornton, Joel A.; Peischl, Jeff; Pollack, Ilana B.; Ryerson, Thomas B.; Veres, Patrick; Roberts, James M.; Neuman, J. Andrew; Nowak, John B.; Wolfe, Glenn M.; Hanisco, Thomas F.; Fried, Alan; Singh, Hanwant B.; Dibb, Jack; Paulot, Fabien; Horowitz, Larry W.

    2018-02-01

    Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July-August 2004), SENEX (June-July 2013), and SEAC4RS (August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (˜ 42-45 %), followed by NOx (31 %), total peroxy nitrates (ΣPNs; 14 %), and total alkyl nitrates (ΣANs; 9-12 %) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

  2. Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

    Directory of Open Access Journals (Sweden)

    J. Li

    2018-02-01

    Full Text Available Widespread efforts to abate ozone (O3 smog have significantly reduced emissions of nitrogen oxides (NOx over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July–August 2004, SENEX (June–July 2013, and SEAC4RS (August–September 2013 and long-term ground measurement networks alongside a global chemistry–climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy in both 2004 and 2013. Among the major RON species, nitric acid (HNO3 is dominant (∼ 42–45 %, followed by NOx (31 %, total peroxy nitrates (ΣPNs; 14 %, and total alkyl nitrates (ΣANs; 9–12 % on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

  3. Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

    International Nuclear Information System (INIS)

    Gmucova, Katarina; Weis, Martin; Nadazdy, Vojtech; Capek, Ignac; Satka, Alexander; Chitu, Livia; Cirak, Julius; Majkova, Eva

    2008-01-01

    Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe 3 O 4 /Fe 2 O 3 ) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their 'orientation ordering' in an energetically favourable position

  4. [Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

    Science.gov (United States)

    Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

    2011-10-01

    Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

  5. Operando XAS Study of the Surface Oxidation State on a Monolayer IrOx on RuOx and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

    2018-01-01

    that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

  6. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki; Traversa, Enrico

    2014-01-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell

  7. Quasiparticle Interference on Cubic Perovskite Oxide Surfaces.

    Science.gov (United States)

    Okada, Yoshinori; Shiau, Shiue-Yuan; Chang, Tay-Rong; Chang, Guoqing; Kobayashi, Masaki; Shimizu, Ryota; Jeng, Horng-Tay; Shiraki, Susumu; Kumigashira, Hiroshi; Bansil, Arun; Lin, Hsin; Hitosugi, Taro

    2017-08-25

    We report the observation of coherent surface states on cubic perovskite oxide SrVO_{3}(001) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a d_{xy}-derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO_{2} plane play a critical role in controlling the coherent surface state via modulating orbital state.

  8. SURFACE AND LIGHTNING SOURCES OF NITROGEN OXIDES OVER THE UNITED STATES: MAGNITUDES, CHEMICAL EVOLUTION, AND OUTFLOW

    Science.gov (United States)

    We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution...

  9. Spectroscopic investigation of oxidized solder surfaces

    International Nuclear Information System (INIS)

    Song, Jenn-Ming; Chang-Chien, Yu-Chien; Huang, Bo-Chang; Chen, Wei-Ting; Shie, Chi-Rung; Hsu, Chuang-Yao

    2011-01-01

    Highlights: → UV-visible spectroscopy is successfully used to evaluate the degree of discoloring of solders. → The surface oxides of solders can also be identified by UV-visible absorption spectra. → The discoloration of solder surface can be correlated with optical characterization of oxides. → A strategy against discoloring by alloying was also suggested. - Abstract: For further understanding of the discoloration of solder surfaces due to oxidation during the assembly and operation of electronic devices, UV-vis and X-ray photoelectron spectroscopic analyses were applied to evaluate the degree of discoloring and identify the surface oxides. The decrease in reflectance of the oxidized solder surface is related to SnO whose absorption band is located within the visible region. A trace of P can effectively depress the discoloration of solders under both solid and semi-solid states through the suppression of SnO.

  10. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni

    Energy Technology Data Exchange (ETDEWEB)

    Biesinger, Mark C., E-mail: biesingr@uwo.ca [Surface Science Western, University of Western Ontario, University of Western Ontario Research Park, Room LL31, 999 Collip Circle, London, Ontario, N6G 0J3 (Canada); ACeSSS (Applied Centre for Structural and Synchrotron Studies), University of South Australia, Mawson Lakes, SA 5095 (Australia); Payne, Brad P. [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, Andrew P. [Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 5C9 (Canada); Lau, Leo W.M. [Surface Science Western, University of Western Ontario, University of Western Ontario Research Park, Room LL31, 999 Collip Circle, London, Ontario, N6G 0J3 (Canada); Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Gerson, Andrea R.; Smart, Roger St.C. [ACeSSS (Applied Centre for Structural and Synchrotron Studies), University of South Australia, Mawson Lakes, SA 5095 (Australia)

    2011-01-15

    Chemical state X-ray photoelectron spectroscopic analysis of first row transition metals and their oxides and hydroxides is challenging due to the complexity of their 2p spectra resulting from peak asymmetries, complex multiplet splitting, shake-up and plasmon loss structure, and uncertain, overlapping binding energies. Our previous paper [M.C. Biesinger et al., Appl. Surf. Sci. 257 (2010) 887-898.] in which we examined Sc, Ti, V, Cu and Zn species, has shown that all the values of the spectral fitting parameters for each specific species, i.e. binding energy (eV), full wide at half maximum (FWHM) value (eV) for each pass energy, spin-orbit splitting values and asymmetric peak shape fitting parameters, are not all normally provided in the literature and data bases, and are necessary for reproducible, quantitative chemical state analysis. A more consistent, practical and effective approach to curve fitting was developed based on a combination of (1) standard spectra from quality reference samples, (2) a survey of appropriate literature databases and/or a compilation of literature references and (3) specific literature references where fitting procedures are available. This paper extends this approach to the chemical states of Cr, Mn, Fe, Co and Ni metals, and various oxides and hydroxides where intense, complex multiplet splitting in many of the chemical states of these elements poses unique difficulties for chemical state analysis. The curve fitting procedures proposed use the same criteria as proposed previously but with the additional complexity of fitting of multiplet split spectra which has been done based on spectra of numerous reference materials and theoretical XPS modeling of these transition metal species. Binding energies, FWHM values, asymmetric peak shape fitting parameters, multiplet peak separation and peak area percentages are presented. The procedures developed can be utilized to remove uncertainties in the analysis of surface states in nano

  11. Surface states and spectra

    International Nuclear Information System (INIS)

    Jaksic, V.; Last, Y.; California Inst. of Tech., Pasadena, CA

    2001-01-01

    Let Z + d+1 =Z d x Z + , let H 0 be the discrete Laplacian on the Hilbert space l 2 (Z + d+1 ) with a Dirichlet boundary condition, and let V be a potential supported on the boundary ∂Z + d+1 . We introduce the notions of surface states and surface spectrum of the operator H=H 0 +V and explore their properties. Our main result is that if the potential V is random and if the disorder is either large or small enough, then in dimension two H has no surface spectrum on σ(H 0 ) with probability one. To prove this result we combine Aizenman-Molchanov theory with techniques of scattering theory. (orig.)

  12. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

    International Nuclear Information System (INIS)

    Biesinger, Mark C.; Lau, Leo W.M.; Gerson, Andrea R.; Smart, Roger St.C.

    2010-01-01

    Chemical state X-ray photoelectron spectroscopic analysis of first row transition metals and their oxides and hydroxides is challenging due to the complexity of the 2p spectra resulting from peak asymmetries, complex multiplet splitting, shake-up and plasmon loss structure, and uncertain, overlapping binding energies. A review of current literature shows that all values necessary for reproducible, quantitative chemical state analysis are usually not provided. This paper reports a more consistent, practical and effective approach to curve-fitting the various chemical states in a variety of Sc, Ti, V, Cu and Zn metals, oxides and hydroxides. The curve-fitting procedures proposed are based on a combination of (1) standard spectra from quality reference samples, (2) a survey of appropriate literature databases and/or a compilation of the literature references, and (3) specific literature references where fitting procedures are available. Binding energies, full-width at half maximum (FWHM) values, spin-orbit splitting values, asymmetric peak-shape fitting parameters, and, for Cu and Zn, Auger parameters values are presented. The quantification procedure for Cu species details the use of the shake-up satellites for Cu(II)-containing compounds and the exact binding energies of the Cu(0) and Cu(I) peaks. The use of the modified Auger parameter for Cu and Zn species allows for corroborating evidence when there is uncertainty in the binding energy assignment. These procedures can remove uncertainties in analysis of surface states in nano-particles, corrosion, catalysis and surface-engineered materials.

  13. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

    Energy Technology Data Exchange (ETDEWEB)

    Biesinger, Mark C., E-mail: biesingr@uwo.ca [Surface Science Western, University of Western Ontario, University of Western Ontario Research Park, Room LL31, 999 Collip Circle, London, Ontario, N6G 0J3 (Canada); ACeSSS (Applied Centre for Structural and Synchrotron Studies), University of South Australia, Mawson Lakes, SA 5095 (Australia); Lau, Leo W.M. [Surface Science Western, University of Western Ontario, University of Western Ontario Research Park, Room LL31, 999 Collip Circle, London, Ontario, N6G 0J3 (Canada); Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Gerson, Andrea R.; Smart, Roger St.C. [ACeSSS (Applied Centre for Structural and Synchrotron Studies), University of South Australia, Mawson Lakes, SA 5095 (Australia)

    2010-11-15

    Chemical state X-ray photoelectron spectroscopic analysis of first row transition metals and their oxides and hydroxides is challenging due to the complexity of the 2p spectra resulting from peak asymmetries, complex multiplet splitting, shake-up and plasmon loss structure, and uncertain, overlapping binding energies. A review of current literature shows that all values necessary for reproducible, quantitative chemical state analysis are usually not provided. This paper reports a more consistent, practical and effective approach to curve-fitting the various chemical states in a variety of Sc, Ti, V, Cu and Zn metals, oxides and hydroxides. The curve-fitting procedures proposed are based on a combination of (1) standard spectra from quality reference samples, (2) a survey of appropriate literature databases and/or a compilation of the literature references, and (3) specific literature references where fitting procedures are available. Binding energies, full-width at half maximum (FWHM) values, spin-orbit splitting values, asymmetric peak-shape fitting parameters, and, for Cu and Zn, Auger parameters values are presented. The quantification procedure for Cu species details the use of the shake-up satellites for Cu(II)-containing compounds and the exact binding energies of the Cu(0) and Cu(I) peaks. The use of the modified Auger parameter for Cu and Zn species allows for corroborating evidence when there is uncertainty in the binding energy assignment. These procedures can remove uncertainties in analysis of surface states in nano-particles, corrosion, catalysis and surface-engineered materials.

  14. Control of Surface and Edge Oxidation on Phosphorene.

    Science.gov (United States)

    Kuntz, Kaci L; Wells, Rebekah A; Hu, Jun; Yang, Teng; Dong, Baojuan; Guo, Huaihong; Woomer, Adam H; Druffel, Daniel L; Alabanza, Anginelle; Tománek, David; Warren, Scott C

    2017-03-15

    Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.

  15. Oxidation of Ethylene Carbonate on Li Metal Oxide Surfaces

    DEFF Research Database (Denmark)

    Østergaard, Thomas M.; Giordano, Livia; Castelli, Ivano Eligio

    2018-01-01

    Understanding the reactivity of the cathode surface is of key importance to the development of batteries. Here, density functional theory is applied to investigate the oxidative decomposition of the electrolyte component, ethylene carbonate (EC), on layered LixMO(2) oxide surfaces. We compare...

  16. Surface Species and Metal Oxidation State during H2-Assisted NH3-SCR of NOx over Alumina-Supported Silver and Indium

    Directory of Open Access Journals (Sweden)

    Linda Ström

    2018-01-01

    Full Text Available Alumina-supported silver and indium catalysts are investigated for the hydrogen-assisted selective catalytic reduction (SCR of NOx with ammonia. Particularly, we focus on the active phase of the catalyst and the formation of surface species, as a function of the gas environment. Diffuse reflectance ultraviolet-visible (UV-vis spectroscopy was used to follow the oxidation state of the silver and indium phases, and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS was used to elucidate the formation of surface species during SCR conditions. In addition, the NOx reduction efficiency of the materials was evaluated using H2-assisted NH3-SCR. The DRIFTS results show that the Ag/Al2O3 sample forms NO-containing surface species during SCR conditions to a higher extent compared to the In/Al2O3 sample. The silver sample also appears to be more reduced by H2 than the indium sample, as revealed by UV-vis spectroscopic experiments. Addition of H2, however, may promote the formation of highly dispersed In2O3 clusters, which previously have been suggested to be important for the SCR reaction. The affinity to adsorb NH3 is confirmed by both temperature programmed desorption (NH3-TPD and in situ DRIFTS to be higher for the In/Al2O3 sample compared to Ag/Al2O3. The strong adsorption of NH3 may inhibit (self-poison the NH3 activation, thereby hindering further reaction over this catalyst, which is also shown by the lower SCR activity compared to Ag/Al2O3.

  17. Coherent states and rational surfaces

    International Nuclear Information System (INIS)

    Brody, Dorje C; Graefe, Eva-Maria

    2010-01-01

    The state spaces of generalized coherent states associated with special unitary groups are shown to form rational curves and surfaces in the space of pure states. These curves and surfaces are generated by the various Veronese embeddings of the underlying state space into higher dimensional state spaces. This construction is applied to the parameterization of generalized coherent states, which is useful for practical calculations, and provides an elementary combinatorial approach to the geometry of the coherent state space. The results are extended to Hilbert spaces with indefinite inner products, leading to the introduction of a new kind of generalized coherent states.

  18. The role of oxidation states in F A1 Tl n+ (n = 1, 3) lasers and CO interactions at the (1 0 0) surface of NaCl: An ab initio study

    International Nuclear Information System (INIS)

    Shalabi, A.S.; Abdel Aal, S.; Kamel, M.A.; Taha, H.O.; Ammar, H.Y.; Abdel Halim, W.S.

    2006-01-01

    The oxidation states of Thallium in F A1 Tl +n (n = 1, 3) color centers at the (1 0 0) surface of NaCl play important role in laser light generation and adsorbate-substrate interactions. Double-well potentials at these surfaces are investigated by using quantum mechanical ab initio methods. Quantum clusters of variable sizes were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and ions that were the nearest neighbors to the F A1 Tl +n (n 1, 3) defect site were allowed to relax to equilibrium.The calculated Stokes shifts suggest that laser light generation is sensitive to the oxidation states of Thallium. The relaxed excited states of the defect-containing surface were deep below the lower edge of the conduction bands of the ground state defect-free surface, suggesting that the F A1 Tl +n (n = 1, 3) centers are suitable laser defects. The dependence of the orientational destruction and recording sensitivity on the oxidation state of Thallium is clarified. The Glasner-Tompkins empirical rule is generalized to include the oxidation state of the impurity cation. The adsorption energies of CO and OC over NaCl(1 0 0) was found to be sensitive to the oxidation state of the impurity cation. F A1 Tl +n (n = 1, 3) centers changed the physical adsorption of CO to chemical adsorption. While the artificial flow of charge was significant in the case of Tl +1 impurity, it was negligible in the case of Tl +3 impurity, and the results were explained in terms of the electrostatic potential curves

  19. Atomic profile imaging of ceramic oxide surfaces

    International Nuclear Information System (INIS)

    Bursill, L.A.; Peng JuLin; Sellar, J.R.

    1989-01-01

    Atomic surface profile imaging is an electron optical technique capable of revealing directly the surface crystallography of ceramic oxides. Use of an image-intensifier with a TV camera allows fluctuations in surface morphology and surface reactivity to be recorded and analyzed using digitized image data. This paper reviews aspects of the electron optical techniques, including interpretations based upon computer-simulation image-matching techniques. An extensive range of applications is then presented for ceramic oxides of commercial interest for advanced materials applications: including uranium oxide (UO 2 ); magnesium and nickel oxide (MgO,NiO); ceramic superconductor YBa 2 Cu 3 O 6.7 ); barium titanate (BaTiO 3 ); sapphire (α-A1 2 O 3 ); haematite (α-Fe-2O 3 ); monoclinic, tetragonal and cubic monocrystalline forms of zirconia (ZrO 2 ), lead zirconium titanate (PZT + 6 mol.% NiNbO 3 ) and ZBLAN fluoride glass. Atomic scale detail has been obtained of local structures such as steps associated with vicinal surfaces, facetting parallel to stable low energy crystallographic planes, monolayer formation on certain facets, relaxation and reconstructions, oriented overgrowth of lower oxides, chemical decomposition of complex oxides into component oxides, as well as amorphous coatings. This remarkable variety of observed surface stabilization mechanisms is discussed in terms of novel double-layer electrostatic depolarization mechanisms, as well as classical concepts of the physics and chemistry of surfaces (ionization and affinity energies and work function). 46 refs., 16 figs

  20. Modelling of low energy ion sputtering from oxide surfaces

    International Nuclear Information System (INIS)

    Kubart, T; Nyberg, T; Berg, S

    2010-01-01

    The main aim of this work is to present a way to estimate the values of surface binding energy for oxides. This is done by fitting results from the binary collisions approximation code Tridyn with data from the reactive sputtering processing curves, as well as the elemental composition obtained from x-ray photoelectron spectroscopy (XPS). Oxide targets of Al, Ti, V, Nb and Ta are studied. The obtained surface binding energies are then used to predict the partial sputtering yields. Anomalously high sputtering yield is observed for the TiO 2 target. This is attributed to the high sputtering yield of Ti lower oxides. Such an effect is not observed for the other studied metals. XPS measurement of the oxide targets confirms the formation of suboxides during ion bombardment as well as an oxygen deficient surface in the steady state. These effects are confirmed from the processing curves from the oxide targets showing an elevated sputtering rate in pure argon.

  1. CO oxidation on PdO surfaces

    DEFF Research Database (Denmark)

    Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika

    2010-01-01

    Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...... oxidation via the Langmuir–Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface...

  2. Surface states in photonic crystals

    Directory of Open Access Journals (Sweden)

    Vojtíšek P.

    2013-05-01

    Full Text Available Among many unusual and interesting physical properties of photonic crystals (PhC, in recent years, the propagation of surface electromagnetic waves along dielectric PhC boundaries have attracted considerable attention, also in connection to their possible applications. Such surfaces states, produced with the help of specialized defects on PhC boundaries, similarly to surfaces plasmons, are localized surfaces waves and, as such, can be used in various sensing applications. In this contribution, we present our recent studies on numerical modelling of surface states (SS for all three cases of PhC dimensionality. Simulations of these states were carried out by the use of plane wave expansion (PWE method via the MIT MPB package.

  3. Surface and Core Electronic Structure of Oxidized Silicon Nanocrystals

    Directory of Open Access Journals (Sweden)

    Noor A. Nama

    2010-01-01

    Full Text Available Ab initio restricted Hartree-Fock method within the framework of large unit cell formalism is used to simulate silicon nanocrystals between 216 and 1000 atoms (1.6–2.65 nm in diameter that include Bravais and primitive cell multiples. The investigated properties include core and oxidized surface properties. Results revealed that electronic properties converge to some limit as the size of the nanocrystal increases. Increasing the size of the core of a nanocrystal resulted in an increase of the energy gap, valence band width, and cohesive energy. The lattice constant of the core and oxidized surface parts shows a decreasing trend as the nanocrystal increases in a size that converges to 5.28 Ǻ in a good agreement with the experiment. Surface and core convergence to the same lattice constant reflects good adherence of oxide layer at the surface. The core density of states shows highly degenerate states that split at the oxygenated (001-(1×1 surface due to symmetry breaking. The nanocrystal surface shows smaller gap and higher valence and conduction bands when compared to the core part, due to oxygen surface atoms and reduced structural symmetry. The smaller surface energy gap shows that energy gap of the nanocrystal is controlled by the surface part. Unlike the core part, the surface part shows a descending energy gap that proves its obedience to quantum confinement effects. Nanocrystal geometry proved to have some influence on all electronic properties including the energy gap.

  4. Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Yuyuan [Northwestern University, Evanston; Wu, Zili [ORNL; Wen, Jianguo [Argonne National Laboratory (ANL); Poeppelmeier, Kenneth R [Northwestern University, Evanston; Marks, Laurence D [Northwestern University, Evanston

    2015-01-01

    Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.

  5. An iterative model for the steady state current distribution in oxide-confined vertical-cavity surface-emitting lasers (VCSELs)

    Science.gov (United States)

    Chuang, Hsueh-Hua

    The purpose of this dissertation is to develop an iterative model for the analysis of the current distribution in vertical-cavity surface-emitting lasers (VCSELs) using a circuit network modeling approach. This iterative model divides the VCSEL structure into numerous annular elements and uses a circuit network consisting of resistors and diodes. The measured sheet resistance of the p-distributed Bragg reflector (DBR), the measured sheet resistance of the layers under the oxide layer, and two empirical adjustable parameters are used as inputs to the iterative model to determine the resistance of each resistor. The two empirical values are related to the anisotropy of the resistivity of the p-DBR structure. The spontaneous current, stimulated current, and surface recombination current are accounted for by the diodes. The lateral carrier transport in the quantum well region is analyzed using drift and diffusion currents. The optical gain is calculated as a function of wavelength and carrier density from fundamental principles. The predicted threshold current densities for these VCSELs match the experimentally measured current densities over the wavelength range of 0.83 mum to 0.86 mum with an error of less than 5%. This model includes the effects of the resistance of the p-DBR mirrors, the oxide current-confining layer and spatial hole burning. Our model shows that higher sheet resistance under the oxide layer reduces the threshold current, but also reduces the current range over which single transverse mode operation occurs. The spatial hole burning profile depends on the lateral drift and diffusion of carriers in the quantum wells but is dominated by the voltage drop across the p-DBR region. To my knowledge, for the first time, the drift current and the diffusion current are treated separately. Previous work uses an ambipolar approach, which underestimates the total charge transferred in the quantum well region, especially under the oxide region. However, the total

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

    Science.gov (United States)

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

    2018-03-01

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

  7. Surface chemistry on interstellar oxide grains

    International Nuclear Information System (INIS)

    Denison, P.; Williams, D.A.

    1981-01-01

    Detailed calculations are made to test the predictions of Duley, Millar and Williams (1978) concerning the chemical reactivity of interstellar oxide grains. A method is established for calculating interaction energies between atoms and the perfect crystal with or without surface vacancy sites. The possibility of reactions between incident atoms and absorbed atoms is investigated. It is concluded that H 2 formation can occur on the perfect crystal surfaces, and that for other diatomic molecules the important formation sites are the Fsub(s)- and V 2- sub(s)-centres. The outline by Duley, Millar and Williams (1979) of interstellar oxide grain growth and destruction is justified by these calculations. (author)

  8. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  9. Modification of polycarbonate surface in oxidizing plasma

    Science.gov (United States)

    Ovtsyn, A. A.; Smirnov, S. A.; Shikova, T. G.; Kholodkov, I. V.

    2017-11-01

    The properties of the surface of the film polycarbonate Lexan 8010 were experimentally studied after treatment in a DC discharge plasma in oxygen and air at pressures of 50-300 Pa and a discharge current of 80 mA. The contact angles of wetting and surface energies are measured. The topography of the surface was investigated by atomic force microscopy. The chemical composition of the surface was determined from the FT-IR spectroscopy data in the variant of total internal reflection, as well as X-ray photoelectron spectroscopy. Treatment in the oxidizing plasma leads to a change in morphology (average roughness increases), an increase in the surface energy, and the concentration of oxygen-containing groups (hydroxyl groups, carbonyl groups in ketones or aldehydes and in oxyketones) on the surface of the polymer. Possible reasons for the difference in surface properties of polymer under the action of oxygen and air plasma on it are discussed.

  10. Mapping the surface (hydr)oxo-groups of titanium oxide and its interface with an aqueous solution: the state of the art and a new approach.

    Science.gov (United States)

    Panagiotou, George D; Petsi, Theano; Bourikas, Kyriakos; Garoufalis, Christos S; Tsevis, Athanassios; Spanos, Nikos; Kordulis, Christos; Lycourghiotis, Alexis

    2008-10-01

    In this article the "titanium oxide/electrolyte solution" interface is studied by taking in advantage the recent developments in the field of Surface and Interface Chemistry relevant to this oxide. Ab-initio calculations were performed in the frame of the DFT theory for estimating the charge of the titanium and oxygen atoms exposed on the anatase (1 0 1), (1 0 0), (0 0 1), (1 0 3)(f) and rutile (1 1 0) crystal faces. These orientations have smaller surface energy with respect to other ones and thus it is more probable to be the real terminations of the anatase and rutile nanocrystallites in the titania polycrystalline powders. Potentiometric titrations for obtaining "fine structured" titration curves as well as microelectrophoresis and streaming potential measurements have been performed. On the basis of ab-initio calculations, and taking into account the relative contribution of each crystal face to the whole surface of the nanocrystals involved in the titania aggregates of a suspension, the three most probable surface ionization models have been derived. These models and the Music model are then tested in conjunction with the "Stern-Gouy-Chapman" and "Basic Stern" electrostatic models. The finally selected surface ionization model (model A) in combination with each one of the two electrostatic models describes very well the protonation/deprotonation behavior of titania. The description is also very good if this model is combined with the Three Plane (TP) model. The application of the "A/(TP)" model allowed mapping the surface (hydr)oxo-groups [TiO(H) and Ti(2)O(H)] of titania exposed in aqueous solutions. At pH>pzc almost all terminal oxygens [TiO] are non-protonated whereas even at low pH values the non-protonated terminal oxygens predominate. The acid-base behavior of the bridging oxygens [Ti(2)O] is different. Thus, even at pH=10 the greater portion of them is protonated. The application of the "A/TP" model in conjunction with potentiometric titrations

  11. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  12. Patterning pentacene surfaces by local oxidation nanolithography

    International Nuclear Information System (INIS)

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

    2010-01-01

    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 36 V for 1 ms. 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 1 mm 2 regions and with a periodicity of less than 1 μm have been generated in a few seconds. We also show that the patterns can be used as templates for the deposition of antibodies.

  13. Temperature effect on surface oxidation of titanium

    International Nuclear Information System (INIS)

    Vaquilla, I.; Barco, J.L. del; Ferron, J.

    1990-01-01

    The effect of temperature on the first stages of the superficial oxidation of polycrystalline titanium was studied using both Auger electron spectroscopy (AES) and emission shreshold (AEAPS). The number of compounds present on the surface was determined by application of the factor analysis technique. Reaction evolution was followed through the relative variation of Auger LMM and LMV transitions which are characteristic of titanium. Also the evolution of the chemical shift was determined by AEAPS. The amount of oxygen on the surface was quantified using transition KLL of oxygen. It was found that superficial oxidation depends on temperature. As much as three different compounds were determined according to substrate temperature and our exposure ranges. (Author). 7 refs., 5 figs

  14. Negative secondary ion emission from oxidized surfaces

    International Nuclear Information System (INIS)

    Gnaser, H.; Kernforschungsanlage Juelich G.m.b.H.

    1984-01-01

    The emission of negative secondary ions from 23 elements was studied for 10 keV O 2 + and 10 keV In + impact at an angle of incidence of 45 0 . Partial oxidation of the sample surfaces was achieved by oxygen bombardment and/or by working at a high oxygen partial pressure. It was found that the emission of oxide ions shows an element-characteristic pattern. For the majority of the elements investigated these features are largely invariant against changes of the surface concentration of oxygen. For the others admission of oxygen strongly changes the relative intensities of oxide ions: a strong increase of MO 3 - signals (M stands for the respective element) is accompanied by a decrease of MO - and M - intensities. Different primary species frequently induce changes of both the relative and the absolute negative ion intensities. Carbon - in contrast to all other elements - does not show any detectable oxide ion emission but rather intense cluster ions Csub(n) - (detected up to n=12) whose intensities oscillate in dependence on n. (orig./RK)

  15. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  16. NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

    Science.gov (United States)

    Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

    2018-07-01

    High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

  17. Oxidation-state maxima in plutonium chemistry

    International Nuclear Information System (INIS)

    Silver, G.L.

    2013-01-01

    Maxima in the fractions of the trivalent and hexavalent oxidation states of plutonium are inherent in the algebra of its disproportionation reactions. The maxima do not support overall disproportionation equations as satisfactory representations of aqueous plutonium. (author)

  18. In-surface confinement of topological insulator nanowire surface states

    International Nuclear Information System (INIS)

    Chen, Fan W.; Jauregui, Luis A.; Tan, Yaohua; Manfra, Michael; Klimeck, Gerhard; Chen, Yong P.; Kubis, Tillmann

    2015-01-01

    The bandstructures of [110] and [001] Bi 2 Te 3 nanowires are solved with the atomistic 20 band tight binding functionality of NEMO5. The theoretical results reveal: The popular assumption that all topological insulator (TI) wire surfaces are equivalent is inappropriate. The Fermi velocity of chemically distinct wire surfaces differs significantly which creates an effective in-surface confinement potential. As a result, topological insulator surface states prefer specific surfaces. Therefore, experiments have to be designed carefully not to probe surfaces unfavorable to the surface states (low density of states) and thereby be insensitive to the TI-effects

  19. In-surface confinement of topological insulator nanowire surface states

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Fan W., E-mail: fanchen@purdue.edu [Department of Physics and Astronomy, Purdue, West Lafayette, Indiana 47907 (United States); Network for Computational Nanotechnology, Purdue, West Lafayette, Indiana 47907 (United States); Jauregui, Luis A. [School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States); Tan, Yaohua [Network for Computational Nanotechnology, Purdue, West Lafayette, Indiana 47907 (United States); School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Manfra, Michael [Department of Physics and Astronomy, Purdue, West Lafayette, Indiana 47907 (United States); School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States); School of Materials Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Klimeck, Gerhard [Network for Computational Nanotechnology, Purdue, West Lafayette, Indiana 47907 (United States); School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States); Chen, Yong P. [Department of Physics and Astronomy, Purdue, West Lafayette, Indiana 47907 (United States); School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States); Kubis, Tillmann [Network for Computational Nanotechnology, Purdue, West Lafayette, Indiana 47907 (United States)

    2015-09-21

    The bandstructures of [110] and [001] Bi{sub 2}Te{sub 3} nanowires are solved with the atomistic 20 band tight binding functionality of NEMO5. The theoretical results reveal: The popular assumption that all topological insulator (TI) wire surfaces are equivalent is inappropriate. The Fermi velocity of chemically distinct wire surfaces differs significantly which creates an effective in-surface confinement potential. As a result, topological insulator surface states prefer specific surfaces. Therefore, experiments have to be designed carefully not to probe surfaces unfavorable to the surface states (low density of states) and thereby be insensitive to the TI-effects.

  20. In-surface confinement of topological insulator nanowire surface states

    Science.gov (United States)

    Chen, Fan W.; Jauregui, Luis A.; Tan, Yaohua; Manfra, Michael; Klimeck, Gerhard; Chen, Yong P.; Kubis, Tillmann

    2015-09-01

    The bandstructures of [110] and [001] Bi2Te3 nanowires are solved with the atomistic 20 band tight binding functionality of NEMO5. The theoretical results reveal: The popular assumption that all topological insulator (TI) wire surfaces are equivalent is inappropriate. The Fermi velocity of chemically distinct wire surfaces differs significantly which creates an effective in-surface confinement potential. As a result, topological insulator surface states prefer specific surfaces. Therefore, experiments have to be designed carefully not to probe surfaces unfavorable to the surface states (low density of states) and thereby be insensitive to the TI-effects.

  1. Reversible Compositional Control of Oxide Surfaces by Electrochemical Potentials

    KAUST Repository

    Mutoro, Eva

    2012-01-05

    Perovskite oxides can exhibit a wide range of interesting characteristics such as being catalytically active and electronically/ionically conducting, and thus, they have been used in a number of solid-state devices such as solid oxide fuel cells (SOFCs) and sensors. As the surface compositions of perovskites can greatly influence the catalytic properties, knowing and controlling their surface compositions 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 compositional changes of La 0.8Sr 0.2CoO 3-δ (LSC 113), (La 0.5Sr 0.5) 2CoO 4±δ (LSC 214), and LSC 214-decorated LSC 113 films (LSC 113/214) were investigated in situ by utilizing synchrotron-based X-ray photoelectron spectroscopy (XPS), where the largest changes of surface Sr were found for the LSC 113/214 surface. These findings offer the potential of reversibly controlling the surface functionality of perovskites. © 2011 American Chemical Society.

  2. Oxidation of scandium thin films on tungsten surface

    International Nuclear Information System (INIS)

    Gorodetskij, D.A.; Martynyuk, A.V.

    1988-01-01

    Presence of Sc on the surface of W in amounts larger than a monolayer coverage leads to a decrease of the work function at the initial oxidation stage, which is attributed to oxygen implantation into the surface layer of the metal. A subsequent oxidation is followed by the formation on the surface of a thin oxide layer and an increase of the work function. An increase of the amount of Sc deposited on the surface before the oxidation decreases the work function of the obtained oxide from 5.8 (clean W surface) down to 3.3 eV (thick Sc layer on W)

  3. Theoretical aspects of studies of oxide and semiconductor surfaces using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2011-01-01

    This paper presents the results of a theoretical study of positron surface and bulk states and annihilation characteristics of surface trapped positrons at the oxidized Cu(100) single crystal and at both As- and Ga-rich reconstructed GaAs(100) surfaces. The variations in atomic structure and chemical composition of the topmost layers of the surfaces associated with oxidation and reconstructions and the charge redistribution at the surfaces are found to affect localization and spatial extent of the positron surface-state wave functions. The computed positron binding energy, work function, and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the surfaces. Theoretical positron annihilation probabilities with relevant core electrons computed for the oxidized Cu(100) surface and the As- and Ga-rich reconstructed GaAs(100) surfaces are compared with experimental ones estimated from the positron annihilation induced Auger peak intensities measured from these surfaces.

  4. Electrolysis of water on (oxidized) metal surfaces

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Logadottir, Ashildur; Nørskov, Jens Kehlet

    2005-01-01

    Density functional theory calculations are used as the basis for an analysis of the electrochemical process, where by water is split to form molecular oxygen and hydrogen. We develop a method for obtaining the thermochemistry of the electrochemical water splitting process as a function of the bias...... directly from the electronic structure calculations. We consider electrodes of Pt(111) and Au(111) in detail and then discuss trends for a series of different metals. We show that the difficult step in the water splitting process is the formation of superoxy-type (OOH) species on the surface...... by the splitting of a water molecule on top an adsorbed oxygen atom. One conclusion is that this is only possible on metal surfaces that are (partly) oxidized. We show that the binding energies of the different intermediates are linearly correlated for a number of metals. In a simple analysis, where the linear...

  5. Band energy control of molybdenum oxide by surface hydration

    Energy Technology Data Exchange (ETDEWEB)

    Butler, Keith T., E-mail: k.t.butler@bath.ac.uk; Walsh, Aron [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Crespo-Otero, Rachel [School of Biological and Chemical Sciences, Queen Mary University London, Mile End Road, London E1 4NS (United Kingdom); Buckeridge, John; Scanlon, David O. [University College London, Kathleen Lonsdale Materials Chemistry, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Bovill, Edward; Lidzey, David [Department of Physics and Astronomy, University of Sheffield, Hicks Building, Hounsfield Road, Sheffield S3 7RH (United Kingdom)

    2015-12-07

    The application of oxide buffer layers for improved carrier extraction is ubiquitous in organic electronics. However, the performance is highly susceptible to processing conditions. Notably, the interface stability and electronic structure is extremely sensitive to the uptake of ambient water. In this study we use density functional theory calculations to asses the effects of adsorbed water on the electronic structure of MoO{sub x}, in the context of polymer-fullerene solar cells based on PCDTBT. We obtain excellent agreement with experimental values of the ionization potential for pristine MoO{sub 3} (010). We find that IP and EA values can vary by as much as 2.5 eV depending on the oxidation state of the surface and that adsorbed water can either increase or decrease the IP and EA depending on the concentration of surface water.

  6. Photocatalysis of Modified Transition Metal Oxide Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Batzill, Matthias [Univ. of South Florida, Tampa, FL (United States). Dept. of Physics

    2018-02-28

    The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anatase TiO2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

  7. Opposing effects of humidity on rhodochrosite surface oxidation.

    Science.gov (United States)

    Na, Chongzheng; Tang, Yuanzhi; Wang, Haitao; Martin, Scot T

    2015-03-03

    Rhodochrosite (MnCO3) is a model mineral representing carbonate aerosol particles containing redox-active elements that can influence particle surface reconstruction in humid air, thereby affecting the heterogeneous transformation of important atmospheric constituents such as nitric oxides, sulfur dioxides, and organic acids. Using in situ atomic force microscopy, we show that the surface reconstruction of rhodochrosite in humid oxygen leads to the formation and growth of oxide nanostructures. The oxidative reconstruction consists of two consecutive processes with distinctive time scales, including a long waiting period corresponding to slow nucleation and a rapid expansion phase corresponding to fast growth. By varying the relative humidity from 55 to 78%, we further show that increasing humidity has opposing effects on the two processes, accelerating nucleation from 2.8(±0.2) × 10(-3) to 3.0(±0.2) × 10(-2) h(-1) but decelerating growth from 7.5(±0.3) × 10(-3) to 3.1(±0.1) × 10(-3) μm(2) h(-1). Through quantitative analysis, we propose that nanostructure nucleation is controlled by rhodochrosite surface dissolution, similar to the dissolution-precipitation mechanism proposed for carbonate mineral surface reconstruction in aqueous solution. To explain nanostructure growth in humid oxygen, a new Cabrera-Mott mechanism involving electron tunneling and solid-state diffusion is proposed.

  8. Theory of quasiparticle surface states in semiconductor surfaces

    International Nuclear Information System (INIS)

    Hybertsen, M.S.; Louie, S.G.

    1988-01-01

    A first-principles theory of the quasiparticle surface-state energies on semiconductor surfaces is developed. The surface properties are calculated using a repeated-slab geometry. Many-body effects due to the electron-electron interaction are represented by the electron self-energy operator including the full surface Green's function and local fields and dynamical screening effects in the Coulomb interaction. Calculated surface-state energies for the prototypical Si(111):As and Ge(111):As surfaces are presented. The calculated energies and dispersions for the occupied surface states (resonances) are in excellent agreement with recent angle-resolved photoemission data. Predictions are made for the position of empty surface states on both surfaces which may be experimentally accessible. The resulting surface state gap at Gamma-bar for Si(111):As agrees with recent scanning-tunneling-spectroscopy measurements. Comparison of the present results to eigenvalues from the local-density-functional calculation reveals substantial corrections for the gaps between empty and occupied surface states. This correction is found to depend on the character of the surface states involved

  9. Surface modification of promising cerium oxide nanoparticles for nanomedicine applications

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-11-14

    Cerium oxide nanoparticles (CNPs) or nanoceria have emerged as a potential nanomedicine for the treatment of several diseases such as cancer. CNPs have a natural tendency to aggregate or agglomerate in their bare state, which leads to sedimentation in a biological environment. Since the natural biological environment is essentially aqueous, nanoparticle surface modification using suitable biocompatible hydrophilic chemical moieties is highly desirable to create effective aqueous dispersions. In this report, (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl)triethoxysilane was used as a functional, biocompatible organosilane to modify the surface of CNPs to produce promising nanoparticles which open substantial therapeutic avenues. The surface modified nanoparticles were produced in situ via an ammonia-induced ethylene glycol-assisted precipitation method and were characterized using complimentary characterization techniques. The interaction between the functional moiety and the nanoparticle was studied using powerful cross polarization/magic angle sample spinning solid state nuclear magnetic resonance spectroscopy. The surface-modified nanoparticles were extremely small and demonstrated a significant improvement in aqueous dispersibility. Moreover, the existence of a strong ionic coordination between the functional moiety and the surface of the nanoparticle was realised, indicating that the surface modified nanoceria are stable and that the nanoparticles should demonstrate an enhanced circulation time in a biological environment. The surface modification approach should be promising for the production of CNPs for nanomedicine applications. © The Royal Society of Chemistry.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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, CO 2 , CH 4 , and H 2 ) 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 Al 2 O 3 layer on the surface. The weight gain was larger in the order of air, helium, and VHTR-helium, while the parabolic rate constants (k p ) at steady-state were similar for all test environments. In both helium environments, the oxide structure consisted of the outer transition Al 2 O 3 with a small amount of Cr 2 O 3 and inner columnar structured Al 2 O 3 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

  11. An ab initio study of plutonium oxides surfaces

    International Nuclear Information System (INIS)

    Jomard, G.; Bottin, F.; Amadon, B.

    2007-01-01

    By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO 2 and β-Pu 2 O 3 in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO 2 in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p O 2 ). We conclude that at room temperature and for p O 2 ∼10 atm., the polar O 2 -(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)

  12. Reduction in the interface-states density of metal-oxide-semiconductor field-effect transistors fabricated on high-index Si (114) surfaces by using an external magnetic field

    International Nuclear Information System (INIS)

    Molina, J.; De La Hidalga, J.; Gutierrez, E.

    2014-01-01

    After fabrication of Metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET) devices on high-index silicon (114) surfaces, their threshold voltage (Vth) and interface-states density (Dit) characteristics were measured under the influence of an externally applied magnetic field of B = 6 μT at room temperature. The electron flow of the MOSFET's channel presents high anisotropy on Si (114), and this effect is enhanced by using an external magnetic field B, applied parallel to the Si (114) surface but perpendicular to the electron flow direction. This special configuration results in the channel electrons experiencing a Lorentzian force which pushes the electrons closer to the Si (114)-SiO 2 interface and therefore to the special morphology of the Si (114) surface. Interestingly, Dit evaluation of n-type MOSFETs fabricated on Si (114) surfaces shows that the Si (114)-SiO 2 interface is of high quality so that Dit as low as ∼10 10  cm −2 ·eV −1 are obtained for MOSFETs with channels aligned at specific orientations. Additionally, using both a small positive Vds ≤ 100 mV and B = 6 μT, the former Dit is reduced by 35% in MOSFETs whose channels are aligned parallel to row-like nanostructures formed atop Si (114) surfaces (channels having a 90° rotation), whereas Dit is increased by 25% in MOSFETs whose channels are aligned perpendicular to these nanostructures (channels having a 0° rotation). From these results, the special morphology of a high-index Si (114) plane having nanochannels on its surface opens the possibility to reduce the electron-trapping characteristics of MOSFET devices having deep-submicron features and operating at very high frequencies

  13. Surface states in an external electric field

    International Nuclear Information System (INIS)

    Steslicka, M.

    1975-10-01

    Under conditions typical for field ion microscopy, true surface states can exist. Their shift towards higher energies can be quite significant and, moreover, additional surface levels at still higher energies can appear. The latter can play an important role in the process of tunneling of image gas electrons into surface states

  14. Electronic structures near surfaces of perovskite type oxides

    International Nuclear Information System (INIS)

    Hara, Toru

    2005-01-01

    This work is intended to draw attention to the origin of the electronic structures near surfaces of perovskite type oxides. Deep states were observed by ultraviolet photoelectron spectroscopic measurements. The film thickness dependent electronic structures near surfaces of (Ba 0.5 Sr 0.5 )TiO 3 thin films were observed. As for the 117-308 nm thick (Ba 0.5 Sr 0.5 )TiO 3 films, deep states were lying at 0.20, 0.55, and 0.85 eV below the quasi-fermi level, respectively. However, as for the 40 nm thick (Ba 0.5 Sr 0.5 )TiO 3 film, the states were overlapped. The A-site doping affected electronic structures near surfaces of SrTiO 3 single crystals. No evolution of deep states in non-doped SrTiO 3 single crystal was observed. However, the evolution of deep states in La-doped SrTiO 3 single crystal was observed

  15. Calculations of oxide formation on low-index Cu surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lian, Xin; Liu, Renlong, E-mail: lrl@cqu.edu.cn, E-mail: henkelman@utexas.edu [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); Xiao, Penghao; Yang, Sheng-Che; Henkelman, Graeme, E-mail: lrl@cqu.edu.cn, E-mail: henkelman@utexas.edu [Department of Chemistry and the Institute for Computational and Engineering Sciences, University of Texas at Austin, Austin, Texas 78712-0165 (United States)

    2016-07-28

    Density-functional theory is used to evaluate the mechanism of copper surface oxidation. Reaction pathways of O{sub 2} dissociation on the surface and oxidation of the sub-surface are found on the Cu(100), Cu(110), and Cu(111) facets. At low oxygen coverage, all three surfaces dissociate O{sub 2} spontaneously. As oxygen accumulates on the surfaces, O{sub 2} dissociation becomes more difficult. A bottleneck to further oxidation occurs when the surfaces are saturated with oxygen. The barriers for O{sub 2} dissociation on the O-saturated Cu(100)-c(2×2)-0.5 monolayer (ML) and Cu(100) missing-row structures are 0.97 eV and 0.75 eV, respectively; significantly lower than those have been reported previously. Oxidation of Cu(110)-c(6×2), the most stable (110) surface oxide, has a barrier of 0.72 eV. As the reconstructions grow from step edges, clean Cu(110) surfaces can dissociatively adsorb oxygen until the surface Cu atoms are saturated. After slight rearrangements, these surface areas form a “1 ML” oxide structure which has not been reported in the literature. The barrier for further oxidation of this “1 ML” phase is only 0.31 eV. Finally the oxidized Cu(111) surface has a relatively low reaction energy barrier for O{sub 2} dissociation, even at high oxygen coverage, and allows for facile oxidation of the subsurface by fast O diffusion through the surface oxide. The kinetic mechanisms found provide a qualitative explanation of the observed oxidation of the low-index Cu surfaces.

  16. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

  17. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  18. Appearance of the minority dz2 surface state and disappearance of the image-potential state: Criteria for clean Fe(001)

    Science.gov (United States)

    Eibl, Christian; Schmidt, Anke B.; Donath, Markus

    2012-10-01

    The unoccupied surface electronic structure of clean and oxidized Fe(001) was studied with spin-resolved inverse photoemission and target current spectroscopy. For the clean surface, we detected a dz2 surface state with minority spin character just above the Fermi level, while the image-potential surface state disappears. The opposite is observed for the ordered p(1×1)O/Fe(001) surface: the dz2-type surface state is quenched, while the image-potential state shows up as a pronounced feature. This behavior indicates enhanced surface reflectivity at the oxidized surface. The appearance and disappearance of specific unoccupied surface states prove to be decisive criteria for a clean Fe(001) surface. In addition, enhanced spin asymmetry in the unoccupied states is observed for the oxidized surface. Our results have implications for the use of clean and oxidized Fe(001) films as spin-polarization detectors.

  19. Topological surface states scattering in antimony

    KAUST Repository

    Narayan, Awadhesh; Rungger, Ivan; Sanvito, Stefano

    2012-01-01

    In this work we study the topologically protected states of the Sb(111) surface by using ab initio transport theory. In the presence of a strong surface perturbation we obtain standing-wave states resulting from the superposition of spin-polarized surface states. By Fourier analysis, we identify the underlying two dimensional scattering processes and the spin texture. We find evidence of resonant transmission across surface barriers at quantum well state energies and evaluate their lifetimes. Our results are in excellent agreement with experimental findings. We also show that despite the presence of a step edge along a different high-symmetry direction, the surface states exhibit unperturbed transmission around the Fermi energy for states with near to normal incidence. © 2012 American Physical Society.

  20. Topological surface states scattering in antimony

    KAUST Repository

    Narayan, Awadhesh

    2012-11-05

    In this work we study the topologically protected states of the Sb(111) surface by using ab initio transport theory. In the presence of a strong surface perturbation we obtain standing-wave states resulting from the superposition of spin-polarized surface states. By Fourier analysis, we identify the underlying two dimensional scattering processes and the spin texture. We find evidence of resonant transmission across surface barriers at quantum well state energies and evaluate their lifetimes. Our results are in excellent agreement with experimental findings. We also show that despite the presence of a step edge along a different high-symmetry direction, the surface states exhibit unperturbed transmission around the Fermi energy for states with near to normal incidence. © 2012 American Physical Society.

  1. Effect of CO on surface oxidation of uranium metal

    International Nuclear Information System (INIS)

    Wang, X.; Fu, Y.; Xie, R.

    1997-01-01

    The surface reactions of uranium metal with carbon monoxide at 25 and 200 deg C have been studied by X-ray photoelectron spectroscopy (XPS);respectively. Adsorption of carbon monoxide on the surface layer of uranium metal leads to partial reduction of surface oxide and results in U4f photoelectron peak shifting to the lower binding energy. The content of oxygen in the surface oxide is decreased and O1s/O4f ratio decreases with increasing the exposure of carbon monoxide. The investigation indicates the surface layer of uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide. (author)

  2. Surfaces and Interfaces of Magnetoelectric Oxide Systems

    Science.gov (United States)

    Cao, Shi

    Magnetoelectric materials Cr2O3, hexagonal LuFeO 3 and YbFeO3 are studied in this thesis. The surface of chromia (Cr2O3) has a surface electronic structure distinct from the bulk. Our work shows that placing a Cr2O3 single crystal into a single domain state will result in net Cr2O 3 spin polarization at the boundary, even in the presence of a gold overlayer. From the Cr 2p3/2 X-ray magnetic circular dichroism signal, there is clear evidence of interface polarization with overlayers of both Pd and Pt on chromia. Cobalt thin films on Cr2O3(0001) show larger magnetic contrast in magnetic force microscopy indicating enhancement of perpendicular anisotropy induced by Cr2O3. The interfacial charge transfer between mechanically exfoliated few-layer graphene and Cr2O3(0001) surfaces has been investigated showing hole doping of few-layer graphene. Density functional theory calculations furthermore confirm the p-type nature of the graphene on top of chromia, and suggest that the chromia is able to induce a significant carrier spin polarization in the graphene layer. The surface termination and the nominal valence states for hexagonal LuFeO3 thin films were characterized. The stable surface terminates in a Fe-O layer. This is consistent wit the results of density functional calculations. The structural transition at about 1000 °C, from the hexagonal to the orthorhombic phase of LuFeO3, has been investigated in thin films of LuFeO3. The electronic structure for the conduction bands of both hexagonal and orthorhombic LuFeO3 thin films have been measured. Dramatic differences in both the spectral features and the linear dichroism are observed. We have also studied the ferrimagnetism in h-YbFeO3 by measuring the magnetization of Fe and Yb separately. The results directly show antialignment of magnetization of Yb and Fe ions in h-YbFeO3 at low temperature, with an exchange field on Yb of about 17 kOe. All ferrimagnets, by default, are magnetoelectrics. These findings directly

  3. Surface and sub-surface thermal oxidation of thin ruthenium films

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kokke, S.; Zoethout, E. [FOM Dutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 1207, 3430 BE Nieuwegein (Netherlands)

    2014-09-29

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low density and high density oxides. Nano-columns grow at the surface of the low density oxide layer, with the growth rate being limited by diffusion of ruthenium through the formed oxide film. Simultaneously, with the growth of the columns, sub-surface high density oxide continues to grow limited by diffusion of oxygen or ruthenium through the oxide film.

  4. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Bo, Maolin [Yangtze Normal University, College of Mechanical and Electrical Engineering, Chongqing 408100 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Liu, Yonghui [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q. [NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China)

    2017-02-28

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O{sup 2−} lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta{sup +} electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta{sup +}; the sp{sup 3}-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent

  5. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

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

  6. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    International Nuclear Information System (INIS)

    Guo, Yongling; Bo, Maolin; Wang, Yan; Liu, Yonghui; Sun, Chang Q.; Huang, Yongli

    2017-01-01

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O"2"− lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta"+ electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta"+; the sp"3-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent insight into the

  7. Low-intensity electromagnetic irradiation of 70.6 and 73 GHz frequencies enhances the effects of disulfide bonds reducer on Escherichia coli growth and affects the bacterial surface oxidation-reduction state

    Energy Technology Data Exchange (ETDEWEB)

    Torgomyan, Heghine [Department of Biophysics of Biology Faculty, Yerevan State University, Yerevan 0025 (Armenia); Trchounian, Armen, E-mail: Trchounian@ysu.am [Department of Biophysics of Biology Faculty, Yerevan State University, Yerevan 0025 (Armenia)

    2011-10-14

    Highlights: {yields} Low intensity 70.6 and 73 GHz electromagnetic irradiation (EMI) strongly suppressed Escherichia coli growth at 73 GHz and pH 7.3. {yields} Reducer DL-dithiothreitol had bactericidal effect and disturbed the SH-groups number. {yields} EMI enhanced E. coli sensitivity toward dithiothreitol. {yields} EMI decreased the SH-groups number of membrane disturbed by ATP and N,N'-dicyclohexycarbodiimide. {yields} The changed membrane oxidation-reduction state could be the primary mechanisms in EMI effects. -- Abstract: Low-intensity electromagnetic irradiation (EMI) of 70.6 and 73 GHz frequencies (flux capacity - 0.06 mW cm{sup -2}) had bactericidal effects on Escherichia coli. This EMI (1 h) exposure suppressed the growth of E. coli K-12({lambda}). The pH value (6.0-8.0) did not significantly affect the growth. The lag-phase duration was prolonged, and the growth specific rate was inhibited, and these effects were more noticeable after 73 GHz irradiation. These effects were enhanced by the addition of DL-dithiothreitol (DTT), a strong reducer of disulfide bonds in surface membrane proteins, which in its turn also has bactericidal effect. Further, the number of accessible SH-groups in membrane vesicles was markedly decreased by EMI that was augmented by N,N'-dicyclohexycarbodiimide and DTT. These results indicate a change in the oxidation-reduction state of bacterial cell membrane proteins that could be the primary membranous mechanism in the bactericidal effects of low-intensity EMI of the 70.6 and 73 GHz frequencies.

  8. Low-intensity electromagnetic irradiation of 70.6 and 73 GHz frequencies enhances the effects of disulfide bonds reducer on Escherichia coli growth and affects the bacterial surface oxidation-reduction state

    International Nuclear Information System (INIS)

    Torgomyan, Heghine; Trchounian, Armen

    2011-01-01

    Highlights: → Low intensity 70.6 and 73 GHz electromagnetic irradiation (EMI) strongly suppressed Escherichia coli growth at 73 GHz and pH 7.3. → Reducer DL-dithiothreitol had bactericidal effect and disturbed the SH-groups number. → EMI enhanced E. coli sensitivity toward dithiothreitol. → EMI decreased the SH-groups number of membrane disturbed by ATP and N,N'-dicyclohexycarbodiimide. → The changed membrane oxidation-reduction state could be the primary mechanisms in EMI effects. -- Abstract: Low-intensity electromagnetic irradiation (EMI) of 70.6 and 73 GHz frequencies (flux capacity - 0.06 mW cm -2 ) had bactericidal effects on Escherichia coli. This EMI (1 h) exposure suppressed the growth of E. coli K-12(λ). The pH value (6.0-8.0) did not significantly affect the growth. The lag-phase duration was prolonged, and the growth specific rate was inhibited, and these effects were more noticeable after 73 GHz irradiation. These effects were enhanced by the addition of DL-dithiothreitol (DTT), a strong reducer of disulfide bonds in surface membrane proteins, which in its turn also has bactericidal effect. Further, the number of accessible SH-groups in membrane vesicles was markedly decreased by EMI that was augmented by N,N'-dicyclohexycarbodiimide and DTT. These results indicate a change in the oxidation-reduction state of bacterial cell membrane proteins that could be the primary membranous mechanism in the bactericidal effects of low-intensity EMI of the 70.6 and 73 GHz frequencies.

  9. Surface oxide formation during corona discharge treatment of AA 1050 aluminium surfaces

    DEFF Research Database (Denmark)

    Minzari, Daniel; Møller, Per; Kingshott, Peter

    2008-01-01

    process modifies aluminium AA 1050 surface, the oxide growth and resulting corrosion properties. The corona treatment is carried out in atmospheric air. Treated surfaces are characterized using XPS, SEM/EDS, and FIB-FESEM and results suggest that an oxide layer is grown, consisting of mixture of oxide...

  10. Protection of surface states in topological nanoparticles

    Science.gov (United States)

    Siroki, Gleb; Haynes, Peter D.; Lee, Derek K. K.; Giannini, Vincenzo

    2017-07-01

    Topological insulators host protected electronic states at their surface. These states show little sensitivity to disorder. For miniaturization one wants to exploit their robustness at the smallest sizes possible. This is also beneficial for optical applications and catalysis, which favor large surface-to-volume ratios. However, it is not known whether discrete states in particles share the protection of their continuous counterparts in large crystals. Here we study the protection of the states hosted by topological insulator nanoparticles. Using both analytical and tight-binding simulations, we show that the states benefit from the same level of protection as those on a planar surface. The results hold for many shapes and sustain surface roughness which may be useful in photonics, spectroscopy, and chemistry. They complement past studies of large crystals—at the other end of possible length scales. The protection of the nanoparticles suggests that samples of all intermediate sizes also possess protected states.

  11. Electron spectroscopy of nanodiamond surface states

    Energy Technology Data Exchange (ETDEWEB)

    Belobrov, P.I.; Bursill, L.A.; Maslakov, K.I.; Dementjev, A.P

    2003-06-15

    Electronic states of nanodiamond (ND) were investigated by PEELS, XPS and CKVV Auger spectra. Parallel electron energy loss spectra (PEELS) show that the electrons inside of ND particles are sp{sup 3} hybridized but there is a surface layer containing distinct hybridized states. The CKVV Auger spectra imply that the HOMO of the ND surface has a shift of 2.5 eV from natural diamond levels of {sigma}{sub p} up to the Fermi level. Hydrogen (H) treatment of natural diamond surface produces a chemical state indistinguishable from that of ND surfaces using CKVV. The ND electronic structure forms {sigma}{sub s}{sup 1}{sigma}{sub p}{sup 2}{pi}{sup 1} surface states without overlapping of {pi}-levels. Surface electronic states, including surface plasmons, as well as phonon-related electronic states of the ND surface are also interesting and may also be important for field emission mechanisms from the nanostructured diamond surface.

  12. Rapid Surface Oxidation as a Source of Surface Degradation Factor for Bi 2 Se 3

    KAUST Repository

    Kong, Desheng

    2011-06-28

    Bismuth selenide (Bi2Se3) is a topological insulator with metallic surface states (SS) residing in a large bulk bandgap. In experiments, synthesized Bi2Se3 is often heavily n-type doped due to selenium vacancies. Furthermore, it is discovered from experiments on bulk single crystals that Bi2Se3 gets additional n-type doping after exposure to the atmosphere, thereby reducing the relative contribution of SS in total conductivity. In this article, transport measurements on Bi2Se3 nanoribbons provide additional evidence of such environmental doping process. Systematic surface composition analyses by X-ray photoelectron spectroscopy reveal fast formation and continuous growth of native oxide on Bi2Se3 under ambient conditions. In addition to n-type doping at the surface, such surface oxidation is likely the material origin of the degradation of topological SS. Appropriate surface passivation or encapsulation may be required to probe topological SS of Bi2Se3 by transport measurements. © 2011 American Chemical Society.

  13. Microarc Oxidation of Product Surfaces without Using a Bath

    Directory of Open Access Journals (Sweden)

    V. K. Shatalov

    2015-01-01

    Full Text Available While using an electrochemical method to cover the large-sized work-pieces, units, and products up to 6 м3 by protective coating, there is a certain difficulty to apply traditional anodizing techniques in a plating vat, and it is necessary to find various processing techniques.To use the existing micro-arc oxide coating (MOC methods for work-pieces of various forms and sizes in a plating vat is complicated in case it is required to provide oxide layers in separate places rather than over entire surface of a work-piece. The challenge is to treat flat surfaces in various directions, external and internal surfaces of rotation bodies, profiled surfaces, intersections, closed and through holes, pipes, as well as spline and thread openings for ensuring anti-seize properties in individual or small-scale production to meet technical requirements and operational properties of products.A design of tools to provide MOC-process of all possible surfaces of various engineering box-type products depends on many factors and can be considerably different even when processing the surfaces of the same forms. An attachment to be used is fixed directly on a large-sized design (a work-piece, a product or fastened in the special tool. The features of technological process, design shape, and arrangement of the processed surfaces define a fastening method of the attachment. Therefore it is necessary to pay much attention to a choice of the processing pattern and a design of tools.The Kaluga-branch of Bauman Moscow State Technical University is an original proposer of methods to form MOC-coatings on the separate surfaces of large-sized work-pieces using the moved and stationary electrodes to solve the above listed tasks.The following results of work will have an impact on development of the offered processing methods and their early implementation in real production:1. To provide oxide coatings on the surfaces of large-sized products or assemblies in a single or small

  14. Regularities of radiation defects build up on oxide materials surface

    International Nuclear Information System (INIS)

    Bitenbaev, M.I.; Polyakov, A.I.; Tuseev, T.

    2005-01-01

    Analysis of experimental data by radiation defects study on different oxide elements (silicon, beryllium, aluminium, rare earth elements) irradiated by the photo-, gamma-, neutron-, alpha- radiation, protons and helium ions show, that gas adsorption process on the surface centers and radiation defects build up in metal oxide correlated between themselves. These processes were described by the equivalent kinetic equations for analysis of radiation defects build up in the different metal oxides. It was revealed in the result of the analysis: number of radiation defects are droningly increasing up to limit value with the treatment temperature growth. Constant of radicals death at ionizing radiation increases as well. Amount of surface defects in different oxides defining absorbing activity of these materials looks as: silicon oxide→beryllium oxide→aluminium oxide. So it was found, that most optimal material for absorbing system preparation is silicon oxide by it power intensity and berylium oxide by it adsorption efficiency

  15. Influence of oxidation state on the pH dependence of hydrous iridium oxide films

    International Nuclear Information System (INIS)

    Steegstra, Patrick; Ahlberg, Elisabet

    2012-01-01

    Many electrochemical reactions taking place in aqueous solution consume or produce protons. The pH in the diffusion layer can therefore be significantly altered during the reaction and there is a need for in situ pH measurements tracing this near surface pH. In the present paper the rotating ring disc technique was used to measure near surface pH changes during oxygen reduction, utilising hydrous iridium oxide as the pH sensing probe. Before such experiments a good understanding of the pH sensing properties of these films is required and the impact of the oxidation state of the film on the pH sensing properties was investigated as well as the influence of solution redox species. The pH sensitivity (depicted by dE/dpH) was found to depend on the average oxidation state of the film in a manner resembling the cyclic voltammetry response. In all cases the pH response is “supernernstian” with more than one proton per electron. The origin of this behaviour is discussed in the context of acid-base properties of the film and the existence of both hydrous and anhydrous oxide phases. The pH response depends also on the redox properties of the solution but can be optimised for various purposes by conditioning the film at different potentials. This was clearly illustrated by adding hydrogen peroxide, an intermediate in the oxygen reduction reaction, to the solution. It was shown that hydrous iridium oxide can be used as a reliable in situ pH sensor provided that care is taken to optimise the oxidation state of the film.

  16. Topological surface states in nodal superconductors.

    Science.gov (United States)

    Schnyder, Andreas P; Brydon, Philip M R

    2015-06-24

    Topological superconductors have become a subject of intense research due to their potential use for technical applications in device fabrication and quantum information. Besides fully gapped superconductors, unconventional superconductors with point or line nodes in their order parameter can also exhibit nontrivial topological characteristics. This article reviews recent progress in the theoretical understanding of nodal topological superconductors, with a focus on Weyl and noncentrosymmetric superconductors and their protected surface states. Using selected examples, we review the bulk topological properties of these systems, study different types of topological surface states, and examine their unusual properties. Furthermore, we survey some candidate materials for topological superconductivity and discuss different experimental signatures of topological surface states.

  17. Effect of Ge surface termination on oxidation behavior

    Science.gov (United States)

    Lee, Younghwan; Park, Kibyung; Cho, Yong Soo; Lim, Sangwoo

    2008-09-01

    Sulfur-termination was formed on the Ge(1 0 0) surface using (NH 4) 2S solution. Formation of Ge-S and the oxidation of the S-terminated Ge surface were monitored with multiple internal reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the 0.5, 5, or 20% (NH 4) 2S solution, H-termination on the Ge(1 0 0) surface was substituted with S-termination in 1 min. When the S-terminated Ge(1 0 0) surface was exposed in air ambient, the oxidation was retarded for about 3600 min. The preservation time of the oxide layer up to one monolayer of S-terminated Ge(1 0 0) surface was about 120 times longer than for the H-terminated Ge(1 0 0) surface. However, the oxidation of S-terminated Ge(1 0 0) surface drastically increased after the threshold time. There was no significant difference in threshold time between S-terminations formed in 0.5, 5, and 20% (NH 4) 2S solutions. With the surface oxidation, desorption of S on the Ge surface was observed. The desorption behavior of sulfur on the S-terminated Ge(1 0 0) surface was independent of the concentration of the (NH 4) 2S solution that forms S-termination. Non-ideal S-termination on Ge surfaces may be related to drastic oxidation of the Ge surface. Finally, with the desulfurization on the S-terminated Ge(1 0 0) surface, oxide growth is accelerated.

  18. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  19. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  20. Surface-bound states in nanodiamonds

    Science.gov (United States)

    Han, Peng; Antonov, Denis; Wrachtrup, Jörg; Bester, Gabriel

    2017-05-01

    We show via ab initio calculations and an electrostatic model that the notoriously low, but positive, electron affinity of bulk diamond becomes negative for hydrogen passivated nanodiamonds and argue that this peculiar situation (type-II offset with a vacuum level at nearly midgap) and the three further conditions: (i) a surface dipole with positive charge on the outside layer, (ii) a spherical symmetry, and (iii) a dielectric mismatch at the surface, results in the emergence of a peculiar type of surface state localized just outside the nanodiamond. These states are referred to as "surface-bound states" and have consequently a strong environmental sensitivity. These type of states should exist in any nanostructure with negative electron affinity. We further quantify the band offsets of different type of nanostructures as well as the exciton binding energy and contrast the results with results for "conventional" silicon quantum dots.

  1. Gravitational states of antihydrogen near material surface

    Energy Technology Data Exchange (ETDEWEB)

    Voronin, Alexei Yu., E-mail: dr.a.voronin@gmail.com [P.N. Lebedev Physical Institute (Russian Federation); Froelich, Piotr [Uppsala University, Department of Quantum Chemistry (Sweden); Nesvizhevsky, Valery V. [Institut Laue-Langevin (ILL) (France)

    2012-12-15

    We present a theoretical study of the motion of antihydrogen atoms in the Earth's gravitational field near a material surface. We predict the existence of long-living quasistationary states of antihydrogen in a superposition of the gravitational and Casimir-van der Waals potentials of the surface. We suggest an interferometric method of measuring the energy difference between such gravitational states, hence the gravitational mass of antihydrogen.

  2. Role of the carbonate impurities on the surface state of pyrite and arsenopyrite under treatment by high power electromagnetic pulses (HPEMP): oxidation of 50-100 μm size particles

    International Nuclear Information System (INIS)

    Filippova, I; Filippov, L; Ryazantseva, M; Chanturiya, V; Bunin, I

    2013-01-01

    Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and Transmission Electron Microscopy (TEM) have shown the variation of surface phase compositions of carbonate bearing pyrite and arsenopyrite as a result of the combined action of chemical oxidation and thermal processes after the treatment by high power electromagnetic pulses (HPEMP). The monitoring of the surface phase composition allowed to determine the correlation between the treatment conditions, the surface phase composition, and the flotation yield. Thus, HPEMP treatment may be regarded as a tool controlling the surface composition and the sorption ability of flotation collector onto minerals surface, and therefore, allowing to control the hydrophobic-hydrophilic surface balance. It was confirmed in this study that the flotation of pyrite with xanthate as a result of the influence HPEMP may vary depending on the presence of impurities such as calcite.

  3. Oxidation and photo-oxidation of water on TiO2 surface

    DEFF Research Database (Denmark)

    Valdes, A.; Qu, Z.W.; Kroes, G.J.

    2008-01-01

    The oxidation and photo-oxidation of water on the rutile TiO2(110) surface is investigated using density functional theory (DFT) calculations. We investigate the relative stability of different surface terminations of TiO2 interacting with H2O and analyze the overpotential needed for the electrol...

  4. Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

    Science.gov (United States)

    Renaud, Gilles

    Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having

  5. XPS study of surface state of novel perovskite system Dy{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-δ} as cathode for solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kautkar, Pranay R.; Acharya, Smita A., E-mail: saha275@yahoo.com; Tumram, Priya V. [Depatment of Physics, Rashtrasant Tukadoji Maharaj Nagpur University Campus, Nagpur-440033 (India); Deshpande, U. P. [UGC-DAE Consortium for scientific Research, University Campus, Khandwa Road, Indore-452001, Madhya Pradesh,India (India)

    2016-05-06

    In the present attempt,novel perovskite oxide Dy{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3–δ} (DSCF) as cathode material has been synthesized by an Ethylene glycol-citrate combined sol-gel combustion route. Orthorhombic symmetry structure is confirmed by X-ray diffraction (XRD) and data is well fitted using Rietveld refinement by Full-Prof software suite. Chemical natureof surface of DSCF has been analyzed by using X-ray photoelectron spectroscopy (XPS). XPS result shows that Dy ions are in +3 oxidation state and Sr in +2 states. However Co2p and Fe2p spectra indicates partial change in oxidation state from Co3+/Fe3+ to Co4+/Fe4+. These attribute to develop active sites on the surface for oxygen ions. O1s XPS spectra shows two oxygen peaks relatedto lattice oxygen in perovskite and absorbed oxygen in oxygen vacancy are detected. O1s spectra demonstrate the existence of adsorbed oxygen species on the surface of DSCF oxide which is quite beneficial for intermediate temperature of Solid Oxide Fuel Cell.

  6. Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

    International Nuclear Information System (INIS)

    Silver, G.L.

    2014-01-01

    Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

  7. Surface-Controlled Metal Oxide Resistive Memory

    KAUST Repository

    Ke, Jr-Jian

    2015-10-28

    To explore the surface effect on resistive random-access memory (ReRAM), the impact of surface roughness on the characteristics of ZnO ReRAM were studied. The thickness-independent resistance and the higher switching probability of ZnO ReRAM with rough surfaces indicate the importance of surface oxygen chemisorption on the switching process. Furthermore, the improvements in switching probability, switching voltage and resistance distribution observed for ReRAM with rough surfaces can be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

  8. Photon density of states for deformed surfaces

    International Nuclear Information System (INIS)

    Emig, T

    2006-01-01

    A new approach to the Helmholtz spectrum for arbitrarily shaped boundaries and a rather general class of boundary conditions is introduced. We derive the boundary induced change of the density of states in terms of the free Green's function from which we obtain both perturbative and non-perturbative results for the Casimir interaction between deformed surfaces. As an example, we compute the lateral electrodynamic Casimir force between two corrugated surfaces over a wide parameter range. Universal behaviour, fixed only by the largest wavelength component of the surface shape, is identified at large surface separations. This complements known short distance expansions which are also reproduced

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

    Science.gov (United States)

    McBriarty, Martin E.

    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.

  10. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  11. Water reactivity with mixed oxide (U,Pu)O2 surfaces

    International Nuclear Information System (INIS)

    Gaillard, Jeremy

    2013-01-01

    The interaction of water with actinides oxide surfaces remains poorly understood. The adsorption of water on PuO 2 surface and (U,Pu)O 2 surface leads to hydrogen generation through radiolysis but also surface evolution. The study of water interaction with mixed oxide (U,Pu)O 2 and PuO 2 surfaces requires the implementation of non intrusive techniques. The study of the hydration of CeO 2 surface is used to study the effectiveness of different techniques. The results show that the water adsorption leads to the surface evolution through the formation of a hydroxide superficial layer. The reactivity of water on the surface depends on the calcination temperature of the oxide precursor. The thermal treatment of hydrated surfaces can regenerate the surface. The study on CeO 2 hydration emphasizes the relevancies of these techniques in studying the hydration of surfaces. The hydrogen generation through water radiolysis is studied with an experimental methodology based on constant relative humidity in the radiolysis cell. The hydrogen accumulation is linear for the first hours and then tends to a steady state content. A mechanism of hydrogen consumption is proposed to explain the existence of the steady state of hydrogen content. This mechanism enables to explain also the evolution of the oxide surface during hydrogen generation experiments as shown by the evolution of hydrogen accumulation kinetics. The accumulation kinetics depends on the dose rate, specific surface area and the relative humidity but also on the oxide aging. The plutonium percentage appears to be a crucial parameter in hydrogen accumulation kinetics. (author) [fr

  12. Mechanism and Thermochemistry of Coal Char Oxidation and Desorption of Surface Oxides

    DEFF Research Database (Denmark)

    Levi, Gianluca; Causà, Mauro; Lacovig, Paolo

    2017-01-01

    The present study investigates the coal char combustion by a combination of thermochemical and X-ray photoemission spectroscopy (XPS) analyses. Thermoanalytical methods (differential thermogravimetry, differential scanning calorimetry, and temperature-programmed desorption) are used to identify...... the key reactive steps that occur upon oxidation and heating of coal char (chemisorption, structural rearrangement and switchover of surface oxides, and desorption) and their energetics. XPS is used to reveal the chemical nature of the surface oxides that populate the char surface and to monitor...... functionalities prevail. The rearrangement of epoxy during preoxidation goes together with activation of the more stable and less reactive carbon sites. Results are in good agreement with semi-lumped kinetic models of carbon oxidation, which include (1) formation of "metastable" surface oxides, (2) complex...

  13. Surface Embedded Metal Oxide Sensors (SEMOS)

    DEFF Research Database (Denmark)

    Jespersen, Jesper Lebæk; Talat Ali, Syed; Pleth Nielsen, Lars

    SEMOS is a joint project between Aalborg University, Danish Technological Institute and Danish Technical University in which micro temperature sensors and metal oxide-based gas sensors are developed and tested in a simulated fuel cell environment as well as in actual working fuel cells. Initially......, sensors for measuring the temperatures in an operating HT-PEM (High Temperature-Proton Exchange Membrane) fuel cell are developed for detecting in-plane temperature variations. 5 different tracks for embedded thermal sensors are investigated. The fuel cell MEA (Membrane Electrode Assembly) is quite...... complex and sensors are not easily implemented in the construction. Hence sensor interface and sensor position must therefore be chosen carefully in order to make the sensors as non-intrusive as possible. Metal Oxide Sensors (MOX) for measuring H2, O2 and CO concentration in a fuel cell environment...

  14. Surface chemistry and cytotoxicity of reactively sputtered tantalum oxide films on NiTi plates

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, K. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Kolaj-Robin, O.; Belochapkine, S.; Laffir, F. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Gandhi, A.A. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Tofail, S.A.M., E-mail: tofail.syed@ul.ie [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland)

    2015-08-31

    NiTi, an equiatomic alloy containing nickel and titanium, exhibits unique properties such as shape memory effect and superelasticity. NiTi also forms a spontaneous protective titanium dioxide (TiO{sub 2}) layer that allows its use in biomedical applications. Despite the widely perceived biocompatibility there remain some concerns about the sustainability of the alloy's biocompatibility due to the defects in the TiO{sub 2} protective layer and the presence of high amount of sub-surface Ni, which can give allergic reactions. Many surface treatments have been investigated to try to improve both the corrosion resistance and biocompatibility of this layer. For such purposes, we have sputter deposited tantalum (Ta) oxide thin films onto the surface of the NiTi alloy. Despite being one of the promising metals for biomedical applications, Ta, and its various oxides and their interactions with cells have received relatively less attention. The oxidation chemistry, crystal structure, morphology and biocompatibility of these films have been investigated. In general, reactive sputtering especially in the presence of a low oxygen mixture yields a thicker film with better control of the film quality. The sputtering power influenced the surface oxidation states of Ta. Both microscopic and quantitative cytotoxicity measurements show that Ta films on NiTi are biocompatible with little to no variation in cytotoxic response when the surface oxidation state of Ta changes. - Highlights: • Reactive sputtering in low oxygen mixture yields thicker better quality films. • Sputtering power influenced surface oxidation states of Ta. • Cytotoxicity measurements show Ta films on NiTi are biocompatible. • Little to no variation in cytotoxic response when oxidation state changes.

  15. Interaction of ammonia with semiconducting oxide surfaces

    Science.gov (United States)

    Nigam, Sandeep; Sahoo, Suman Kalyan; Majumder, Chiranjib

    2018-04-01

    Using density functional theory (DFT) we have investigated the adsorption of NH3 molecule on the rutile SnO2(110) and mixed Sn0.5Ti0.5O2(110) surfaces. NH3 molecule gets absorbed on the 5-coordinated Sn atom (Sn5c) of the surface in tilted mode having an additional hydrogen bond with nearby surface bridged oxygen (Obr) atom. After adsorption, 3a1 molecular orbital of ammonia undergo significant dispersal as it donates its electron to surface atoms. The adsorption energy is found to be 1.4-1.6eV. Inclusion of Ti atoms in the SnO2 lattice leads to decrease in the adsorption energy value.

  16. Surface-Controlled Metal Oxide Resistive Memory

    KAUST Repository

    Ke, Jr-Jian; Namura, Kyoko; Duran Retamal, Jose Ramon; Ho, Chin-Hsiang; Minamitake, Haruhiko; Wei, Tzu-Chiao; Tsai, Dung-Sheng; Lin, Chun-Ho; Suzuki, Motofumi; He, Jr-Hau

    2015-01-01

    be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

  17. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

  18. Topological surface states in nodal superconductors

    International Nuclear Information System (INIS)

    Schnyder, Andreas P; Brydon, Philip M R

    2015-01-01

    Topological superconductors have become a subject of intense research due to their potential use for technical applications in device fabrication and quantum information. Besides fully gapped superconductors, unconventional superconductors with point or line nodes in their order parameter can also exhibit nontrivial topological characteristics. This article reviews recent progress in the theoretical understanding of nodal topological superconductors, with a focus on Weyl and noncentrosymmetric superconductors and their protected surface states. Using selected examples, we review the bulk topological properties of these systems, study different types of topological surface states, and examine their unusual properties. Furthermore, we survey some candidate materials for topological superconductivity and discuss different experimental signatures of topological surface states. (topical review)

  19. Measuring Forces between Oxide Surfaces Using the Atomic Force Microscope

    DEFF Research Database (Denmark)

    Pedersen, Henrik Guldberg; Høj, Jakob Weiland

    1996-01-01

    The interactions between colloidal particles play a major role in processing of ceramics, especially in casting processes. With the Atomic Force Microscope (AFM) it is possible to measure the inter-action force between a small oxide particle (a few micron) and a surface as function of surface...

  20. Fractional surface termination of diamond by electrochemical oxidation.

    Science.gov (United States)

    Hoffmann, René; Obloh, Harald; Tokuda, Norio; Yang, Nianjun; Nebel, Christoph E

    2012-01-10

    The crystalline form of sp(3)-hybridized carbon, diamond, offers various electrolyte-stable surface terminations. The H-termination-selective attachment of nitrophenyl diazonium, imaged by AFM, shows that electrochemical oxidation can control the fractional hydrogen/oxygen surface termination of diamond on the nanometer scale. This is of particular interest for all applications relying on interfacial electrochemistry, especially for biointerfaces.

  1. Heterogeneous nucleation of calcium oxalate on native oxide surfaces

    International Nuclear Information System (INIS)

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

    1994-04-01

    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

  2. Surface states in crystals with low-index surfaces

    International Nuclear Information System (INIS)

    Wang Hui-Ping; Tao Rui-Bao

    2015-01-01

    For most of the conventional crystals with low-index surfaces, the hopping between the nearest neighbor (1NN) crystal planes (CPs) is dominant and the ones from the nNN (2 ≤ n < ∞) CPs are relatively weak, considered as small perturbations. The recent theoretical analysis [1] has demonstrated the absence of surface states at the level of the hopping approximation between the 1NN CPs when the original infinite crystal has the geometric reflection symmetry (GRS) for each CP. Meanwhile, based on the perturbation theory, it has also been shown that small perturbations from the hopping between the nNN (2 ≤ n < ∞) CPs and surface relaxation have no impact on the above conclusion. However, for the crystals with strong intrinsic spin-orbit coupling (SOC), the dominant terms of intrinsic SOC associate with two 1NN bond hoppings. Thus SOC will significantly contribute the hoppings from the 1NN and/or 2NN CPs except the ones within each CP. Here, we will study the effect of the hopping between the 2NN CPs on the surface states in model crystals with three different type structures (Type I: “···–P–P–P–P–···”, Type II: “···–P–Q–P–Q–···” and Type III: “···–P=Q–P=Q–···” where P and Q indicate CPs and the signs “−” and “=” mark the distance between the 1NN CPs). In terms of analytical and numerical calculations, we study the behavior of surface states in three types after the symmetric/asymmetric hopping from the 2NN CPs is added. We analytically prove that the symmetric hopping from the 2NN CPs cannot induce surface states in Type I when each CP has only one electron mode. The numerical calculations also provide strong support for the conclusion, even up to 5NN. However, in general, the coupling from the 2NN CPs (symmetric and asymmetric) is favorable to generate surface states except Type I with single electron mode only. (paper)

  3. Surface study of liquid 3He using surface state electrons

    International Nuclear Information System (INIS)

    Shirahama, K.; Ito, S.; Suto, H.; Kono, K.

    1995-01-01

    We have measured the mobility of surface state electrons (SSE) on liquid 3 He, μ 3 , aiming to study the elementary surface excitations of the Fermi liquid. A gradual increase of μ 3 below 300 mK is attributed to the scattering of electrons by ripplons. Ripplons do exist in 3 He down to 100 mK. We observe an abrupt decrease of μ 3 , due to the transition to the Wigner solid (WS). The dependences of the WS conductivity and mobility on temperature and magnetic field differ from the SSE behavior on liquid 4 He

  4. Layer Dependence of Graphene for Oxidation Resistance of Cu Surface

    Institute of Scientific and Technical Information of China (English)

    Yu-qing Song; Xiao-ping Wang

    2017-01-01

    We studied the oxidation resistance of graphene-coated Cu surface and its layer dependence by directly growing monolayer graphene with different multilayer structures coexisted,diminishing the influence induced by residue and transfer technology.It is found that the Cu surface coated with the monolayer graphene demonstrate tremendous difference in oxidation pattern and oxidation rate,compared to that coated with the bilayer graphene,which is considered to be originated from the strain-induced linear oxidation channel in monolayer graphene and the intersection of easily-oxidized directions in each layer of bilayer graphene,respectively.We reveal that the defects on the graphene basal plane but not the boundaries are the main oxidation channel for Cu surface under graphene protection.Our finding indicates that compared to putting forth efforts to improve the quality of monolayer graphene by reducing defects,depositing multilayer graphene directly on metal is a simple and effective way to enhance the oxidation resistance of graphene-coated metals.

  5. Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2012-02-01

    The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. 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. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

  6. Surface properties of nanostructured NiO undergoing electrochemical oxidation in 3-methoxy-propionitrile

    Science.gov (United States)

    Bonomo, Matteo; Marrani, Andrea Giacomo; Novelli, Vittoria; Awais, Muhammad; Dowling, Denis P.; Vos, Johannes G.; Dini, Danilo

    2017-05-01

    Nanostructured nickel oxide (NiO) was deposited in the configuration of thin film (thickness, l = 2-6 μm) onto fluorine-doped tin oxide (FTO) substrates via plasma-assisted rapid discharge sintering (RDS). Electrochemical cycling of RDS NiO in 3-methoxy-propionitrile (3-MPN) revealed two characteristic peaks of NiO oxidation which were associated to the surface-confined redox processes Ni(II) → Ni(III) and Ni(III) → Ni(IV). Grazing angle X-ray photoelectron spectroscopy (XPS) was conducted ex-situ on NiO electrodes in both pristine and oxidized states. Oxidized NiO samples for XPS experiments were obtained in the potentiostatic mode through the polarization of NiO at its two characteristic potentials of oxidation. The XPS analysis allowed to ascertain the electronic structure of the nanoporous NiO framework, and verify the adsorption of perchlorate and chloride anions onto NiO surface due to the compensation of the charge stored in oxidized NiO. XPS also revealed that the spectrum within the region characteristic of Ni 2p ionization does not vary considerably with the state of charge of the nickel centres. This finding is in evident contrast to what has been observed for the same system when it undergoes electrochemical oxidation in aqueous electrolyte.

  7. Volcano Relations for Oxidation of Hydrogen Halides over Rutile Oxide Surfaces

    DEFF Research Database (Denmark)

    Toftelund, Anja; Man, Isabela C.; Hansen, Heine A.

    2012-01-01

    over a range of different rutile oxide surfaces. Based on the scaling relations, two descriptors are identified that describe the reactions uniquely. By combining scaling with the micro-kinetic model, activity volcanoes for the three different oxidation reactions are derived. It is found...

  8. Photoelectron binding energy shifts observed during oxidation of group IIA, IIIA and IVA elemental surfaces

    International Nuclear Information System (INIS)

    Heide, P.A.W. van der

    2006-01-01

    An extensive re-evaluation of XPS binding energies (BE's) and binding energy shifts (ΔBE's) from metals, oxides and the carbonates of the group II, III and IVA elements (exceptions are Be, Mg and Hf) has been carried out using a substrate specific BE referencing approach. From this, O-1s BE's are found to fall into surface oxide, bulk oxide and carbonate groupings, with bulk oxides showing the lowest BE's followed by surface oxides (+∼1.5 eV) and then carbonates (+∼3.0 eV). The O-1s BE's from the bulk oxides also appear to scale with 1/d, where d is inter-atomic distance. The same is noted in the ΔBE's observed from the metallic counterparts during oxidation of the elemental surfaces. This, and the decreasing BE exhibited by Ca, Sr and Ba on oxidation is explained within the charge potential model as resulting from competing inter- and intra-atomic effects, and is shown to be consistent with partial covalency arguments utilizing Madulung potentials. The ΔBE's also fall into groups according to the elements location in the periodic table, i.e. s, p or d block. These trends open up the possibility of approximating ΔBE's arising from initial and final state effects, and bond distances

  9. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    Science.gov (United States)

    2014-10-27

    Diamond. Phys. Rev. Lett. 2000, 84, 5160−5163. (31) Ownby, P. D.; Yang, X.; Liu, J. Calculated X-Ray-Diffraction Data for Diamond Polytypes. J. Am. Ceram...Surfaces from Ab-Initio Calculations . Phys. Rev. B 1995, 51, 14669−14685. (39) Ferrari, A. C.; Robertson, J. Raman Spectroscopy of Amorphous, Nanostructured...Y.; Takami, S.; Kubo , M.; Belosludov, R. V.; Miyamoto, A.; Imamura, A.; Gamo, M. N.; Ando, T. First-Principle Study on Reactions of Diamond (100

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

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

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

  11. Novel exchange mechanisms in the surface diffusion of oxides

    International Nuclear Information System (INIS)

    Harris, Duncan J; Lavrentiev, Mikhail Yu; Harding, John H; Allan, Neil L; Purton, John A

    2004-01-01

    We use temperature-accelerated dynamics to show the importance of exchange mechanisms in surface diffusion and growth of simple oxides. Such mechanisms can dominate transport processes both on terraces and steps for both homoepitaxial and heteroepitaxial growth. We suggest that the mixing inevitable when an exchange mechanism is present must be considered when attempts are made to grow sharp interfaces in oxide nanostructures. (letter to the editor)

  12. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    Science.gov (United States)

    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

    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.

  13. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    International Nuclear Information System (INIS)

    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

    2014-01-01

    A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al 2 O 3 and Fe 3 O 4 , 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.

  14. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    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, E-mail: lian2010@lut.cn

    2014-06-01

    A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al{sub 2}O{sub 3} and Fe{sub 3}O{sub 4}, 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.

  15. Surface characterization of low-temperature grown yttrium oxide

    Science.gov (United States)

    Krawczyk, Mirosław; Lisowski, Wojciech; Pisarek, Marcin; Nikiforow, Kostiantyn; Jablonski, Aleksander

    2018-04-01

    The step-by-step growth of yttrium oxide layer was controlled in situ using X-ray photoelectron spectroscopy (XPS). The O/Y atomic concentration (AC) ratio in the surface layer of finally oxidized Y substrate was found to be equal to 1.48. The as-grown yttrium oxide layers were then analyzed ex situ using combination of Auger electron spectroscopy (AES), elastic-peak electron spectroscopy (EPES) and scanning electron microscopy (SEM) in order to characterize their surface chemical composition, electron transport phenomena and surface morphology. Prior to EPES measurements, the Y oxide surface was pre-sputtered by 3 kV argon ions, and the resulting AES-derived composition was found to be Y0.383O0.465C0.152 (O/Y AC ratio of 1.21). The SEM images revealed different surface morphology of sample before and after Ar sputtering. The oxide precipitates were observed on the top of un-sputtered Y oxide layer, whereas the oxide growth at the Ar ion-sputtered surface proceeded along defects lines normal to the layer plane. The inelastic mean free path (IMFP) characterizing electron transport was evaluated as a function of energy in the range of 0.5-2 keV from the EPES method. Two reference materials (Ni and Au) were used in these measurements. Experimental IMFPs determined for the Y0.383O0.465C0.152 and Y2O3 surface compositions, λ, were uncorrected for surface excitations and approximated by the simple function λ = kEp at electron energies E between 500 eV and 2000 eV, where k and p were fitted parameters. These values were also compared with IMFPs resulting from the TPP-2 M predictive equation for both oxide compositions. The fitted functions were found to be reasonably consistent with the measured and predicted IMFPs. In both cases, the average value of the mean percentage deviation from the fits varied between 5% and 37%. The IMFPs measured for Y0.383O0.465C0.152 surface composition were found to be similar to the IMFPs for Y2O3.

  16. Surface Passivation of CIGS Solar Cells Using Gallium Oxide

    KAUST Repository

    Garud, Siddhartha

    2018-02-27

    This work proposes gallium oxide grown by plasma-enhanced atomic layer deposition, as a surface passivation material at the CdS buffer interface of Cu(In,Ga)Se2 (CIGS) solar cells. In preliminary experiments, a metal-insulator-semiconductor (MIS) structure is used to compare aluminium oxide, gallium oxide, and hafnium oxide as passivation layers at the CIGS-CdS interface. The findings suggest that gallium oxide on CIGS may show a density of positive charges and qualitatively, the least interface trap density. Subsequent solar cell results with an estimated 0.5 nm passivation layer show an substantial absolute improvement of 56 mV in open-circuit voltage (VOC), 1 mA cm−2 in short-circuit current density (JSC), and 2.6% in overall efficiency as compared to a reference (with the reference showing 8.5% under AM 1.5G).

  17. Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Stubbs, Joanne E.; Biwer, Craig A.; Chaka, Anne M. [Pacific Northwest; Ilton, Eugene S. [Pacific Northwest; Du, Yingge [Pacific Northwest; Bargar, John R. [Stanford Synchrotron; Eng, Peter J.

    2017-11-07

    Uranium oxide is central to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that during corrosion of the UO2 (111) surface under either 1 atm O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we present results from surface x-ray scattering that reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ~52 Å below the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy indicates U is present as U(IV), U(V), and U(VI).

  18. Mechanical tearing of graphene on an oxidizing metal surface

    International Nuclear Information System (INIS)

    George, Lijin; Gupta, Aparna; Shaina, P R; Jaiswal, Manu; Gupta, Nandita Das

    2015-01-01

    Graphene, the thinnest possible anticorrosion and gas-permeation barrier, is poised to transform the protective coatings industry for a variety of surface applications. In this work, we have studied the structural changes of graphene when the underlying copper surface undergoes oxidation upon heating. Single-layer graphene directly grown on a copper surface by chemical vapour deposition was annealed under ambient atmosphere conditions up to 400 °C. The onset temperature of the surface oxidation of copper is found to be higher for graphene-coated foils. Parallel arrays of graphene nanoripples are a ubiquitous feature of pristine graphene on copper, and we demonstrate that these form crucial sites for the onset of the oxidation of copper, particularly for ∼0.3–0.4 μm ripple widths. In these regions, the oxidation proceeds along the length of the nanoripples, resulting in the formation of parallel stripes of oxidized copper regions. We demonstrate from temperature-dependent Raman spectroscopy that the primary defect formation process in graphene involves boundary-type defects rather than vacancy or sp"3-type defects. This observation is consistent with a mechanical tearing process that splits graphene into small polycrystalline domains. The size of these is estimated to be sub-50 nm. (paper)

  19. Mechanical tearing of graphene on an oxidizing metal surface.

    Science.gov (United States)

    George, Lijin; Gupta, Aparna; Shaina, P R; Das Gupta, Nandita; Jaiswal, Manu

    2015-12-11

    Graphene, the thinnest possible anticorrosion and gas-permeation barrier, is poised to transform the protective coatings industry for a variety of surface applications. In this work, we have studied the structural changes of graphene when the underlying copper surface undergoes oxidation upon heating. Single-layer graphene directly grown on a copper surface by chemical vapour deposition was annealed under ambient atmosphere conditions up to 400 °C. The onset temperature of the surface oxidation of copper is found to be higher for graphene-coated foils. Parallel arrays of graphene nanoripples are a ubiquitous feature of pristine graphene on copper, and we demonstrate that these form crucial sites for the onset of the oxidation of copper, particularly for ∼0.3-0.4 μm ripple widths. In these regions, the oxidation proceeds along the length of the nanoripples, resulting in the formation of parallel stripes of oxidized copper regions. We demonstrate from temperature-dependent Raman spectroscopy that the primary defect formation process in graphene involves boundary-type defects rather than vacancy or sp(3)-type defects. This observation is consistent with a mechanical tearing process that splits graphene into small polycrystalline domains. The size of these is estimated to be sub-50 nm.

  20. Surface chemical state of Ti powders and its alloys: Effect of storage conditions and alloy composition

    Energy Technology Data Exchange (ETDEWEB)

    Hryha, Eduard, E-mail: hryha@chalmers.se [Department of Materials and Manufacturing Technology, Chalmers University of Technology, Rännvägen 2A, SE - 412 96 Gothenburg (Sweden); Shvab, Ruslan [Department of Materials and Manufacturing Technology, Chalmers University of Technology, Rännvägen 2A, SE - 412 96 Gothenburg (Sweden); Bram, Martin; Bitzer, Martin [Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), D-52425 Jülich (Germany); Nyborg, Lars [Department of Materials and Manufacturing Technology, Chalmers University of Technology, Rännvägen 2A, SE - 412 96 Gothenburg (Sweden)

    2016-12-01

    Highlights: • Powder particles of Ti, NiTi and Ti6Al4V are covered by homogeneous Ti-oxide layer. • Thickness of the Ti-oxide layer is in the range of 2.9 to 4.2 nm in as-atomized state. • Exposure to the air results in immediate oxide thickness increase of up to 30%. • Oxide thickness increase of only 15% during storage for 8 years. • High passivation of the Ti, NiTi and Ti6Al4V powder surface by Ti-oxide layer. - Abstract: High affinity of titanium to oxygen in combination with the high surface area of the powder results in tremendous powder reactivity and almost inevitable presence of passivation oxide film on the powder surface. Oxide film is formed during the short exposure of the powder to the environment at even a trace amount of oxygen. Hence, surface state of the powder determines its usefulness for powder metallurgy processing. Present study is focused on the evaluation of the surface oxide state of the Ti, NiTi and Ti6Al4V powders in as-atomized state and after storage under air or Ar for up to eight years. Powder surface oxide state was studied by X-ray photoelectron spectroscopy (XPS) and high resolution scanning electron microscopy (HR SEM). Results indicate that powder in as-atomized state is covered by homogeneous Ti-oxide layer with the thickness of ∼2.9 nm for Ti, ∼3.2 nm and ∼4.2 nm in case of Ti6Al4V and NiTi powders, respectively. Exposure to the air results in oxide growth of about 30% in case of Ti and only about 10% in case of NiTi and Ti6Al4V. After the storage under the dry air for two years oxide growth of only about 3-4% was detected in case of both, Ti and NiTi powders. NiTi powder, stored under the dry air for eight years, indicates oxide thickness of about 5.3 nm, which is about 30% thicker in comparison with the as-atomized powder. Oxide thickness increase of only ∼15% during the storage for eight years in comparison with the powder, shortly exposed to the air after manufacturing, was detected. Results indicate a

  1. Surface and sub-surface thermal oxidation of ruthenium thin films

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    For next generation Extreme UV photolithography, multilayer coatings may require protective capping layers against surface contamination. Ruthenium, as a low-oxidation metal, is often used as a reference material. The oxidation behaviour of Ru thin films has been studied using X-ray reflectometry

  2. Investigation of the Si(111) surface in uhv: oxidation and the effect of surface phosphorus

    International Nuclear Information System (INIS)

    Tom, H.W.K.; Zhu, X.D.; Shen, Y.R.; Somorjai, G.A.

    1984-06-01

    We have studied the initial stages of oxidation, the segregation of phosphorus, and the effect of phosphorus on oxidation of the Si(111) 7 x 7 surface using optical second-harmonic generation. We have also observed a (√3 x √3)R30 0 LEED pattern for P on Si

  3. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  4. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  5. Photoinduced hydrophobic surface of graphene oxide thin films

    International Nuclear Information System (INIS)

    Zhang Xiaoyan; Song Peng; Cui Xiaoli

    2012-01-01

    Graphene oxide (GO) thin films were deposited on transparent conducting oxide substrates and glass slides by spin coating method at room temperature. The wettability of GO thin films before and after ultraviolet (UV) irradiation was characterized with water contact angles, which increased from 27.3° to 57.6° after 3 h of irradiation, indicating a photo-induced hydrophobic surface. The UV–vis absorption spectra, Raman spectroscopy, X-ray photoelectron spectroscopy, and conductivity measurements of GO films before and after UV irradiation were taken to study the mechanism of photoinduced hydrophobic surface of GO thin films. It is demonstrated that the photoinduced hydrophobic surface is ascribed to the elimination of oxygen-containing functional groups on GO molecules. This work provides a simple strategy to control the wettability properties of GO thin films by UV irradiation. - Highlights: ► Photoinduced hydrophobic surface of graphene oxide thin films has been demonstrated. ► Elimination of oxygen-containing functional groups in graphene oxide achieved by UV irradiation. ► We provide novel strategy to control surface wettability of GO thin films by UV irradiation.

  6. Phenol by direct hydroxylation of benzene with nitrous oxide - role of surface oxygen species in the reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Reitzmann, A.; Klemm, E.; Emig, G. [Erlangen-Nuernberg Univ., Erlangen (Germany). Lehrstuhl fuer Technische Chemie 1; Buchholz, S.A.; Zanthoff, H.W. [Bochum Univ. (Germany). Inst. of Technical Chemistry

    1998-12-31

    Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a pseudo steady state phenol yield. (orig.)

  7. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

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

    Science.gov (United States)

    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...

  9. Anchoring of alkyl chain molecules on oxide surface using silicon alkoxide

    Energy Technology Data Exchange (ETDEWEB)

    Narita, Ayumi, E-mail: narita.ayumi@jaea.go.jp [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Graduate School of Science and Engineering, Ibaraki University, Bunnkyo, Mito-shi, Ibaraki-ken 310-8512 (Japan); Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Yaita, Tsuyoshi [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Graduate School of Science and Engineering, Ibaraki University, Bunnkyo, Mito-shi, Ibaraki-ken 310-8512 (Japan)

    2012-01-01

    Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides.

  10. The early stages of oxidation of magnesium single crystal surfaces

    International Nuclear Information System (INIS)

    Hayden, B.E.; Schweizer, E.; Koetz, R.; Bradshaw, A.M.

    1981-01-01

    The early stages of oxidation of Mg(001) and Mg(100) single crystal surfaces at 300 K have been investigated by LEED, ELS, work function and ellipsometric measurements. A sharp decrease in work function on both surfaces during the first 12 L exposure indicates the incorporation of oxygen in the earliest stages of the interaction. The incorporated oxygen on Mg(001) gives rise to a broadening of the integral order LEED spots for an exposure 3 L. (orig.)

  11. Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

    Energy Technology Data Exchange (ETDEWEB)

    Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira [Chemical and Biological Engineering, The University of Alabama, Tuscaloosa , AL 35487 (United States); Qin, Ying [Alabama Innovation and Mentoring of Entrepreneurs, The University of Alabama, Tuscaloosa, AL 35487 (United States); Bao, Yuping, E-mail: ybao@eng.ua.edu [Chemical and Biological Engineering, The University of Alabama, Tuscaloosa , AL 35487 (United States)

    2017-04-01

    We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

  12. Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

    International Nuclear Information System (INIS)

    Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira; Qin, Ying; Bao, Yuping

    2017-01-01

    We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

  13. Deposition of heated whey proteins on a chromium oxide surface.

    NARCIS (Netherlands)

    Jeurnink, Th.; Verheul, M.; Cohen Stuart, M.A.; Kruif, de C.G.

    1996-01-01

    Whey protein solutions were given different heat treatments after which their deposition on a chromium oxide surface (the outer layer of stainless steel) was measured by reflectometry. The deposition was studied under controlled flow conditions by using a stagnation point flow configuration. The

  14. Mechanical Properties of Glass Surfaces Coated with Tin Oxide

    DEFF Research Database (Denmark)

    Swindlehurst, W. E.; Cantor, B.

    1978-01-01

    The effect of tin oxide coatings on the coefficient of friction and fracture strength of glass surfaces is studied. Experiments were performed partly on commercially treated glass bottles and partly on laboratory prepared microscope slides. Coatings were applied in the laboratory by decomposition...

  15. Ceramic coated Y1 magnesium alloy surfaces by microarc oxidation

    Indian Academy of Sciences (India)

    The magnesium alloys occupy an important place in marine applications, but their poor corrosion resistance, wear resistance, hardness and so on, have limited their application. To meet these defects, some techniques are developed. Microarc oxidation is a one such recently developed surface treatment technology under ...

  16. Topological surface states of Bi{sub 2}Te{sub 2}Se are robust against surface chemical modification

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, Conor R.; Sahasrabudhe, Girija; Kushwaha, Satya Kumar; Cava, Robert J.; Schwartz, Jeffrey [Department of Chemistry, Princeton University, Princeton, NJ (United States); Xiong, Jun [Department of Physics, Princeton University, Princeton, NJ (United States)

    2014-12-01

    The robustness of the Dirac-like electronic states on the surfaces of topological insulators (TIs) during materials process-ing is a prerequisite for their eventual device application. Here, the (001) cleavage surfaces of crystals of the topological insulator Bi{sub 2}Te{sub 2}Se (BTS) were subjected to several surface chemical modification procedures that are common for electronic materials. Through measurement of Shubnikov-de Hass (SdH) oscillations, which are the most sensitive measure of their quality, the surface states of the treated surfaces were compared to those of pristine BTS that had been exposed to ambient conditions. In each case - surface oxidation, deposition of thin layers of Ti or Zr oxides, or chemical modification of the surface oxides - the robustness of the topological surface electronic states was demonstrated by noting only very small changes in the frequency and amplitude of the SdH oscillations. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  17. Indium tin oxide surface smoothing by gas cluster ion beam

    CERN Document Server

    Song, J H; Choi, W K

    2002-01-01

    CO sub 2 cluster ions are irradiated at the acceleration voltage of 25 kV to remove hillocks on indium tin oxide (ITO) surfaces and thus to attain highly smooth surfaces. CO sub 2 monomer ions are also bombarded on the ITO surfaces at the same acceleration voltage to compare sputtering phenomena. From the atomic force microscope results, the irradiation of monomer ions makes the hillocks sharper and the surfaces rougher from 1.31 to 1.6 nm in roughness. On the other hand, the irradiation of CO sub 2 cluster ions reduces the height of hillocks and planarize the ITO surfaces as smooth as 0.92 nm in roughness. This discrepancy could be explained by large lateral sputtering yield of the cluster ions and re-deposition of sputtered particles by the impact of the cluster ions on surfaces.

  18. Oxidation of clean silicon surfaces studied by four-point probe surface conductance measurements

    DEFF Research Database (Denmark)

    Petersen, Christian Leth; Grey, Francois; Aono, M.

    1997-01-01

    We have investigated how the conductance of Si(100)-(2 x 1) and Si(111)-(7 x 7) surfaces change during exposure to molecular oxygen. A monotonic decrease in conductance is seen as the (100) surfaces oxidizes. In contract to a prior study, we propose that this change is caused by a decrease in sur...

  19. Positron annihilation induced Auger electron spectroscopic studies of oxide surfaces

    Science.gov (United States)

    Nadesalingam, Manori

    2005-03-01

    Defects on oxide surfaces are well known to play a key role in catalysis. TiO2, MgO, SiO2 surfaces were investigated using Time-Of-Flight Positron induced Auger Electron Spectroscopy (TOF-PAES). Previous work in bulk materials has demonstrated that positrons are particularly sensitive to charged defects. In PAES energetic electron emission results from Auger transitions initiated by annihilation of core electrons with positrons trapped in an image-potential well at the surface. Annealed samples in O2 environment show a strong Auger peak of Oxygen. The implication of these results will be discussed

  20. Oxidation-reduction induced roughening of platinum (111) surface

    International Nuclear Information System (INIS)

    You, H.; Nagy, Z.

    1993-06-01

    Platinum (111) single crystal surface was roughened by repeated cycles of oxidation and reduction to study dynamic evolution of surface roughening. The interface roughens progressively upon repeated cycles. The measured width of the interface was fit to an assumed pow law, W ∼t β , with β = 0.38(1). The results are compared with a simulation based on a random growth model. The fraction of the singly stepped surface apparently saturates to 0. 25 monolayer, which explains the apparent saturation to a steady roughness observed in previous studies

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

    Science.gov (United States)

    Entringer, Anthony G.

    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

  2. Surface Characterization and Electrochemical Oxidation of Metal Doped Uranium Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jeongmook; Kim, Jandee; Youn, Young-Sang; Kim, Jong-Goo; Ha, Yeong-Keong; Kim, Jong-Yun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    Trivalent element in UO{sub 2} matrix makes the oxygen vacancy from loss of oxygen for charge compensation. Tetravalent element alters lattice parameter of UO{sub 2} due to diameter difference between the tetravalent element and replaced U. These structural changes have significant effect on not only relevant fuel performance but also the kinetics of fuel oxidation. Park and Olander explained the stabilization of Ln (III)-doped UO{sub 2} against oxidation based on oxygen potential calculations. In this work, we have been investigated the effect of Gd{sup 3+} and Th{sup 4+} doping on the UO{sub 2} structure with Raman spectroscopy and X-ray diffraction to characterize the surface structure of nuclear fuel material. For Gd doped UO{sub 2}, its electrochemical oxidation behaviors are also investigated. The Gd and Th doped uranium dioxide solid solution pellets with various doping level were investigated by XRD, Raman spectroscopy, SEM, electrochemical experiments to investigate surface structure and electro chemical oxidation behaviors. The lattice parameter evaluated from XRD spectra indicated the formation of solid solutions. Raman spectra showed the existence of the oxygen vacancy. SEM images showed the grain structure on the surface of Gd doped uranium dioxide depending on doping level and oxygen-to-metal ratio.

  3. Macromolecular surface design: photopatterning of functional stable nitrile oxides.

    Science.gov (United States)

    Altintas, Ozcan; Glassner, Mathias; Rodriguez-Emmenegger, Cesar; Welle, Alexander; Trouillet, Vanessa; Barner-Kowollik, Christopher

    2015-05-04

    The efficient trapping of photogenerated thioaldehydes with functional shelf-stable nitrile oxides in a 1,3-dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end-group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI-MS). X-ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time-of-flight secondary-ion mass spectrometry (ToF-SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface-initiated atom transfer radical polymerization (SI-ATRP) as confirmed by TOF-SIMS, XPS as well as ellipsometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

    DEFF Research Database (Denmark)

    Man, Isabela Costinela; Su, Hai-Yan; Vallejo, Federico Calle

    2011-01-01

    with the computational standard hydrogen electrode (SHE) model. We showed that by the discovery of a universal scaling relation between the adsorption energies of HOO* vs HO*, it is possible to analyze the reaction free energy diagrams of all the oxides in a general way. This gave rise to an activity volcano......Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination...

  5. Oxidative nanopatterning of titanium generates mesoporous surfaces with antimicrobial properties

    Directory of Open Access Journals (Sweden)

    Variola F

    2014-05-01

    Full Text Available Fabio Variola,1,2 Sylvia Francis Zalzal,3 Annie Leduc,3 Jean Barbeau,3 Antonio Nanci31Faculty of Engineering, Department of Mechanical Engineering, 2Faculty of Science, Department of Physics, University of Ottawa, Ottawa, ON, 3Faculty of Dental Medicine, Université de Montréal, Montreal, QC, CanadaAbstract: 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

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

    Science.gov (United States)

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

    2013-08-01

    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.

  7. Ion bombardment effect on surface state of metal

    International Nuclear Information System (INIS)

    Vaulin, E.P.; Georgieva, N.E.; Martynenko, T.P.

    1990-01-01

    The effect of slow argon ion bombardment on the surface microstructure of polycrystalline copper as well as the effect of surface state on sputtering of D-16 polycrystalline alloy are experimentally studied. Reduction of copper surface roughness is observed. It is shown that the D-16 alloy sputtering coefficient is sensitive to the surface state within the limits of the destructed surface layer

  8. Oxide nanostructures on a Nb surface and related systems: experiments and ab initio calculations

    International Nuclear Information System (INIS)

    Kuznetsov, Mikhail V; Razinkin, A S; Ivanovskii, Alexander L

    2011-01-01

    This review discusses the state of the art in two related research areas: the surfaces of niobium and of its related group IV-VI transition metals, and surface (primarily oxide) nanostructures that form on niobium (and group IV-VI d-metals) due to gas adsorption or impurity diffusion from the bulk. Experimental (X-ray photoelectron spectroscopy, photoelectron diffraction, scanning tunneling microscopy) and theoretical (ab initio simulation) results on d-metal surfaces are summarized and reviewed. (reviews of topical problems)

  9. Surface oxidation phenomena of boride coatings grown on iron

    International Nuclear Information System (INIS)

    Carbucicchio, M.; Palombarini, G.; Sambogna, G.

    1992-01-01

    Very hard boride coatings are grown on various metals using thermochemical as well as chemical vapour deposition techniques. In this way many surface properties, and in particular the wear resistance, can be considerably improved. Usually, also the corrosion behaviour of the treated components is important. In particular, oxidizing atmospheres are involved in many applications where, therefore, coating-environment interactions can play a relevant role. In a previous work, the early stages of the oxidation of iron borides were studied by treating single phase compacted powders in flowing oxygen at low temperatures (300-450deg C). In the present paper, the attention is addressed to the oxidation of both single phase and polyphase boride coatings thermochemically grown on iron. The single phase boride coatings were constituted by Fe 2 B, while the polyphase coatings were constituted by an inner Fe 2 B layer and an outer FeB-base layer. All the boride layers displayed strong (002) preferred crystallographic orientations. (orig.)

  10. Mechanism of glucose electrochemical oxidation on gold surface

    KAUST Repository

    Pasta, Mauro; La Mantia, Fabio; Cui, Yi

    2010-01-01

    The complex oxidation of glucose at the surface of gold electrodes was studied in detail in different conditions of pH, buffer and halide concentration. As observed in previous studies, an oxidative current peak occurs during the cathodic sweep showing a highly linear dependence on glucose concentration, when other electrolyte conditions are unchanged. The effect of the different conditions on the intensity of this peak has stressed the limitations of the previously proposed mechanisms. A mechanism able to explain the presence of this oxidative peak was proposed. The mechanism takes into account ion-sorption and electrochemical adsorption of OH-, buffer species (K2HPO4/KH2PO4) and halides. © 2010 Elsevier Ltd. All rights reserved.

  11. Mechanism of glucose electrochemical oxidation on gold surface

    KAUST Repository

    Pasta, Mauro

    2010-08-01

    The complex oxidation of glucose at the surface of gold electrodes was studied in detail in different conditions of pH, buffer and halide concentration. As observed in previous studies, an oxidative current peak occurs during the cathodic sweep showing a highly linear dependence on glucose concentration, when other electrolyte conditions are unchanged. The effect of the different conditions on the intensity of this peak has stressed the limitations of the previously proposed mechanisms. A mechanism able to explain the presence of this oxidative peak was proposed. The mechanism takes into account ion-sorption and electrochemical adsorption of OH-, buffer species (K2HPO4/KH2PO4) and halides. © 2010 Elsevier Ltd. All rights reserved.

  12. Designing porous metallic glass compact enclosed with surface iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Jae Young; Park, Hae Jin; Hong, Sung Hwan; Kim, Jeong Tae; Kim, Young Seok; Park, Jun-Young; Lee, Naesung [Hybrid Materials Center (HMC), Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Seo, Yongho [Graphene Research Institute (GRI) & HMC, Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Park, Jin Man, E-mail: jinman_park@hotmail.com [Global Technology Center, Samsung Electronics Co., Ltd, 129 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-742 (Korea, Republic of); Kim, Ki Buem, E-mail: kbkim@sejong.ac.kr [Hybrid Materials Center (HMC), Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of)

    2015-06-25

    Highlights: • Porous metallic glass compact was developed using electro-discharge sintering process. • Uniform PMGC can only be achieved when low electrical input energy was applied. • Functional iron-oxides were formed on the surface of PMGCs by hydrothermal technique. - Abstract: Porous metallic glass compact (PMGC) using electro-discharge sintering (EDS) process of gas atomized Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5} metallic glass powder was developed. The formation of uniform PMGC can only be achieved when low electrical input energy was applied. Functional iron-oxides were formed on the surface of PMGCs by hydrothermal technique. This finding suggests that PMGC can be applied in the new area such as catalyst via hydrothermal technique and offer a promising guideline for using the metallic glasses as a potential functional application.

  13. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

  14. Nano- and Micro-Scale Oxidative Patterning of Titanium Implant Surfaces for Improved Surface Wettability.

    Science.gov (United States)

    Kim, In-hye; Son, Jun Sik; Choi, Seok Hwa; Kim, Kyo-han; Kwon, Tae-yub

    2016-02-01

    A simple and scalable surface modification treatment is demonstrated, in which nano- and microscale features are introduced into the surface of titanium (Ti) substrates by means of a novel and eco-friendly oxidative aqueous solution composed of hydrogen peroxide (H202) and sodium bicarbonate (NaHCO3). By immersing mirror-polished Ti discs in an aqueous mixture of 30 wt% H2O2/5 wt% NaHCO3 at 23 +/- 3 degrees C for 4 h, it was confirmed that this mixture is capable of generating microscale topographies on Ti surfaces. It also simultaneously formed nanochannels that were regularly arranged in a comb-like pattern on the Ti surface, thus forming a hierarchical surface structure. Further, these nano/micro-textured Ti surfaces showed great surface roughness and excellent wettability when compared with control Ti surfaces. This study demonstrates that a H2O2/NaHCO3 mixture can be effectively utilized to create reproducible nano/microscale topographies on Ti implant surfaces, thus providing an economical new oxidative solution that may be used effectively and safely as a Ti surface modification treatment.

  15. Surface energy for electroluminescent polymers and indium-tin-oxide

    International Nuclear Information System (INIS)

    Zhong Zhiyou; Yin Sheng; Liu Chen; Zhong Youxin; Zhang Wuxing; Shi Dufang; Wang Chang'an

    2003-01-01

    The contact angles on the thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and indium-tin-oxide (ITO) were measured by the sessile-drop technique. The surface energies of the films were calculated using the Owens-Wendt (OW) and van Oss-Chaudhury-Good (vOCG) approaches. The overall total surface energies of MEH-PPV and the as-received ITO were 30.75 and 30.07 mJ/m 2 , respectively. Both approaches yielded almost the same surface energies. The surface energies were mainly contributed from the dispersion interactions or Lifshitz-van der Waals (LW) interactions for both MEH-PPV and ITO. The changes in the contact angles and surface energies of the ITO films, due to different solvent cleaning processes and oxygen plasma treatments, were analyzed. Experimental results revealed that the total surface energy of the ITO films increased after various cleaning processes. In comparison with different solvents used in this study, we found that methanol is an effective solvent for ITO cleaning, as a higher surface energy was observed. ITO films treated with oxygen plasma showed the highest surface energy. This work demonstrated that contact angle measurement is a useful method to diagnose the cleaning effect on ITO films

  16. Interaction of dimethylamine with clean and partially oxidized copper surfaces

    Science.gov (United States)

    Kelber, J. A.; Rogers, J. W.; Banse, B. A.; Koel, B. E.

    1990-05-01

    The interaction of dimethylamine (DMA) with partially oxidized polycrystalline copper [Cu(poly)] and clean and partially oxidized Cu(110) between 110 and 500 K has been examined using electron stimulated desorption (ESD), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). ESD mass spectra of the DMA adsorbed on O/Cu(poly) between 112 and 230 K consistently display peaks at 44 amu [(CH 3) 2N] + and 46 amu [(CH 3) 2NH-H] +, but no significant parent peak at 45 amu [(CH 3) 2NH] +, even though this last feature is prominent in the gas-phase mass spectrum. OH - is not observed at temperatures below 184 K and the yield at higher temperatures is much less than that of O +. HREELS of DMA on clean and oxygen covered Cu(110) obtained at temperatures between 100 and 320 K show characteristic vibrational spectra for molecular DMA and no OH(a) vibrational modes. TPD results show that the desorption profiles of all the major peaks in the DMA mass spectrum follow that of the parent peak with no evidence for production of H 2O. The ESD, HREELS and TPD results all indicate that DMA is molecularly and reversibly adsorbed, with no significant formation of surface hydroxyl species. The results indicate that preferential adsorption of amines from amine/epoxy mixtures onto metal oxide surfaces could passivate the surface and prevent subsequent bonding to the epoxy resin.

  17. Surface properties of nanostructured NiO undergoing electrochemical oxidation in 3-methoxy-propionitrile

    Energy Technology Data Exchange (ETDEWEB)

    Bonomo, Matteo [Department of Chemistry, University of Rome “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy); Marrani, Andrea Giacomo, E-mail: andrea.marrani@uniroma1.it [Department of Chemistry, University of Rome “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy); Novelli, Vittoria [Department of Chemistry, University of Rome “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy); Awais, Muhammad [Department of Industrial Engineering, “King Abdulaziz” University, Rabigh (Saudi Arabia); Solar Energy Conversion Strategic Research Cluster, University College Dublin (UCD), Belfield, Dublin 4 (Ireland); Dowling, Denis P. [Solar Energy Conversion Strategic Research Cluster, University College Dublin (UCD), Belfield, Dublin 4 (Ireland); School of Mechanical and Materials Engineering, University College Dublin (UCD), Belfield, Dublin 4 (Ireland); Vos, Johannes G. [School of Chemical Sciences, Dublin City University (DCU), Glasnevin, Dublin 9 (Ireland); Dini, Danilo [Department of Chemistry, University of Rome “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy); Solar Energy Conversion Strategic Research Cluster, University College Dublin (UCD), Belfield, Dublin 4 (Ireland)

    2017-05-01

    Highlights: • NiO porous thin films were prepared via RDS technique. • NiO electrodes were characterized in a nitrile based electrochemical cell. • NiO electrodes were studied by means of XPS. • The XP spectra excluded the formation of phases other than NiO. • The presence of ClO{sub 4}{sup −} as charge balancing species was evidenced. - Abstract: Nanostructured nickel oxide (NiO) was deposited in the configuration of thin film (thickness, l = 2–6 μm) onto fluorine-doped tin oxide (FTO) substrates via plasma-assisted rapid discharge sintering (RDS). Electrochemical cycling of RDS NiO in 3-methoxy-propionitrile (3-MPN) revealed two characteristic peaks of NiO oxidation which were associated to the surface-confined redox processes Ni(II) → Ni(III) and Ni(III) → Ni(IV). Grazing angle X-ray photoelectron spectroscopy (XPS) was conducted ex-situ on NiO electrodes in both pristine and oxidized states. Oxidized NiO samples for XPS experiments were obtained in the potentiostatic mode through the polarization of NiO at its two characteristic potentials of oxidation. The XPS analysis allowed to ascertain the electronic structure of the nanoporous NiO framework, and verify the adsorption of perchlorate and chloride anions onto NiO surface due to the compensation of the charge stored in oxidized NiO. XPS also revealed that the spectrum within the region characteristic of Ni 2p ionization does not vary considerably with the state of charge of the nickel centres. This finding is in evident contrast to what has been observed for the same system when it undergoes electrochemical oxidation in aqueous electrolyte.

  18. Surface properties of nanostructured NiO undergoing electrochemical oxidation in 3-methoxy-propionitrile

    International Nuclear Information System (INIS)

    Bonomo, Matteo; Marrani, Andrea Giacomo; Novelli, Vittoria; Awais, Muhammad; Dowling, Denis P.; Vos, Johannes G.; Dini, Danilo

    2017-01-01

    Highlights: • NiO porous thin films were prepared via RDS technique. • NiO electrodes were characterized in a nitrile based electrochemical cell. • NiO electrodes were studied by means of XPS. • The XP spectra excluded the formation of phases other than NiO. • The presence of ClO 4 − as charge balancing species was evidenced. - Abstract: Nanostructured nickel oxide (NiO) was deposited in the configuration of thin film (thickness, l = 2–6 μm) onto fluorine-doped tin oxide (FTO) substrates via plasma-assisted rapid discharge sintering (RDS). Electrochemical cycling of RDS NiO in 3-methoxy-propionitrile (3-MPN) revealed two characteristic peaks of NiO oxidation which were associated to the surface-confined redox processes Ni(II) → Ni(III) and Ni(III) → Ni(IV). Grazing angle X-ray photoelectron spectroscopy (XPS) was conducted ex-situ on NiO electrodes in both pristine and oxidized states. Oxidized NiO samples for XPS experiments were obtained in the potentiostatic mode through the polarization of NiO at its two characteristic potentials of oxidation. The XPS analysis allowed to ascertain the electronic structure of the nanoporous NiO framework, and verify the adsorption of perchlorate and chloride anions onto NiO surface due to the compensation of the charge stored in oxidized NiO. XPS also revealed that the spectrum within the region characteristic of Ni 2p ionization does not vary considerably with the state of charge of the nickel centres. This finding is in evident contrast to what has been observed for the same system when it undergoes electrochemical oxidation in aqueous electrolyte.

  19. An ab initio study of plutonium oxides surfaces; Etude ab initio des surfaces d'oxydes de Pu

    Energy Technology Data Exchange (ETDEWEB)

    Jomard, G.; Bottin, F.; Amadon, B

    2007-07-01

    By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO{sub 2} and {beta}-Pu{sub 2}O{sub 3} in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO{sub 2} in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p{sub O{sub 2}}). We conclude that at room temperature and for p{sub O{sub 2}}{approx}10 atm., the polar O{sub 2}-(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)

  20. Templated electrodeposition of Ag7NO11 nanowires with very high oxidation states of silver

    NARCIS (Netherlands)

    Rodijk, E.J.B.; Maijenburg, A.W.; Maas, M.G.; Blank, David H.A.; ten Elshof, Johan E.

    2011-01-01

    The templated electrodeposition of 200 nm diameter nanowires of the argentic oxynitrate Ag(Ag3O4)2NO3 phase is reported. Their high surface-to-volume ratio and the high average oxidation state of Ag make these wires promising candidates for nanoscale redox processes in which both a high volumetric

  1. Effect of particle size on iron nanoparticle oxidation state

    International Nuclear Information System (INIS)

    Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

    2012-01-01

    Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

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

    Science.gov (United States)

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

    1988-01-01

    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.

  3. First principles studies of complex oxide surfaces and interfaces

    International Nuclear Information System (INIS)

    Noguera, Claudine; Finocchi, Fabio; Goniakowski, Jacek

    2004-01-01

    Oxides enter our everyday life and exhibit an impressive variety of physical and chemical properties. The understanding of their behaviour, which is often determined by the electronic and atomic structures of their surfaces and interfaces, is a key question in many fields, such as geology, environmental chemistry, catalysis, thermal coatings, microelectronics, and bioengineering. In the last decade, first principles methods, mainly those based on the density functional theory, have been frequently applied to study complex oxide surfaces and interfaces, complementing the experimental observations. In this work, we discuss some of these contributions, with emphasis on several issues that are especially important when dealing with oxides: the local electronic structure at interfaces, and its connection with chemical reactivity; the charge redistribution and the bonding variations, in relation to screening properties; and the possibility of bridging the gap between model and real systems by taking into account the chemical environments and the effect of finite temperatures, and by performing simulations on systems of an adequate (large) size

  4. Insights into the Surface Reactivity of Cermet and Perovskite Electrodes in Oxidizing, Reducing, and Humid Environments.

    Science.gov (United States)

    Paloukis, Fotios; Papazisi, Kalliopi M; Dintzer, Thierry; Papaefthimiou, Vasiliki; Saveleva, Viktoriia A; Balomenou, Stella P; Tsiplakides, Dimitrios; Bournel, Fabrice; Gallet, Jean-Jacques; Zafeiratos, Spyridon

    2017-08-02

    Understanding the surface chemistry of electrode materials under gas environments is important in order to control their performance during electrochemical and catalytic applications. This work compares the surface reactivity of Ni/YSZ and La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , which are commonly used types of electrodes in solid oxide electrochemical devices. In situ synchrotron-based near-ambient pressure photoemission and absorption spectroscopy experiments, assisted by theoretical spectral simulations and combined with microscopy and electrochemical measurements, are used to monitor the effect of the gas atmosphere on the chemical state, the morphology, and the electrical conductivity of the electrodes. It is shown that the surface of both electrode types readjusts fast to the reactive gas atmosphere and their surface composition is notably modified. In the case of Ni/YSZ, this is followed by evident changes in the oxidation state of nickel, while for La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , a fine adjustment of the Cr valence and strong Sr segregation is observed. An important difference between the two electrodes is their capacity to maintain adsorbed hydroxyl groups on their surface, which is expected to be critical for the electrocatalytic properties of the materials. The insight gained from the surface analysis may serve as a paradigm for understanding the effect of the gas environment on the electrochemical performance and the electrical conductivity of the electrodes.

  5. NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2016-04-18

    The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  6. Nanoscale probing of bandgap states on oxide particles using electron energy-loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States); March, Katia [Laboratoire de Physique des Solides, Bâtiment 510, Université Paris-Sud, 91405 Orsay Cedex (France); Crozier, Peter A., E-mail: CROZIER@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States)

    2017-07-15

    Surface and near-surface electronic states were probed with nanometer spatial resolution in MgO and TiO{sub 2} anatase nanoparticles using ultra-high energy resolution electron energy-loss spectroscopy (EELS) coupled to a scanning transmission electron microscope (STEM). This combination allows the surface electronic structure determined with spectroscopy to be correlated with nanoparticle size, morphology, facet etc. By acquiring the spectra in aloof beam mode, radiation damage to the surface can be significantly reduced while maintaining the nanometer spatial resolution. MgO and TiO{sub 2} showed very different bandgap features associated with the surface/sub-surface layer of the nanoparticles. Spectral simulations based on dielectric theory and density of states models showed that a plateau feature found in the pre-bandgap region in the spectra from (100) surfaces of 60 nm MgO nanocubes is consistent with a thin hydroxide surface layer. The spectroscopy shows that this hydroxide species gives rise to a broad filled surface state at 1.1 eV above the MgO valence band. At the surfaces of TiO{sub 2} nanoparticles, pronounced peaks were observed in the bandgap region, which could not be well fitted to defect states. In this case, the high refractive index and large particle size may make Cherenkov or guided light modes the likely causes of the peaks. - Highlights: • Bandgap states detected with aloof beam monochromated EELS on oxide nanoparticle surfaces. • Dielectric theory applied to simulate the spectra and interpret surface structure. • Density of states models also be employed to understand the surface electronic structure. • In MgO, one states associate with water species was found close to the valence band edge. • In anatase, two mid-gap states associated with point defects were found.

  7. Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Carriere, B.; Deville, J.P.; El Maachi, A.

    1987-06-01

    The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

  8. Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

    Science.gov (United States)

    Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

    2011-06-01

    Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

  9. Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

    International Nuclear Information System (INIS)

    Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

    2011-01-01

    Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ∼550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M 2,3 VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

  10. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    International Nuclear Information System (INIS)

    Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

    2015-01-01

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr

  11. Studies of Oxidation of the Cu(100) Surface Using Low Energy Positrons

    International Nuclear Information System (INIS)

    Fazleev, N. G.; Maddox, W. B.; Nadesalingam, M.; Rajeshwar, K.; Weiss, A. H.

    2009-01-01

    Changes in the surface of an oxidized Cu(100) single crystal resulting from vacuum annealing have been investigated using positron annihilation induced Auger electron spectroscopy (PAES). PAES measurements show a large increase in the intensity of the positron annihilation induced Cu M 2,3 VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The intensity then decreases monotonically as the annealing temperature is increased to ∼600 deg. C. Experimental PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface, surface reconstructions, and electron-positron correlations effects. Possible explanation for the observed behavior of the intensity of positron annihilation induced Cu M 2,3 VV Auger peak with changes of the annealing temperature is proposed.

  12. Initial oxidation processes of Si(001) surfaces by supersonic O2 molecular beams. Different oxidation mechanisms for clean and partially-oxidized surfaces

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2002-01-01

    Potential energy barriers for dissociative chemisorption of O 2 molecules on Si(001) clean surfaces were investigated using supersonic O 2 molecular beams and photoemission spectroscopy. Relative initial sticking probabilities of O 2 molecules and the saturated oxygen amount on the Si(001) surface were measured as a function of incident energy of O 2 molecules. Although the probability was independent on the incident energy in the region larger than 1 eV, the saturated oxygen amount was dependent on the incident energy without energy thresholds. An Si-2p photoemission spectrum of the Si(001) surface oxidized by thermal O 2 gas revealed the oxygen insertion into dimer backbond sites. These facts indicate that a reaction path of the oxygen insertion into dimer backbonds through bridge sites is open for the clean surface oxidation, and the direct chemisorption probability at the backbonds is negligibly small comparing with that at the bridge sites. (author)

  13. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

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

    Science.gov (United States)

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

    2018-03-06

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

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

    Science.gov (United States)

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

    1982-01-01

    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.

  16. Preferred hydride growth orientations on oxide-coated gadolinium surfaces

    International Nuclear Information System (INIS)

    Benamar, G.M.; Schweke, D.; Kimmel, G.; Mintz, M.H.

    2012-01-01

    Highlights: ► The preferred hydride growth orientations on gadolinium metal coated by a thin oxide layer are presented. ► A preferred growth of the (1 0 0) h plane of the face centered cubic (FCC) GdH 2 is observed for the hydride spots forming below the oxidation layer. ► A change to the (1 1 1) h plane of the cubic hydride dominates for the hydride's Growth Centers. ► The texture change is attributed to the surface normal compressive stress component exerted by the oxidation layer on the developing hydride. - Abstract: The initial development of hydrides on polycrystalline gadolinium (Gd), as on some other hydride forming metals, is characterized by two sequential steps. The first step involves the rapid formation of a dense pattern of small hydride spots (referred to as the “small family” of hydrides) below the native oxidation layer. The second stage takes place when some of the “small family” nucleants (referred to as “growth centers”, GCs) break the oxide layer, leading to their rapid growth and finally to the massive hydriding of the sample. In the present study, the texture of the two hydride families was studied, by combining X-ray diffraction (XRD) analysis with a microscopic analysis of the hydride, using scanning electron microscopy (SEM) and atomic force microscopy (AFM). It has been observed that for the “small family”, a preferred growth of the (1 0 0) h plane of the cubic GdH 2 takes place, whereas for the GCs, a change to the (1 1 1) h plane of the cubic hydride dominates. These preferred growth orientations were analyzed by their structure relation with the (0 0 .1) m basal plane of the Gd metal. It has been concluded that the above texture change is due to the surface normal compressive stress component exerted by the oxidation overlayer on the developing hydride, preventing the (0 0 .1) m ||(1 1 1) h growth orientation. This stress is relieved upon the rupture of that overlayer and the development of the GCs, leading to

  17. Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

    International Nuclear Information System (INIS)

    Angermann, Heike

    2014-01-01

    Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D it (E), and density D it,min of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly based on

  18. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-11-03

    The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium)-doped cerium oxide nanoparticles (SmCNPs) as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl) triethoxysilane (MEEETES) were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  19. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-01-01

    The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium)-doped cerium oxide nanoparticles (SmCNPs) as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl) triethoxysilane (MEEETES) were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  20. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    Directory of Open Access Journals (Sweden)

    Himansu Sekhar Nanda

    2016-11-01

    Full Text Available The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium-doped cerium oxide nanoparticles (SmCNPs as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy-ethoxy]-ethoxy}-hexyl triethoxysilane (MEEETES were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  1. Characterization of SCC crack tips and surface oxide layers in alloy 600

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Katsuhiko; Fukuya, Koji [Inst. of Nuclear Safety System Inc., Mihama, Fukui (Japan)

    2002-09-01

    In order to investigate the mechanism of primary water stress corrosion cracking (SCC), direct observation of microstructures of SCC crack tips and surface oxide layers in alloy 600 were carried out. A focused-ion beam (FIB) micro-processing technique was applied to prepare electron transparent foils including the crack tip and the surface oxide layer without any damage to those microstructures. Transmission electron microscopy and analysis were used to characterize the crack tips and surface oxide layers. Cr-rich oxides and a metal-Ni phase were identified in the crack tips and grain boundaries ahead of the crack tips independent of dissolved hydrogen concentrations. >From the fact that the Cr-rich oxides and metal-Ni phase were observed in the inner surface oxide layer, the same oxidation mechanism as the surface is proposed for the crack tip region and internal oxidation accompanying selective Cr oxidation is suggested as the mechanism. (author)

  2. Sintering of uranium oxide of high specific surface area

    International Nuclear Information System (INIS)

    Bel, Alain; Francois, Bernard; Delmas, Roger; Caillat, Roger

    1959-01-01

    The extent to which a uranium oxide powder deriving from ammonium uranate or uranium peroxide lends itself to the sintering process depends largely on its specific surface area. When this is greater than 5 m 2 / g there is an optimum temperature for sintering in hydrogen. This temperature becomes less as the specific area of the powder is greater. Reprint of a paper published in Comptes rendus des seances de l'Academie des Sciences, t. 249, p. 1045-1047, sitting of 21 September 1959 [fr

  3. Carbon monoxide oxidation on bimetallic Ru/Au(111 surfaces

    Directory of Open Access Journals (Sweden)

    ROLF-JÜRGEN BEHM

    2001-02-01

    Full Text Available The electrochemical deposition of Ru on Au(111 was performed in 0.5 M H2SO4+10-4 M RuCl3 . The obtained bimetallic Ru/Au(111 surfaces were character-ised by cyclic voltammetry and in situ STM in 0.5 MH2SO4. The Ru deposit consists of nanoscale islands, which merge with increasing coverage. Two different types of bimetallic Ru/Au(111 surfaces with respect to the distribution of Ru islands over the Au(111 substrate surface were obtained. When the deposition was performed at potentials more positive than the range of Au(111 reconstruction, homogeneous nucleation occured resulting in a random distribution of Ru islands. When the deposition was performed on reconstructed Au(111 at low overpotentials, selective nucleation occured resulting in the replication of the Au(111 reconstruction. Only at higher deposition overpotentials, can multilayer deposits be formed, which exhibit a very rough surface morphology. The electrocatalytic activity of such structurally well defined Ru/Au(111 bimetallic surfaces was studied towards CO oxidation with the Ru coverage ranging from submonolayer to several monolayer. COstripping commences at about 0.2 Vand occurs over a broad potential range. The observed influence of the Ru structure on the CO stripping voltammetry is explained by local variations in the COadsorption energy, caused by differences in the local Ru structure and by effects induced by the Au(111 substrate.

  4. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

  5. Charge state of oxide layer of SIMOX-structures

    CERN Document Server

    Askinazi, A Y; Dmitriev, V A; Miloglyadova, L V

    2001-01-01

    The charge state of the oxide layer of the SIMOX-structures, obtained in the course of forming the oxide layers, bricked up in the silicon volume, through the oxygen ions implantation into the Si, is studied. The charge state of the given structures is studied through the method of the layer-by-layer profiling, which makes it possible to obtain the dependence of the plane zones potential on the oxide layer thickness. It is established, that during the process of the SIMOX-structures formation in the oxide layer near the boundary with the Si there appear defects, responsible for the charge. The radiation from the near-the-ultraviolet (NUV) area without the applied electric field neutralizes the given charge. The simultaneous impact of the NUV-radiation and electric field leads to the formation of significantly positive charge

  6. Surface Preparation and Deposited Gate Oxides for Gallium Nitride Based Metal Oxide Semiconductor Devices

    Directory of Open Access Journals (Sweden)

    Paul C. McIntyre

    2012-07-01

    Full Text Available The literature on polar Gallium Nitride (GaN surfaces, surface treatments and gate dielectrics relevant to metal oxide semiconductor devices is reviewed. The significance of the GaN growth technique and growth parameters on the properties of GaN epilayers, the ability to modify GaN surface properties using in situ and ex situ processes and progress on the understanding and performance of GaN metal oxide semiconductor (MOS devices are presented and discussed. Although a reasonably consistent picture is emerging from focused studies on issues covered in each of these topics, future research can achieve a better understanding of the critical oxide-semiconductor interface by probing the connections between these topics. The challenges in analyzing defect concentrations and energies in GaN MOS gate stacks are discussed. Promising gate dielectric deposition techniques such as atomic layer deposition, which is already accepted by the semiconductor industry for silicon CMOS device fabrication, coupled with more advanced physical and electrical characterization methods will likely accelerate the pace of learning required to develop future GaN-based MOS technology.

  7. Energetic Surface Smoothing of Complex Metal-Oxide Thin Films

    International Nuclear Information System (INIS)

    Willmott, P.R.; Herger, R.; Schlepuetz, C.M.; Martoccia, D.; Patterson, B.D.

    2006-01-01

    A novel energetic smoothing mechanism in the growth of complex metal-oxide thin films is reported from in situ kinetic studies of pulsed laser deposition of La 1-x Sr x MnO 3 on SrTiO 3 , using x-ray reflectivity. Below 50% monolayer coverage, prompt insertion of energetic impinging species into small-diameter islands causes them to break up to form daughter islands. This smoothing mechanism therefore inhibits the formation of large-diameter 2D islands and the seeding of 3D growth. Above 50% coverage, islands begin to coalesce and their breakup is thereby suppressed. The energy of the incident flux is instead rechanneled into enhanced surface diffusion, which leads to an increase in the effective surface temperature of ΔT≅500 K. These results have important implications on optimal conditions for nanoscale device fabrication using these materials

  8. Structure and nano-mechanical characteristics of surface oxide layers on a metallic glass.

    Science.gov (United States)

    Caron, A; Qin, C L; Gu, L; González, S; Shluger, A; Fecht, H-J; Louzguine-Luzgin, D V; Inoue, A

    2011-03-04

    Owing to their low elastic moduli, high specific strength and excellent processing characteristics in the undercooled liquid state, metallic glasses are promising materials for applications in micromechanical systems. With miniaturization of metallic mechanical components down to the micrometer scale, the importance of a native oxide layer on a glass surface is increasing. In this work we use TEM and XPS to characterize the structure and properties of the native oxide layer grown on Ni(62)Nb(38) metallic glass and their evolution after annealing in air. The thickness of the oxide layer almost doubled after annealing. In both cases the oxide layer is amorphous and consists predominantly of Nb oxide. We investigate the friction behavior at low loads and in ambient conditions (i.e. at T = 295 K and 60% air humidity) of both as-cast and annealed samples by friction force microscopy. After annealing the friction coefficient is found to have significantly increased. We attribute this effect to the increase of the mechanical stability of the oxide layer upon annealing.

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

    Science.gov (United States)

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

    2018-05-01

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

  10. Efficiency improvement of multicrystalline silicon solar cells after surface and grain boundaries passivation using vanadium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Derbali, L., E-mail: rayan.slat@yahoo.fr [Photovoltaiec Laboratory, Research and Technology Center of Energy, Technopole de Borj-Cedria, BP 95, Hammam-Lif 2050 (Tunisia); Ezzaouia, H. [Photovoltaiec Laboratory, Research and Technology Center of Energy, Technopole de Borj-Cedria, BP 95, Hammam-Lif 2050 (Tunisia)

    2012-08-01

    Highlights: Black-Right-Pointing-Pointer Evaporation of vanadium pentoxide onto the front surface leads to reduce the surface reflectivity considerably. Black-Right-Pointing-Pointer An efficient surface passivation can be obtained after thermal treatment of obtained films. Black-Right-Pointing-Pointer Efficiency of the obtained solar cells has been improved noticeably after thermal treatment of deposited thin films. - Abstract: The aim of this work is to investigate the effect of vanadium oxide deposition onto the front surface of multicrystalline silicon (mc-Si) substrat, without any additional cost in the fabrication process and leading to an efficient surface and grain boundaries (GBs) passivation that have not been reported before. The lowest reflectance of mc-Si coated with vanadium oxide film of 9% was achieved by annealing the deposited film at 600 Degree-Sign C. Vanadium pentoxide (V{sub 2}O{sub 5}) were thermally evaporated onto the surface of mc-Si substrates, followed by a short annealing duration at a temperature ranging between 600 Degree-Sign C and 800 Degree-Sign C, under O{sub 2} atmosphere. The chemical composition of the films was analyzed by means of Fourier transform infrared spectroscopy (FTIR). Surface and cross-section morphology were determined by atomic force microscope (AFM) and a scanning electron microscope (SEM), respectively. The deposited vanadium oxide thin films make the possibility of combining in one processing step an antireflection coating deposition along with efficient surface state passivation, as compared to a reference wafer. Silicon solar cells based on untreated and treated mc-Si wafers were achieved. We showed that mc-silicon solar cells, subjected to the above treatment, have better short circuit currents and open-circuit voltages than those made from untreated wafers. Thus, the efficiency of obtained solar cells has been improved.

  11. Efficiency improvement of multicrystalline silicon solar cells after surface and grain boundaries passivation using vanadium oxide

    International Nuclear Information System (INIS)

    Derbali, L.; Ezzaouia, H.

    2012-01-01

    Highlights: ► Evaporation of vanadium pentoxide onto the front surface leads to reduce the surface reflectivity considerably. ► An efficient surface passivation can be obtained after thermal treatment of obtained films. ► Efficiency of the obtained solar cells has been improved noticeably after thermal treatment of deposited thin films. - Abstract: The aim of this work is to investigate the effect of vanadium oxide deposition onto the front surface of multicrystalline silicon (mc-Si) substrat, without any additional cost in the fabrication process and leading to an efficient surface and grain boundaries (GBs) passivation that have not been reported before. The lowest reflectance of mc-Si coated with vanadium oxide film of 9% was achieved by annealing the deposited film at 600 °C. Vanadium pentoxide (V 2 O 5 ) were thermally evaporated onto the surface of mc-Si substrates, followed by a short annealing duration at a temperature ranging between 600 °C and 800 °C, under O 2 atmosphere. The chemical composition of the films was analyzed by means of Fourier transform infrared spectroscopy (FTIR). Surface and cross-section morphology were determined by atomic force microscope (AFM) and a scanning electron microscope (SEM), respectively. The deposited vanadium oxide thin films make the possibility of combining in one processing step an antireflection coating deposition along with efficient surface state passivation, as compared to a reference wafer. Silicon solar cells based on untreated and treated mc-Si wafers were achieved. We showed that mc-silicon solar cells, subjected to the above treatment, have better short circuit currents and open-circuit voltages than those made from untreated wafers. Thus, the efficiency of obtained solar cells has been improved.

  12. Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

    Science.gov (United States)

    Story, Mary E.; Webler, Bryan A.

    2018-05-01

    In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

  13. Topological surface states on Bi$_{1-x}$Sb$_x$

    DEFF Research Database (Denmark)

    Zhu, Xie-Gang; Hofmann, Philip

    2014-01-01

    Topological insulators support metallic surface states whose existence is protected by the bulk band structure. It has been predicted early that the topology of the surface state Fermi contour should depend on several factors, such as the surface orientation and termination and this raises the qu...

  14. Effect of microorganisms on the plutonium oxidation states

    International Nuclear Information System (INIS)

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-01-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

  15. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  16. The surface oxide as a source of oxygen on Rh(1 1 1)

    Energy Technology Data Exchange (ETDEWEB)

    Lundgren, E. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden)]. E-mail: edvin.lundgren@sljus.lu.se; Gustafson, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Resta, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Weissenrieder, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Mikkelsen, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Andersen, J.N. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Koehler, L. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Kresse, G. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Klikovits, J. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Biederman, A. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Schmid, M. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Varga, P. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria)

    2005-06-15

    The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.

  17. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    Science.gov (United States)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

  18. Photocatalytic oxidation of NOx gases using TiO2: a surface spectroscopic approach

    International Nuclear Information System (INIS)

    Dalton, J.S.; Janes, P.A.; Jones, N.G.; Nicholson, J.A.; Hallam, K.R.; Allen, G.C.

    2002-01-01

    X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to study surface reactions between nitrogen oxides and TiO 2 on surfaces. - The bandgap of solid-state TiO 2 (3.2 eV) enables it to be a useful photocatalyst in the ultraviolet (λ 2 surface in the presence of sunlight therefore enables the removal of harmful NO x gases from the atmosphere by oxidation to nitrates. These properties, in addition to the whiteness, relative cheapness and non-toxicity, make TiO 2 ideal for the many de-NOX catalysts that are currently being commercially exploited both in the UK and Japan for concrete paving materials in inner cities. There is need, however, for further academic understanding of the surface reactions involved. Hence, we have used surface specific techniques, including X-ray photoelectron spectroscopy and Raman spectroscopy, to investigate the NO x adsorbate reaction at the TiO 2 substrate surface

  19. Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

    Science.gov (United States)

    Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

    2009-04-15

    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.

  20. Role of surface chemistry in modified ACF (activated carbon fiber)-catalyzed peroxymonosulfate oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Shiying, E-mail: ysy@ouc.edu.cn [Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100 (China); College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Shandong Provincial Key Laboratory of Marine Environment and Geological Engineering (MEGE), Qingdao 266100 (China); Li, Lei [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Xiao, Tuo [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); China City Environment Protection Engineering Limited Company, Wuhan 430071 (China); Zheng, Di; Zhang, Yitao [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China)

    2016-10-15

    Highlights: • ACF can efficiently activate peroxymonosulfate to degrade organic pollutants. • Basic functional groups may mainly increase the adsorption capacity of ACF. • C1, N1, N2 have promoting effect on the ACF catalyzed PMS oxidation. • Modification by heat after nitric acid is also a way of ACF regeneration. - Abstract: A commercial activated carbon fiber (ACF-0) was modified by three different methods: nitration treatment (ACF-N), heat treatment (ACF-H) and heat treatment after nitration (ACF-NH), and the effects of textural and chemical properties on the ability of the metal-free ACF-catalyzed peroxymonosulfate (PMS) oxidation of Reactive Black 5 (RB5), an azo dye being difficultly adsorbed onto ACF, in aqueous solution were investigated in this work. Surface density of functional groups, surface area changes, surface morphology and the chemical state inside ACF samples were characterized by Boehm titration, N{sub 2} adsorption, scanning electron microscopy in couple with energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), respectively. XPS spectra deconvolution was applied to figure out the importance of surface nitrogen-containing function groups. We found that π-π, pyridine and amine have promoting effect on the catalytic oxidation while the −NO{sub 2} has inhibitory effect on the ACF/PMS systems for RB5 destroy. Sustainability and renewability of the typical ACF-NH for catalytic oxidation of RB5 were also discussed in detail. Information about our conclusions are useful to control and improve the performance of ACF-catalyzed PMS oxidation for organic pollutants in wastewater treatment.

  1. Variation on wettability of anodic zirconium oxide nanotube surface

    International Nuclear Information System (INIS)

    Wang, Lu-Ning; Shen, Chen; Shinbine, Alyssa; Luo, Jing-Li

    2013-01-01

    The present study reports the effect of fabrication conditions and environmental conditions, such as anodization voltage and aging period, on the wetting of zirconium dioxide nanotube (ZrNT) surfaces. Comparing with intact zirconium foil, which was inherently less hydrophilic, possessing an approximate contact angle of 60–70°, the as-formed ZrNT surfaces were much hydrophilic with an approximate contact angle of 18°. However, the hydrophilicity of the surfaces exhibited a decrease when the nanotubular opening diameters decreased while maintaining the nanotubular layer thickness. This phenomenon was attributed to the balance of capillary force and force generated by compressed air in the ZrNTs. The annealing treatment further increased the hydrophilic property of the ZrNTs. In addition, it was found that the wettability of ZrNTs, when aged in air over a period of 105 days, demonstrated a decrease in hydrophilic characteristics and exhibited, to some extent, an increase in hydrophobic characteristics. It was believed that the surface wettability was able to be changed due to the decreasing content of hydroxyl groups in ambient atmosphere. This work can provide guidelines for improving the structural and environmental conditions responsible for changing surface wettability of ZrNT surfaces for biomedical application. - Highlights: ► Wettability of zirconium oxide nanotubes (ZrNTs) was observed and characterized. ► Increasing of nanotubular diameter decreased the hydrophilicity of ZrNTs. ► Annealing processes enhanced the hydrophilicity of ZrNTs. ► Long term aging resulted in the hydrophobicity of ZrNTs

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

    Science.gov (United States)

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

    1987-01-01

    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.

  3. Multitechnique characterisation of 304L surface states oxidised at high temperature in steam and air atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Mamede, Anne-Sophie, E-mail: anne-sophie.mamede@ensc-lille.fr [University Lille, CNRS, ENSCL, Centrale Lille, University Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, F-59000 Lille (France); Nuns, Nicolas, E-mail: nicolas.nuns@univ-lille1.fr [University Lille, CNRS, ENSCL, Centrale Lille, University Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, F-59000 Lille (France); Cristol, Anne-Lise, E-mail: anne-lise.cristol@ec-lille.fr [University Lille, CNRS, Centrale Lille, Arts et Métiers Paris Tech, FRE 3723 – LML – Laboratoire de Mécanique de Lille, F-59000 Lille (France); Cantrel, Laurent, E-mail: laurent.cantrel@irsn.fr [Institut de Radioprotection et de Sûreté Nucléaire, PSN-RES, Cadarache, Saint Paul lez Durance, 13115 (France); Laboratoire de Recherche Commun IRSN-CNRS-Lille 1: «Cinétique Chimique, Combustion, Réactivité» (C3R), Cadarache, Saint Paul lez Durance, 13115 (France); Souvi, Sidi, E-mail: sidi.souvi@irsn.fr [Institut de Radioprotection et de Sûreté Nucléaire, PSN-RES, Cadarache, Saint Paul lez Durance, 13115 (France); Laboratoire de Recherche Commun IRSN-CNRS-Lille 1: «Cinétique Chimique, Combustion, Réactivité» (C3R), Cadarache, Saint Paul lez Durance, 13115 (France); and others

    2016-04-30

    Graphical abstract: - Highlights: • Mutitechnique characterisation of oxidised 304L. • Oxidation at high temperature under steam and air conditions of 304L stainless steel. • Chromium and manganese oxides formed in the outer layer. • Oxide profiles differ in air or steam atmosphere. - Abstract: In case of a severe accident occurring in a nuclear reactor, surfaces of the reactor coolant system (RCS), made of stainless steel (304L) rich in Cr (>10%) and Ni (8–12%), are oxidised. Fission products (FPs) are released from melt fuel and flow through the RCS. A part of them is deposited onto surfaces either by vapour condensation or by aerosol deposition mechanisms. To be able to understand the nature of interactions between these FPs and the RCS surfaces, a preliminary step is to characterize the RSC surface states in steam and air atmosphere at high temperatures. Pieces of 304L stainless steel have been treated in a flow reactor at two different temperatures (750 °C and 950 °C) for two different exposition times (24 h and 72 h). After surfaces analysing by a unique combination of surface analysis techniques (XPS, ToF-SIMS and LEIS), for 304L, the results show a deep oxide scale with multi layers and the outer layer is composed of chromium and manganese oxides. Oxide profiles differ in air or steam atmosphere. Fe{sub 2}O{sub 3} oxide is observed but in minor proportion and in all cases no nickel is detected near the surface. Results obtained are discussed and compared with the literature data.

  4. Surface states in thin versus thick organic quantum wells

    International Nuclear Information System (INIS)

    Nguyen Ba An; Hanamura, E.

    1995-08-01

    Surface states are studied in dependence on thickness or organic quantum wells within the nearest layer approximation. It is shown that there is a material-dependent critical thickness. Structures, that have thickness thinner or thicker than the critical one, exhibit qualitatively different characteristics of surface states. Criteria for existence and sign rules for location of energy levels of surface states are established which are general and contain the results of the previous works as particular cases. (author). 18 refs, 3 figs

  5. Tailor-made surface plasmon polaritons above the bulk plasma frequency: a design strategy for indium tin oxide

    International Nuclear Information System (INIS)

    Brand, S; Abram, R A; Kaliteevski, M A

    2010-01-01

    A simple phase-matching approach is employed as a design aid to engineer surface plasmon polariton states at the interface of an indium tin oxide layer on the top of a Bragg reflector. By altering the details of the reflector, and in particular the ordering of the layers and the thickness of the layer adjacent to the indium tin oxide, it is possible to readily adjust the energy of these states. Examples of structures engineered to give rise to distinctive features in the reflectivity spectra above the bulk screened plasma frequency for states of both possible polarizations are presented.

  6. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  7. Surface Plasmon Resonance (SPR Phenomenon of the Oxidizing and Reducing Polypyrrole

    Directory of Open Access Journals (Sweden)

    Nurlaila Rajabiah

    2016-12-01

    Full Text Available Surface Plasmon Resonance (SPR phenomenon of the oxidizing and reducing polypyrrole (PPy have been observed using a modified Au/PPy Kretschmann configuration. The observation was carried out through simulation Winspall 3.02 software and compared with some experimental data refractive index (n, absorbance index (, and thickness (τ reported in other literatures with spectroscopy ellipsometry. This simulation assumed that the SPR system use BK-7 halfcylinder prism (n= 1,515 and the laser beam was generated by HeNe (λ= 632,8 nm. The result showed that the optimum layer thickness of polypyrrole with neutral electrolyte solution in the reduction state is of about 20 nm. The polypyrrole with an acid solution in the oxidation state showed that the reflectivity curve is sharper and the width of the curve is smaller than the neutral electrolyte solution in the reduction state with the SPR angle of about 46,810 and the reflectivity value of about 0,217. Polypyrrole in a state of oxidation and reduction, related to the absorption, film thickness, and dielectric constant of materials, affected to the SPR angle shift and dip curve

  8. Minimal model for spoof acoustoelastic surface states

    Directory of Open Access Journals (Sweden)

    J. Christensen

    2014-12-01

    Full Text Available Similar to textured perfect electric conductors for electromagnetic waves sustaining artificial or spoof surface plasmons we present an equivalent phenomena for the case of sound. Aided by a minimal model that is able to capture the complex wave interaction of elastic cavity modes and airborne sound radiation in perfect rigid panels, we construct designer acoustoelastic surface waves that are entirely controlled by the geometrical environment. Comparisons to results obtained by full-wave simulations confirm the feasibility of the model and we demonstrate illustrative examples such as resonant transmissions and waveguiding to show a few examples of many where spoof elastic surface waves are useful.

  9. Data-driven exploration of copper mineralogy and its application to Earth's near-surface oxidation

    Science.gov (United States)

    Morrison, S. M.; Eleish, A.; Runyon, S.; Prabhu, A.; Fox, P. A.; Ralph, J.; Golden, J. J.; Downs, R. T.; Liu, C.; Meyer, M.; Hazen, R. M.

    2017-12-01

    Earth's atmospheric composition has changed radically throughout geologic history.1,2 The oxidation of our atmosphere, driven by biology, began with the Great Oxidation Event (GOE) 2.5 Ga and has heavily influenced Earth's near surface mineralogy. Therefore, temporal trends in mineral occurrence elucidate large and small scale geologic and biologic processes. Cu, and other first-row transition elements, are of particular interest due to their variation in valance state and sensitivity to ƒO2. Widespread formation of oxidized Cu mineral species (Cu2+) would not have been possible prior to the GOE and we have found that the proportion of oxidized Cu minerals increased steadily with the increase in atmospheric O2 on Earth's surface (see Fig. 1). To better characterize the changes in Cu mineralogy through time, we have employed advanced analytical and visualization methods. These techniques rely on large and growing mineral databases (e.g., rruff.info, mindat.org, earthchem.org, usgs.gov) and allow us to quantify and visualize multi-dimensional trends.5

  10. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  11. Effect of dynamic surface polarization on the oxidative stability of solvents in nonaqueous Li-O 2 batteries

    Science.gov (United States)

    Khetan, Abhishek; Pitsch, Heinz; Viswanathan, Venkatasubramanian

    2017-09-01

    Polarization-induced renormalization of the frontier energy levels of interacting molecules and surfaces can cause significant shifts in the excitation and transport behavior of electrons. This phenomenon is crucial in determining the oxidative stability of nonaqueous electrolytes in high-energy density electrochemical systems such as the Li-O2 battery. On the basis of partially self-consistent first-principles Sc G W0 calculations, we systematically study how the electronic energy levels of four commonly used solvent molecules, namely, dimethylsulfoxide (DMSO), dimethoxyethane (DME), tetrahydrofuran (THF), and acetonitrile (ACN), renormalize when physisorbed on the different stable surfaces of Li2O2 , the main discharge product. Using band level alignment arguments, we propose that the difference between the solvent's highest occupied molecular orbital (HOMO) level and the surface's valence-band maximum (VBM) is a refined metric of oxidative stability. This metric and a previously used descriptor, solvent's gas phase HOMO level, agree quite well for physisorbed cases on pristine surfaces where ACN is oxidatively most stable followed by DME, THF, and DMSO. However, this effect is intrinsically linked to the surface chemistry of the solvent's interaction with the surface states and defects, and depends strongly on their nature. We conclusively show that the propensity of solvent molecules to oxidize will be significantly higher on Li2O2 surfaces with defects as compared to pristine surfaces. This suggests that the oxidative stability of a solvent is dynamic and is a strong function of surface electronic properties. Thus, while gas phase HOMO levels could be used for preliminary solvent candidate screening, a more refined picture of solvent stability requires mapping out the solvent stability as a function of the state of the surface under operating conditions.

  12. PEGylated graphene oxide elicits strong immunological responses despite surface passivation

    Science.gov (United States)

    Luo, Nana; Weber, Jeffrey K.; Wang, Shuang; Luan, Binquan; Yue, Hua; Xi, Xiaobo; Du, Jing; Yang, Zaixing; Wei, Wei; Zhou, Ruhong; Ma, Guanghui

    2017-02-01

    Engineered nanomaterials promise to transform medicine at the bio-nano interface. However, it is important to elucidate how synthetic nanomaterials interact with critical biological systems before such products can be safely utilized in humans. Past evidence suggests that polyethylene glycol-functionalized (PEGylated) nanomaterials are largely biocompatible and elicit less dramatic immune responses than their pristine counterparts. We here report results that contradict these findings. We find that PEGylated graphene oxide nanosheets (nGO-PEGs) stimulate potent cytokine responses in peritoneal macrophages, despite not being internalized. Atomistic molecular dynamics simulations support a mechanism by which nGO-PEGs preferentially adsorb onto and/or partially insert into cell membranes, thereby amplifying interactions with stimulatory surface receptors. Further experiments demonstrate that nGO-PEG indeed provokes cytokine secretion by enhancing integrin β8-related signalling pathways. The present results inform that surface passivation does not always prevent immunological reactions to 2D nanomaterials but also suggest applications for PEGylated nanomaterials wherein immune stimulation is desired.

  13. Bulk-surface relationship of an electronic structure for high-throughput screening of metal oxide catalysts

    International Nuclear Information System (INIS)

    Kweun, Joshua Minwoo; Li, Chenzhe; Zheng, Yongping; Cho, Maenghyo; Kim, Yoon Young; Cho, Kyeongjae

    2016-01-01

    Graphical abstract: - Highlights: • Bulk-surface relationship was predicted by the ligand field nature of metal oxides. • Antibonding and bonding d-bands occupancy clarified the bulk-surface relationship. • Different surface relaxations were explained by the bulk electronic structures. • Transition from the bulk to the surface state was simulated by oxygen adsorption. - Abstract: Designing metal-oxides consisting of earth-abundant elements has been a crucial issue to replace precious metal catalysts. To achieve efficient screening of metal-oxide catalysts via bulk descriptors rather than surface descriptors, we investigated the relationship between the electronic structure of bulk and that of the surface for lanthanum-based perovskite oxides, LaMO_3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Through density functional theory calculations, we examined the d-band occupancy of the bulk and surface transition-metal atoms (n_B_u_l_k and n_S_u_r_f) and the adsorption energy of an oxygen atom (E_a_d_s) on (001), (110), and (111) surfaces. For the (001) surface, we observed strong correlation between the n_B_u_l_k and n_S_u_r_f with an R-squared value over 94%, and the result was interpreted in terms of ligand field splitting and antibonding/bonding level splitting. Moreover, the E_a_d_s on the surfaces was highly correlated with the n_B_u_l_k with an R-squared value of more than 94%, and different surface relaxations could be explained by the bulk electronic structure (e.g., LaMnO_3 vs. LaTiO_3). These results suggest that a bulk-derived descriptor such as n_B_u_l_k can be used to screen metal-oxide catalysts.

  14. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  15. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2010-01-01

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  16. Influence of metallic surface states on electron affinity of epitaxial AlN films

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Monu; Krishna, Shibin; Aggarwal, Neha [Advanced Materials and Devices Division, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-NPL Campus, Dr. K.S. Krishnan Marg, New Delhi 110012 (India); Gupta, Govind, E-mail: govind@nplindia.org [Advanced Materials and Devices Division, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-NPL Campus, Dr. K.S. Krishnan Marg, New Delhi 110012 (India)

    2017-06-15

    The present article investigates surface metallic states induced alteration in the electron affinity of epitaxial AlN films. AlN films grown by plasma-assisted molecular beam epitaxy system with (30% and 16%) and without metallic aluminium on the surface were probed via photoemission spectroscopic measurements. An in-depth analysis exploring the influence of metallic aluminium and native oxide on the electronic structure of the films is performed. It was observed that the metallic states pinned the Fermi Level (FL) near valence band edge and lead to the reduction of electron affinity (EA). These metallic states initiated charge transfer and induced changes in surface and interface dipoles strength. Therefore, the EA of the films varied between 0.6–1.0 eV due to the variation in contribution of metallic states and native oxide. However, the surface barrier height (SBH) increased (4.2–3.5 eV) adversely due to the availability of donor-like surface states in metallic aluminium rich films.

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

    International Nuclear Information System (INIS)

    Shih, C.-C.; Shih, C.-M.; Su, Y.-Y.; Chang, M.-S.; Lin, S.-J.

    2003-01-01

    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

  18. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    International Nuclear Information System (INIS)

    Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

    2010-01-01

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  19. Tunneling spectroscopy on semiconductors with a low surface state density

    OpenAIRE

    Sommerhalter, Christof; Matthes, Thomas W.; Boneberg, Johannes; Leiderer, Paul; Lux-Steiner, Martha Christina

    1997-01-01

    A detailed study of tunneling spectroscopy concerning semiconductors with a low surface state density is presented. For this purpose, I V curves under dark conditions and under illumination were measured on the (0001) van der Waals surface of a p-type WS2 single crystal, which is known to be free of intrinsic surface states. The measurements are interpreted by an analytical one-dimensional metal-insulator-semiconductor model, which shows that the presence of the finite tunneling current has ...

  20. Study on the surface oxidation of uranium in different gaseous atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou

    1996-03-01

    The studying for the surface oxidation of uranium and oxide by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), secondary ion mass spectroscopy (SIMS), and the surface oxidation of uranium in different gaseous atmospheres such as O 2 , H 2 , CO, CO 2 , H 2 O(v) and air were reviewed. The surface oxidation of uranium is greatly influenced by a number of parameters including atmospheric temperature, pressure, diffusion of adsorbed gas atoms through the oxide layer, surface and interface chemical component, and defect structure and electron nature of the oxide layer. The initial oxidation mechanism and kinetics have been discussed. Suggestions for future work have also been presented. (32 refs., 7 figs., 5 tabs.)

  1. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  2. Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media.

    Science.gov (United States)

    Kloser, Elisabeth; Gray, Derek G

    2010-08-17

    Aqueous suspensions of poly(ethylene oxide)-grafted nanocrystalline cellulose (PEO-grafted NCC) were prepared in order to achieve steric instead of electrostatic stabilization. A two-step process was employed: in the first step NCC suspensions prepared by sulfuric acid hydrolysis were desulfated with sodium hydroxide, and in the second step the surfaces of the crystals were functionalized with epoxy-terminated poly(ethylene oxide) (PEO epoxide) under alkaline conditions. The PEO-grafted samples were analyzed by conductometric titration, ATR-IR, solid-state NMR, MALDI-TOF MS, SEC MALLS, and AFM. The covalent nature of the linkage was confirmed by weight increase and MALDI-TOF analysis. The PEO-grafted cellulose nanocrystals (CNCs) formed a stable colloidal suspension that remained well dispersed, while the desulfated nanoparticles aggregated and precipitated. Upon concentration of the PEO-grafted aqueous NCC suspension, a chiral nematic phase was observed.

  3. Oxidative Stress and Heart Failure in Altered Thyroid States

    Directory of Open Access Journals (Sweden)

    Pallavi Mishra

    2012-01-01

    Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

  4. Atomic layer-by-layer oxidation of Ge (100) and (111) surfaces by plasma post oxidation of Al2O3/Ge structures

    International Nuclear Information System (INIS)

    Zhang, Rui; Huang, Po-Chin; Lin, Ju-Chin; Takenaka, Mitsuru; Takagi, Shinichi

    2013-01-01

    The ultrathin GeO x /Ge interfaces formed on Ge (100) and (111) surfaces by applying plasma post oxidation to thin Al 2 O 3 /Ge structures are characterized in detail using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy. It is found that the XPS signals assigned to Ge 1+ and the 2+ states in the GeO x layers by post plasma oxidation have oscillating behaviors on Ge (100) surfaces in a period of ∼0.3 nm with an increase in the GeO x thickness. Additionally, the oscillations of the signals assigned to Ge 1+ and 2+ states show opposite phase to each other. The similar oscillation behaviors are also confirmed on Ge (111) surfaces for Ge 1+ and 3+ states in a period of ∼0.5 nm. These phenomena can be strongly regarded as an evidence of the atomic layer-by-layer oxidation of GeO x /Ge interfaces on Ge (100) and (111) surfaces.

  5. Rapid Surface Oxidation as a Source of Surface Degradation Factor for Bi 2 Se 3

    KAUST Repository

    Kong, Desheng; Cha, Judy J.; Lai, Keji; Peng, Hailin; Analytis, James G.; Meister, Stefan; Chen, Yulin; Zhang, Hai-Jun; Fisher, Ian R.; Shen, Zhi-Xun; Cui, Yi

    2011-01-01

    Bismuth selenide (Bi2Se3) is a topological insulator with metallic surface states (SS) residing in a large bulk bandgap. In experiments, synthesized Bi2Se3 is often heavily n-type doped due to selenium vacancies. Furthermore, it is discovered from

  6. Preparation of self-organized porous anodic niobium oxide microcones and their surface wettability

    International Nuclear Information System (INIS)

    Oikawa, Y.; Minami, T.; Mayama, H.; Tsujii, K.; Fushimi, K.; Aoki, Y.; Skeldon, P.; Thompson, G.E.; Habazaki, H.

    2009-01-01

    Porous anodic niobium oxide with a pore size of ∼10 nm was formed at 10 V in glycerol electrolyte containing 0.6 mol dm -3 K 2 HPO 4 and 0.2 mol dm -3 K 3 PO 4 at 433 K. After prolonged anodizing for 5.4 ks, niobium oxide microcones develop on the surface. X-ray diffraction patterns of the anodized specimens revealed that the initially formed anodic oxide is amorphous, but an amorphous-to-crystalline transition occurs during anodizing. As a consequence of the preferential chemical dissolution of the initially formed amorphous oxide, due to different solubility of the amorphous and crystalline oxides, crystalline oxide microcones appear on the film surface after prolonged anodizing. The surface is superhydrophilic. After coating with fluorinated alkylsilane, the surface becomes superhydrophobic with a contact angle of 158 o for water. The surface is also oil repellent, with a contact angle as high as 140 o for salad oil.

  7. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  8. State promotion and neutralization of ions near metal surface

    International Nuclear Information System (INIS)

    Zinoviev, A.N.

    2011-01-01

    Research highlights: → Multiply charged ion and the charge induced in the metal form a dipole. → Dipole states are promoted into continuum with decreasing ion-surface distance. → These states cross the states formed from metal atom. → Proposed model explains the dominant population of deep bound states. → Observed spectra of emitted Auger electrons prove this promotion model. -- Abstract: When a multiply charged ion with charge Z approaches the metal surface, a dipole is formed by the multiply charged ion and the charge induced in the metal. The states for such a dipole are promoted into continuum with decreasing ion-surface distance and cross the states formed from metal atom. The model proposed explains the dominant population of deep bound states in collisions considered.

  9. Study on the surface oxidation resistance of uranium metal in the atmosphere of carbon monoxide

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1999-01-01

    The surface reactions of different layers on uranium metal with carbon monoxide at 25, 80 and 200 degree C are studied by X-ray photoelectron spectroscopy (XPS). The experimental results show that the carbon monoxide is adsorbed on the surface oxide layer of uranium and interacted each other. The content of oxygen in the surface oxide and O/U ratio are decreased with increasing the exposure of carbon monoxide to the surface layer. The effect of reduction on the metal surface is more obviously with a higher temperature and increasing of layer thickness. The investigation indicates the uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide

  10. Improved the Surface Roughness of Silicon Nanophotonic Devices by Thermal Oxidation Method

    Energy Technology Data Exchange (ETDEWEB)

    Shi Zujun; Shao Shiqian; Wang Yi, E-mail: ywangwnlo@mail.hust.edu.cn [Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, No. 1037, Luoyu Street, Wuhan 430074 (China)

    2011-02-01

    The transmission loss of the silicon-on-insulator (SOI) waveguide and the coupling loss of the SOI grating are determined to a large extent by the surface roughness. In order to obtain smaller loss, thermal oxidation is a good choice to reduce the surface roughness of the SOI waveguide and grating. Before the thermal oxidation, the root mean square of the surface roughness is over 11 nm. After the thermal oxidation, the SEM figure shows that the bottom of the grating is as smooth as quartz surface, while the AFM shows that the root mean square of the surface is less than 5 nm.

  11. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    Energy Technology Data Exchange (ETDEWEB)

    Kulagin, N.A., E-mail: nkulagin@bestnet.kharkov.u [Kharkiv National University for Radio Electronics, Avenue Shakespeare 6-48, 61045 Kharkiv (Ukraine)

    2011-03-15

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr{sup +4} ions in oxides, Cu{sup +2} in HTSC, Nd{sup +2} in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10{sup -9} m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: External influence and variation of technology induce changes in valence of nl ions in compounds. Wave function of cluster presented as anti-symmetrical set of ions wave functions. The main equation describes the self-consistent field depending on state of all electrons of cluster. Level scheme of Cr{sup 4+} ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. Plasma treatment effects in appearance of systems of unit crystallites with size of about 10{sup -6}-10{sup -9} m.

  12. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    International Nuclear Information System (INIS)

    Kulagin, N.A.

    2011-01-01

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr +4 ions in oxides, Cu +2 in HTSC, Nd +2 in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10 -9 m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: → External influence and variation of technology induce changes in valence of nl ions in compounds. → Wave function of cluster presented as anti-symmetrical set of ions wave functions. → The main equation describes the self-consistent field depending on state of all electrons of cluster. → Level scheme of Cr 4+ ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. → Plasma treatment effects in appearance of systems of unit crystallites with size of about 10 -6 -10 -9 m.

  13. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-10-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

  14. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-01-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

  15. XPS study of vanadium surface oxidation by oxygen ion bombardment

    Czech Academy of Sciences Publication Activity Database

    Alov, N.; Kutsko, D.; Spirovová, Ilona; Bastl, Zdeněk

    2006-01-01

    Roč. 600, č. 8 (2006), s. 1628-1631 ISSN 0039-6028 R&D Projects: GA ČR GA104/04/0467 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium oxide * oxide film * ion-beam oxidation * X-ray photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.880, year: 2006

  16. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  17. Study of uranium oxidation states in geological material.

    Science.gov (United States)

    Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

    2013-10-01

    A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. High temperature oxidation behavior of AISI 304L stainless steel—Effect of surface working operations

    International Nuclear Information System (INIS)

    Ghosh, Swati; Kumar, M. Kiran; Kain, Vivekanand

    2013-01-01

    Highlights: ► Surface working resulted in thinner oxide on the surface. ► Oxides on machined/ground surfaces richer in Cr, higher in specific resistivity. ► Additional ionic transport process at the metal-oxide for ground sample established. ► Presence of fragmented grains and martensite influenced oxide nature/morphology. - Abstract: The oxidation behavior of grade 304L stainless steel (SS) subjected to different surface finishing (machining and grinding) operations was followed in situ by contact electric resistance (CER) and electrochemical impedance spectroscopy (EIS) measurements using controlled distance electrochemistry (CDE) technique in high purity water (conductivity −1 ) at 300 °C and 10 MPa in an autoclave connected to a recirculation loop system. The results highlight the distinct differences in the oxidation behavior of surface worked material as compared to solution annealed material in terms of specific resistivity and low frequency Warburg impedance. The resultant oxide layer was characterized for (a) elemental analyses by glow discharge optical emission spectroscopy (GDOES) and (b) morphology by scanning electron microscopy (SEM). Oxide layers with higher specific resistivity and chromium content were formed in case of machined and ground conditions. Presence of an additional ionic transport process has also been identified for the ground condition at the metal/oxide interface. These differences in electrochemical properties and distinct morphological features of the oxide layer as a result of surface working were attributed to the prevalence of heavily fragmented grain structure and presence of martensite.

  19. Surface morphology study on chromium oxide growth on Cr films by Nd-YAG laser oxidation process

    International Nuclear Information System (INIS)

    Dong Qizhi; Hu Jiandong; Guo Zuoxing; Lian Jianshe; Chen Jiwei; Chen Bo

    2002-01-01

    Grain sized (60-100 nm) Cr 2 O 3 thin films were prepared on Cr thin film surfaces by Nd-YAG laser photothermal oxidation process. Surface morphology study showed crack-free short plateau-like oxide films formed. Increase of dislocation density after pulsed laser irradiation was found. Thin film external surfaces, grain boundaries and dislocations are main paths of laser surface oxidation. Pinning and sealing of grain boundary was the reason that deeper oxidation did not produce. Grain growth and agglomeration of Cr sub-layer yielded tensile stress on the surface Cr 2 O 3 thin film. It was the reason that short plateau-like surface morphology formed and cracks appeared sometimes. In oxygen annealing at 700 deg. C, grain boundaries were considered not to be pinned at the surface, mixture diffusion was main mechanism in growth of oxide. Compression stress development in whole film led to extrusion of grains that was the reason that multiple appearances such as pyramid-like and nutshell-like morphology formed

  20. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  1. Decontamination of U-metal surface by an oxidation etching system

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R.B.; Kansa, E.J.; Shaffer, R.J.; Weed, H.C. [California Univ., Livermore, CA (United States). Lawrence Livermore National Lab

    2001-07-01

    A surface treatment to remove surface contamination from uranium (U) metal and/or hydrides of uranium and heavy metals (HM) from U-metal parts is described. 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 oxidation process to create 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 significantly 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. (authors)

  2. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-04-05

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

  3. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

  4. Study on the influence of carbon monoxide to the surface oxide layer of uranium metal

    International Nuclear Information System (INIS)

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

    1997-01-01

    The influence of carbon monoxide to the surface oxide layer of uranium metal has been studied by X-ray photoelectron spectroscopy (XPS) and gas chromatography (GC). Carbon monoxide adsorption on the oxide layer resulted in U4f peak shifting to the lower binding energy. The content of oxygen in the oxide is decreased and the atomic ratio (O/U) is decreased by 7.2%. The amount of carbon dioxide in the atmosphere after the surface reaction is increased by 11.0%. The investigation indicates that the surface layer can prevent the further oxidation uranium metal in the atmosphere of carbon monoxide

  5. Effect of gamma-ray irradiation on the surface states of MOS tunnel junctions

    Science.gov (United States)

    Ma, T. P.; Barker, R. C.

    1974-01-01

    Gamma-ray irradiation with doses up to 8 megarad produces no significant change on either the C(V) or the G(V) characteristics of MOS tunnel junctions with intermediate oxide thicknesses (40-60 A), whereas the expected flat-band shift toward negative electrode voltages occurs in control thick oxide capacitors. A simple tunneling model would explain the results if the radiation-generated hole traps are assumed to lie below the valence band of the silicon. The experiments also suggest that the observed radiation-generated interface states in conventional MOS devices are not due to the radiation damage of the silicon surface.

  6. Real-time monitoring of initial thermal oxidation on Si(001) surfaces by synchrotron radiation photoemission spectroscopy

    CERN Document Server

    Yoshigoe, A; Teraoka, Y

    2003-01-01

    The thermal oxidation of Si(001) surfaces at 860 K, 895 K, 945 K and 1000 K under the O sub 2 pressure of 1 x 10 sup - sup 4 Pa has been investigated by time-resolved photoemission measurements with synchrotron radiation. Based on time evolution analyses by reaction kinetics models, it was found that the oxidation at 860 K, 895 K and 945 K has progressed with the Langmuir adsorption type, whereas the oxidation at 1000 K has showed the character of the two-dimensional island growth involving SiO desorption. The oxidation rates increases with increasing surface temperature in the passive oxidation condition. The time evolution of each Si oxidation state (Si sup n sup + : n = 1, 2, 3, 4) derived from the Si-2p core-level shifts has also been analyzed. The results revealed that the thermal energy contribution to the migration process of the adsorbed oxygen and the emission of the bulk silicon atoms. Thus, the fraction of the Si sup 4 sup + bonding state, i.e. SiO sub 2 structure, was increased. (author)

  7. Electrochemical and morphological analyses on the titanium surface modified by shot blasting and anodic oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Szesz, Eduardo M., E-mail: eszesz@neoortho.com.br [Neoortho Research Institute, Rua Ângelo Domingos Durigan, 607-Cascatinha, CEP 82025-100 Curitiba, PR (Brazil); Pereira, Bruno L., E-mail: brnl7@hotmail.com [Physics Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Kuromoto, Neide K., E-mail: kuromoto@fisica.ufpr.br [Physics Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Marino, Claudia E.B., E-mail: claudiamarino@yahoo.com [Mechanical Engineering Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Souza, Gelson B. de, E-mail: gelsonbs@uepg.br [Physics Department, Universidade Estadual de Ponta Grossa, 84051-510 Ponta Grossa, PR (Brazil); Soares, Paulo, E-mail: pa.soares@pucpr.br [Mechanical Engineering Department, Pontifícia Universidade Católica do Paraná, 80215-901 Curitiba, PR (Brazil)

    2013-01-01

    In recent years, many surface modification processes have been developed in order to induce the osseointegration on titanium surface and thus to improve the implants' biocompatibility. In this work, Ti surface has been modified by shot blasting followed by anodic oxidation process in order to associate the good surface characteristics of both processes to obtain a rough and porous surface able to promote the titanium surface bioactivity. Commercially pure titanium (grade 2) plates were used on the surface treatments that were as follows: Shot blasting (SB) performed using alumina (Al{sub 2}O{sub 3}) particles, and anodic oxidation (AO) using NaOH electrolyte. The morphology, structural changes and the open-circuit potentials (OCP) of the surfaces were analyzed. It can be observed that an increase on the roughness of the blasted surface and a rough and porous surface happens after the AO process. The anodic film produced is thin and followed the blasted surface topography. It can be observed that there are small pores with regular shape covering the entire surface. X-ray diffraction results showed the presence of the anatase and rutile phases on the blasted and anodized surface after heat treatment at 600 °C/1 h. Concerning electrochemical measurements, when the different samples were submitted to open-circuit conditions in a physiological electrolyte, the protective effect increases with the oxidation process due to the oxide layer. When the surface was blasted, the OCP was more negative when compared with the Ti surface without surface treatments. - Highlights: ► A combination of shot blasting and anodic oxidation surface treatments is proposed. ► Both processes produced an increase in roughness compared to the polished surface. ► The combination of processes produced a rough and porous surface. ► Open circuit results show that the protective effect increases with oxidation process. ► The combination of processes presents the better results in this

  8. Surface plasmon resonance based fiber optic detection of chlorine utilizing polyvinylpyrolidone supported zinc oxide thin films.

    Science.gov (United States)

    Tabassum, Rana; Gupta, Banshi D

    2015-03-21

    A highly sensitive chlorine sensor for an aqueous medium is fabricated using an optical fiber surface plasmon resonance (OFSPR) system. An OFSPR-based chlorine sensor is designed with a multilayer-type platform by zinc oxide (ZnO) and polyvinylpyrollidone (PVP) film morphology manipulations. Among all the methodologies of transduction reported in the field of solid state chemical and biochemical sensing, our attention is focused on the Kretschmann configuration optical fiber sensing technique using the mechanism of surface plasmon resonance. The optical fiber surface plasmon resonance (SPR) chlorine sensor is developed using a multimode optical fiber with the PVP-supported ZnO film deposited over a silver-coated unclad core of the fiber. A spectral interrogation mode of operation is used to characterize the sensor. In an Ag/ZnO/PVP multilayer system, the absorption of chlorine in the vicinity of the sensing region is performed by the PVP layer and the zinc oxide layer enhances the shift in resonance wavelength. It is, experimentally, demonstrated that the SPR wavelength shifts nonlinearly towards the red side of the visible region with an increase in the chlorine concentration in an aqueous medium while the sensitivity of the sensor decreases linearly with an increase in the chlorine concentration. As the proposed sensor utilizes an optical fiber, it possesses the additional advantages of fiber such as less signal degradation, less susceptibility to electromagnetic interference, possibility of remote sensing, probe miniaturization, probe re-usability, online monitoring, small size, light weight and low cost.

  9. Studies of the Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2010-01-01

    The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  10. Studies of Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2011-01-01

    The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  11. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    Science.gov (United States)

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  12. Synergistic Effect of Superhydrophobicity and Oxidized Layers on Corrosion Resistance of Aluminum Alloy Surface Textured by Nanosecond Laser Treatment.

    Science.gov (United States)

    Boinovich, Ludmila B; Emelyanenko, Alexandre M; Modestov, Alexander D; Domantovsky, Alexandr G; Emelyanenko, Kirill A

    2015-09-02

    We report a new efficient method for fabricating a superhydrophobic oxidized surface of aluminum alloys with enhanced resistance to pitting corrosion in sodium chloride solutions. The developed coatings are considered very prospective materials for the automotive industry, shipbuilding, aviation, construction, and medicine. The method is based on nanosecond laser treatment of the surface followed by chemisorption of a hydrophobic agent to achieve the superhydrophobic state of the alloy surface. We have shown that the surface texturing used to fabricate multimodal roughness of the surface may be simultaneously used for modifying the physicochemical properties of the thick surface layer of the substrate itself. Electrochemical and wetting experiments demonstrated that the superhydrophobic state of the metal surface inhibits corrosion processes in chloride solutions for a few days. However, during long-term contact of a superhydrophobic coating with a solution, the wetted area of the coating is subjected to corrosion processes due to the formation of defects. In contrast, the combination of an oxide layer with good barrier properties and the superhydrophobic state of the coating provides remarkable corrosion resistance. The mechanisms for enhancing corrosion protective properties are discussed.

  13. Study on the solid state chemistry of ternary uranium oxides

    International Nuclear Information System (INIS)

    Yamashita, Toshiyuki

    1988-03-01

    With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

  14. Tailoring the surface chemical bond states of the NbN films by doping Ag: Achieving hard hydrophobic surface

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Ping; Zhang, Kan; Du, Suxuan [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun, 130012 (China); Meng, Qingnan [College of Construction Engineering, Jilin University, Changchun, 130026 (China); He, Xin [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun, 130012 (China); Wang, Shuo [Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871 (China); Wen, Mao, E-mail: wenmao225@jlu.edu.cn [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun, 130012 (China); Zheng, Weitao, E-mail: WTZheng@jlu.edu.cn [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun, 130012 (China)

    2017-06-15

    Highlights: • Intrinsically hydrophilic NbN films can transfer to hydrophobic Nb-Ag-N films by doping Ag atoms into NbN sublattice. • Solute Ag can promote that the hydrophobic Ag{sub 2}O groups formed on the Nb-Ag-N film surface through self-oxidation. • The present work may provide a straightforward approach for the production of robust hydrophobic ceramic surfaces. - Abstract: Robust hydrophobic surfaces based on ceramics capable of withstanding harsh conditions such as abrasion, erosion and high temperature, are required in a broad range of applications. The metal cations with coordinative saturation or low electronegativity are commonly chosen to achieve the intrinsically hydrophobic ceramic by reducing Lewis acidity, and thus the ceramic systems are limited. In this work, we present a different picture that robust hydrophobic surface with high hardness (≥20 GPa) can be fabricated through doping Ag atoms into intrinsically hydrophilic ceramic film NbN by reactive co-sputtering. The transition of wettability from hydrophilic to hydrophobic of Nb-Ag-N films induced by Ag doping results from the appearance of Ag{sub 2}O groups on the films surfaces through self-oxidation, because Ag cations (Ag{sup +}) in Ag{sub 2}O are the filled-shell (4d{sup 10}5S{sup 0}) electronic structure with coordinative saturation that have no tendency to interact with water. The results show that surface Ag{sub 2}O benefited for hydrophobicity comes from the solute Ag atoms rather than precipitate metal Ag, in which the more Ag atoms incorporated into Nb-sublattice are able to further improve the hydrophobicity, whereas the precipitation of Ag nanoclusters would worsen it. The present work opens a window for fabricating robust hydrophobic surface through tailoring surface chemical bond states by doping Ag into transition metal nitrides.

  15. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    Science.gov (United States)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  16. Predicting spent fuel oxidation states in a tuff repository

    International Nuclear Information System (INIS)

    Einziger, R.E.; Woodley, R.E.

    1987-01-01

    Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

  17. Influence of carbon monoxide to the surface layer of uranium metal and its oxides

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-09-01

    The surface structures of uranium metal and triuranium octaoxide (U 3 O 8 ) and the influence of carbon monoxide to the surface layers have been studied by X-ray photoelectron spectroscopy (XPS). After exposure to carbon monoxide, contents of oxygen in the surface oxides of uranium metal and U 3 O 8 are decreased and O/U ratios decrease 7.2%, 8.0% respectively. The investigation indicated the surface layers of uranium metal and its oxides were forbidden to further oxidation in the atmosphere of carbon monoxide. (11 refs., 9 figs., 2 tabs.)

  18. Modeling Manganese Sorption and Surface Oxidation During Filtration

    OpenAIRE

    Bierlein, Kevin Andrew

    2012-01-01

    Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the â natural greensand effect,â in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Mer...

  19. The oxidation state of sulfur in apatite: A new oxybarometer?

    Science.gov (United States)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  20. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    KAUST Repository

    Li, Jingrui

    2015-07-29

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  1. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    KAUST Repository

    Li, Jingrui; Li, Hong; Winget, Paul; Bredas, Jean-Luc

    2015-01-01

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  2. Chelation and stabilization of berkelium in oxidation state +IV

    Science.gov (United States)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  3. In-situ oxidation study of Pd(100) by surface x-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Kilic, Volkan; Franz, Dirk; Stierle, Andreas [AG Grenzflaechen, Universitaet Siegen (Germany); Martin, Natalia; Lundgren, Edvin [Department of Synchrotron Radiation Research, Lund University (Sweden); Mantilla, Miguel [MPI fuer Metallforschung, Stuttgart (Germany)

    2011-07-01

    The oxidation of the Pd(100) surface at oxygen pressures in the 10{sup -6} mbar to 10{sup 3} mbar range and temperatures up to 1000 K has been studied in-situ by surface x-ray diffraction (SXRD). The SXRD experiments were performed at the MPI beamline at the Angstrom Quelle Karlsruhe (ANKA). We present the surface and crystal truncation rod (CTR) data from the ({radical}(5) x {radical}(5)) surface layer. We show that the transformation from the surface oxide to PdO bulk oxide can be observed in-situ under specific pressure and temperature conditions. We compare our results with previously proposed structure models based on low energy electron diffraction (LEED) I(V) curves and density functional theory calculations. Finally, we elucidate the question of commensurability of the surface oxide layer with respect to the Pd(100) substrate.

  4. Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

    Science.gov (United States)

    Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

    2013-05-14

    A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

  5. Surface studies of YBa2Cu3O7-x -matching oxide substrates and interfaces

    International Nuclear Information System (INIS)

    Enevold Thaulov Andersen, J.

    1990-11-01

    Crystallographic changes as a result of heat-treatment at 700-900 deg. C are found for SrTiO 3 (100), MgO(100) and LaAlO 3 (100). The p(2x2) reconstruction of the SrTiO 3 (100) and the superstructures on MgO(100) and on LaAlO 3 (100) thus observed are suggested to be induced by segregation of impurities to the surface. The surface charge-effects which disturb electron- and photon-impact experiments with these insulators are removed by heat-treatments. Deposition of copper results in formation of copper islands on SrTiO 3 (100) and on LaAlO 3 (100). Yttrium forms islands on LaAlO 3 (100) and grows in a layer-by-layer mode on SrTiO 3 (100) and on MgO(100). An yttrium 1x1 epitaxy is observed on the MgO(100) surface, which is suggested to be an YO superstructure. Oxidation of the 1x1 Y/MgO(100) systems diminishes the charge-effects and improves all diffraction and spectroscopic measurements. This may be due to the formation of metallic states around the Fermi level when the film is oxidized. An in situ synthesized YBa 2 Cu 3 O 7 thin film on SrTiO 3 (100) compared to a thick epitaxial YBa 2 Cu 3 O 7-x (001) film on MgO(100) reveals differences in surface electronic structures but not in surface stoichiometries. (au) 18 refs

  6. Effect of surface stress state on dissolution property of Alloy 690 in simulated primary water condition

    International Nuclear Information System (INIS)

    Kim, Kyung Mo; Shim, Hee-Sang; Lee, Eun Hee; Seo, Myung Ji; Han, Jung Ho; Hur, Do Haeng

    2014-01-01

    The dissolution control of nickel is important to reduce the radioactive dose rate and deterioration of fuel performance in the operation of nuclear power plants (PWR). The corrosion properties are affected by the metal surface residual stress introduced in manufacture process such as work hardening. This work studied the effect of surface modification on the release rate of Alloy 690, nickel-base alloy for a steam generator tube, in the test condition of simulated primary water chemistry in PWRs. The surface stress modification was applied by the electro-polishing and shot peening method. Shot peening process was applied using ceramic beads with different intensities through the variation of air pressure. The corrosion release tests performed at 330degC with LiOH 2 ppm and H 3 BO 4 1200 ppm, DH(dissolved hydrogen) 35 cc/kg (STP) and about 20 ppb of DO(dissolved oxygen) condition. The corrosion release rate was evaluated by a gravimetric analysis method and the surface analysed by SEM and optical microscope. The surface residual stress was measured by an X-ray diffractometer, and the distribution of stress state was evaluated by a micro-hardness tester. The metal ion release rate of alloy 690 was evaluated from the influence of the stress state on the metal surface. The oxide property and structure was affected by the residual stress in the oxide layer. (author)

  7. Statistical contact angle analyses; "slow moving" drops on a horizontal silicon-oxide surface.

    Science.gov (United States)

    Schmitt, M; Grub, J; Heib, F

    2015-06-01

    Sessile drop experiments on horizontal surfaces are commonly used to characterise surface properties in science and in industry. The advancing angle and the receding angle are measurable on every solid. Specially on horizontal surfaces even the notions themselves are critically questioned by some authors. Building a standard, reproducible and valid method of measuring and defining specific (advancing/receding) contact angles is an important challenge of surface science. Recently we have developed two/three approaches, by sigmoid fitting, by independent and by dependent statistical analyses, which are practicable for the determination of specific angles/slopes if inclining the sample surface. These approaches lead to contact angle data which are independent on "user-skills" and subjectivity of the operator which is also of urgent need to evaluate dynamic measurements of contact angles. We will show in this contribution that the slightly modified procedures are also applicable to find specific angles for experiments on horizontal surfaces. As an example droplets on a flat freshly cleaned silicon-oxide surface (wafer) are dynamically measured by sessile drop technique while the volume of the liquid is increased/decreased. The triple points, the time, the contact angles during the advancing and the receding of the drop obtained by high-precision drop shape analysis are statistically analysed. As stated in the previous contribution the procedure is called "slow movement" analysis due to the small covered distance and the dominance of data points with low velocity. Even smallest variations in velocity such as the minimal advancing motion during the withdrawing of the liquid are identifiable which confirms the flatness and the chemical homogeneity of the sample surface and the high sensitivity of the presented approaches. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. Ice nucleation on nanotextured surfaces: the influence of surface fraction, pillar height and wetting states.

    Science.gov (United States)

    Metya, Atanu K; Singh, Jayant K; Müller-Plathe, Florian

    2016-09-29

    In this work, we address the nucleation behavior of a supercooled monatomic cylindrical water droplet on nanoscale textured surfaces using molecular dynamics simulations. The ice nucleation rate at 203 K on graphite based textured surfaces with nanoscale roughness is evaluated using the mean fast-passage time method. The simulation results show that the nucleation rate depends on the surface fraction as well as the wetting states. The nucleation rate enhances with increasing surface fraction for water in the Cassie-Baxter state, while contrary behavior is observed for the case of Wenzel state. Based on the spatial histogram distribution of ice formation, we observed two pathways for ice nucleation. Heterogeneous nucleation is observed at a high surface fraction. However, the probability of homogeneous ice nucleation events increases with decreasing surface fraction. We further investigate the role of the nanopillar height in ice nucleation. The nucleation rate is enhanced with increasing nanopillar height. This is attributed to the enhanced contact area with increasing nanopillar height and the shift in nucleation events towards the three-phase contact line associated with the nanotextured surface. The ice-surface work of adhesion for the Wenzel state is found to be 1-2 times higher than that in the Cassie-Baxter state. Furthermore, the work of adhesion of ice in the Wenzel state is found to be linearly dependent on the contour length of the droplet, which is in line with that reported for liquid droplets.

  9. Fenton Redox Chemistry : Arsenite Oxidation by Metallic Surfaces

    NARCIS (Netherlands)

    Borges Freitas, S.C.; Van Halem, D.; Badruzzaman, A.B.M.; Van der Meer, W.G.J.

    2014-01-01

    Pre-oxidation of As(III) is necessary in arsenic removal processes in order to increase its efficiency. Therefore, the Fenton Redox Chemistry is defined by catalytic activation of H2O2 and currently common used for its redox oxidative properties. In this study the effect of H2O2 production catalysed

  10. Influence of surface treatment on the oxidation behavior of zirconium and zircaloy-4

    International Nuclear Information System (INIS)

    Costa, I.; Ramanathan, L.V.

    1986-01-01

    The influence of fluoride concentration in surface treatment solutions on the oxidation behavior of Zr and Zircaloy-4 in the temperature range 350-760 0 C have been studied by means of thermogravimetric analysis. Two solutions containing different concentrations of hydrofluoric acid have been used for surface treatments, following which surface roughness measurements were also carried out. The influence of fluoride ion concentration on oxidation behavior has been found to be significant at higher temperatures. (Author) [pt

  11. Tritium contaminated surface monitoring with a solid - state device

    International Nuclear Information System (INIS)

    Culcer, Mihai; Iliescu, Mariana; Curuia, Marian; Enache, Adrian; Stefanescu, Ioan; Ducu, Catalin; Malinovschi, Viorel

    2004-01-01

    The low energy of betas makes tritium difficult to detect. However, there are several methods used in tritium detection, such as liquid scintillation and ionization chambers. Tritium on or near a surface can be also detected using proportional counters and, recently, solid state devices. The paper presents our results in the design and achievement of a surface tritium monitor using a PIN photodiode as a solid state charged particle detector to count betas emitted from the surface. That method allows continuous, real-time and non-destructively measuring of tritium. (authors)

  12. A time effect in the early stages of a surface oxidation of a Pt(111 plane in alkaline solution

    Directory of Open Access Journals (Sweden)

    J. D. LOVIC

    2001-12-01

    Full Text Available A time effect in the early stages of surface oxidation of a Pt(111 plane in 0.1 M NaOH solution was studied by examining the reduction parts of the j/E profile recorded after holding the potential for various times at several values at the end of anodic-going sweeps. The processes associated with the two peaks, which appear in the anodic part of the voltammogram, are assigned to the early stages of a surface oxidation. Two OHad states are suggested based on the existence of reversibly or weakly bound OHad species and irreversibly or strongly bound OHad species. The reversibly bound OHad species are involved in the “normal” structure of the butterfly peak, while the irreversibly adsorbed OHad species can be obtained only by the slow diffusion of a part of the initially electrosorbed OH species from sites with low to sites with higher binding energies. The irreversibly reduced OHad species cannot be completely removed from the surface causing, therefore, some permanent transformation of the initial state of the surface. This kind of species was not detected in the area of the second oxidation peak. The phenomena observed in the reduction part of the j/E profile induced by a time effect in the second peak could be associated with a place-exchange mechanism between oxygen containing species, whatever they are, and the platinum surface.

  13. Surface modification of PLGA nanoparticles to deliver nitric oxide to inhibit Escherichia coli growth

    Energy Technology Data Exchange (ETDEWEB)

    Reger, Nina A. [Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282 (United States); Meng, Wilson S. [Division of Pharmaceutical Sciences, Duquesne University, Pittsburgh, PA 15282 (United States); Gawalt, Ellen S., E-mail: gawalte@duq.edu [Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282 (United States); McGowan Institute for Regenerative Medicine, University of Pittsburgh, Pittsburgh, PA 15219 (United States)

    2017-04-15

    Highlights: • Thin film functionalized PLGA nanoparticles were modified to release nitric oxide from an s-nitrosothiol donor. • The nitric oxide modified nanoparticles were bacteriostatic against Escherichia coli. • The nitric oxide modified nanoparticles increased the effectiveness of tetracycline against Escherichia coli. • The modified nitric oxide nanoparticles did not exhibit cytotoxic effects against fibroblasts. - Abstract: Polymer nanoparticles consisting of poly (DL-lactic-co-glycolic acid) were surface functionalized to deliver nitric oxide. These biodegradable and biocompatible nanoparticles were modified with an S-nitrosothiol molecule, S-nitrosocysteamine, as the nitric oxide delivery molecule. S-nitrosocysteamine was covalently immobilized on the nanoparticle surface using small organic molecule linkers and carbodiimide coupling. Nanoparticle size, zeta potential, and morphology were determined using dynamic light scattering and scanning electron microscopy, respectively. Subsequent attachment of the S-nitrosothiol resulted in a nitric oxide release of 37.1 ± 1.1 nmol per milligram of nanoparticles under physiological conditions. This low concentration of nitric oxide reduced Escherichia coli culture growth by 31.8%, indicating that the nitric oxide donor was effective at releasing nitric oxide even after attachment to the nanoparticle surface. Combining the nitric oxide modified nanoparticles with tetracycline, a commonly prescribed antibiotic for E. coli infections, increased the effectiveness of the antibiotic by 87.8%, which allows for lower doses of antibiotics to be used in order to achieve the same effect. The functionalized nanoparticles were not cytotoxic to mouse fibroblasts.

  14. Surface modification of PLGA nanoparticles to deliver nitric oxide to inhibit Escherichia coli growth

    International Nuclear Information System (INIS)

    Reger, Nina A.; Meng, Wilson S.; Gawalt, Ellen S.

    2017-01-01

    Highlights: • Thin film functionalized PLGA nanoparticles were modified to release nitric oxide from an s-nitrosothiol donor. • The nitric oxide modified nanoparticles were bacteriostatic against Escherichia coli. • The nitric oxide modified nanoparticles increased the effectiveness of tetracycline against Escherichia coli. • The modified nitric oxide nanoparticles did not exhibit cytotoxic effects against fibroblasts. - Abstract: Polymer nanoparticles consisting of poly (DL-lactic-co-glycolic acid) were surface functionalized to deliver nitric oxide. These biodegradable and biocompatible nanoparticles were modified with an S-nitrosothiol molecule, S-nitrosocysteamine, as the nitric oxide delivery molecule. S-nitrosocysteamine was covalently immobilized on the nanoparticle surface using small organic molecule linkers and carbodiimide coupling. Nanoparticle size, zeta potential, and morphology were determined using dynamic light scattering and scanning electron microscopy, respectively. Subsequent attachment of the S-nitrosothiol resulted in a nitric oxide release of 37.1 ± 1.1 nmol per milligram of nanoparticles under physiological conditions. This low concentration of nitric oxide reduced Escherichia coli culture growth by 31.8%, indicating that the nitric oxide donor was effective at releasing nitric oxide even after attachment to the nanoparticle surface. Combining the nitric oxide modified nanoparticles with tetracycline, a commonly prescribed antibiotic for E. coli infections, increased the effectiveness of the antibiotic by 87.8%, which allows for lower doses of antibiotics to be used in order to achieve the same effect. The functionalized nanoparticles were not cytotoxic to mouse fibroblasts.

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

    Science.gov (United States)

    McKee, Rodney A.; Walker, Frederick J.

    1995-01-01

    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.

  16. Deformation and stability of surface states in Dirac semimetals

    Science.gov (United States)

    Kargarian, Mehdi; Lu, Yuan-Ming; Randeria, Mohit

    2018-04-01

    The unusual surface states of topological semimetals have attracted a lot of attention. Recently, we showed [Proc. Natl. Acad. Sci. USA 113, 8648 (2016), 10.1073/pnas.1524787113] that for a Dirac semimetal (DSM) arising from band inversion, such as Na3Bi and Cd3As2 , the expected double Fermi arcs on the surface are not topologically protected. Quite generally, the arcs deform into states similar to those on the surface of a strong topological insulator. Here we address two questions related to deformation and stability of surface states in DSMs. First, we discuss why certain perturbations, no matter how large, are unable to destroy the double Fermi arcs. We show that this is related to a certain extra (particle-hole) symmetry, which is nongeneric in materials. Second, we discuss situations in which the surface states are completely destroyed without breaking any symmetry or impacting the bulk Dirac nodes. We are not aware of any experimental or density functional theory (DFT) candidates for a material which is a bulk DSM without any surface states, but our results clearly show that this is possible.

  17. Rashba split surface states in BiTeBr

    International Nuclear Information System (INIS)

    Eremeev, S V; Rusinov, I P; Nechaev, I A; Chulkov, E V

    2013-01-01

    Within density functional theory, we study the bulk band structure and surface states of BiTeBr. We consider both ordered and disordered phases, which differ in atomic order in the Te–Br sublattice. On the basis of relativistic ab initio calculations, we show that the ordered BiTeBr is energetically preferable as compared with the disordered one. We demonstrate that both Te- and Br-terminated surfaces of the ordered BiTeBr hold surface states with a giant spin–orbit splitting. The Te-terminated surface-state spin splitting has Rashba-type behavior with the coupling parameter α R ∼ 2 eVÅ. (paper)

  18. Surface Relaxation and Electronic States of Pt(111) Surface with Varying Slab Thickness

    International Nuclear Information System (INIS)

    Kaushal, Ashok K.; Mullick, Shanta; Ahluwalia, P. K.

    2011-01-01

    Surface relaxation and electronic DOS's of Pt(111) surface have been studied with varying slab thickness using ab-initio SIESTA method. We found the expansion in the top layer and contraction in the subsurface layers of Pt(111) surface. Our results match with the experimental results. Also observing electronic density of states we found that as we increase the thickness of slab, the PDOS of Pt(111) surface goes towards the bulk density of states and Fermi energy shifts towards the bulk fermi energy.

  19. Exotic Paired States with Anisotropic Spin-Dependent Fermi Surfaces

    International Nuclear Information System (INIS)

    Feiguin, Adrian E.; Fisher, Matthew P. A.

    2009-01-01

    We propose a model for realizing exotic paired states in cold Fermi gases by using a spin-dependent optical lattice to engineer mismatched Fermi surfaces for each hyperfine species. The BCS phase diagram shows a stable paired superfluid state with coexisting pockets of momentum space with gapless unpaired carriers, similar to the Sarma state in polarized mixtures, but in our case the system is unpolarized. We propose the possible existence of an exotic 'Cooper-pair Bose-metal' phase, which has a gap for single fermion excitations but gapless and uncondensed 'Cooper-pair' excitations residing on a 'Bose surface' in momentum space.

  20. Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

    Energy Technology Data Exchange (ETDEWEB)

    Angermann, Heike, E-mail: angermann@helmholtz-berlin.de

    2014-09-01

    Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D{sub it}(E), and density D{sub it,min} of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly

  1. Microstructure and optical appearance of anodized friction stir processed Al - Metal oxide surface composites

    DEFF Research Database (Denmark)

    Gudla, Visweswara Chakravarthy; Jensen, Flemming; Bordo, Kirill

    2014-01-01

    Multiple-pass friction stir processing (FSP) was employed to impregnate Ti, Y and Ce oxide powders into the surface of an Aluminium alloy. The FSP processed surface composite was subsequently anodized with an aim to develop optical effects in the anodized layer owing to the presence of incorporated...... oxide particles which will influence the scattering of light. This paper presents the investigations on relation between microstructure of the FSP zone and optical appearance of the anodized layer due to incorporation of metal oxide particles and modification of the oxide particles due to the anodizing...

  2. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-10-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  3. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-01-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  4. Surface adhesion properties of graphene and graphene oxide studied by colloid-probe atomic force microscopy

    International Nuclear Information System (INIS)

    Ding Yanhuai; Zhang Ping; Ren Huming; Zhuo Qin; Yang Zhongmei; Jiang Xu; Jiang Yong

    2011-01-01

    Surface adhesion properties are important to various applications of graphene-based materials. Atomic force microscopy is powerful to study the adhesion properties of samples by measuring the forces on the colloidal sphere tip as it approaches and retracts from the surface. In this paper we have measured the adhesion force between the colloid probe and the surface of graphene (graphene oxide) nanosheet. The results revealed that the adhesion force on graphene and graphene oxide surface were 66.3 and 170.6 nN, respectively. It was found the adhesion force was mainly determined by the water meniscus, which was related to the surface contact angle of samples.

  5. Decomposition of SnH{sub 4} molecules on metal and metal–oxide surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ugur, D. [TNO, Stieltjesweg 1, 2628 CK Delft (Netherlands); Delft University of Technology, Department of Materials Science and Engineering, Mekelweg 2, 2628 CD Delft (Netherlands); Storm, A.J.; Verberk, R. [TNO, Stieltjesweg 1, 2628 CK Delft (Netherlands); Brouwer, J.C. [Delft University of Technology, Department of Materials Science and Engineering, Mekelweg 2, 2628 CD Delft (Netherlands); Sloof, W.G., E-mail: w.g.sloof@tudelft.nl [Delft University of Technology, Department of Materials Science and Engineering, Mekelweg 2, 2628 CD Delft (Netherlands)

    2014-01-01

    Atomic hydrogen cleaning is a promising method for EUV lithography systems, to recover from surface oxidation and to remove carbon and tin contaminants. Earlier studies showed, however, that tin may redeposit on nearby surfaces due to SnH{sub 4} decomposition. This phenomenon of SnH{sub 4} decomposition during tin cleaning has been quantified for various metallic and metal-oxide surfaces using X-ray photoelectron spectroscopy (XPS). It was observed that the metal oxide surfaces (TiO{sub 2} and ZrO{sub 2}) were significantly less contaminated than metallic surfaces. Tin contamination due to SnH{sub 4} decomposition can thus be reduced or even mitigated by application of a suitable metal-oxide coating.

  6. Surface effects in metal oxide-based nanodevices

    KAUST Repository

    Lien, Der Hsien

    2015-10-29

    As devices shrink to the nanoscale, surface-to-volume ratio increases and the surface-environment interaction becomes a major factor for affecting device performance. The variation of electronic properties, including the surface band bending, gas chemisorption or photodesorption, native surface defects, and surface roughness, is called "surface effects". Such effects are ambiguous because they can be either negative or beneficial effects, depending on the environmental conditions and device application. This review provides an introduction to the surface effects on different types of nanodevices, offering the solutions to respond to their benefits and negative effects and provides an outlook on further applications regarding the surface effect. This review is beneficial for designing nano-enabled photodetectors, harsh electronics, memories, sensors and transistors via surface engineering.

  7. Surface effects in metal oxide-based nanodevices

    KAUST Repository

    Lien, Der Hsien; Duran Retamal, Jose Ramon; Ke, Jr Jian; Kang, Chen Fang; He, Jr-Hau

    2015-01-01

    As devices shrink to the nanoscale, surface-to-volume ratio increases and the surface-environment interaction becomes a major factor for affecting device performance. The variation of electronic properties, including the surface band bending, gas chemisorption or photodesorption, native surface defects, and surface roughness, is called "surface effects". Such effects are ambiguous because they can be either negative or beneficial effects, depending on the environmental conditions and device application. This review provides an introduction to the surface effects on different types of nanodevices, offering the solutions to respond to their benefits and negative effects and provides an outlook on further applications regarding the surface effect. This review is beneficial for designing nano-enabled photodetectors, harsh electronics, memories, sensors and transistors via surface engineering.

  8. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  9. Persistence of oxidation state III of gold in thione coordination

    Science.gov (United States)

    Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

    2017-05-01

    Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

  10. Heat-induced redistribution of surface oxide in uranium

    International Nuclear Information System (INIS)

    Swissa, E.; Shamir, N.; Bloch, J.; Mintz, M.H.; Israel Atomic Energy Commission, Beersheba. Nuclear Research Center-Negev)

    1990-01-01

    The redistribution of oxygen and uranium metal at the vicinity of the metal-oxide interface of native and grown oxides due to vacuum thermal annealing was studied for uranium and uranium-chromium alloy using Auger depth profiling and metallographic techniques. It was found that uranium metal is segregating out through the uranium oxide layer for annealing temperatures above 450deg C. At the same time the oxide is redistributed in the metal below the oxide-metal interface in a diffusion like process. By applying a diffusion equation of a finite source, the diffusion coefficients for the process were obtained from the oxygen depth profiles measured for different annealing times. An Arrhenius like behavior was found for the diffusion coefficient between 400 and 800deg C. The activation energy obtained was E a =15.4±1.9 kcal/mole and the pre-exponential factor, D 0 =1.1x10 -8 cm 2 /s. An internal oxidation mechanism is proposed to explain the results. (orig.)

  11. Heat-induced redistribution of surface oxide in uranium

    Science.gov (United States)

    Swissa, Eli; Shamir, Noah; Mintz, Moshe H.; Bloch, Joseph

    1990-09-01

    The redistribution of oxygen and uranium metal at the vicinity of the metal-oxide interface of native and grown oxides due to vacuum thermal annealing was studied for uranium and uranium-chromium alloy using Auger depth profiling and metallographic techniques. It was found that uranium metal is segregating out through the uranium oxide layer for annealing temperatures above 450°C. At the same time the oxide is redistributed in the metal below the oxide-metal interface in a diffusion like process. By applying a diffusion equation of a finite source, the diffusion coefficients for the process were obtained from the oxygen depth profiles measured for different annealing times. An Arrhenius like behavior was found for the diffusion coefficient between 400 and 800°C. The activation energy obtained was Ea = 15.4 ± 1.9 kcal/mole and the pre-exponential factor, D0 = 1.1 × 10 -8cm2/ s. An internal oxidation mechanism is proposed to explain the results.

  12. Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma

    Energy Technology Data Exchange (ETDEWEB)

    Vesel, Alenka, E-mail: alenka.vesel@guest.arnes.si [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Mozetic, Miran [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Balat-Pichelin, Marianne [PROMES-CNRS Laboratory, 7 Rue du four solaire, 66120 Font Romeu Odeillo (France)

    2016-11-30

    Highlights: • Oxidized Inconel alloy was exposed to hydrogen at temperatures up to 1500 K. • Oxide reduction in hydrogen plasma started at approximately 1300 K. • AES depth profiling revealed complete reduction of oxides in plasma. • Oxides were not reduced, if the sample was heated just in hydrogen atmosphere. • Surface of reduced Inconel preserved the same composition as the bulk material. - Abstract: Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.

  13. Surface-electronic-state effects in electron emission from the Be(0001) surface

    International Nuclear Information System (INIS)

    Archubi, C. D.; Gravielle, M. S.; Silkin, V. M.

    2011-01-01

    We study the electron emission produced by swift protons impinging grazingly on a Be(0001) surface. The process is described within a collisional formalism using the band-structure-based (BSB) approximation to represent the electron-surface interaction. The BSB model provides an accurate description of the electronic band structure of the solid and the surface-induced potential. Within this approach we derive both bulk and surface electronic states, with these latter characterized by a strong localization at the crystal surface. We found that such surface electronic states play an important role in double-differential energy- and angle-resolved electron emission probabilities, producing noticeable structures in the electron emission spectra.

  14. Surface-electronic-state effects in electron emission from the Be(0001) surface

    Energy Technology Data Exchange (ETDEWEB)

    Archubi, C. D. [Instituto de Astronomia y Fisica del Espacio, casilla de correo 67, sucursal 28, C1428EGA, Buenos Aires (Argentina); Gravielle, M. S. [Instituto de Astronomia y Fisica del Espacio, casilla de correo 67, sucursal 28, C1428EGA, Buenos Aires (Argentina); Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires (Argentina); Silkin, V. M. [Donostia International Physics Center, E-20018 San Sebastian (Spain); Departamento de Fisica de Materiales, Facultad de Ciencias Quimicas, Universidad del Pais Vasco, Apartado 1072, E-20080 San Sebastian (Spain); IKERBASQUE, Basque Foundation for Science, E-48011 Bilbao (Spain)

    2011-07-15

    We study the electron emission produced by swift protons impinging grazingly on a Be(0001) surface. The process is described within a collisional formalism using the band-structure-based (BSB) approximation to represent the electron-surface interaction. The BSB model provides an accurate description of the electronic band structure of the solid and the surface-induced potential. Within this approach we derive both bulk and surface electronic states, with these latter characterized by a strong localization at the crystal surface. We found that such surface electronic states play an important role in double-differential energy- and angle-resolved electron emission probabilities, producing noticeable structures in the electron emission spectra.

  15. Proteomic indicators of oxidation and hydration state in colorectal cancer

    Directory of Open Access Journals (Sweden)

    Jeffrey M. Dick

    2016-07-01

    Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  16. Composition and oxidation state of sulfur in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    A. F. Longo

    2016-10-01

    Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  17. Site-Specific Molecule-Surface Interactions on Metal Oxides

    National Research Council Canada - National Science Library

    Reisler, Hanna

    1998-01-01

    .... At low incident energies rotational and translational temperatures of scattered HCl were equal to the surface temperature, and residence times in the millisecond regime were observed at low surface temperature. When HCl(v=2, J=1...

  18. Local equivalence, surface-code states, and matroids

    International Nuclear Information System (INIS)

    Sarvepalli, Pradeep; Raussendorf, Robert

    2010-01-01

    Recently, Ji et al. disproved the local-unitary-local Clifford (LU-LC) conjecture and showed that the local unitary (LU) and local Clifford (LC) equivalence classes of the stabilizer states are not always the same. Despite the fact that this settles the LU-LC conjecture, a sufficient condition for stabilizer states that violate the LU-LC conjecture is not known. In this paper, we investigate further the properties of stabilizer states with respect to local equivalence. Our first result shows that there exist infinitely many stabilizer states that violate the LU-LC conjecture. In particular, we show that for all numbers of qubits n≥28, there exist distance-two stabilizer states which are counterexamples to the LU-LC conjecture. We prove that, for all odd n≥195, there exist stabilizer states with distance greater than two that are LU equivalent but not LC equivalent. Two important classes of stabilizer states that are of great interest in quantum computation are the cluster states and stabilizer states of the surface codes. We show that, under some minimal restrictions, both these classes of states preclude any counterexamples. In this context, we also show that the associated surface codes do not have any encoded non-Clifford transversal gates. We characterize the Calderbank-Shor-Steane (CSS) surface-code states in terms of a class of minor closed binary matroids. In addition to making a connection to an important open problem in binary matroid theory, this characterization does in some cases provide an efficient test for CSS states that are not counterexamples.

  19. The law of corresponding states and surface tension of metals

    International Nuclear Information System (INIS)

    Digilov, R.

    2001-01-01

    Full Text: Surface tension of liquid metals is one of fundamental and most important quantities in theory and practice of material processing and its temperature dependence leads to the well-known Marangoni convection. Although currently methods are sufficiently precise to measure the surface tension, there are uncertainties in experimental data and its temperature dependence mainly due to impurity, which even a trace of it strongly affects the results of measurements. The theoretical treatment from the first principles is unwieldy and not always permits one to calculate the surface tension with certainty. Another active research field deals with empirical correlation between the surface tension and bulk thermodynamic properties, which we interpret as a simple consequence of the law of corresponding states. In order to relate the surface tension and to bulk properties of liquid metals the reduced formula is derived by scaling with the melting point T m (0) at p = 0 and atomic volume Ω 0 2/3 at T = 0 K as macroscopic parameters for scaling ε and a characterizing the interatomic potential in metals. The reduced surface tension and the reduced surface entropy obtained in high temperature limit are discussed and compared with the experiment. The reduced temperature coefficient of the surface tension found is a universal constant for the metals of the same structure. It is shown that pressure dependence of the surface tension, so called baric coefficient of the surface tension, can be described by pressure dependence of scaling parameters T m (p) and Ω 0 (p). (author)

  20. Oxidation behaviour of cast aluminium matrix composites with Ce surface coatings

    International Nuclear Information System (INIS)

    Pardo, A.; Merino, M.C.; Arrabal, R.; Feliu, S.; Viejo, F.

    2007-01-01

    The oxidation behaviour of SiC-reinforced aluminium matrix composites (A3xx.x/SiCp) has been studied after Ce-based treatments. Kinetics data of oxidation process were obtained from gravimetric tests performed at different temperatures (350, 425 and 500 o C). The nature of the oxidation layer was analyzed by scanning electron and atomic force microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and X-ray diffraction. The extent of oxidation degradation in untreated composites was preferentially localized in matrix/SiCp interfaces favouring the MgO formation. Ce coatings favoured a uniform oxidation of the composite surface with MgAl 2 O 4 spinel formation. This oxide increased the surface hardness of the materials

  1. Charge state of ions scattered by metal surface

    International Nuclear Information System (INIS)

    Kishinevsky, L.M.; Parilis, E.S.; Verleger, V.K.

    1976-01-01

    A model for description of charge distributions for scattering of heavy ions in the keV region, on metal surfaces developing and improving the method of Van der Weg and Bierman, and taking into account the connection between the ion charge state and scattering kinematics, is proposed. It is shown that multiple charged particles come from ions with a vacancy in the inner shell while the outer shell vacancies give only single charged ions and neutrals. The approximately linear increase of degree of ionization with normal velocity, and the non-monotonic charge dependence of the energy spectrum established by Chicherov and Buck et al is explained by considering irreversible neutralization in the depth of the metal, taking into account the connection of the charge state with the shape of trajectory and its location relative to the metal surface. The dependence of charge state on surface structure is discussed. Some new experiments are proposed. (author)

  2. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Dyatkin, Boris [Drexel Univ., Philadelphia, PA (United States); Zhang, Yu [Vanderbilt Univ., Nashville, TN (United States); Mamontov, Eugene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kolesnikov, Alexander I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cheng, Yongqiang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meyer, III, Harry M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cummings, Peter T. [Vanderbilt Univ., Nashville, TN (United States); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

    2016-04-07

    Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces and enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.

  3. Oxidation states of Fe and Ti in blue sapphire

    International Nuclear Information System (INIS)

    Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

    2016-01-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

  4. Growth of micrometric oxide layers to explore laser decontamination of metallic surfaces

    OpenAIRE

    Carvalho Luisa; Pacquentin Wilfried; Tabarant Michel; Maskrot Hicham; Semerok Alexandre

    2017-01-01

    The nuclear industry produces a wide range of radioactive waste in terms of hazard level, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop safe techniques for dismantling and for decontamination, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. In this paper we propose a method for the creation of oxide layers on stai...

  5. Growth of micrometric oxide layers for the study of metallic surfaces decontamination by laser

    OpenAIRE

    Carvalho Luisa; Pacquentin Wilfried; Tabarant Michel; Maskrot Hicham; Semerok Alexandre

    2017-01-01

    The nuclear industry produces a wide range of radioactive waste in term of level of hazard, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop techniques for dismantling and for decontamination in a safe way, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. We propose a method of formation of oxide layer on stainless st...

  6. Adsorption and revaporisation studies on iodine oxide aerosols deposited on containment surface materials in LWR

    Energy Technology Data Exchange (ETDEWEB)

    Tietze, S.; Foreman, M.R.StJ.; Ekberg, C. [Chalmers Univ. of Technology, Goeteborg (Sweden); Kaerkelae, T.; Auvinen, A.; Tapper, U.; Lamminmaeki, S.; Jokiniemi, J. [VTT Technical Research Centre of Finland, Espoo (Finland)

    2012-12-15

    During a hypothetical severe nuclear accident, the radiation field will be very high in the nuclear reactor containment building. As a result gaseous radiolysis products will be formed. Elemental iodine can react in the gaseous phase with ozone to form solid iodine oxide aerosol particles (iodine oxide). Within the AIAS (Adsorption of Iodine oxide Aerosols on Surfaces) project the interactions of iodine oxide (IOx) aerosols with common containment surface materials were investigated. Common surface materials in Swedish and Finnish LWRs are Teknopox Aqua V A paint films and metal surfaces such as Cu, Zn, Al and SS, as well as Pt and Pd surfaces from hydrogen recombiners. Non-radioactive and {sup 131}I labelled iodine oxide aerosols were produced with the EXSI CONT facility from elemental iodine and ozone at VTT Technical Research Centre of Finland. The iodine oxide deposits were analysed with microscopic and spectroscopic measurement techniques to identify the kind of iodine oxide formed and if a chemical conversion on the different surface materials occurs. The revaporisation behaviour of the deposited iodine oxide aerosol particles from the different surface materials was studied under the influence of heat, humidity and gamma irradiation at Chalmers University of Technology, Sweden. Studies on the effects of humidity were performed using the FOMICAG facility, while heat and irradiation experiments were performed in a thermostated heating block and with a gammacell 22 having a dose rate of 14 kGy/h. The revaporisation losses were measured using a HPGe detector. The revaporisated {sup 131}I species from the surfaces were chemically tested for elemental iodine formation. The parameter dominating the degradation of the produced iodine oxide aerosols was humidity. Cu and Zn surfaces were found to react with iodine from the iodine oxide aerosols to form iodides, while no metal iodides were detected for Al and SS samples. Most of the iodine oxide aerosols are assumed to

  7. Adsorption and revaporisation studies on iodine oxide aerosols deposited on containment surface materials in LWR

    International Nuclear Information System (INIS)

    Tietze, S.; Foreman, M.R.StJ.; Ekberg, C.; Kaerkelae, T.; Auvinen, A.; Tapper, U.; Lamminmaeki, S.; Jokiniemi, J.

    2012-12-01

    During a hypothetical severe nuclear accident, the radiation field will be very high in the nuclear reactor containment building. As a result gaseous radiolysis products will be formed. Elemental iodine can react in the gaseous phase with ozone to form solid iodine oxide aerosol particles (iodine oxide). Within the AIAS (Adsorption of Iodine oxide Aerosols on Surfaces) project the interactions of iodine oxide (IOx) aerosols with common containment surface materials were investigated. Common surface materials in Swedish and Finnish LWRs are Teknopox Aqua V A paint films and metal surfaces such as Cu, Zn, Al and SS, as well as Pt and Pd surfaces from hydrogen recombiners. Non-radioactive and 131 I labelled iodine oxide aerosols were produced with the EXSI CONT facility from elemental iodine and ozone at VTT Technical Research Centre of Finland. The iodine oxide deposits were analysed with microscopic and spectroscopic measurement techniques to identify the kind of iodine oxide formed and if a chemical conversion on the different surface materials occurs. The revaporisation behaviour of the deposited iodine oxide aerosol particles from the different surface materials was studied under the influence of heat, humidity and gamma irradiation at Chalmers University of Technology, Sweden. Studies on the effects of humidity were performed using the FOMICAG facility, while heat and irradiation experiments were performed in a thermostated heating block and with a gammacell 22 having a dose rate of 14 kGy/h. The revaporisation losses were measured using a HPGe detector. The revaporisated 131 I species from the surfaces were chemically tested for elemental iodine formation. The parameter dominating the degradation of the produced iodine oxide aerosols was humidity. Cu and Zn surfaces were found to react with iodine from the iodine oxide aerosols to form iodides, while no metal iodides were detected for Al and SS samples. Most of the iodine oxide aerosols are assumed to be

  8. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    International Nuclear Information System (INIS)

    Brymora, Katarzyna; Fouineau, Jonathan; Eddarir, Asma; Chau, François; Yaacoub, Nader; Grenèche, Jean-Marc; Pinson, Jean; Ammar, Souad; Calvayrac, Florent

    2015-01-01

    Combining ab initio modeling and 57 Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces

  9. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Science.gov (United States)

    Brymora, Katarzyna; Fouineau, Jonathan; Eddarir, Asma; Chau, François; Yaacoub, Nader; Grenèche, Jean-Marc; Pinson, Jean; Ammar, Souad; Calvayrac, Florent

    2015-11-01

    Combining ab initio modeling and 57Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal-oxygen-carbon bonding and not a metal-carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  10. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Brymora, Katarzyna [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Fouineau, Jonathan; Eddarir, Asma; Chau, François [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Yaacoub, Nader; Grenèche, Jean-Marc [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Pinson, Jean; Ammar, Souad [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Calvayrac, Florent, E-mail: florent.calvayrac@univ-lemans.fr [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France)

    2015-11-15

    Combining ab initio modeling and {sup 57}Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  11. Metastable states of plasma particles close to a charged surface

    Energy Technology Data Exchange (ETDEWEB)

    Shavlov, A. V., E-mail: shavlov@ikz.ru [The Institute of the Earth Cryosphere, RAS Siberian branch, 625000, P.O. 1230, Tyumen (Russian Federation); Tyumen State Oil and Gas University, 38, Volodarskogo St., 625000, Tyumen (Russian Federation); Dzhumandzhi, V. A. [The Institute of the Earth Cryosphere, RAS Siberian branch, 625000, P.O. 1230, Tyumen (Russian Federation)

    2015-09-15

    The free energy of the plasma particles and the charged surface that form an electroneutral system is calculated on the basis of the Poisson-Boltzmann equation. It is shown that, owing to correlation of light plasma particles near the charged surface and close to heavy particles of high charge, there can be metastable states in plasma. The corresponding phase charts of metastable states of the separate components of plasma, and plasma as a whole, are constructed. These charts depend on temperature, the charge magnitude, the size of the particles, and the share of the charge of the light carriers out of the total charge of the plasma particles.

  12. N-Oxide-N-oxide interactions and Cl...Cl halogen bonds in pentachloropyridine N-oxide: the many-body approach to interactions in the crystal state.

    Science.gov (United States)

    Wzgarda-Raj, Kinga; Rybarczyk-Pirek, Agnieszka J; Wojtulewski, Sławomir; Palusiak, Marcin

    2018-02-01

    Pentachloropyridine N-oxide, C 5 Cl 5 NO, crystallizes in the monoclinic space group P2 1 /c. In the crystal structure, molecules are linked by C-Cl...Cl halogen bonds into infinite ribbons extending along the crystallographic [100] direction. These molecular aggregates are further stabilized by very short intermolecular N-oxide-N-oxide interactions into herringbone motifs. Computations based on quantum chemistry methods allowed for a more detailed description of the N-oxide-N-oxide interactions and Cl...Cl halogen bonds. For this purpose, Hirshfeld surface analysis and the many-body approach to interaction energy were applied.

  13. Surface chemistry of metals and their oxides in high temperature water

    International Nuclear Information System (INIS)

    Tomlinson, M.

    1975-01-01

    Examination of oxide and metal surfaces in water at high temperature by a broad spectrum of techniques is bringing understanding of corrosion product movement and alleviation of activity transport in CANDU-type reactor primary coolant circuits. (Author)

  14. Intrinsic stress evolution during amorphous oxide film growth on Al surfaces

    International Nuclear Information System (INIS)

    Flötotto, D.; Wang, Z. M.; Jeurgens, L. P. H.; Mittemeijer, E. J.

    2014-01-01

    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 2 O 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

  15. Modification of implant material surface properties by means of oxide nano-structured coatings deposition

    Science.gov (United States)

    Safonov, Vladimir; Zykova, Anna; Smolik, Jerzy; Rogowska, Renata; Lukyanchenko, Vladimir; Kolesnikov, Dmitrii

    2014-08-01

    The deposition of functional coatings on the metal surface of artificial joints is an effective way of enhancing joint tribological characteristics. It is well-known that nanostructured oxide coatings have specific properties advantageous for future implant applications. In the present study, we measured the high hardness parameters, the adhesion strength and the low friction coefficient of the oxide magnetron sputtered coatings. The corrosion test results show that the oxide coating deposition had improved the corrosion resistance by a factor of ten for both stainless steel and titanium alloy substrates. Moreover, the hydrophilic nature of coated surfaces in comparison with the metal ones was investigated in the tensiometric tests. The surfaces with nanostructured oxide coatings demonstrated improved biocompatibility for in vitro and in vivo tests, attributed to the high dielectric constants and the high values of the surface free energy parameters.

  16. Surface electronic and structural properties of nanostructured titanium oxide grown by pulsed laser deposition

    NARCIS (Netherlands)

    Fusi, M.; Maccallini, E.; Caruso, T.; Casari, C. S.; Bassi, A. Li; Bottani, C. E.; Rudolf, P.; Prince, K. C.; Agostino, R. G.

    Titanium oxide nanostructured thin films synthesized by pulsed laser deposition (PLD) were here characterized with a multi-technique approach to investigate the relation between surface electronic, structural and morphological properties. Depending on the growth parameters, these films present

  17. Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

    Science.gov (United States)

    Becker, J S; Breuer, U; Westheide, J; Saprykin, A I; Holzbrecher, H; Nickel, H; Dietze, H J

    1996-06-01

    For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

  18. Emissions of nitrous oxide and methane from surface and ground waters in Germany

    International Nuclear Information System (INIS)

    Hiessl, H.

    1993-01-01

    The paper provides a first estimation of the contribution of inland freshwater systems (surface waters and ground waters) to the emission of the greenhouse gases nitrous oxide and methane in Germany. These amounts are compared to other main sources for the emission of nitrous oxide and methane. (orig.) [de

  19. Surface crack testing - state of technique and trends in development

    International Nuclear Information System (INIS)

    1991-01-01

    This Seminar contains 12 lectures on the following subjects: State of technique in magnetic powder testing (K. Goebbels); Recognisability of faults and probability of faults in surface crack testing (W. Morgner); Requirements for picture processing systems for proving and assessing crack indications (M. Stadthaus); Possibilities and limits of automatic crack recognition in magnetic powder testing (V. Deutsch); Development of equipment for eddy current testing (M. Junger); Signal processing - a way of improving the recognisability of faults in eddy current testing (R. Becker); Methods of testing steel products for surface faults and their practical limits of fault recognisability (D. Thiery); Surface crack testing in pipe manufacture (R. Pawelletz); Surface crack testing in powerstation construction (L. v. Bernus); Trends in automation in surface crack testing (G. Maier); Eddy current testing in engine construction (E. Dickhaut); Eddy current testing in aircraft repair (F. Schur). (orig.) [de

  20. Enhanced magnetic properties of Fe soft magnetic composites by surface oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Guoliang; Wu, Chen, E-mail: chen_wu@zju.edu.cn; Yan, Mi, E-mail: mse_yanmi@zju.edu.cn

    2016-02-01

    Fe soft magnetic composites (SMCs) with low core loss were fabricated via surface oxidation of the Fe powders by H{sub 2}O and O{sub 2} at elevated temperatures. Surface oxidation prevents magnetic dilution due to the formation of the ferromagnetic iron oxide coating layer, giving rise to high magnetic flux density and effective permeability of the SMCs compared with those fabricated with traditional phosphate coating. Mechanism of the oxidation process has been investigated where Fe{sub 3}O{sub 4} forms by reactions of Fe with H{sub 2}O and O{sub 2}. The Fe{sub 3}O{sub 4} coating layer tends to convert into γ-Fe{sub 2}O{sub 3} with increased oxidation temperature and time. By controlling composition of the coating layer, low core loss of 688.9 mW/cm{sup 3} (measured at 50 mT and 100 kHz) and higher effective permeability of 88.3 can be achieved for the Fe SMCs. - Highlights: • Surface oxidation as a new method to fabricate Fe Soft magnetic composite (SMCs). • Oxidation mechanism revealed where Fe reacts with H2O and O2 at high temperatures. • Evolution of the iron oxide coating with growth temperature and time investigated. • The iron oxide insulation coating results in improved magnetic performance.

  1. NRC Information No. 88-98: Electrical relay degradation caused by oxidation of contact surfaces

    International Nuclear Information System (INIS)

    Rossi, C.E.

    1992-01-01

    The NRC staff was recently informed by Clinton Power Station that a reactor scram on June 24, 1988, was caused by an electrical relay failure from oxide buildup on relay contact surfaces. Other information on relay failure from contact oxidation indicates that this problem may be more prevalent than previously thought. For example, a July 17, 1988, 10 CFR Part 21 report from Palo Verde, Unit 2, reported relay failures from contact oxidation that were due to the low current application of the relays. The relay contact surfaces in both of these examples are silver-nickel alloys, and both applications were for low current (i.e., milli-ampere current). Electrical relay contacts made of silver-nickel or silver-cadmium alloys will oxidize (tarnish) when used in low current applications because of the absence of contact surface sparking from the typical relay contact ''making and breaking'' functions. The sparking in the contact surfaces promotes a self-cleaning mechanism that reduces the tarnish buildup on the silver-nickel or silver-cadmium contacts. Discussions with one relay manufacturer revealed that the normal industry practice for low current circuit applications is either to use a contact surface material that will not oxidize or to compensate for the oxidation by increased maintenance activities to ensure reliability. The applied voltage may also influence contact oxidation

  2. Preserving half-metallic surface states in Cr O2 : Insights into surface reconstruction rules

    Science.gov (United States)

    Deng, Bei; Shi, X. Q.; Chen, L.; Tong, S. Y.

    2018-04-01

    The issue of whether the half-metallic (HM) nature of Cr O2 could be retained at its surface has been a standing problem under debate for a few decades, but until now is still controversial. Here, based on the density functional theory calculations we show, in startling contrast to the previous theoretical understandings, that the surfaces of Cr O2 favorably exhibit a half-metallic-semiconducting (SmC) transition driven by means of a surface electronic reconstruction largely attributed to the participation of the unexpected local charge carriers (LCCs), which convert the HM double exchange surface state into a SmC superexchange state and in turn, stabilize the surface as well. On the basis of the LCCs model, a new insight into the surface reconstruction rules is attained. Our novel finding not only provided an evident interpretation for the widely observed SmC character of Cr O2 surface, but also offered a novel means to improve the HM surface states for a variety of applications in spintronics and superconductors, and promote the experimental realization of the quantum anomalous Hall effect in half-metal based systems.

  3. Electrochemical Properties of High Surface Area Vanadium Oxide Aerogels

    National Research Council Canada - National Science Library

    Dong, Winny

    2001-01-01

    .... Traditional composite electrode structures have prevented truly quantitative analysis of surface area effects in nanoscale battery materials, as well as a study of their innate electrochemical behavior...

  4. Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2017-01-15

    Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

  5. Surface characteristics of coated polyester fabric with reduced graphene oxide and polypyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Berendjchi, Amirhosein [Department of Textile Engineering, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Khajavi, Ramin, E-mail: khajavi@azad.ac.ir [Nano Technology Research Center, South Tehran Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Yousefi, Ali Akbar [Faculty of Polymer Processing, Iran Polymer and Petrochemical Institute, Tehran (Iran, Islamic Republic of); Yazdanshenas, Mohammad Esmail [Department of Textile Engineering, Yazd Branch, Islamic Azad University, Yazd (Iran, Islamic Republic of)

    2016-03-30

    Graphical abstract: - Highlights: • PET in form of film or membrane is hydrophobic and its wetting behavior follows the Wenzel wetting theory. In the form of textile materials it shows hydrophilicity. • rGO coated PET fabric shows hydrophobicity and its wetting behavior places between Wenzel and Cassie–Baxter models. • PET coated fabric by PPy shows superhydrophobicity and its wetting behavior is consistence with Cassie–Baxter model. • Due to oxidation of the rGO during in situ synthesis of PPy the rGO–PPy coated PET shows hydrophilicity. - Abstract: In this study, the influence of coating polyethylene terephthalate (PET) fabric with reduced graphene oxide (rGO) and polypyrrole (PPy), individually or in combination (rGO–PPy), on surface chemistry and roughness (focusing on wetting behavior), were analyzed systematically. Characterization was carried out by observing the topography (atomic force microscopy – AFM) and stating surface analysis (X-ray photoelectron spectroscopy – XPS), contact angles (goniometry), water shedding angles, and surface energy values of the samples. The results showed that the contact angles of pristine (uncoated), GO and rGO–PPy coated samples were 0°, while it was 92°, 123° and 151° for hot pressed (2nd pristine sample), rGO and PPy samples, respectively. A zero contact angle for PET sample was due to its wicking ability. Results were interpreted with Young, Wenzel and Cassie Baxter equations. It was found that PPy coated samples were consistent with Cassie–Baxter equation, while rGO placed between Wenzel and Cassie–Baxter wetting models.

  6. Surface modification of indium tin oxide for direct writing of silver nanoparticulate ink micropatterns

    International Nuclear Information System (INIS)

    Vunnam, Swathi; Ankireddy, Krishnamraju; Kellar, Jon; Cross, William

    2013-01-01

    Surface treatment techniques were deployed to alter the surface of indium tin oxide (ITO) samples to attain a favorable interface between printed nano-inks and ITO surface. Surface free energy components of treated ITO substrates were calculated for each treatment using the van Oss–Chaudhury–Good method. The surface treatments of ITO changed the Lifshitz–van der Waals and Lewis acid–base components, and contact angle hysteresis significantly. Among all the surface treatments, air plasma treated samples showed high polar in nature, whereas dodecyltrichlorosilane self-assembled monolayer treated sample showed the lowest. In addition to the polarity and homogeneity, the surface roughness of the ITO was studied with respect to the surface treatment. Silver nanoparticulate ink was printed on treated ITO surfaces using aerosol jet printing system. Printed silver nano-ink line width and morphology strongly depended on the surface treatment of the ITO, ink properties and printing parameters. - Highlights: ► Surface treatments on indium tin oxide (ITO) altered its surface free energy. ► Surface free energies were studied in terms of acid–base components. ► ITO surface morphology and roughness were changed with the surface treatment. ► Silver ink was printed on treated ITO samples using aerosol jet printing system. ► Line widths of printed patterns clearly depended on the surface free energy of ITO

  7. Surface modification of indium tin oxide for direct writing of silver nanoparticulate ink micropatterns

    Energy Technology Data Exchange (ETDEWEB)

    Vunnam, Swathi, E-mail: swathi.vunnam@mines.sdsmt.edu [Nanoscience and Nanoengineering Department, South Dakota School of Mines and Technology, Rapid City, SD-57701 (United States); Ankireddy, Krishnamraju; Kellar, Jon; Cross, William [Department of Materials and Metallurgical Engineering, South Dakota School of Mines and Technology, Rapid City, SD-57701 (United States)

    2013-03-01

    Surface treatment techniques were deployed to alter the surface of indium tin oxide (ITO) samples to attain a favorable interface between printed nano-inks and ITO surface. Surface free energy components of treated ITO substrates were calculated for each treatment using the van Oss–Chaudhury–Good method. The surface treatments of ITO changed the Lifshitz–van der Waals and Lewis acid–base components, and contact angle hysteresis significantly. Among all the surface treatments, air plasma treated samples showed high polar in nature, whereas dodecyltrichlorosilane self-assembled monolayer treated sample showed the lowest. In addition to the polarity and homogeneity, the surface roughness of the ITO was studied with respect to the surface treatment. Silver nanoparticulate ink was printed on treated ITO surfaces using aerosol jet printing system. Printed silver nano-ink line width and morphology strongly depended on the surface treatment of the ITO, ink properties and printing parameters. - Highlights: ► Surface treatments on indium tin oxide (ITO) altered its surface free energy. ► Surface free energies were studied in terms of acid–base components. ► ITO surface morphology and roughness were changed with the surface treatment. ► Silver ink was printed on treated ITO samples using aerosol jet printing system. ► Line widths of printed patterns clearly depended on the surface free energy of ITO.

  8. Analysis of anti-condensation mechanism on superhydrophobic anodic aluminum oxide surface

    International Nuclear Information System (INIS)

    Wu, Yanpeng; Zhang, Chaoying

    2013-01-01

    Wetting theory about superhydrophobic surfaces reveals that hydrophobicity of surfaces has great relationship with surface roughness and surface free energy. Adopt electrochemical plus fluorine silane modified method to prepare superhydrophobic surface on anodic aluminum oxide surface, which not only enhances surface roughness, but also reduces surface free energy, even the static contact angle can reach 159.2° and anti-condensation is authenticated. Based on the experimental findings, analyze the reason of anti-condensation on superhydrophobic surfaces: one is that the density of droplets formed on superhydrophobic surfaces is low and the number of droplets is little; the other is bigger static contact angle and smaller rolling angle on superhydrophobic surfaces make droplets easy to detach on smaller tilt angle. This research can solve some condensation problems of equipment using in HVAC systems, such as heat exchangers in air conditioning system, cold radiation boards, air supply outlets, and so on. Highlights: • Prepare superhydrophobic surface on anodic aluminum oxide surface. • Analyze the reason of anti-condensation on superhydrophobic surfaces. • The density of droplets formed on superhydrophobic surfaces is low. • Droplets on superhydrophobic surfaces are easy to detach. • This research can solve some problems of equipment using in HVAC systems

  9. Determination of the oxidation states of metals and metalloids: An analytical review

    Science.gov (United States)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  10. Trends in Metal Oxide Stability for Nanorods, Nanotubes, and Surfaces

    DEFF Research Database (Denmark)

    Mowbray, Duncan; Martinez, Jose Ignacio; Vallejo, Federico Calle

    2011-01-01

    The formation energies of nanostructures play an important role in determining their properties, including their catalytic activity. For the case of 15 different rutile and 8 different perovskite metal oxides, we used density functional theory (DFT) to calculate the formation energies of (2,2) na...

  11. DFT studies of elemental mercury oxidation mechanism by gaseous advanced oxidation method: Co-interaction with H2O2 on Fe3O4 (111) surface

    Science.gov (United States)

    Zhou, Changsong; Song, Zijian; Zhang, Zhiyue; Yang, Hongmin; Wang, Ben; Yu, Jie; Sun, Lushi

    2017-12-01

    Density functional theory calculations have been carried out for H2O2 and Hg0 co-interaction on Fe3O4 (111) surface. On the Fetet1-terminated Fe3O4 (111) surface, the most favored configurations are H2O2 decomposition and produce two OH groups, which have strong interaction with Hg atom to form an OHsbnd Hgsbnd OH intermediate. The adsorbed OHsbnd Hgsbnd OH is stable and hardly detaches from the catalyst surface due to the highly endothermic process. A large amount of electron transfer has been found from Hg to the produced OH groups and has little irreversible effect on the Fe3O4 (111) surface. On the Feoct2-terminated Fe3O4 (111) surface, the Feoct2 site is more active than Fetet1 site. H2O2 decomposition and Hg0 oxidation processes are more likely to occur due to that the Feoct2 site both contains Fe2+ and Fe3+ cations. The calculations reveal that Hg0 oxidation by the OH radical produced from H2O2 is energetically favored. Additionally, Hg0 and H2O2 co-interaction mechanism on the Fe3O4 (111) interface has been investigated on the basis of partial local density of state calculation.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

    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.

  13. Quantum beats from the coherent interaction of hole states with surface state in near-surface quantum well

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Salahuddin; Jayabalan, J., E-mail: jjaya@rrcat.gov.in; Chari, Rama; Pal, Suparna [Laser Physics Applications Section, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India); Porwal, Sanjay; Sharma, Tarun Kumar; Oak, S. M. [Semiconductor Physics and Devices Lab., Solid State Laser Division, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India)

    2014-08-18

    We report tunneling assisted beating of carriers in a near-surface single GaAsP/AlGaAs quantum well using transient reflectivity measurement. The observed damped oscillating signal has a period of 120 ± 6 fs which corresponds to the energy difference between lh1 and hh2 hole states in the quantum well. Comparing the transient reflectivity signal at different photon energies and with a buried quantum well sample, we show that the beating is caused by the coherent coupling between surface state and the hole states (lh1 and hh2) in the near-surface quantum well. The dependence of decay of coherence of these tunneling carriers on the excitation fluence is also reported. This observation on the coherent tunneling of carrier is important for future quantum device applications.

  14. Quantum beats from the coherent interaction of hole states with surface state in near-surface quantum well

    International Nuclear Information System (INIS)

    Khan, Salahuddin; Jayabalan, J.; Chari, Rama; Pal, Suparna; Porwal, Sanjay; Sharma, Tarun Kumar; Oak, S. M.

    2014-01-01

    We report tunneling assisted beating of carriers in a near-surface single GaAsP/AlGaAs quantum well using transient reflectivity measurement. The observed damped oscillating signal has a period of 120 ± 6 fs which corresponds to the energy difference between lh1 and hh2 hole states in the quantum well. Comparing the transient reflectivity signal at different photon energies and with a buried quantum well sample, we show that the beating is caused by the coherent coupling between surface state and the hole states (lh1 and hh2) in the near-surface quantum well. The dependence of decay of coherence of these tunneling carriers on the excitation fluence is also reported. This observation on the coherent tunneling of carrier is important for future quantum device applications.

  15. Surfactant-assisted growth of anodic nanoporous niobium oxide with a grained surface

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Jeong Eun [Department of Chemical Engineering, Inha University, 253 Yonghyun Dong, Nam-Gu, Incheon 402-751 (Korea, Republic of); Choi, Jinsub, E-mail: jinsub@inha.ac.k [Department of Chemical Engineering, Inha University, 253 Yonghyun Dong, Nam-Gu, Incheon 402-751 (Korea, Republic of)

    2010-07-15

    Nanoporous niobium oxide film with a maximum thickness of 520 nm was prepared by anodizing niobium in a mixture of 1 wt% HF, 1 M H{sub 3}PO{sub 4}, and a small amount of Sodium Dodecyl Sulfate (SDS) surfactant. The porosity of the anodic niobium oxide prepared without SDS is irregular with the surface of the oxide suggesting a grained surface pattern rather than an ordered porous structure. A proper amount of SDS addition can prepare a pore arrangement with stripe patterns. The pore depth and surface pattern were strongly affected by the concentration of SDS and bath temperature. We found that the addition of SDS surfactant facilitated improvement in the chemical resistance of niobium oxide, leading to the formation of pores with a longer length compared to those prepared without a SDS surfactant. This can be in part ascribed to the protection of the surface by the physical adsorption of SDS on the surface due to a charge-charge interaction and be in part attributed to the formation of Nb=O bonding on the outermost oxide layer by SDS. When anodization was carried out for 4 h, the surface dissolution of niobium oxide was observed, which means that the maximum tolerance time against chemical dissolution was less than 4 h.

  16. Oxidizing dissolution of spent MOX47 fuel subjected to water radiolysis: Solution chemistry and surface characterization by Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Jegou, C., E-mail: christophe.jegou@cea.f [Commissariat a l' Energie Atomique (CEA), Marcoule Reasearch Center, B.P. 17171, F-30207 Bagnols-sur-Ceze Cedex (France); Caraballo, R.; De Bonfils, J.; Broudic, V.; Peuget, S. [Commissariat a l' Energie Atomique (CEA), Marcoule Reasearch Center, B.P. 17171, F-30207 Bagnols-sur-Ceze Cedex (France); Vercouter, T. [Commissariat a l' Energie Atomique (CEA), Saclay Reasearch Center, B.P. 11, F-91191 Gif-sur-Yvette Cedex (France); Roudil, D. [Commissariat a l' Energie Atomique (CEA), Marcoule Reasearch Center, B.P. 17171, F-30207 Bagnols-sur-Ceze Cedex (France)

    2010-04-01

    The mechanisms of oxidizing dissolution of spent MOX fuel (MIMAS TU2 (registered) ) subjected to water radiolysis were investigated experimentally by leaching spent MOX47 fuel samples in pure water at 25 deg. C under different oxidizing conditions (with and without external gamma irradiation); the leached surfaces were characterized by Raman spectroscopy. The highly oxidizing conditions resulting from external gamma irradiation significantly increased the concentration of plutonium (Pu(V)) and uranium (U(VI)) compared with a benchmark experiment (without external irradiation). The oxidation behavior of the plutonium-enriched aggregates differed significantly from that of the UO{sub 2} matrix after several months of leaching in water under gamma irradiation. The plutonium in the aggregates appears to limit fuel oxidation. The only secondary phases formed and identified to date by Raman spectroscopy are uranium peroxides that generally precipitate on the surface of the UO{sub 2} grains. Concerning the behavior of plutonium, solution analysis results appear to be compatible with a conventional explanation based on an equilibrium with a Pu(OH){sub 4(am)} phase. The fission product release - considered as a general indicator of matrix alteration - from MOX47 fuel also increases under external gamma irradiation and a change in the leaching mode is observed. Diffusive leaching was clearly identified, coinciding with the rapid onset of steady-state actinide concentrations in the bulk solution.

  17. Passivation of surface states of α-Fe2O3(0001) surface by deposition of Ga2O3 overlayers: A density functional theory study.

    Science.gov (United States)

    Ulman, Kanchan; Nguyen, Manh-Thuong; Seriani, Nicola; Gebauer, Ralph

    2016-03-07

    There is a big debate in the community regarding the role of surface states of hematite in the photoelectrochemical water splitting. Experimental studies on non-catalytic overlayers passivating the hematite surface states claim a favorable reduction in the overpotential for the water splitting reaction. As a first step towards understanding the effect of these overlayers, we have studied the system Ga2O3 overlayers on hematite (0001) surfaces using first principles computations in the PBE+U framework. Our computations suggest that stoichiometric terminations of Ga2O3 overlayers are energetically more favored than the bare surface, at ambient oxygen chemical potentials. Energetics suggest that the overlayers prefer to grow via a layer-plus-island (Stranski-Krastanov) growth mode with a critical layer thickness of 1-2 layers. Thus, a complete wetting of the hematite surface by an overlayer of gallium oxide is thermodynamically favored. We establish that the effect of deposition of the Ga2O3 overlayers on the bare hematite surface is to passivate the surface states for the stoichiometric termination. For the oxygen terminated surface which is the most stable termination under photoelectrochemical conditions, the effect of deposition of the Ga2O3 overlayer is to passivate the hole-trapping surface state.

  18. Manganese oxidation state mediates toxicity in PC12 cells

    International Nuclear Information System (INIS)

    Reaney, S.H.; Smith, D.R.

    2005-01-01

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

  19. Friction stir processed Al - Metal oxide surface composites: Anodization and optical appearance

    DEFF Research Database (Denmark)

    Gudla, Visweswara Chakravarthy; Jensen, Flemming; Canulescu, Stela

    2014-01-01

    Multiple-pass friction stir processing (FSP) was employed to impregnate metal oxide (TiO2, Y2O3 and CeO2) particles into the surface of an Aluminium alloy. The surface composites were then anodized in a sulphuric acid electrolyte. The effect of anodizing parameters on the resulting optical...... dark to greyish white. This is attributed to the localized microstructural and morphological differences around the metal oxide particles incorporated into the anodic alumina matrix. The metal oxide particles in the FSP zone electrochemically shadowed the underlying Al matrix and modified the local...

  20. Dye-Sensitized Solar Cells Based on High Surface Area Nanocrystalline Zinc Oxide Spheres

    Directory of Open Access Journals (Sweden)

    Pavuluri Srinivasu

    2011-01-01

    Full Text Available High surface area nanocrystalline zinc oxide material is fabricated using mesoporous nanostructured carbon as a sacrificial template through combustion process. The resulting material is characterized by XRD, N2 adsorption, HR-SEM, and HR-TEM. The nitrogen adsorption measurement indicates that the materials possess BET specific surface area ca. 30 m2/g. Electron microscopy images prove that the zinc oxide spheres possess particle size in the range of 0.12 μm–0.17 μm. The nanocrystalline zinc oxide spheres show 1.0% of energy conversion efficiency for dye-sensitized solar cells.

  1. Pt-Si Bifunctional Surfaces for CO and Methanol Electro-Oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia A.; Han, Binghong; Jensen, Jens Oluf

    2015-01-01

    and storage. Here we report on Pt-Si bulk samples prepared by arc-melting, for the first time, with high activities toward the electro-oxidation of CO and methanol. Increasing the Si concentration on the surface was correlated with the shifts of onset oxidation potentials to lower values and higher activities...... for CO and methanol electro-oxidation. It is proposed that the reaction on the Pt-Si catalyst could follow a Langmuir-Hinshelwood type of mechanism, where substantially enhanced catalytic activity is attributed to the fine-tuning of the surface Pt-Si atomic structure....

  2. Large optical conductivity of Dirac semimetal Fermi arc surface states

    Science.gov (United States)

    Shi, Li-kun; Song, Justin C. W.

    2017-08-01

    Fermi arc surface states, a hallmark of topological Dirac semimetals, can host carriers that exhibit unusual dynamics distinct from that of their parent bulk. Here we find that Fermi arc carriers in intrinsic Dirac semimetals possess a strong and anisotropic light-matter interaction. This is characterized by a large Fermi arc optical conductivity when light is polarized transverse to the Fermi arc; when light is polarized along the Fermi arc, Fermi arc optical conductivity is significantly muted. The large surface spectral weight is locked to the wide separation between Dirac nodes and persists as a large Drude weight of Fermi arc carriers when the system is doped. As a result, large and anisotropic Fermi arc conductivity provides a novel means of optically interrogating the topological surfaces states of Dirac semimetals.

  3. Nonaqueous electrocatalytic water oxidation by a surface-bound Ru(bda)(L)₂ complex.

    Science.gov (United States)

    Sheridan, Matthew V; Sherman, Benjamin D; Wee, Kyung-Ryang; Marquard, Seth L; Gold, Alexander S; Meyer, Thomas J

    2016-04-21

    The rate of electrocatalytic water oxidation by the heterogeneous water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], , (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate) on metal oxide surfaces is greatly enhanced relative to water as the solvent. In these experiments with propylene carbonate (PC) as the nonaqueous solvent, water is the limiting reagent. Mechanistic studies point to atom proton transfer (APT) as the rate limiting step in water oxidation catalysis.

  4. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  5. Ester oxidation on an aluminum surface using chemiluminescence

    Science.gov (United States)

    Jones, William R., Jr.; Meador, Michael A.; Morales, Wilfredo

    1986-01-01

    The oxidation characteristics of a pure ester (trimethyolpropane triheptanoate) were studied by using a chemiluminescence technique. Tests were run in a thin film microoxidation apparatus with an aluminum alloy catalyst. Conditions included a pure oxygen atmosphere and a temperature range of 176 to 206 C. Results indicated that oxidation of the ester (containing .001 M diphenylanthracene as an intensifier) was accompanied by emission of light. The maximum intensity of light emission was a function of the amount of ester, the concentration of intensifier, and the test temperature. The induction period, or the time to reach one-half of maximum intensity was inversely proportional to test temperature. Decreases in light emission at the later stages of a test were caused by depletion of the intensifier.

  6. In-vacuum scattered light reduction with black cupric oxide surfaces for sensitive fluorescence detection.

    Science.gov (United States)

    Norrgard, E B; Sitaraman, N; Barry, J F; McCarron, D J; Steinecker, M H; DeMille, D

    2016-05-01

    We demonstrate a simple and easy method for producing low-reflectivity surfaces that are ultra-high vacuum compatible, may be baked to high temperatures, and are easily applied even on complex surface geometries. Black cupric oxide (CuO) surfaces are chemically grown in minutes on any copper surface, allowing for low-cost, rapid prototyping, and production. The reflective properties are measured to be comparable to commercially available products for creating optically black surfaces. We describe a vacuum apparatus which uses multiple blackened copper surfaces for sensitive, low-background detection of molecules using laser-induced fluorescence.

  7. The surface oxidation kinetics of zirconium-niobium alloys and aα-Fe with prevailing cubical texture

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Kargin, D.B.; Chalaya, O. V.; Berber, N.N.

    2002-01-01

    ), the third by we function nearly linear (n≅1) and the fourth stage is described by he close to parabolic (n≅2). At the first stage the oxide film formation is conditioned by the oxygen ions transfer by the electrical field in oxide into a reactionary zone on the metal - oxide interface (reaction type 3Fe (sol) + 4O=Fe 3 O 4 ). The self-deceleration of the oxide film growth in time descends from of the electrical field reduction. At the expense of its shielding by the bulk charge of particles which are available in solid-state plasma of oxide. At the second stage, when the field intensity in oxide becomes negligible, the growth of a film is controlled by the oxygen ions diffusion. The growth of oxide film under the linear law after the break point shows that the process is limited by the reaction speed on the metal - oxide interface. The abrupt increase of ratio Fe 3 O 4 /Fe 2 O 3 phases observed in oxide film on α-Fe surface and the emergence of the metallically conductivity in corrosion films of Zr-Nb alloys allow to make the supposition that these processes are caused by the metal ions

  8. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

    DEFF Research Database (Denmark)

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

    2012-01-01

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V...

  9. Intermolecular potential energy surface and thermophysical properties of ethylene oxide.

    Science.gov (United States)

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

    2014-10-28

    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.

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

    Science.gov (United States)

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

    2013-02-01

    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.

  11. Local electrical properties of thermally grown oxide films formed on duplex stainless steel surfaces

    Science.gov (United States)

    Guo, L. Q.; Yang, B. J.; He, J. Y.; Qiao, L. J.

    2018-06-01

    The local electrical properties of thermally grown oxide films formed on ferrite and austenite surfaces of duplex stainless steel at different temperatures were investigated by Current sensing atomic force microscopy, X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). The current maps and XPS/AES analyses show that the oxide films covering austenite and ferrite surfaces formed at different temperatures exhibit different local electrical characteristics, thickness and composition. The dependence of electrical conductivity of oxide films covering austenite and ferrite surface on the formation temperature is attributed to the film thickness and semiconducting structures, which is intrinsically related to thermodynamics and kinetics process of film grown at different temperature. This is well elucidated by corresponding semiconductor band structures of oxide films formed on austenite and ferrite phases at different temperature.

  12. The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

    International Nuclear Information System (INIS)

    Kiselev, Yurii M; Tretyakov, Yuri D

    1999-01-01

    The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

  13. Investigation on the dominant key to achieve superior Ge surface passivation by GeOx based on the ozone oxidation

    International Nuclear Information System (INIS)

    Wang, Xiaolei; Xiang, Jinjuan; Wang, Wenwu; Xiong, Yuhua; Zhang, Jing; Zhao, Chao

    2015-01-01

    Highlights: • The dominant key to achieve superior Ge passivation by GeO x is investigated. • The interface state density decreases with increasing the GeO x thickness. • The Ge 3+ oxide component is the dominant key to passivate the Ge surface. • The atomic structure at the GeO x /Ge interface is built by XPS. - Abstract: The dominant key to achieve superior Ge surface passivation by GeO x interfacial layer is investigated based on ozone oxidation. The interface state density (D it ) measured from low temperature conduction method is found to decrease with increasing the GeO x thickness (0.26–1.06 nm). The X-ray photoelectron spectroscopy (XPS) is employed to demonstrate the interfacial structure of GeO x /Ge with different GeO x thicknesses. And the XPS results show that Ge 3+ oxide component is responsible to the decrease of the D it due to the effective passivation of Ge dangling bonds. Therefore, the formation of Ge 3+ component is the dominant key to achieve low D it for Ge gate stacks. Our work confirms that the same physical mechanism determines the Ge surface passivation by the GeO x regardless of the oxidation methods to grow the GeO x interfacial layer. As a result, to explore a growth process that can realize sufficient Ge 3+ component in the GeO x interlayer as thin as possible is important to achieve both equivalent oxide thickness scaling and superior interfacial property simultaneously. This conclusion is helpful to engineer the optimization of the Ge gate stacks.

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

    Science.gov (United States)

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

    2007-11-28

    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.

  15. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    KAUST Repository

    Zhu, Yihan

    2012-03-19

    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Surface area of antimony oxide by isotope exchange and other methods

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Y.K.; Acharya, B.V.; Rangamannar, B.

    1985-06-17

    Specific surface areas of antimony oxide samples, one commercial, the other prepared from antimony trichloride were measured by heterogeneous isotope exchange, gas adsorption, air permeability and microscopic methods. Specific surface areas obtained by these four methods for the two samples were compared and the observed differences are explained.

  17. The role of cold work and applied stress on surface oxidation of 304 stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Lozano-Perez, Sergio, E-mail: sergio.lozano-perez@materials.ox.ac.uk [Department of Materials, University of Oxford, Parks Rd., Oxford OX1 3PH (United Kingdom); Kruska, Karen [Department of Materials, University of Oxford, Parks Rd., Oxford OX1 3PH (United Kingdom); Iyengar, Ilya [Winchester College, College Street, Winchester SO23 9LX (United Kingdom); Terachi, Takumi; Yamada, Takuyo [Institute of Nuclear Safety System (INSS), 64 Sata, Mihama-cho, Mikata-gun, Fukui 919-1205 (Japan)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer FIB 3D sequential sectioning is an ideal technique to characterize surface oxidation. Black-Right-Pointing-Pointer 3D models of the oxide can be produced with nanometre resolution. Black-Right-Pointing-Pointer The effects of stress and cold work in grain boundary oxidation have been analysed. Black-Right-Pointing-Pointer At least three different oxidation modes are observed when stress is applied. - Abstract: FIB 3-dimensional (3D) sequential sectioning has been used to characterize environmental degradation of 304 stainless steels in pressurized water reactor (PWR) simulated primary water. In particular, the effects of cold work and applied stress on oxidation have been studied in detail. It was found that a description of the oxidation behaviour of this alloy is only complete if it is treated statistically, since it can suffer from high variability depending on the feature described.

  18. Surface and sub-surface thermal oxidation of thin ruthenium films

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Kokke, S.; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low

  19. Final state effects in photoemission studies of Fermi surfaces

    International Nuclear Information System (INIS)

    Kurtz, Richard L; Browne, Dana A; Mankey, Gary J

    2007-01-01

    Photoelectron spectroscopy is one of the most important methods for extracting information about the Fermi surface (FS) of materials. An electron photoexcited from the FS is emitted from the crystal conserving the parallel momentum, k parallel , while the perpendicular momentum k perpendicular is reduced due to the surface potential barrier. A simple interpretation of the process assumes the final state is free-electron-like allowing one to 'map' the detected photoelectron back to its initial k momentum. There are multiple final state effects that can complicate the interpretation of photoelectron data and these effects are reviewed here. These can involve both energy and k broadening, which can give rise to shadow or ghost FS contours, scattering and final state diffraction effects that modify intensities, and matrix element effects which reflect the symmetries of the states involved and can be highly dependent on photon polarization. These matrix elements result in contours of photoelectron intensity that follow the dispersion in k-space of the initial state, the FS, and the final state. Locations where intensities go to zero due to matrix element and symmetry effects can result in gaps where FS contours 'disappear'. Recognition that these effects can play a significant role in determining the measured angular distributions is crucial in developing an informed model of where the FS contours actually lie in relation to measured intensity contours

  20. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  1. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    Science.gov (United States)

    González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

    2016-08-01

    A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  2. Experimental investigation into the surface oxidation of lignite high temperature coke

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, H G; Dallmann, W [Technische Hochschule Aachen (Germany, F.R.). Lehrgebiet Kokerei und Brikettierung

    1979-11-01

    It was intended to produce lignite high temperature coke (BHFK) in the laboratory comparable to that produced with the Salem-Lurgi-open hearth process and quench them according to the prescribed condition. By this means, the surface oxide formation could be continually recorded gravimetrically. The self-sustaining reaction of the physical and chemical adsorption on the loose material were observed under consideration that the adsorption or surface oxide can exist in a gaseous as well as in a liquid aggregate. The established steam isotherms and electron-microscope photos identified the product BFHK as a material which shows in the range of high-humidity capillary condensation. The continuous gravimetric adsorption leads to 1,9 per cent by weight on dry surface oxides. On the other hand, oxidized coke in the presence of water builds up on the surface to 2,3 per cent by weight. It became apparent that the finest capillary water is not involved in the formation of the oxide. For the dry accumulation, which is a reaction of the first degree, the equation for the accumulation of the oxygen is given. From the BET surface, made up from the graphite-like ring structure of the carbon surface, as well as the dposited quantity of oxide, the surface density of the oxygen atoms is indicated in relation to the quantity of carbon atoms, or alternatively the six-ring. The dry deposition leads to a proportion of 1,5 oxygen atoms to 10 carbon atoms. In a wet reaction, the ratio is 1,8 to 10. With increasing quantities of oxide, the content of volatile matter, the sparking point and reactivity increase, while the porosity diminishes as a consequence.

  3. Oxidation of hydrogen terminated Ge(1 0 0) surface in the presence of iodine in methanol

    International Nuclear Information System (INIS)

    Lee, Younghwan; Park, Kibyung; Lim, Sangwoo

    2008-01-01

    Surface reaction on Ge(1 0 0) in liquid methanol (MeOH) was systematically studied. In particular, the characteristics of the Ge surface in the presence of iodine (I 2 ) in MeOH were investigated. MeOH treatment of the Ge surface in the presence of 0.05 or 0.005 mM of I 2 exhibited a similar result to that without I 2 , which produces a GeO x -dominant oxide structure. However, when the concentration of I 2 in MeOH increased to 0.5 mM, Ge surface revealed a GeO 2 -dominant oxide structure. Therefore, it is believed that the addition of enough I 2 in MeOH modifies the Ge oxidation mechanism. Hydroxide produced by the reaction between MeOH and the iodine radical may oxidize the Ge surface to form a Ge-O layer. Because MeOH is greatly consumed by chain and series reactions when I 2 concentration is high, a GeO 2 structure is not etched and a GeO 2 -dominant oxide structure is obtained with the addition of 0.5 mM I 2 in MeOH. The modified oxide layer prepared in MeOH with 0.5 mM I 2 exhibited an atomically smoother surface compared to a pure MeOH- or H 2 O 2 -treated Ge surface and a much thinner oxide layer than H 2 O 2 treatment.

  4. Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces

    DEFF Research Database (Denmark)

    Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine Anton

    2016-01-01

    A detailed understanding of the electrochemical reduction of CO2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO2(1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO2 reduction...... and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits...

  5. Hydrophobic cotton textile surfaces using an amphiphilic graphene oxide (GO) coating

    International Nuclear Information System (INIS)

    Tissera, Nadeeka D.; Wijesena, Ruchira N.; Perera, J. Rangana; Nalin de Silva, K.M.; Amaratunge, Gehan A.J.

    2015-01-01

    Graphical abstract: - Highlights: • Different GO dispersions were prepared by sonicating different amounts of GO in water. Degree of exfoliation of these GO sheets in water was analyzed using Atomic Force Microscopy (AFM). • AFM results obtained showed higher the GO concentration on water more the size of GO sheets and lesser the degree of exfoliation. • GO with different amounts was deposited on cotton fabric using simple dyeing method. • High GO loading on cotton increase the surface area coverage of the textile fibers with GO sheets. This led to less edge to mid area ratio of grafted GO sheets. • As contribution of mid area of GO increase on fiber surface cotton fabric becomes more hydrophobic. • Amphiphilic property of GO sheets was used to lower the surface energy of the cotton fibers leading to hydrophobic property. - Abstract: We report for the first time hydrophobic properties on cotton fabric successfully achieved by grafting graphene oxide on the fabric surface, using a dyeing method. Graphite oxide synthesized by oxidizing natural flake graphite employing improved Hummer's method showed an inter layer spacing of ∼1 nm from XRD. Synthesized graphite oxide was exfoliated in water using ultrasound energy to obtain graphene oxide (GO). AFM data obtained for the graphene oxide dispersed in an aqueous medium revealed a non-uniform size distribution. FTIR characterization of the synthesized GO sheets showed both hydrophilic and hydrophobic functional groups present on the nano sheets giving them an amphiphilic property. GO flakes of different sizes were successfully grafted on to a cotton fabric surface using a dip dry method. Loading different amounts of graphene oxide on the cotton fiber surface allowed the fabric to demonstrate different degrees of hydrophobicity. The highest observed water contact angle was at 143° with the highest loading of graphene oxide. The fabric surfaces grafted with GO also exhibits adhesive type hydrophobicity

  6. Growth of micrometric oxide layers to explore laser decontamination of metallic surfaces

    Directory of Open Access Journals (Sweden)

    Carvalho Luisa

    2017-01-01

    Full Text Available The nuclear industry produces a wide range of radioactive waste in terms of hazard level, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop safe techniques for dismantling and for decontamination, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. In this paper we propose a method for the creation of oxide layers on stainless steel 304L with europium (Eu as contaminant. This technique consists in spraying an Eu-solution on stainless steel samples. The specimens are firstly treated with a pulsed nanosecond laser after which the steel samples are placed in a 873 K furnace for various durations in order to grow an oxide layer. The oxide structure and in-depth distribution of Eu in the oxide layer were analyzed by scanning electron microscopy coupled to an energy-dispersive X-ray microanalyzer, as well as by glow discharge optical emission or mass spectrometry. The oxide layers were grown to thicknesses in the range of 200 nm–4.5 μm depending on the laser treatment parameters and the heating duration. These contaminated oxides had a ‘duplex structure’ with a mean concentration of the order of 6 × 1016 atoms/cm2 (15 μg/cm2 of europium in the volume of the oxide layer. It appears that europium implementation prevented the oxide growth in the furnace. Nevertheless, the presence of the contamination had no impact on the thickness of the oxide layers obtained by preliminary laser treatment. These oxide layers were used to study the decontamination of metallic surfaces such as stainless steel 304L using a nanosecond pulsed laser.

  7. Eta products, BPS states and K3 surfaces

    Energy Technology Data Exchange (ETDEWEB)

    He, Yang-Hui [Department of Mathematics, City University,London, EC1V 0HB (United Kingdom); School of Physics, NanKai University,Tianjin, 300071 (China); Merton College, University of Oxford,Oxford, OX14JD (United Kingdom); McKay, John [Department of Mathematics and Statistics, Concordia University,1455 de Maisonneuve Blvd. West, Montreal, Quebec, H3G 1M8 (Canada)

    2014-01-22

    Inspired by the multiplicative nature of the Ramanujan modular discriminant, Δ, we consider physical realizations of certain multiplicative products over the Dedekind eta-function in two parallel directions: the generating function of BPS states in certain heterotic orbifolds and elliptic K3 surfaces associated to congruence subgroups of the modular group. We show that they are, after string duality to type II, the same K3 surfaces admitting Nikulin automorphisms. In due course, we will present identities arising from q-expansions as well as relations to the sporadic Mathieu group M{sub 24}.

  8. Electrochemical chlorine evolution at rutile oxide (110) surfaces

    DEFF Research Database (Denmark)

    Hansen, Heine Anton; Man, Isabela Costinela; Studt, Felix

    2010-01-01

    -sites are established for MO2 (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function...... the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus...... of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity...

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

    Science.gov (United States)

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

    2014-01-30

    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Band mapping of surface states vs. adsorbate coverage

    International Nuclear Information System (INIS)

    Rotenberg, E.; Kevan, S.D.; Denlinger, J.D.; Chung, Jin-Wook

    1997-01-01

    The theory of electron bands, which arises from basic quantum mechanical principles, has been the cornerstone of solid state physics for over 60 years. Simply put, an energy band is an electron state in a solid whose energy varies with its momentum (similar to, but with a more complicated dependence than, how a free electron's energy is proportional to its momentum squared). Much attention over the last 15 years has been given to the study of band structure of surfaces and interfaces, especially as the applications of these two-dimensional systems have become increasingly important to industry and science. The ultraESCA endstation at beamline 7.01 at the Advanced Light Source was developed for very high-energy - (∼50 meV) and angular - ( 12 photons/sec) makes the detailed study of the evolution of bands possible. The authors are interested in learning how, when one forms a chemical bond between a metal and an overlaying atom or molecule, the resulting charge transfer to or from the adsorbate affects the surface bands. In some cases of interest, intermediate coverages lead to different band structure than at the extremes of clean and saturated surfaces. Surfaces of tungsten are particularly interesting, as their atomic geometry has been shown to be exquisitely sensitive to both the surface vibrational and electronic properties. In this study, the authors looked at the surface bands of tungsten ((110) surface), as a function both of coverage and mass of overlaying atoms. The adsorbed atoms were hydrogen and the alkali atoms lithium and cesium

  11. Synthesis of Graphite Oxide with Different Surface Oxygen Contents Assisted Microwave Radiation

    Directory of Open Access Journals (Sweden)

    Adriana Ibarra-Hernández

    2018-02-01

    Full Text Available Graphite oxide is synthesized via oxidation reaction using oxidant compounds that have lattice defects by the incorporation of unlike functional groups. Herein, we report the synthesis of the graphite oxide with diverse surface oxygen content through three (B, C, D different modified versions of the Hummers method assisted microwave radiation compared with the conventional graphite oxide sample obtained by Hummers method (A. These methods allow not only the production of graphite oxide but also reduced graphene oxide, without undergoing chemical, thermal, or mechanical reduction steps. The values obtained of C/O ratio were ~2, 3.4, and ~8.5 for methodologies C, B, and D, respectively, indicating the presence of graphite oxide and reduced graphene oxide, according to X-ray photoelectron spectroscopy. Raman spectroscopy of method D shows the fewest structural defects compared to the other methodologies. The results obtained suggest that the permanganate ion produces reducing species during graphite oxidation. The generation of these species is attributed to a reversible reaction between the permanganate ion with π electrons, ions, and radicals produced after treatment with microwave radiation.

  12. Surface characterization and corrosion behavior of micro-arc oxidized Ti surface modified with hydrothermal treatment and chitosan coating

    International Nuclear Information System (INIS)

    Neupane, Madhav Prasad; Park, Il Song; Lee, Min Ho

    2014-01-01

    In the present work, we describe the surface modification of commercially pure titanium (CP-Ti) by a composite/multilayer coating approach for biomedical applications. CP-Ti samples were treated by micro-arc oxidation (MAO) and subsequently some of the samples were coated with chitosan (Chi) by dip coating method, while others were subjected to hydrothermal treatment (HT) followed by chitosan coating. The MAO, MAO/Chi, and MAO/HT/Chi coated Ti were characterized and their characteristics were compared with CP-Ti. X-ray diffraction and scanning electron microscopy were used to assess the structural and morphological characteristics. The average surface roughness was determined using a surface profilometer. The corrosion resistance of untreated and surface modified Ti in commercial saline at 298 K was evaluated by potentiodynamic polarization test. The results indicated that the chitosan coating is very well integrated with the MAO and MAO/HT coating by physically interlocking itself with the coated layer and almost sealed all the pores. The surface roughness of hydrothermally treated and chitosan coated MAO film was superior evidently to that with other sample groups. The corrosion studies demonstrated that the MAO, hydrothermally treated and chitosan coated sample enhanced the corrosion resistance of titanium. The result indicates that fabrication of hydrothermally treated MAO surface coatings with chitosan is a significant approach to protect the titanium from corrosion, hence enhancing the potential use of titanium as bio-implants. - Highlights: • Micro-arc oxidized (MAO) and hydrothermally treated (HT) Ti surfaces are coated with chitosan (Chi). • The MAO/HT/Chi surface exhibits pores sealing and enhanced the surface roughness. • The MAO/HT/Chi surface significantly increase the corrosion resistance. • The MAO/HT/Chi can be a potential surface of titanium for bio-implants

  13. High temperature oxidation behavior of aluminide on a Ni-based single crystal superalloy in different surface orientations

    Institute of Scientific and Technical Information of China (English)

    Fahamsyah H.Latief; Koji Kakehi; El-Sayed M.Sherif

    2014-01-01

    An investigation on oxidation behavior of coated Ni-based single crystal superalloy in different surface orientations has been carried out at 1100 1C. It has been found that the {100} surface shows a better oxidation resistance than the {110} one, which is attributed that the {110}surface had a slightly higher oxidation rate when compared to the {100} surface. The experimental results also indicated that the anisotropic oxidation behavior took place even with a very small difference in the oxidation rates that was found between the two surfaces. The differences of the topologically close packed phase amount and its penetration depth between the two surfaces, including the ratio of α-Al2O3 after 500 h oxidation, were responsible for the oxidation anisotropy.

  14. Modifying zirconia solid electrolyte surface property to enhance oxide transport

    Energy Technology Data Exchange (ETDEWEB)

    Liaw, B.Y.; Song, S.Y. [Univ. of Hawaii, Honolulu, HI (United States)

    1996-12-31

    Bismuth-strontium-calcium-copper oxide (Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, BSCCO) is known for its high T{sub c} superconducting behavior and mixed conducting property. The applicability of similar high T{sub c} cuprates for intermediate-temperature solid oxide fuel cell (SOFC) application has been studied recently. We investigated the electrochemical behavior of several Ag{vert_bar}BSCCO{vert_bar}10 mol% yttria-stabilized zirconia (YSZ){vert_bar}Ag and Ag{vert_bar}YSZ{vert_bar}Ag cells using complex impedance spectroscopy. A highly uniform and porous microstructure was observed at the interface of the YSZ and BSCCO. The ionic conductivity determined from the Nyquest plots in the temperature range of 200-700{degrees}C agrees with the values reported in the literature. The specific resistance of the BSCCO{vert_bar}YSZ interface was also determined to be lower than those of the conventional manganite electrode, suggesting that BSCCO seems attractive for cathode applications in SOFC.

  15. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

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

    Science.gov (United States)

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

    2012-05-01

    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.

  17. Effect of process parameters on surface oxides on chromium-alloyed steel powder during sintering

    International Nuclear Information System (INIS)

    Chasoglou, D.; Hryha, E.; Nyborg, L.

    2013-01-01

    The use of chromium in the PM steel industry today puts high demands on the choice and control of the atmosphere during the sintering process due to its high affinity to oxygen. Particular attention is required in order to control the surface chemistry of the powder which in turn is the key factor for the successful sintering and production of PM parts. Different atmosphere compositions, heating rates and green densities were employed while performing sintering trials on water atomized steel powder pre-alloyed with 3 wt.% Cr in order to evaluate the effect on surface chemical reactions. Fracture surfaces of sintered samples were examined using high resolution scanning electron microscopy combined with X-ray microanalysis. The investigation was complemented with thermogravimetric (TG) studies. Reaction products in particulate form containing strong-oxide forming elements such as Cr, Si and Mn were formed during sintering for all conditions. Processing in vacuum results in intensive inter-particle neck development during the heating stage and consequently in the excessive enclosure of surface oxide which is reflected in less good final mechanical properties. Enhanced oxide reduction was observed in samples processed in hydrogen-containing atmospheres independent of the actual content in the range of 3–10 vol.%. An optimum heating rate was required for balancing reduction/oxidation processes. A simple model for the enclosure and growth of oxide inclusions during the sinter-neck development is proposed. The obtained results show that significant reduction of the oxygen content can be achieved by adjusting the atmosphere purity/composition. - Highlights: ► A local atmosphere microclimate is very important for sintering of PM steels. ► High risk of surface oxide enclosure between 800 and 1000 °C. ► Coalescence and agglomeration of enclosed oxides take place during sintering. ► The effect of different process parameters on the oxide reduction is examined. ► A

  18. A Classical Potential to Model the Adsorption of Biological Molecules on Oxidized Titanium Surfaces.

    Science.gov (United States)

    Schneider, Julian; Ciacchi, Lucio Colombi

    2011-02-08

    The behavior of titanium implants in physiological environments is governed by the thin oxide layer that forms spontaneously on the metal surface and mediates the interactions with adsorbate molecules. In order to study the adsorption of biomolecules on titanium in a realistic fashion, we first build up a model of an oxidized Ti surface in contact with liquid water by means of extensive first-principles molecular dynamics simulations. Taking the obtained structure as reference, we then develop a classical potential to model the Ti/TiOx/water interface. This is based on the mapping with Coulomb and Lennard-Jones potentials of the adsorption energy landscape of single water and ammonia molecules on the rutile TiO2(110) surface. The interactions with arbitrary organic molecules are obtained via standard combination rules to established biomolecular force fields. The transferability of our potential to the case of organic molecules adsorbing on the oxidized Ti surface is checked by comparing the classical potential energy surfaces of representative systems to quantum mechanical results at the level of density functional theory. Moreover, we calculate the heat of immersion of the TiO2 rutile surface and the detachment force of a single tyrosine residue from steered molecular dynamics simulations, finding good agreement with experimental reference data in both cases. As a first application, we study the adsorption behavior of the Arg-Gly-Asp (RGD) peptide on the oxidized titanium surface, focusing particularly on the calculation of the free energy of desorption.

  19. Dynamic and Impure Perovskite Structured Metal Oxide Surfaces

    DEFF Research Database (Denmark)

    Hansen, Karin Vels; Norrman, Kion; Traulsen, Marie Lund

    2017-01-01

    Surfaces of LSF and LSCF perovskite model electrodes were investigated using a variety of analytical methods on flat model electrodes that were prepared as either pellets or as thin films on top of YSZ pellets in other to throw more light on the widely discussed segregation of layers and particles...

  20. Determining the energetics of vicinal perovskite oxide surfaces

    NARCIS (Netherlands)

    Wessels, W.A.; Bollmann, Tjeerd Rogier Johannes; Koster, Gertjan; Zandvliet, Henricus J.W.; Rijnders, Augustinus J.H.M.

    2017-01-01

    The energetics of vicinal SrTiO3(001) and DyScO3(110), prototypical perovskite vicinal surfaces, has been studied using topographic atomic force microscopy imaging. The kink formation and strain relaxation energies are extracted from a statistical analysis of the step meandering. Both perovskite

  1. Oxidation of aqueous HF-treated Si(001) surface induced by translational kinetic energy of O sub 2 at room temperature

    CERN Document Server

    Yoshigoe, A

    2003-01-01

    The oxidation induced by the translational kinetic energy of O sub 2 on the Si(001) surface treated with HF solution were investigated by combining synchrotron radiation photoemission spectroscopy with the supersonic molecular beam techniques. The oxidation at room temperature did not progress up to 3600 L of O sub 2 exposure with incident energy of 0.04 eV, whereas the oxidation states of up to Si sup 4 sup + species were formed in the case of 3.0 eV. The oxide-layer thickness was estimated to be 0.26 nm at the final oxidation stages. We concluded that the Si atoms at the top layers were oxidized by the incident energy of 3.0 eV.

  2. Quantum confinement-induced tunable exciton states in graphene oxide.

    Science.gov (United States)

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology.

  3. High-Surface-Area Nitrogen-Doped Reduced Graphene Oxide for Electric Double-Layer Capacitors.

    Science.gov (United States)

    Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong; Jaye, Cherno; Fischer, Daniel A; Lee, Chang-Wook; Yang, Xiao-Qing; Roh, Kwang Chul; Kim, Kwang-Bum

    2015-06-08

    A two-step method consisting of solid-state microwave irradiation and heat treatment under NH3 gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007 m(2)  g(-1) ), high electrical conductivity (1532 S m(-1) ), and low oxygen content (1.5 wt %) for electrical double-layer capacitor applications. The specific capacitance of N-RGO was 291 F g(-1) at a current density of 1 A g(-1) , and a capacitance of 261 F g(-1) was retained at 50 A g(-1) , which indicated a very good rate capability. N-RGO also showed excellent cycling stability and preserved 96 % of the initial specific capacitance after 100 000 cycles. Near-edge X-ray absorption fine-structure spectroscopy results provided evidenced for the recovery of π conjugation in the carbon networks with the removal of oxygenated groups and revealed chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

    Science.gov (United States)

    Lee, Austin W H; Gates, Byron D

    2017-09-05

    Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

  5. Effect of surface finishing on the oxidation behaviour of a ferritic stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Ardigo-Besnard, M.R., E-mail: maria-rosa.ardigo-besnard@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), UMR 6303 CNRS—Université de Bourgogne Franche-Comté, BP 47870, 21078 Dijon Cedex (France); Popa, I.; Heintz, O.; Chassagnon, R. [Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), UMR 6303 CNRS—Université de Bourgogne Franche-Comté, BP 47870, 21078 Dijon Cedex (France); Vilasi, M. [Institut Jean Lamour, UMR 7198 CNRS—Université de Lorraine, Parc de Saurupt, 54011 Nancy (France); Herbst, F. [Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), UMR 6303 CNRS—Université de Bourgogne Franche-Comté, BP 47870, 21078 Dijon Cedex (France); Girardon, P. [APERAM, Centre de Recherche, BP15, 62330 Isbergues (France); Chevalier, S. [Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), UMR 6303 CNRS—Université de Bourgogne Franche-Comté, BP 47870, 21078 Dijon Cedex (France)

    2017-08-01

    Highlights: • Study of surface finishing effect on the corrosion behaviour of a stainless steel. • Mirror polished samples were compared to as-rolled material. • Two oxidation mechanisms were identified depending on the surface finishing. • Before oxidation, native chemical phases are identical for both samples. • Subsurface dislocations generated by the polishing process promote Cr{sub 2}O{sub 3} formation. - Abstract: The corrosion behaviour and the oxidation mechanism of a ferritic stainless steel, K41X (AISI 441), were evaluated at 800 °C in water vapour hydrogen enriched atmosphere. Mirror polished samples were compared to as-rolled K41X material. Two different oxidation behaviours were observed depending on the surface finishing: a protective double (Cr,Mn){sub 3}O{sub 4}/Cr{sub 2}O{sub 3} scale formed on the polished samples whereas external Fe{sub 3}O{sub 4} and (Cr,Fe){sub 2}O{sub 3} oxides grew on the raw steel. Moreover, isotopic marker experiments combined with SIMS analyses revealed different growth mechanisms. The influence of surface finishing on the corrosion products and growth mechanisms was apprehended by means of X-ray photoelectron spectroscopy (XPS) and residual stress analyses using XRD at the sample surfaces before ageing.

  6. Free energy surfaces in the superconducting mixed state

    Science.gov (United States)

    Finnemore, D. K.; Fang, M. M.; Bansal, N. P.; Farrell, D. E.

    1989-01-01

    The free energy surface for Tl2Ba2Ca2Cu3O1O has been measured as a function of temperature and magnetic field to determine the fundamental thermodynamic properties of the mixed state. The change in free energy, G(H)-G(O), is found to be linear in temperature over a wide range indicating that the specific heat is independent of field.

  7. Growth of micrometric oxide layers for the study of metallic surfaces decontamination by laser

    Science.gov (United States)

    Carvalho, Luisa; Pacquentin, Wilfried; Tabarant, Michel; Maskrot, Hicham; Semerok, Alexandre

    2017-09-01

    The nuclear industry produces a wide range of radioactive waste in term of level of hazard, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop techniques for dismantling and for decontamination in a safe way, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. We propose a method of formation of oxide layer on stainless steel 304L with europium (Eu) as contaminant marker. In this method, an Eu-solution is sprayed on the stainless steel samples. The specimen are firstly treated with a pulsed nanosecond laser and secondly the steel samples are exposed to a 600°C furnace for various durations in order to grow an oxide layer. The oxide structure and in-depth distribution of Eu in the oxide layer are analysed by scanning electron microscopy coupled with energy dispersive X-ray microanalyzer, and by glow discharge optical emission or mass spectrometry. The oxide layers were grown to thicknesses in the range of 200 nm to 4.5 μm regarding to the laser treatment parameters and the heating duration. These contaminated oxides have a `duplex structure' with a mean weight percentage of 0.5% of europium in the volume of the oxide layer. It appears that europium implementation prevents the oxide growth by furnace but has no impact on laser heating. These oxide layers are used to study the decontamination of metallic surfaces such as stainless steel 304L using a nanosecond pulsed laser.

  8. Growth of micrometric oxide layers for the study of metallic surfaces decontamination by laser

    Directory of Open Access Journals (Sweden)

    Carvalho Luisa

    2017-01-01

    Full Text Available The nuclear industry produces a wide range of radioactive waste in term of level of hazard, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop techniques for dismantling and for decontamination in a safe way, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. We propose a method of formation of oxide layer on stainless steel 304L with europium (Eu as contaminant marker. In this method, an Eu-solution is sprayed on the stainless steel samples. The specimen are firstly treated with a pulsed nanosecond laser and secondly the steel samples are exposed to a 600°C furnace for various durations in order to grow an oxide layer. The oxide structure and in-depth distribution of Eu in the oxide layer are analysed by scanning electron microscopy coupled with energy dispersive X-ray microanalyzer, and by glow discharge optical emission or mass spectrometry. The oxide layers were grown to thicknesses in the range of 200 nm to 4.5 μm regarding to the laser treatment parameters and the heating duration. These contaminated oxides have a ‘duplex structure’ with a mean weight percentage of 0.5% of europium in the volume of the oxide layer. It appears that europium implementation prevents the oxide growth by furnace but has no impact on laser heating. These oxide layers are used to study the decontamination of metallic surfaces such as stainless steel 304L using a nanosecond pulsed laser.

  9. Humidity Sensing Properties of Surface Modified Polyaniline Metal Oxide Composites

    Directory of Open Access Journals (Sweden)

    S. C. Nagaraju

    2014-01-01

    Full Text Available Polyaniline- (PANI praseodymium Oxide (Pr2O3 composites have been synthesized by in situ polymerization method with different weight percentages. The synthesized composites have been characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The temperature dependent conductivity shows that the conductivity is due to the hopping of polarons and bipolarons. These composites show negative thermal coefficient (α behavior as a function of temperature, which is characteristic behavior of semiconducting materials. Sensor studies have been carried out by two-probe method and found that the sensitivity increases with increase in % RH. It is noticed that stability increase is due to the presence of Pr2O3 in polyaniline up to 30 wt%. A fast recovery and response time along with high sensitivity make these composites suitable for humidity sensors.

  10. Zinc (hydr)oxide/graphite oxide/AuNPs composites: role of surface features in H₂S reactive adsorption.

    Science.gov (United States)

    Giannakoudakis, Dimitrios A; Bandosz, Teresa J

    2014-12-15

    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. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2014-11-01

    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

  12. Growth and decay of surface charges in grafts of Teflon in electrets states

    International Nuclear Information System (INIS)

    Spinelli, I.M.M.

    1971-01-01

    The greatest problem founded in a cardiovascular implant is the thrombus formation. Teflon grafts were used in electret state for prothesis in vena cava of dogs. To put these grafts in an electret state a corona discharge in air was used and homocharge was formed predominantly. To measure the formed surface charge the oscillating capacitor technique was used. In the electret state the grafts have showed an initial density of charge of 10- 8 C/cm 2 and the charge decay and time decay of the samples were measured under many conditions. We found two activation energies, E 2 =0.17 e V and E 3 =1.12 e V, due to rapid and slow decay, respectively. The charged grafts were sterilized with ethilene gas oxide and this process apparently did not influence the charges

  13. The Influences of Water Vapor/Hydrogen Ratio, Gas-Flow Rate and Antimony on the Surface Oxidation of Trip Steels

    International Nuclear Information System (INIS)

    Kwon, You Jong; Zhu, Jing Xi; Sridhar, Seetharaman; Sohn, Il Ryong

    2011-01-01

    In the current paper, we are reporting the results from an investigation of the surface and sub-surface oxidation of a TRIP steel containing 2 wt.% Mn and 0.5 wt.% Al with and without 0.03 wt.% Sb. The oxidizing conditions in the gas were successively varied in terms of the linear gas flow-rate and dew-point, from conditions were gas-phase mass transport limited conditions prevailed, to those were solid state processes became the rate determining conditions. It was found, that at sufficient low oxidizing conditions (defined as flow-rate/dew-point), the metal surfaces were clear of any external oxides, and as the oxidizing conditions were increased, Mn- and Si- oxide nodules formed along with magnetite. As the oxidizing conditions were increased further, a dense magnetite layer was present. The limits of the various regions were experimentally quantified and a proposed hypothesis for their occurrences is presented. No obvious effect of Sb was noted in this micro-structural research of the oxides that results from the various conditions investigated in this study

  14. Deposition of thin layer (monoatomic layer) of barium on gold single crystal surfaces and studies of its oxidation employing X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Ahmad, H.; Ahmad, R.; Khalid, M.; Alvi, R.A.

    2007-01-01

    Due to the high reactivity of barium with oxygen, some oxygen diffuse into the bulk to form bulk oxide and it is very difficult to differentiate the oxide over layer and the bulk oxide. To study the oxidation of barium surface layer, a thin layer (monolayer) of barium is developed over gold single crystal surface. Gold is selected as support because it is one of the least reactive metal in transition metal group and have very low probability of reaction with oxygen at room temperature (300K). Nitrous oxide (N/sub 2/O) was used as oxidant. Thin layer of barium was deposited on Au(100) surface. The barium coverage on gold surface was calculated that varied from 0.4 to 1.4 monolayer (ML). Photoelectron spectra for O(ls), N(ls), Ba (3d), and Au (4f) have been recorded on X-ray photoelectron spectrometer at different binding energy region specific for each element. The decomposition of nitrous oxide has been observed in all cases. It has found that nitrogen is evolved in the gaseous state and oxygen is adsorbed/chemisorbed on barium over layer. (author)

  15. Surface States and Effective Surface Area on Photoluminescent P-Type Porous Silicon

    Science.gov (United States)

    Weisz, S. Z.; Porras, A. Ramirez; Resto, O.; Goldstein, Y.; Many, A.; Savir, E.

    1997-01-01

    The present study is motivated by the possibility of utilizing porous silicon for spectral sensors. Pulse measurements on the porous-Si/electrolyte system are employed to determine the surface effective area and the surface-state density at various stages of the anodization process used to produce the porous material. Such measurements were combined with studies of the photoluminescence spectra. These spectra were found to shift progressively to the blue as a function of anodization time. The luminescence intensity increases initially with anodization time, reaches a maximum and then decreases with further anodization. The surface state density, on the other hand, increases with anodization time from an initial value of about 2 x 10(exp 12)/sq cm surface to about 1013 sq cm for the anodized surface. This value is attained already after -2 min anodization and upon further anodization remains fairly constant. In parallel, the effective surface area increases by a factor of 10-30. This behavior is markedly different from the one observed previously for n-type porous Si.

  16. HREM of metallized {111} iron oxide nanoparticle surfaces

    International Nuclear Information System (INIS)

    Lovely, G R; Brown, A P; Brydson, R; Kirkland, A I; Meyer, R; Chang, L Y; Jefferson, D A; Falke, M; Bleloch, A

    2006-01-01

    Mixed phase Fe 3 O 4 - γ-Fe 2 O 3 (magnetite-maghemite) nanoparticles have been fabricated by colloidal routes. HR(S)TEM images, taken on both aberration corrected and uncorrected (S)TEMs, and indirect reconstruction of images of the nanoparticles show the presence of {111} facets that terminate with enhanced contrast. This extra contrast is shown to be real and is due to additional octahedral cations occupying the {111} surfaces

  17. Temperature effects on surface activity and application in oxidation ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. The γcmc values of CTAB–SDS decrease from 63⋅67 mN/m at 10°C to 36⋅38 mN/m at 90°C, slightly lower than those of either CTAB or SDS. Correspondingly, the CMC of CTAB–SDS decreases almost by half. The increase of surface activity of CTAB–SDS can be attributed to the relatively weak electrostatic ...

  18. Creation of hydrophobic surfaces using a paint containing functionalized oxide particles

    Science.gov (United States)

    Sino, Paul Albert L.; Herrera, Marvin U.; Balela, Mary Donnabelle L.

    2017-05-01

    Hydrophobic surfaces were created by coating various substrates (aluminum sheet, soda-lime glass, silicon carbide polishing paper, glass with double-sided adhesive) with paint containing functionalized oxide particles. The paint was created by functionalizing oxide particles (ground ZnO, TiO2 nanoparticles, or TiO2 microparticles) with fluorosilane molecules in absolute ethanol. Water contact angle of samples shows that the coated substrate becomes hydrophobic (water contact angle ≥ 90°). Among the oxides that were used, ground ZnO yielded contact angle exemplifying superhydrophobicity (water contact angle ≥ 150°). Scanning electron micrograph of paint-containing TiO2 nanoparticles shows rough functionalized oxides structures which probably increase the hydrophobicity of the surface.

  19. Effect of surface oxidation on the nm-scale wear behavior of a metallic glass

    International Nuclear Information System (INIS)

    Caron, A.; Louzguine-Luzguin, D. V.; Sharma, P.; Inoue, A.; Shluger, A.; Fecht, H.-J.

    2011-01-01

    Metallic glasses are good candidates for applications in micromechanical systems. With size reduction of mechanical components into the micrometer and submicrometer range, the native surface oxide layer starts playing an important role in contact mechanical applications of metallic glasses. We use atomic force microscopy to investigate the wear behavior of the Ni 62 Nb 38 metallic glass with a native oxide layer and with an oxide grown after annealing in air. After the annealing, the wear rate is found to have significantly decreased. Also the dependency of the specific wear on the velocity is found to be linear in the case of the as spun sample while it follows a power law in the case of the sample annealed in air. We discuss these results in relation to the friction behavior and properties of the surface oxide layer obtained on the same alloy.

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

    International Nuclear Information System (INIS)

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

    1986-01-01

    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 of the supported oxide ranges from about 0.5 to 25 weight percent metal oxide on the titania support based on the total support composition and the catalyst contains at least about 2 milligrams of iron, calculated as Fe/sub 2/O/sub 3/, per square meter of support surface

  1. Effect of dew point on the formation of surface oxides of twinning-induced plasticity steel

    International Nuclear Information System (INIS)

    Kim, Yunkyum; Lee, Joonho; Shin, Kwang-Soo; Jeon, Sun-Ho; Chin, Kwang-Geun

    2014-01-01

    The surface oxides of twinning-induced plasticity (TWIP) steel annealed at 800 °C for 43 s were investigated using transmission electron microscopy. During the annealing process, the oxygen potential was controlled by adjusting the dew point in a 15%H 2 –N 2 gas atmosphere. It was found that the type of surface oxides formed and the thickness of the oxide layer were determined by the dew point. In a gas mixture with a dew point of − 20 °C, a MnO layer with a thickness of ∼ 100 nm was formed uniformly on the steel surface. Under the MnO layer, a MnAl 2 O 4 layer with a thickness of ∼ 15 nm was formed with small Mn 2 SiO 4 particles that measured ∼ 70 nm in diameter. Approximately 500 nm below the MnAl 2 O 4 layer, Al 2 O 3 was formed at the grain boundaries. On the other hand, in a gas mixture with a dew point of − 40 °C, a MnAl 2 O 4 layer with a thickness of ∼ 5 nm was formed on most parts of the surface. On some parts of the surface, Mn 2 SiO 4 particles were formed irregularly up to a thickness of ∼ 50 nm. Approximately 200 nm below the MnAl 2 O 4 layer, Al 2 O 3 was found at the grain boundaries. Thermodynamic calculations were performed to explain the experimental results. The calculations showed that when a O2 > ∼ 1.26 × 10 −28 , MnO, MnAl 2 O 4 , and Mn 2 SiO 4 can be formed together, and the major oxide is MnO. When a O2 is in the range of 1.26 × 10 −28 –2.51 × 10 −31 , MnO is not stable but MnAl 2 O 4 is the major oxide. When a O2 < ∼ 2.51 × 10 −31 , only Al 2 O 3 is stable. Consequently, the effective activity of oxygen is considered the dominant factor in determining the type and shape of surface oxides of TWIP steel. - Highlights: • The surface oxides of TWIP steel annealed at 800 °C were investigated using TEM. • The surface oxides were determined by the dew point during the annealing process. • The activity of oxygen is the major factor determining the oxides of TWIP steel

  2. V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

    Science.gov (United States)

    Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

    2013-01-28

    An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

  3. Solid state solubility of copper oxides in hydroxyapatite

    Science.gov (United States)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  4. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  5. Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

    International Nuclear Information System (INIS)

    Gaigeot, Marie-Pierre; Sprik, Michiel; Sulpizi, Marialore

    2012-01-01

    The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, ‘ice-like’ and ‘liquid-like’ features in these spectra are interpreted as the result of hydrogen bonds of different strengths between surface silanols/aluminols and water. (paper)

  6. Nitride surface passivation of GaAs nanowires: impact on surface state density.

    Science.gov (United States)

    Alekseev, Prokhor A; Dunaevskiy, Mikhail S; Ulin, Vladimir P; Lvova, Tatiana V; Filatov, Dmitriy O; Nezhdanov, Alexey V; Mashin, Aleksander I; Berkovits, Vladimir L

    2015-01-14

    Surface nitridation by hydrazine-sulfide solution, which is known to produce surface passivation of GaAs crystals, was applied to GaAs nanowires (NWs). We studied the effect of nitridation on conductivity and microphotoluminescence (μ-PL) of individual GaAs NWs using conductive atomic force microscopy (CAFM) and confocal luminescent microscopy (CLM), respectively. Nitridation is found to produce an essential increase in the NW conductivity and the μ-PL intensity as well evidence of surface passivation. Estimations show that the nitride passivation reduces the surface state density by a factor of 6, which is of the same order as that found for GaAs/AlGaAs nanowires. The effects of the nitride passivation are also stable under atmospheric ambient conditions for six months.

  7. Effect of surface roughness and surface modification of indium tin oxide electrode on its potential response to tryptophan

    International Nuclear Information System (INIS)

    Khan, Md. Zaved Hossain; Nakanishi, Takuya; Kuroiwa, Shigeki; Hoshi, Yoichi; Osaka, Tetsuya

    2011-01-01

    Highlights: → We examine factors affecting potential response of ITO electrode to tryptophan. → Surface roughness of ITO electrode affects the stability of its rest potential. → Surface modification is effective for ITO electrode with a certain roughness. → Optimum values of work function exist for potential response of ITO to tryptophan. - Abstract: The effect of surface modification of indium tin oxide (ITO) electrode on its potential response to tryptophan was investigated for ITO substrates with different surface roughness. It was found that a small difference in surface roughness, between ∼1 and ∼2 nm of R a evaluated by atomic force microscopy, affects the rest potential of ITO electrode in the electrolyte. A slight difference in In:Sn ratio at the near surface of the ITO substrates, measured by angle-resolved X-ray photoelectron spectrometry and Auger electron spectroscopy is remarkable, and considered to relate with surface roughness. Interestingly, successive modification of the ITO surface with aminopropylsilane and disuccinimidyl suberate, of which essentiality to the potential response to indole compounds we previously reported, improved the stability of the rest potential and enabled the electrodes to respond to tryptophan in case of specimens with R a values ranging between ∼2 and ∼3 nm but not for those with R a of ∼1 nm. It was suggested that there are optimum values of effective work function of ITO for specific potential response to tryptophan, which can be obtained by the successive modification of ITO surface.

  8. Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

    Science.gov (United States)

    Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

    2015-09-15

    Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

    Science.gov (United States)

    Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

    2018-06-08

    A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

  10. A TPD-MS study of glassy carbon surfaces oxidized by CO2 and O2

    Directory of Open Access Journals (Sweden)

    MILA D. LAUSEVIC

    2002-11-01

    Full Text Available The temperature-programmed desorption (TPD method combined with mass spectrometric (MS analysis has been applied to investigate the surface properties of carbon materials. The apparatus consisting of a temperature-programmed furnace and a quadrupole mass spectrometer was constructed in order to characterize the surface of differently treated glassy carbon samples. In this work, samples of glassy carbon exposed to air, CO2 and O2 were examined. The desorption of H2O, CO and CO2, as major products, indicated the presence of different oxide groups. The amount of these groups for all samples was calculated. It is concluded that oxidation affects the nature and the amount of the surface oxide groups and contributes to their increased stability.

  11. Surface oxidation: an effective way to induce piezoelectricity in 2D black phosphorus

    Science.gov (United States)

    Li, Jiabin; Zhao, Ting; He, Chaoyu; Zhang, Kaiwang

    2018-03-01

    In this letter, first-principles methods are employed to investigate the elastic stiffness and piezoelectric tensors of surface-oxidized black phosphorene. Our results show that the piezoelectric coefficients d 11 and d 12 for surface-oxidized black phosphorene are 88.54 pm V-1 and  -1.94 pm V-1, respectively, which are comparable to those of group-IV monochalcogenides and more remarkable than those of the experimentally viable h-BN and MoS2. These results indicate that surface-oxidization is an effective way to make black phosphorene into an excellent piezoelectric material for potential applications in sensors, actuators, electric field generators and any other applications requiring electrical and mechanical energy conversion. We expect further experimental exploration on this interesting result to confirm our predictions.

  12. An evaluation of the effect of surface chromium concentration on the oxidation of a stainless steel

    International Nuclear Information System (INIS)

    Lobb, R.C.; Evans, H.E.

    1983-01-01

    Short-term oxidation tests have been performed at 850 deg C in a CO 2 -based atmosphere on 20Cr-25Ni-Nb-stabilized steels previously exposed to dynamic vacuum at 1000 deg C. This pre-treatment preferentially removes chromium from the metal surface and is always detrimental to the oxidation properties. It is shown that porous, iron-rich oxides initially form on specimens with surface chromium concentrations 18.5 w/o chromium, a protective surface layer is produced. It is suggested that the transition between these extremes is determined by nucleation conditions and, in the present steels, it is shown how the metal grain size plays a significant role. (author)

  13. Surface structure and oxidation reactivity of oil sand coke particles

    Energy Technology Data Exchange (ETDEWEB)

    Fairbridge, C.; Palmer, A.D.; Ng, S.H.; Furimsky, E.

    1987-05-01

    Fractions of particles of varying mean diameter were isolated from coke obtained from the fluid coking of Athabasca bitumen. Correlations were established between the rate of oxygen sorption and the apparent surface area as measured by carbon dioxide adsorption. The rate of oxygen sorption, r/sub o/, could be related to particle radius, R, by r/sub o/ varying with R/sup D/ T over a range of particle size where D is the fractal dimension of the coke. The existence of such correlations may be related to the iterative processes which form the particles. 14 refs., 5 figs., 2 tabs.

  14. Defects in oxide surfaces studied by atomic force and scanning tunneling microscopy

    Directory of Open Access Journals (Sweden)

    Thomas König

    2011-01-01

    Full Text Available Surfaces of thin oxide films were investigated by means of a dual mode NC-AFM/STM. Apart from imaging the surface termination by NC-AFM with atomic resolution, point defects in magnesium oxide on Ag(001 and line defects in aluminum oxide on NiAl(110, respectively, were thoroughly studied. The contact potential was determined by Kelvin probe force microscopy (KPFM and the electronic structure by scanning tunneling spectroscopy (STS. On magnesium oxide, different color centers, i.e., F0, F+, F2+ and divacancies, have different effects on the contact potential. These differences enabled classification and unambiguous differentiation by KPFM. True atomic resolution shows the topography at line defects in aluminum oxide. At these domain boundaries, STS and KPFM verify F2+-like centers, which have been predicted by density functional theory calculations. Thus, by determining the contact potential and the electronic structure with a spatial resolution in the nanometer range, NC-AFM and STM can be successfully applied on thin oxide films beyond imaging the topography of the surface atoms.

  15. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    International Nuclear Information System (INIS)

    Swaminathan, Srinivasan; Spiegel, Michael

    2007-01-01

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N 2 -5% H 2 gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal

  16. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    Energy Technology Data Exchange (ETDEWEB)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T

    2004-05-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters {psi} and {delta} at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance.

  17. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    International Nuclear Information System (INIS)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T.

    2004-01-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters Ψ and Δ at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance

  18. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, Srinivasan [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)]. E-mail: s.swaminathan@mpie.de; Spiegel, Michael [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)

    2007-03-15

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N{sub 2}-5% H{sub 2} gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal.

  19. Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

    Science.gov (United States)

    Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Thomas, Iorwerth O; Netzer, Falko P; Ferrari, Anna Maria; Fortunelli, Alessandro

    2012-02-14

    Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression. This flow can also depend on the thickness of the film and be reduced in passing from ML to BL systems. A regular trend is observed along first-row transition metals, exhibiting a maximum for CuO, in which the charge flow to the oxide is so strong as to reverse the direction of rumpling. A simple protocol to estimate separately the contribution due to charge compression is discussed, and the difference between the work function of the bare metal surface and a Pauling-like electronegativity of the free oxide slabs is used as a descriptor quantity to predict the direction of charge transfer.

  20. Surface interactions affect the toxicity of engineered metal oxide nanoparticles toward Paramecium.

    Science.gov (United States)

    Li, Kungang; Chen, Ying; Zhang, Wen; Pu, Zhichao; Jiang, Lin; Chen, Yongsheng

    2012-08-20

    To better understand the potential impacts of engineered metal oxide nanoparticles (NPs) in the ecosystem, we investigated the acute toxicity of seven different types of engineered metal oxide NPs against Paramecium multimicronucleatum, a ciliated protozoan, using the 48 h LC(50) (lethal concentration, 50%) test. Our results showed that the 48 h LC(50) values of these NPs to Paramecium ranged from 0.81 (Fe(2)O(3) NPs) to 9269 mg/L (Al(2)O(3) NPs); their toxicity to Paramecium increased as follows: Al(2)O(3) Paramecium; this implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in unicellular organisms.

  1. Effect of mass density on surface morphology of electrodeposited manganese oxide films

    Science.gov (United States)

    Singh, Avtar; Kumar, Davinder; Thakur, Anup; Kaur, Raminder

    2018-05-01

    This work focus on high surface area morphology of manganese oxide films which are currently required for electrochemical capacitor electrode to enhance their performance. Electrodeposition of manganese oxide films was carried out using Chronoamperometry for different deposition time ranging from 30 to 120 sec. Cronoamperomertic I-T integrated data have been used to analyze active mass of all electrodeposited films. Morphological study of the deposited films with different mass was carried out through scanning electron microscopy. Film deposited for 30 sec time show highest porous morphology than others. Manganese oxide films with high porosity are suitable for electrochemical capacitor electrode.

  2. A parametric study of laser induced ablation-oxidation on porous silicon surfaces

    International Nuclear Information System (INIS)

    De Stefano, Luca; Rea, Ilaria; Nigro, M Arcangela; Della Corte, Francesco G; Rendina, Ivo

    2008-01-01

    We have investigated the laser induced ablation-oxidation process on porous silicon layers having different porosities and thicknesses by non-destructive optical techniques. In particular, the interaction between a low power blue light laser and the porous silicon surfaces has been characterized by variable angle spectroscopic ellipsometry and Fourier transform infrared spectroscopy. The oxidation profiles etched on the porous samples can be tuned as functions of the layer porosity and laser fluence. Oxide stripes of width less than 2 μm and with thicknesses between 100 nm and 5 μm have been produced, depending on the porosity of the porous silicon, by using a 40 x focusing objective

  3. Super-oxidation of silicon nanoclusters: magnetism and reactive oxygen species at the surface

    Energy Technology Data Exchange (ETDEWEB)

    Lepeshkin, Sergey; Baturin, Vladimir; Tikhonov, Evgeny; Matsko, Nikita; Uspenskii, Yurii; Naumova, Anastasia; Feya, Oleg; Schoonen, Martin A.; Oganov, Artem R.

    2016-01-01

    Oxidation of silicon nanoclusters depending on the temperature and oxygen pressure is explored from first principles using the evolutionary algorithm, and structural and thermodynamic analysis. From our calculations of 90 SinOm clusters we found that under normal conditions oxidation does not stop at the stoichiometric SiO2 composition, as it does in bulk silicon, but goes further placing extra oxygen atoms on the cluster surface. These extra atoms are responsible for light emission, relevant to reactive oxygen species and many of them are magnetic. We argue that the super-oxidation effect is size-independent and discuss its relevance to nanotechnology and miscellaneous applications, including biomedical ones.

  4. Non-activated high surface area expanded graphite oxide for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Vermisoglou, E.C.; Giannakopoulou, T.; Romanos, G.E.; Boukos, N.; Giannouri, M. [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece); Lei, C.; Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 7XH (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece)

    2015-12-15

    Graphical abstract: - Highlights: • One-step exfoliation and reduction of graphite oxide via microwave irradiation. • Effect of pristine graphite (type, flake size) on the microwave expanded material. • Effect of pretreatment and oxidation cycles on the produced expanded material. • Expanded graphene materials with high BET surface areas (940 m{sup 2}/g–2490 m{sup 2}/g). • Non-activated graphene based materials suitable for supercapacitors. - Abstract: Microwave irradiation of graphite oxide constitutes a facile route toward production of reduced graphene oxide, since during this treatment both exfoliation and reduction of graphite oxide occurs. In this work, the effect of pristine graphite (type, size of flakes), pretreatment and oxidation cycles on the finally produced expanded material was examined. All the types of graphite that were tested afforded materials with high BET surface areas ranging from 940 m{sup 2}/g to 2490 m{sup 2}/g, without intervening an activation stage at elevated temperature. SEM and TEM images displayed exfoliated structures, where the flakes were significantly detached and curved. The quality of the reduced graphene oxide sheets was evidenced both by X-ray photoelectron spectroscopy and Raman spectroscopy. The electrode material capacitance was determined via electrochemical impedance spectroscopy and cyclic voltammetry. The materials with PEDOT binder had better performance (∼97 F/g) at low operation rates while those with PVDF binder performed better (∼20 F/g) at higher rates, opening up perspectives for their application in supercapacitors.

  5. Metal/metal-oxide interfaces: A surface science approach to the study of adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Peden, C.H.F.; Kidd, K.B.; Shinn, N.D. (Sandia National Laboratories, Albuquerque, New Mexico 87185-5800 (USA))

    1991-05-01

    Metal-oxide/metal interfaces play an important role, for example, in the joining of an oxide ceramic to a metal for sealing applications. In order to probe the chemical and physical properties of such an interface, we have performed Auger electron spectroscopic (AES) and temperature programed desorption (TPD) experiments on a model system composed of very thin films of Cr, Fe, Ni, or Cu evaporated onto a very thin thermally grown oxide on a W single crystal. Monolayer films of Fe and Cr were found (by AES) to completely wet the oxide surface upon deposition, and were stable up to temperatures at which the films desorbed ({approx}1300 K). In contrast, monolayer Ni and Cu films formed three-dimensional islands exposing the oxidized W surface either upon annealing (Ni) or even upon room-temperature deposition (Cu). The relative interfacial interaction between the overlayer metal and the oxide, as assessed by TPD, increases in the series Cu{lt}Ni{lt}Fe{lt}Cr. This trend follows the heats of formation of the various oxides of these metals.

  6. Ozone Oxidation of Self-Assembled Monolayers on SiOx-Coated Zinc Selenide Surfaces

    Science.gov (United States)

    McIntire, T. M.; Ryder, O. S.; Finlayson-Pitts, B. J.

    2008-12-01

    Airborne particles are important for visibility, human health, climate, and atmospheric reactions. Atmospheric particles contain a significant fraction of organics and such compounds present on airborne particles are susceptible to oxidation by atmospheric oxidants, such as OH, ozone, halogen atoms, and nitrogen trioxide. Oxidized organics associated with airborne particles are thought to be polar, hygroscopic species with enhanced cloud-nucleating properties. Oxide layers on silicon, or SiO2-coated substrates, act as models of environmentally relevant surfaces such as dust particles upon which organics adsorb. We have shown previously that ozone oxidation of unsaturated self-assembled monolayers (SAMs) on silicon attenuated total reflectance (ATR) crystals leads to the formation of carbonyl groups and micron-sized, hydrophobic organic aggregates surrounded by carbon depleted substrate that do not have increased water uptake as previously assumed. Reported here are further ATR-FTIR studies of the oxidation of alkene SAMs on ZnSe and SiO2-coated ZnSe. These substrates have the advantage that they transmit below 1500 cm-1, allowing detection of additional product species. These experiments show that the loss of C=C and formation of carbonyl groups is also accompanied by formation of a peak at 1110 cm-1, attributed to the secondary ozonide. Details concerning the products and mechanism of ozonolysis of alkene SAMs on surfaces based on these new data are presented and the implications for the oxidation of alkenes on airborne dust particles are discussed.

  7. Plasma decontamination of uranium oxide from stainless steel surfaces

    International Nuclear Information System (INIS)

    Veilleux, J.M.; El-Genk, M.S.; Chamberlin, E.P.

    1997-01-01

    The U.S. Department of Energy (DOE) is expected to have 845000 m 3 of transuranic (TRU) waste by the year 2000 that has accumulated during the development and assembly of the nation's nuclear stockpile. The TRU disposal costs alone range up to $28000/m 3 , which could be reduced to $1800/m 3 or less by treating and converting the material to low-level waste. Plasma-based processes have been shown to remove plutonium and uranium surface contaminants from metallic components and could be used to treat TRU with significant cost avoidance, estimated at over $1.0 billion. Martz and Hess conducted the initial work of plutonium etching in low-power radio-frequency (rf) plasma with etch rates ranging from 0.007 to 0.025 kg/m 2 ·h. Veilleux et al. reported that plasma decontamination of uranium from the interior of aluminum objects results in etch rates an order of magnitude greater. The current work reports on removal rates of uranium from stainless steel surfaces and includes estimates of the etch rates and characteristic times for removal

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

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

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

  9. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    International Nuclear Information System (INIS)

    González, J.; Chen, L.F.; Wang, J.A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J.L.

    2016-01-01

    Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V 2 O 5 /Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H 2 O 2 as oxidant. ODS activity was found to be proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts, indicating that the surface vanadium pentoxide (V 2 O 5 ) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V 2 O 5 ) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V 2 O 5 /Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  10. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  11. Thorium binding by biochar fibres derived from Luffa Cylindrica after controlled surface oxidation

    Science.gov (United States)

    Liatsou, Ioanna; Christodoulou, Eleni; Paschalidis, Ioannis

    2017-04-01

    Controlled surface modification of biochar fibres derived from Luffa Cylindrica sponges has been carried out by nitric acid and the degree of oxidation could be controlled by changing the acid concentration or the reaction time. The extent of surface oxidation has been quantified by acid-base titration and FTIR-spectroscopy. Furthermore, thorium binding has been studied as a function of various parameters and the experimental results show that even under strong acidic conditions the relative sorption is above 70% and the sorption capacity of the biochar fibres for Th(IV) at pH 3 is qmax= 70 gṡkg-1.

  12. A process to enhance the specific surface area and capacitance of hydrothermally reduced graphene oxide

    KAUST Repository

    Alazmi, Amira

    2016-08-26

    The impact of post-synthesis processing in reduced graphene oxide materials for supercapacitor electrodes has been analyzed. A comparative study of vacuum, freeze and critical point drying was carried out for hydrothermally reduced graphene oxide demonstrating that the optimization of the specific surface area and preservation of the porous network are critical to maximize its supercapacitance performance. As described below, using a supercritical fluid as the drying medium, unprecedented values of the specific surface area (364 m2 g−1) and supercapacitance (441 F g−1) for this class of materials have been achieved.

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

    Science.gov (United States)

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

    2014-05-01

    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

  14. A process to enhance the specific surface area and capacitance of hydrothermally reduced graphene oxide

    KAUST Repository

    Alazmi, Amira; El Tall, Omar; Rasul, Shahid; Hedhili, Mohamed N.; Patole, Shashikant P.; Da Costa, Pedro M. F. J.

    2016-01-01

    The impact of post-synthesis processing in reduced graphene oxide materials for supercapacitor electrodes has been analyzed. A comparative study of vacuum, freeze and critical point drying was carried out for hydrothermally reduced graphene oxide demonstrating that the optimization of the specific surface area and preservation of the porous network are critical to maximize its supercapacitance performance. As described below, using a supercritical fluid as the drying medium, unprecedented values of the specific surface area (364 m2 g−1) and supercapacitance (441 F g−1) for this class of materials have been achieved.

  15. Effects of surface crystallization and oxidation in nanocrystalline FeNbCuSiB(P) ribbons

    Energy Technology Data Exchange (ETDEWEB)

    Butvinová, B., E-mail: beata.butvinova@savba.sk [Institute of Physics SAS, Dúbravská cesta 9, 845 11 Bratislava (Slovakia); Butvin, P. [Institute of Physics SAS, Dúbravská cesta 9, 845 11 Bratislava (Slovakia); Brzózka, K. [Department of Physics, University of Technology and Humanities in Radom, Krasickiego 54, 26-600 Radom (Poland); Kuzminski, M. [Institute of Physics PAS, Al. Lotnikow 36/42, 02-668 Warsaw (Poland); Maťko, I.; Švec Sr, P. [Institute of Physics SAS, Dúbravská cesta 9, 845 11 Bratislava (Slovakia); Chromčíková, M. [Institute of Inorg. Chem. SAS, Centrum VILA, Študentská 2, 911 50 Trenčín (Slovakia)

    2017-02-15

    Si-poor Fe{sub 74}Nb{sub 3}Cu{sub 1}Si{sub 8}B{sub 14−x}P{sub x}, (x=0, 3) nanocrystalline ribbon-form alloys often form surfaces, which exert in-plane force on underlying ribbon interior when nanocrystallized in even modest presence of oxygen. Mostly unwanted hard-ribbon-axis magnetic anisotropy is standard result. Essential sources of the surface-caused stress have been sought and influence of P instead of B substitution on this effect was studied too. Preferred surface crystallization (PSC) was found to be the major reason. However P substitution suppresses PSC and promotes Fe-oxide formation, which eases the stress, softens the surfaces and provides different annealing evolution of surface properties. - Highlights: • Ar anneal of low-Si FeNbCuBSi ribbons produce surfaces that stress ribbon interior. • The stress comes mainly from preferred crystallization of surfaces. • Partial substitution of B by P changes annealing evolution of surface properties. • Without P, more crystalline surfaces significantly reduce ribbon's elasticity. • P suppresses surface crystallinity, promotes oxides and reduces mutual stress.

  16. Spent-fuel special-studies progress report: probable mechanisms for oxidation and dissolution of single-crystal UO2 surfaces

    International Nuclear Information System (INIS)

    Wang, R.

    1981-03-01

    Due to the complexity of the structural, microstructural and compositional characteristics of spent fuel, basic leaching and dissolution mechanisms were studied with UO 2 matrix material, specifically with single-crystal UO 2 , to isolate individual contributory factors. The effects of oxidation and oxidation-dissolution were investigated in different oxidation conditions, such as in air, oxygenated solutions and deionized water containing H 2 O 2 . In addition, the effects of temperature on dissolution of UO 2 were studied in autoclaves at 75 and 150 0 C. Also, oxidation and dissolution measurements were investigated via electrochemical methods to determine if those techniques could be applied to the characterization of leaching and dissolution of spent fuel in a hot cell. Finally, the effects of radiation were explored since the radiolysis of water may create a localized oxidizing condition at or near the spent fuel-solution interface, even in neutral or reducing conditions as commonly found in deep geological environments. The oxidation and oxidation-dissolution mechanisms for UO 2 are proposed as follows: The UO 2 surface is first oxidized in solution to form a UO/sub 2+x/ surface layer several angstroms thick. This oxidized surface has a high dissolution rate since the UO/sub 2+x/ reacts with the dissolved O 2 , or H 2 O 2 , to form uranyl complex ions in a U(VI) state. As the uranyl ions exceed the solubility limits in solution, they become hydrolyzed to form solid deposits and suspended particles of UO 3 hydrates. The thickness and porosity of the deposited UO 3 hydrate surface-film is dependent on temperature, pH and deposition time. A long-term dissolution rate is then determined by the nature of the surface film, such as porosity, solubility and mechanical properties

  17. Mechanisms for formation and disruption of surface oxides: Final report

    International Nuclear Information System (INIS)

    Lumsden, J.B.

    1987-08-01

    Mill-annealed alloys 600, 690 and 800 were exposed to 10 and 50% caustic solutions containing 1% Na 2 CO 3 to initiate IGA. IGA reproducibly occurred in all three alloys in the 10% caustic solution at 350 0 C after a 240 h exposure and in the 50% caustic solution at 320 0 C after a 120 h exposure. Reproducible IGA did not occur in the 10% caustic solution at 320 0 C after a 120 h exposure. IGA was not observed in mill annealed plus thermally treated alloys 600 and 690 after exposure to any of the test conditions. IGA initiation was correlated with a dealloying mechanism in which the more active alloying metals, iron and chromium, selectively dissolve. Boric acid and calcium hydroxide additives were found to slow or prevent IGA by inhibiting dealloying. Titanates prevented IGA in alloys 600, 690 and 800, passivating the surface with a nickel titanate film

  18. Adhesion mapping of chemically modified and poly(ethylene oxide)-grafted glass surfaces

    OpenAIRE

    Jogikalmath, G.; Stuart, J.K.; Pungor, A.; Hlady, V.

    1999-01-01

    Two-dimensional mapping of the adhesion pull-off forces was used to study the origin of surface heterogeneity in the grafted poly(ethylene oxide) (PEO) layer. The variance of the pull-off forces measured over the μm-sized regions after each chemical step of modifying glass surfaces was taken to be a measure of the surface chemical heterogeneity. The attachment of γ-glycidoxypropyltrimethoxy silane (GPS) to glass decreased the pull-off forces relative to the clean glass and made the surface mo...

  19. Indium-tin oxide surface treatments: Effects on the performance of liquid crystal devices

    International Nuclear Information System (INIS)

    Abderrahmen, A.; Romdhane, F.F.; Ben Ouada, H.; Gharbi, A.

    2006-01-01

    In this work, we investigate the effect of indium tin oxide (ITO) substrate cleaning on the surface properties. Wettability technique was used to measure the contact angle and the surface energy of the different treated ITO substrates. It is found that treatment with the methanol without dehydration gives the lowest water contact angle (most hydrophilic surface) and the highest surface energy compared to other solvents. This result was confirmed by impedance measurements performed on nematic liquid crystal cells with ITO electrodes. Indeed, we check the decrease of ionic entities in the interface ITO/liquid crystal. The polarity and dielectric parameters of the used solvents explain the obtained results

  20. Indium-tin oxide surface treatments: Effects on the performance of liquid crystal devices

    Energy Technology Data Exchange (ETDEWEB)

    Abderrahmen, A. [Laboratoire de physique et chimie des interfaces, Faculte des sciences, 5000, Monastir (Tunisia)]. E-mail: asma_abderrahmen@yahoo.fr; Romdhane, F.F. [Laboratoire de la matiere molle, Faculte des sciences, Tunis (Tunisia); Ben Ouada, H. [Laboratoire de physique et chimie des interfaces, Faculte des sciences, 5000, Monastir (Tunisia); Gharbi, A. [Laboratoire de la matiere molle, Faculte des sciences, Tunis (Tunisia)

    2006-03-15

    In this work, we investigate the effect of indium tin oxide (ITO) substrate cleaning on the surface properties. Wettability technique was used to measure the contact angle and the surface energy of the different treated ITO substrates. It is found that treatment with the methanol without dehydration gives the lowest water contact angle (most hydrophilic surface) and the highest surface energy compared to other solvents. This result was confirmed by impedance measurements performed on nematic liquid crystal cells with ITO electrodes. Indeed, we check the decrease of ionic entities in the interface ITO/liquid crystal. The polarity and dielectric parameters of the used solvents explain the obtained results.

  1. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

    Science.gov (United States)

    Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

    2018-06-13

    The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2010-12-21

    Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Effect of surface oxidation on thermomechanical behavior of NiTi shape memory alloy wire

    Science.gov (United States)

    Ng, Ching Wei; Mahmud, Abdus Samad

    2017-12-01

    Nickel titanium (NiTi) alloy is a unique alloy that exhibits special behavior that recovers fully its shape after being deformed to beyond elastic region. However, this alloy is sensitive to any changes of its composition and introduction of inclusion in its matrix. Heat treatment of NiTi shape memory alloy to above 600 °C leads to the formation of the titanium oxide (TiO2) layer. Titanium oxide is a ceramic material that does not exhibit shape memory behaviors and possess different mechanical properties than that of NiTi alloy, thus disturbs the shape memory behavior of the alloy. In this work, the effect of formation of TiO2 surface oxide layer towards the thermal phase transformation and stress-induced deformation behaviors of the NiTi alloy were studied. The NiTi wire with composition of Ti-50.6 at% Ni was subjected to thermal oxidation at 600 °C to 900 °C for 30 and 60 minutes. The formation of the surface oxide layers was characterized by using the Scanning Electron Microscope (SEM). The effect of surface oxide layers with different thickness towards the thermal phase transformation behavior was studied by using the Differential Scanning Calorimeter (DSC). The effect of surface oxidation towards the stress-induced deformation behavior was studied through the tensile deformation test. The stress-induced deformation behavior and the shape memory recovery of the NiTi wire under tensile deformation were found to be affected marginally by the formation of thick TiO2 layer.

  4. Characterization of structures and surface states of the nanodiamond synthesized by detonation

    International Nuclear Information System (INIS)

    Zou, Q.; Li, Y.G.; Zou, L.H.; Wang, M.Z.

    2009-01-01

    Nanodiamond is a relatively new nanomaterial with broad prospects for application. In this paper, a variety of methods were used to analyze comprehensively the structures and the surface states of the nanodiamond synthesized by detonation, for example, X-ray diffraction (XRD) spectroscopy, energy diffraction spectroscopy (EDS), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy (Raman) and differential scanning calorimeter (DSC). The results show that, the nanodiamond particles are spherical or elliptical in shape. The average grain size is approximately 5 nm. The surfaces of the nanodiamond contain hydroxy, carbonyl, carboxyl, ether-based resin, and other functional groups. The initial oxidation temperature of the nanodiamond in the air is about 550 deg. C, which is lower than that of the bulk diamond.

  5. Characterization of structures and surface states of the nanodiamond synthesized by detonation

    Energy Technology Data Exchange (ETDEWEB)

    Zou, Q., E-mail: zq@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei (China); Li, Y.G.; Zou, L.H.; Wang, M.Z. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei (China)

    2009-11-15

    Nanodiamond is a relatively new nanomaterial with broad prospects for application. In this paper, a variety of methods were used to analyze comprehensively the structures and the surface states of the nanodiamond synthesized by detonation, for example, X-ray diffraction (XRD) spectroscopy, energy diffraction spectroscopy (EDS), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy (Raman) and differential scanning calorimeter (DSC). The results show that, the nanodiamond particles are spherical or elliptical in shape. The average grain size is approximately 5 nm. The surfaces of the nanodiamond contain hydroxy, carbonyl, carboxyl, ether-based resin, and other functional groups. The initial oxidation temperature of the nanodiamond in the air is about 550 deg. C, which is lower than that of the bulk diamond.

  6. Development of highly faceted reduced graphene oxide-coated copper oxide and copper nanoparticles on a copper foil surface

    Directory of Open Access Journals (Sweden)

    Rebeca Ortega-Amaya

    2016-07-01

    Full Text Available This work describes the formation of reduced graphene oxide-coated copper oxide and copper nanoparticles (rGO-Cu2ONPs, rGO-CuNPs on the surface of a copper foil supporting graphene oxide (GO at annealing temperatures of 200–1000 °C, under an Ar atmosphere. These hybrid nanostructures were developed from bare copper oxide nanoparticles which grew at an annealing temperature of 80 °C under nitrogen flux. The predominant phase as well as the particle size and shape strongly depend on the process temperature. Characterization with transmission electron microscopy and scanning electron microscopy indicates that Cu or Cu2O nanoparticles take rGO sheets from the rGO network to form core–shell Cu–rGO or Cu2O–rGO nanostructures. It is noted that such ones increase in size from 5 to 800 nm as the annealing temperature increases in the 200–1000 °C range. At 1000 °C, Cu nanoparticles develop a highly faceted morphology, displaying arm-like carbon nanorods that originate from different facets of the copper crystal structure.

  7. A method of eliminating the surface defect in low-temperature oxidation powder added UO2 pellet

    International Nuclear Information System (INIS)

    Yoo, H. S.; Lee, S. J.; Kim, J. I.; Jeon, K. R.; Kim, J. W.

    2002-01-01

    A study on methods to eliminate surface defect shown in low-temperature oxidation powder added UO 2 pellet has been performed. Powders oxidized at 350 .deg. C for 4 hrs were prepared and mixed with UO 2 powder after crushing them. After being sintered, surfaces of the pellet were inspected both visually and optically. A large number of defects were observed on the surface of the specimens in which low-temperature oxidation powders were directly mixed or master mixed with UO 2 powder while both specimens produced from mixed powders including milled oxidation powders and powders that were milled totally after mixing had clean surfaces. However, optical examination showed considerably large defected pores in the milled oxidation powder added pellet and it was confirmed that the inner defects can be eliminated completely only when milling the entire mixture on UO 2 and low-temperature oxidation powder, but not by crushing only oxidation powder

  8. Investigation of electrochemical behaviour and structure of oxide films on Ni60Nb40 alloy in amorphous and crystalline states

    International Nuclear Information System (INIS)

    Tomashov, N.D.; Skvortsova, I.B.; Gorodetskij, A.E.; Bogomolov, D.B.

    1987-01-01

    Electrochemical properties of Ni 60 Nb 40 alloy in amorphous and crystalline states as well as structure of oxide films forming during anode polarization in electrolytes on the surface of this alloy in both its states are investigated. It is stated that increased passive ability of Ni 60 Nb 40 alloys in amorphous state and high efficiency of chlorine evolution (2 n NaCl+HCl up to pH=0) anode process in comparison with crystalline state are defined by increased homogeneity and uniformity of passive films forming on amorphous alloy and their increased electron conductivity, that is in direct dependence on different structure of passive films forming on alloys in amorphous and crystalline states

  9. Internal state distributions of molecules scattering and desorbing from surfaces

    International Nuclear Information System (INIS)

    Auerbach, D.J.

    1983-01-01

    Attempts are made to interpret scattering experiments of NO molecules on Ag(111) where a (rotational) state-specific detector has been used. A model using an anisotropic potential is proposed to explain the observed incoming energy- and angle dependence. The so-called rotational rainbows are explained. It is concluded, that in this way information on intermolecular potentials and the transfer of translational to rotational energy in the dynamics of trapping and sticking of molecules on surfaces can be extracted. (G.Q.)

  10. Surface acoustic wave solid-state rotational micromotor

    Science.gov (United States)

    Shilton, Richie J.; Langelier, Sean M.; Friend, James R.; Yeo, Leslie Y.

    2012-01-01

    Surface acoustic waves (SAWs) are used to drive a 1 mm diameter rotor at speeds exceeding 9000 rpm and torque of nearly 5 nNm. Unlike recent high-speed SAW rotary motors, however, the present design does not require a fluid coupling layer but interestingly exploits adhesive stiction as an internal preload, a force usually undesirable at these scales; with additional preloads, smaller rotors can be propelled to 15 000 rpm. This solid-state motor has no moving parts except for the rotor and is sufficiently simple to allow integration into miniaturized drive systems for potential use in microfluidic diagnostics, optical switching and microrobotics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Latifi, Afrooz, E-mail: afroozlatifi@yahoo.com [Department of Biomaterials, Biomedical Engineering Faculty, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Imani, Mohammad [Novel Drug Delivery Systems Dept., Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran (Iran, Islamic Republic of); Khorasani, Mohammad Taghi [Biomaterials Dept., Iran Polymer and Petrochemical Institute, P.O. Box 14965/159, Tehran (Iran, Islamic Republic of); Daliri Joupari, Morteza [Animal and Marine Biotechnology Dept., National Institute of Genetic Engineering and Biotechnology, P.O. Box 14965/161, Tehran (Iran, Islamic Republic of)

    2014-11-30

    Highlights: • Stainless steel 316L was surface modified by plasma surface oxidation (PSO) and silicone rubber (SR) coating. • On the PSO substrates, concentration of oxide species was increased ca. 2.5 times comparing to non-PSO substrates. • The surface wettability was improved to 12.5°, in terms of water contact angle, after PSO. • Adhesion strength of SR coating on the PSO substrates was improved by more than two times comparing to non-PSO ones. • After pull-off test, the fractured area patterns for SR coating were dependent on the type of surface modifications received. - Abstract: 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{sup −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.

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

    OpenAIRE

    Jarlbring, Mathias

    2004-01-01

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

  13. Terrestrial Ecosystems - Land Surface Forms of the Conterminous United States

    Science.gov (United States)

    Cress, Jill J.; Sayre, Roger G.; Comer, Patrick; Warner, Harumi

    2009-01-01

    As part of an effort to map terrestrial ecosystems, the U.S. Geological Survey has generated land surface form classes to be used in creating maps depicting standardized, terrestrial ecosystem models for the conterminous United States, using an ecosystems classification developed by NatureServe . A biophysical stratification approach, developed for South America and now being implemented globally, was used to model the ecosystem distributions. Since land surface forms strongly influence the differentiation and distribution of terrestrial ecosystems, they are one of the key input layers in this biophysical stratification. After extensive investigation into various land surface form mapping methodologies, the decision was made to use the methodology developed by the Missouri Resource Assessment Partnership (MoRAP). MoRAP made modifications to Hammond's land surface form classification, which allowed the use of 30-meter source data and a 1-km2 window for analyzing the data cell and its surrounding cells (neighborhood analysis). While Hammond's methodology was based on three topographic variables, slope, local relief, and profile type, MoRAP's methodology uses only slope and local relief. Using the MoRAP method, slope is classified as gently sloping when more than 50 percent of the area in a 1-km2 neighborhood has slope less than 8 percent, otherwise the area is considered moderately sloping. Local relief, which is the difference between the maximum and minimum elevation in a neighborhood, is classified into five groups: 0-15 m, 16-30 m, 31-90 m, 91-150 m, and >150 m. The land surface form classes are derived by combining slope and local relief to create eight landform classes: flat plains (gently sloping and local relief = 90 m), low hills (not gently sloping and local relief = 150 m). However, in the USGS application of the MoRAP methodology, an additional local relief group was used (> 400 m) to capture additional local topographic variation. As a result, low

  14. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun

    2016-03-30

    © 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

  15. Reactivity of surface of metal oxide particles: from adsorption of ions to deposition of colloidal particles

    International Nuclear Information System (INIS)

    Lefevre, Gregory

    2010-01-01

    In this Accreditation to supervise research (HDR), the author proposes an overview of his research works in the field of chemistry. These works more particularly addressed the understanding of the surface reactivity of metal oxide particles and its implication on sorption and adherence processes. In a first part, he addresses the study of surface acidity-alkalinity: measurement of surface reactivity by acid-base titration, stability of metal oxides in suspension, effect of morphology on oxide-hydroxide reactivity. The second part addresses the study of sorption: reactivity of iron oxides with selenium species, sorption of sulphate ions on magnetite, attenuated total reflection infrared spectroscopy (ATR-IR). Adherence effects are addressed in the third part: development of an experimental device to study adherence in massive substrates, deposition of particles under turbulent flow. The last part presents a research project on the effect of temperature on ion sorption at solids/solutions interfaces, and on the adherence of metal oxide particles. The author gives his detailed curriculum, and indicates his various publications, teaching activities, research and administrative responsibilities

  16. DFT study of cyanide oxidation on surface of Ge-embedded carbon nanotube

    Science.gov (United States)

    Gao, Wei; Milad Abrishamifar, Seyyed; Ebrahimzadeh Rajaei, Gholamreza; Razavi, Razieh; Najafi, Meysam

    2018-03-01

    In recent years, the discovery of suitable catalyst to oxidation of the cyanide (CN) has high importance in the industry. In present study, in the first step, the carbon nanotube (CNT) with the Ge atom embedded and the surface of Ge-CNT via the O2 molecule activated. In second step, the oxidation of CN on surface of the Ge-CNT via the Langmuir Hinshelwood (LH) and the Eley Rideal (ER) mechanisms was investigated. Results show that O2-Ge-CNT oxidized the CN molecule via the Ge-CNT-O-O∗ + CN → Ge-CNT-O-O∗-CN → Ge-CNT-O∗ + OCN and the Ge-CNT-O∗ + CN → Ge-CNT + OCN reactions. Results show that oxidation of CN on surface of Ge-CNT via the LH mechanism has lower energy barrier than ER mechanism. Finally, calculated parameters reveal that Ge-CNT is acceptable catalyst with high performance for CN oxidation, form theoretical point of view.

  17. Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

    Science.gov (United States)

    Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

    2017-07-19

    An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .

  18. Determination of surface oxide compositions on Alloy 600 using Rutherford backscattering

    International Nuclear Information System (INIS)

    Hanson, A.L.; Kraner, H.W.

    1984-01-01

    The surface composition of oxides formed on Alloy 600 under conditions similar to those in the primary side of PWR heat exchangers has been studied as a function of potential using Rutherford backscattering and proton inelastic scattering. Electropolished samples of Alloy 600 were exposed at several potentials to a solution of 0.18M H 3 BO 3 (2000ppm B) with 0.21mM LiOH (1.5ppm Li) at 300 0 C for 450 hours. The potentials relative to an internal hydrogen electrode ranged from -.09 to 750 mV. RBS analysis showed little or no oxide formation on samples exposed at 0 mV. Above 0 mV oxide layers formed whose thicknesses increased with potential. In addition the RBS showed a significantly enhanced concentration of aluminum and silicon in oxide. Both the oxygen and the sum of the aluminum and silicon content appeared to maintain a fixed surface concentration independent of the oxide thickness. Boron and lithium concentrations were analyzed with proton inelastic scattering. No lithium was detected in any sample. The boron concentration was found to follow the thickness of the oxide