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Sample records for oxidized cu110 surface

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

    SciTech Connect

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

    2013-04-18

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

  2. Water adsorbate influence on the Cu(110) surface optical response

    NASA Astrophysics Data System (ADS)

    Baghbanpourasl, Amirreza; Schmidt, Wolf Gero; Denk, Mariella; Cobet, Christoph; Hohage, Michael; Zeppenfeld, Peter; Hingerl, Kurt

    2015-11-01

    Surface reflectance anisotropy may be utilized for characterizing surfaces, interfaces, and adsorption structures. Here, the reflectance anisotropy and surface dielectric functions of the thermodynamically most favored water adsorbate structures on the Cu(110) surface (i.e. hexagonal bilayers, pentagonal chains, and partially dissociated water structures) are calculated from density-functional theory and compared with recent experimental data. It is shown that the water overlayer structures modify in a geometry-specific way the optical anisotropy of the bare surface which can be exploited for in situ determination of the adsorption structures. For hexagonal bilayer overlayer geometries, strong features in the vacuum ultraviolet region are predicted. The theoretical analysis shows a noticeable influence of intraband transitions also for higher photon energies and rather slight influences of the van der Waals interaction on the spectral signatures. Water induced strain effects on the surface optical response are found to be negligible.

  3. Surface Chirality of Gly-Pro Dipeptide Adsorbed on a Cu(110) Surface.

    PubMed

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

    2015-07-01

    The adsorption of chiral Gly-Pro dipeptide on Cu(110) has been characterized by combining in situ polarization modulation infrared reflection absorption spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS). The chemical state of the dipeptide, and its anchoring points and adsorption geometry, were determined at various coverage values. Gly-Pro molecules are present on Cu(110) in their anionic form (NH2 /COO(-)) and adsorb under a 3-point binding via both oxygen atoms of the carboxylate group and via the nitrogen atom of the amine group. Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) have shown the presence of an extended 2D chiral array, sustained via intermolecular H-bonds interactions. Furthermore, due to the particular shape of the molecule, only one homochiral domain is formed, creating thus a truly chiral surface. PMID:25847844

  4. Reaction pathways in the oxydehydrogenation of ammonia at Cu(110) surfaces

    NASA Astrophysics Data System (ADS)

    Afsin, B.; Davies, P. R.; Pashusky, A.; Roberts, M. W.; Vincent, D.

    1993-03-01

    The activation of ammonia by oxygen at Cu(110) has been investigated by X-ray photoelectron and electron energy loss spectroscopies. The chemistry observed is dependent on the temperature, whether oxygen is preadsorbed and its surface coverage, or whether the oxygen is coadsorbed with ammonia. Amide species NH 2(a) are formed only when adsorbed ammonia is exposed to dioxygen at low temperatures. With increasing temperature further step-wise dehydrogenation occurs to give imide NH(a) and nitrogen adatoms N(a). For an ammonia-rich dioxygen-ammonia mixture a facile reaction to form exclusively bent imide species occurs at 295 K with no evidence for chemisorbed oxygen being present until ?NH approaches unity. A hot transient O -(s) species is implicated in the reaction mechanism. On the other hand for ?oxygen ? 1.0 the oxygen overlayer is relatively unreactive, imide formation being kinetically slow and limited in extent. Furthermore there is no evidence in the HREEL spectra for a loss peak characteristic of ? nh although a ? NH loss peak is present. This suggests a linear form of NH(a) in contrast to the bent form generated by coadsorption of ammonia and dioxygen. Two different oxygen species can exist at the copper surface: one that is highly reactive to ammonia and undergoes chemisorptive replacement, the other inactive. We suggest that the former is O --like and associated with isolated oxygen atoms and the latter O 2--like and associated with multi-oxygen atom copper nuclei. High catalytic oxydehydrogenation activity can be maintained during the coadsorption of dioxygen and ammonia, provided the development of O 2- species (oxide growth associated with surface reconstruction) is suppressed. The latter has been shown to occur even at low oxygen coverages ( ? ? 0.1) the ammonia molecule acting as a sensitive and specific probe for the isolated O --like species. The O -(s) species are therefore transients in the development of the chemisorbed oxygen overlayer and characterised by high chemical reactivity. Support for this model comes from recent scanning tunnelling microscope studies of the Al(111)-oxygen system of Ertl and coworkers [Phys. Rev. Lett. 68 (1992) 624] (ref. [1]).

  5. Thermally and Vibrationally Induced Tautomerization of Single Porphycene Molecules on a Cu(110) Surface

    NASA Astrophysics Data System (ADS)

    Kumagai, Takashi; Hanke, Felix; Gawinkowski, Sylwester; Sharp, John; Kotsis, Konstantinos; Waluk, Jacek; Persson, Mats; Grill, Leonhard

    2013-12-01

    We report the direct observation of intramolecular hydrogen atom transfer reactions (tautomerization) within a single porphycene molecule on a Cu(110) surface by scanning tunneling microscopy. It is found that the tautomerization can be induced via inelastic electron tunneling at 5 K. By measuring the bias-dependent tautomerization rate of isotope-substituted molecules, we can assign the scanning tunneling microscopy-induced tautomerization to the excitation of specific molecular vibrations. Furthermore, these vibrations appear as characteristic features in the dI/dV spectra measured over individual molecules. The vibrational modes that are associated with the tautomerization are identified by density functional theory calculations. At higher temperatures above ˜75K, tautomerization is induced thermally and an activation barrier of about 168 meV is determined from an Arrhenius plot.

  6. The structure of sulfur adlayers at Cu(110) surfaces: an STM and XPS study

    NASA Astrophysics Data System (ADS)

    Carley, Albert F.; Davies, Philip R.; Jones, Rhys V.; Harikumar, K. R.; Kulkarni, Giri U.; Roberts, M. Wyn

    2000-02-01

    A detailed understanding of the sulfur phases formed by the dissociation of hydrogen sulfide and methyl mercaptan at Cu(110) surfaces has been obtained in a combined STM/X-ray photoelectron spectroscopy study. At low concentrations adsorbed sulfur atoms are mobile at room temperature, forming the ordered c(2×2) structures only when the concentration of sulfur reaches approximately 3.8×10 14 cm -2. Surface oxygen inhibits sulfur diffusion and ordered c(2×2) sulfur structures are formed at much lower sulfur concentrations in its presence, the sulfur also influences the oxygen structure inhibiting the formation of large oxygen islands. Sulfur concentration ( ?s) limits for the c(2×2) ( ?s<4.4×10 14 cm -2), p(5×2) (4.4×10 14 cm -2< ?s<6.6 ×10 14 cm -2) and the p(3×2) ( ?s=7.1×10 14 cm -2) sulfur phases have been established. Models, involving surface buckling, have been suggested for these structures which reconcile the previous LEED, STM and SEXAFS data. The adsorption of methyl mercaptan at 295 K results in mercaptide formation but no ordered structures; a herringbone type structure is, however, observed when methyl mercaptan is adsorbed at 70 K and then warmed to room temperature. On heating to 450 K mercaptide dissociates with the complete desorption of carbon as hydrocarbons, providing an alternative route to high chemisorbed sulfur concentration structures. On the basis of XP spectra of methyl mercaptan and a correlation between the XP data and the STM images, the total photoionisation cross-section of the S 2p orbital reported in the literature has been shown to be in error and a new value (2.10, relative to the C 1s cross-section) derived.

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

    SciTech Connect

    Ma Qiang; Zaera, Francisco

    2013-01-15

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

  8. The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Fujitani, T.; Uchijima, T.; Nakamura, J.

    1998-03-01

    The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO 2 and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0< ?Zn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.

  9. Thermal chemistry of copper(I)-N,N '-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces

    SciTech Connect

    Ma Qiang; Zaera, Francisco; Gordon, Roy G.

    2012-01-15

    The surface chemistry of copper(I)-N,N'-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces has been characterized under ultrahigh vacuum by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy. A series of thermal stepwise conversions were identified, starting with the partial dissociative adsorption of the copper acetamidinate dimers into a mixture of monomers and dimers on the surface. An early dissociation of a C-N bond leads to the production of N-sec-butylacetamidine, which is detected in TPD experiments in three temperature regimes, the last one centered around 480 K. Butene, and a small amount of butane, is also detected above approximately 500 K, and hydrogen production, an indication of dehydrogenation of surface fragments, is observed at 460, 550 and 670 K. In total, only about 10% of the initial copper(I)-N,N'-di-sec-butylacetamidinate adsorbed monolayer decomposes, and only about {approx}3% of carbon is left behind on the surface after heating to high temperatures. The implications of this surface chemistry to the design of chemical film growth processes using copper acetamidinates as precursors are discussed.

  10. Superatom orbitals of Sc3N@C80 and their intermolecular hybridization on Cu(110)-(2×1)-O surface

    NASA Astrophysics Data System (ADS)

    Huang, Tian; Zhao, Jin; Feng, Min; Petek, Hrvoje; Yang, Shangfeng; Dunsch, Lothar

    2010-02-01

    We investigate the electronic structure of an endohedral fullerene, Sc3N@C80 , chemisorbed on Cu(110)-(2×1)-O surface by scanning tunneling microscopy and density-functional theory. Scanning tunneling microscopy and spectroscopy identify a series of delocalized atomlike superatom molecular orbitals (SAMOs) in the Sc3N@C80 and its aggregates. By contrast to C60 , the encapsulated Sc3N cluster in Sc3N@C80 distorts the nearly-spherical central potential of the carbon cage, imparting an asymmetric spatial distribution to the SAMOs. When Sc3N@C80 molecules form dimers and trimers, however, the strong intermolecular hybridization results in highly symmetric hybridized SAMOs with clear bonding and antibonding characteristics. The electronic-structure calculations on Sc3N@C80 and its aggregates confirm the existence of SAMOs and reproduce their hybridization as observed in the experiment.

  11. Chemical versus van der Waals Interaction: The Role of the Heteroatom in the Flat Absorption of Aromatic Molecules C6H6, C5NH5, and C4N2H4 on the Cu(110) Surface

    NASA Astrophysics Data System (ADS)

    Atodiresei, N.; Caciuc, V.; Lazi?, P.; Blügel, S.

    2009-04-01

    We perform first-principles calculations aimed at investigating the role of a heteroatom such as N in the chemical and long-range van der Waals (vdW) interactions for a flat adsorption of several ?-conjugated molecules on the Cu(110) surface. Our study reveals that the alignment of the molecular orbitals at the adsorbate-substrate interface depends on the number of heteroatoms. As a direct consequence, the molecule-surface vdW interactions involve not only ?-like orbitals which are perpendicular to the molecular plane but also ?-like orbitals delocalized in the molecular plane.

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

    SciTech Connect

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

    2013-10-31

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

  13. Methanol adsorption on Cu(110) and the angular distribution of the reaction products.

    PubMed

    Demirci, E; Stettner, J; Kratzer, M; Schennach, R; Winkler, A

    2007-04-28

    Integral and angle resolved thermal desorption spectroscopies were used to study methanol adsorption and oxidation on clean and oxygen covered Cu(110) surfaces. Special emphasis was put on the Cu-CuO stripe phase, which forms when the Cu(110) surface is covered with 0.25 ML of oxygen. In the temperature regime between 200 and 300 K associative desorption of methanol and water takes place, showing a normal desorption character with peaks shifting to lower temperature with increasing coverage and with a nearly cosine angular desorption distribution. In the temperature range of about 350 K formaldehyde, hydrogen, and again methanol desorb nearly concomitantly in the form of a very narrow peak (full width at half maximum=10 K), with peaks shifting to higher temperature with increasing methanol coverage. The angular distribution of these peaks is strongly forward focused, indicating activation barriers being involved. In the case of the Cu-CuO stripe phase the angular distribution of the desorption products is clearly different in the [110] and [001] azimuthal directions, demonstrating the influence of the border lines between the copper and the copper oxide stripes on the desorption process. PMID:17477627

  14. c2 2 Water-Hydroxyl Layer on Cu(110): AWetting Layer Stabilized by Bjerrum Defects Matthew Forster,1

    E-print Network

    Alavi, Ali

    cð2 Â 2Þ Water-Hydroxyl Layer on Cu(110): AWetting Layer Stabilized by Bjerrum Defects Matthew the composition and stability of mixed water-hydroxyl layers is a key step in describing wetting and how surfaces, structures containing an excess of water over hydroxyl are stabilized on Cu (110) by forming a distorted

  15. Configuration change of NO on Cu(110) as a function of temperature

    SciTech Connect

    Shiotari, A.; Mitsui, T.; Okuyama, H. Hatta, S.; Aruga, T.; Koitaya, T.; Yoshinobu, J.

    2014-06-07

    The bonding structure of nitric oxide (NO) on Cu(110) is studied by means of scanning tunneling microscopy, reflection absorption infrared spectroscopy, and electron energy loss spectroscopy at 6–160 K. At low temperatures, the NO molecule adsorbs at the short bridge site via the N end in an upright configuration. At around 50 K, this turns into a flat configuration, in which both the N and O atoms interact with the surface. The flat configuration is characterized by the low-frequency N–O stretching mode at 855 cm{sup ?1}. The flat-lying NO flips back and forth when the temperature increases to ?80 K, and eventually dissociates at ?160 K. We propose a potential energy diagram for the conversion of NO on the surface.

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

    SciTech Connect

    Brandstetter, T.; Draxler, M.; Hohage, M.; Zeppenfeld, P.; Stehrer, T.; Heitz, J.; Georgiev, N.; Martinotti, D.; Ernst, H.-J.

    2008-07-15

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

  17. Oxide surfaces.

    PubMed

    Willmott, Phil

    2008-07-01

    Although the history of metal oxides and their surfaces goes back several decades to landmark studies, such as Mott and Peierls' explanation of electrical insulation in materials that are predicted in band theory to be conducting, or the observation by Morin of the superfast metal-to-insulator transition in vanadium dioxide, it is only in the last two decades that the world of condensed matter physics has become increasingly dominated by research into complex metal oxides. This has been driven most notably by an attempt to better understand and describe the fundamental physical processes behind their seemingly endless spectrum of properties, which in turn has also led to the discovery of novel phenomena, most prominently demonstrated by the discovery of high-temperature superconductivity in 1986, colossal magnetoresistance in 1994, and most recently, the formation of a two-dimensional conducting layer at the interface between two band insulators in 2004. One important reason why metal oxides, particularly in the form of thin films, have become such a popular subject for basic condensed matter research is that they offer a uniquely versatile materials base for the development of novel technologies. They owe this versatility both to the many different elemental combinations that lead to structurally similar forms, and also to the fact that in many cases, the strong interaction between the valence electrons means that there is a subtle interplay between structure and magnetic and electronic properties. This aspect has led in recent years to the birth or renaissance of research fields such as spintronics, orbital ordering, and multiferroics. Surfaces and interfaces are especially interesting in these strongly-correlated electron systems, where the rearrangement of electrical charge resulting from a minimization of surface or interfacial energy can have unexpected and often exciting consequences. Indeed, as the drive to miniaturize devices well below the micron size continues, the fraction of material constituting `non-bulklike' properties is becoming increasingly significant. On the other hand, the degree of sophistication needed to understand and predict these complex systems has driven a complementary thrust in theoretical modelling, beginning as long ago as 1963, with Hubbard's addition to the tight-binding model of the formulation of conduction in terms of a hopping integral. The present level of understanding is now so advanced that theory and experiment are no longer so distinct, both gaining further insights from one another. The aim of this special issue in the Journal of Physics: Condensed Matter is to convey to the reader the most up-to-date understanding of the physics of the surfaces, interfaces, and thin films of complex metal oxides, in a clear and accessible manner. The order of the 16 contributions reflects the broad range of disciplines within this field, beginning with general considerations and theoretical models, continuing with film growth techniques and characterization, and concluding with material types and devices. It is fairly safe to assume that research in this area will enjoy as illustrious and long-lived a future as it has had a past. As such, it is hoped that this contribution will accurately reflect this status in the first decade of the 21st Century and long provide a reference for physicists continuing on this exciting Odyssey. PMID:21694334

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

    PubMed Central

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

    2014-01-01

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

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

    E-print Network

    Gao, Hongjun

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

  20. From Graphene Nanoribbons on Cu(111) to Nanographene on Cu(110): Critical Role of Substrate Structure in the Bottom-Up Fabrication Strategy.

    PubMed

    Simonov, Konstantin A; Vinogradov, Nikolay A; Vinogradov, Alexander S; Generalov, Alexander V; Zagrebina, Elena M; Svirskiy, Gleb I; Cafolla, Attilio A; Carpy, Thomas; Cunniffe, John P; Taketsugu, Tetsuya; Lyalin, Andrey; Mårtensson, Nils; Preobrajenski, Alexei B

    2015-09-22

    Bottom-up strategies can be effectively implemented for the fabrication of atomically precise graphene nanoribbons. Recently, using 10,10'-dibromo-9,9'-bianthracene (DBBA) as a molecular precursor to grow armchair nanoribbons on Au(111) and Cu(111), we have shown that substrate activity considerably affects the dynamics of ribbon formation, nonetheless without significant modifications in the growth mechanism. In this paper we compare the on-surface reaction pathways for DBBA molecules on Cu(111) and Cu(110). Evolution of both systems has been studied via a combination of core-level X-ray spectroscopies, scanning tunneling microscopy, and theoretical calculations. Experimental and theoretical results reveal a significant increase in reactivity for the open and anisotropic Cu(110) surface in comparison with the close-packed Cu(111). This increased reactivity results in a predominance of the molecular-substrate interaction over the intermolecular one, which has a critical impact on the transformations of DBBA on Cu(110). Unlike DBBA on Cu(111), the Ullmann coupling cannot be realized for DBBA/Cu(110) and the growth of nanoribbons via this mechanism is blocked. Instead, annealing of DBBA on Cu(110) at 250 °C results in the formation of a new structure: quasi-zero-dimensional flat nanographenes. Each nanographene unit has dehydrogenated zigzag edges bonded to the underlying Cu rows and oriented with the hydrogen-terminated armchair edge parallel to the [1-10] direction. Strong bonding of nanographene to the substrate manifests itself in a high adsorption energy of -12.7 eV and significant charge transfer of 3.46e from the copper surface. Nanographene units coordinated with bromine adatoms are able to arrange in highly regular arrays potentially suitable for nanotemplating. PMID:26301684

  1. Orientation and bonding of benzoic acid, phthalic anhydride and pyromellitic dianhydride on Cu(110)

    NASA Astrophysics Data System (ADS)

    Frederick, B. G.; Ashton, M. R.; Richardson, N. V.; Jones, T. S.

    1993-07-01

    The interaction of the polyimide precursor pyromellitic dianhydride (PMDA), and the related compounds benzoic acid and phthalic anhydride, with Cu(110) has been studied by high resolution electron energy loss spectroscopy (HREELS). For benzoic acid, deprotonation of the carboxylic acid group occurs on adsorption leading to the formation of a surface benzoate species (C 6H 5COO-). Bonding to the surface occurs through a carboxylate linkage via two equivalent oxygen atoms. The HREEL spectrum is characterised by an intense dipole active band, the symmetric O?C?O stretching vibration, at ˜ 1420 cm -1. The plane of the carboxylate group is aligned perpendicular to the surface as is the plane of the benzene ring. A similar species is found following exposure of Cu(110) to phthalic anhydride. The carboxylate linkage results from disruption of the anhydride ring with loss of the C?O character (C 6H 4COO-). In the case of the dianhydride species PMDA, only one of the anhydride units is used in bonding to the surface; the second unit points away from the surface and is characterised by the symmetric anhydride stretch at 1255 cm -1 and weak OO stretching vibrations at ˜ 1850 cm -1. In both cases, changes in the intensity of some of the bands compared with benzoic acid suggest that the carboxylate group is tilted away from the surface normal due to an interaction between one of the carbons of the aromatic ring and the copper surface. This implies that the plane of the aromatic ring is now twisted out of the plane of the carboxylate group and, although still perpendicular to the surface, the axis is tilted to allow one of the ?-carbon atoms to interact with the surface. In all cases, off-specular measurements at a primary electron energy of ˜ 8 eV are dominated by the intense C?H stretching vibration. Measurements of the intensity of this mode, in the surface benzoate species, as a function of incident electron energy suggest that excitation of this mode occurs via a resonance scattering mechanism.

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

    SciTech Connect

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

    2000-04-13

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

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

    SciTech Connect

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

    2001-01-01

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

  4. Electronic and structural properties at the interface between iron-phthalocyanine and Cu(110)

    NASA Astrophysics Data System (ADS)

    Hu, Fang; Mao, Hongying; Zhang, Hanjie; Wu, Ke; Cai, Yiliang; He, Pimo

    2014-03-01

    Electronic structure and adsorption geometry of Iron-Phthalocyanine (FePc) adsorbed on Cu(110) were investigated by using ultraviolet photoelectron spectroscopy (UPS) and first-principles density functional theory (DFT) calculations. The emission features ?, ?, ?, and ? originating from the FePc molecules in UPS spectra are located at 3.42, 5.04, 7.36, and 10.28 eV below Fermi level. The feature ? is mostly deriving from Fe 3d orbital with some contributions from C 2p orbital. A considerable charge transfer from the Cu substrate to the Fe 3d orbital occurs upon the adsorption of FePc molecules. The angle-resolved UPS measurements indicate that FePc molecules adopt lying-down configurations with their molecular plane nearly parallel to the Cu(110) substrate at monolayer stage. In combination with the DFT calculations, the adsorption structure is determined to be that FePc molecule adsorbs on the top site of Cu(110) with an angle of 45° between the lobes of FePc and the [1bar 10] azimuth of the substrate.

  5. Electronic and structural properties at the interface between iron-phthalocyanine and Cu(110)

    SciTech Connect

    Hu, Fang; Fundamental Department, Ningbo Institute of Technology, Ningbo 315100 ; Mao, Hongying; Zhang, Hanjie; Wu, Ke; Cai, Yiliang; He, Pimo

    2014-03-07

    Electronic structure and adsorption geometry of Iron-Phthalocyanine (FePc) adsorbed on Cu(110) were investigated by using ultraviolet photoelectron spectroscopy (UPS) and first-principles density functional theory (DFT) calculations. The emission features ?, ?, ?, and ? originating from the FePc molecules in UPS spectra are located at 3.42, 5.04, 7.36, and 10.28 eV below Fermi level. The feature ? is mostly deriving from Fe 3d orbital with some contributions from C 2p orbital. A considerable charge transfer from the Cu substrate to the Fe 3d orbital occurs upon the adsorption of FePc molecules. The angle-resolved UPS measurements indicate that FePc molecules adopt lying-down configurations with their molecular plane nearly parallel to the Cu(110) substrate at monolayer stage. In combination with the DFT calculations, the adsorption structure is determined to be that FePc molecule adsorbs on the top site of Cu(110) with an angle of 45° between the lobes of FePc and the [11{sup ¯}0] azimuth of the substrate.

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  7. Preface: Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Willmott, Phil

    2008-07-01

    Although the history of metal oxides and their surfaces goes back several decades to landmark studies, such as Mott and Peierls' explanation of electrical insulation in materials that are predicted in band theory to be conducting, or the observation by Morin of the superfast metal-to-insulator transition in vanadium dioxide, it is only in the last two decades that the world of condensed matter physics has become increasingly dominated by research into complex metal oxides. This has been driven most notably by an attempt to better understand and describe the fundamental physical processes behind their seemingly endless spectrum of properties, which in turn has also led to the discovery of novel phenomena, most prominently demonstrated by the discovery of high-temperature superconductivity in 1986, colossal magnetoresistance in 1994, and most recently, the formation of a two-dimensional conducting layer at the interface between two band insulators in 2004. One important reason why metal oxides, particularly in the form of thin films, have become such a popular subject for basic condensed matter research is that they offer a uniquely versatile materials base for the development of novel technologies. They owe this versatility both to the many different elemental combinations that lead to structurally similar forms, and also to the fact that in many cases, the strong interaction between the valence electrons means that there is a subtle interplay between structure and magnetic and electronic properties. This aspect has led in recent years to the birth or renaissance of research fields such as spintronics, orbital ordering, and multiferroics. Surfaces and interfaces are especially interesting in these strongly-correlated electron systems, where the rearrangement of electrical charge resulting from a minimization of surface or interfacial energy can have unexpected and often exciting consequences. Indeed, as the drive to miniaturize devices well below the micron size continues, the fraction of material constituting `non-bulklike' properties is becoming increasingly significant. On the other hand, the degree of sophistication needed to understand and predict these complex systems has driven a complementary thrust in theoretical modelling, beginning as long ago as 1963, with Hubbard's addition to the tight-binding model of the formulation of conduction in terms of a hopping integral. The present level of understanding is now so advanced that theory and experiment are no longer so distinct, both gaining further insights from one another. The aim of this special issue in the Journal of Physics: Condensed Matter is to convey to the reader the most up-to-date understanding of the physics of the surfaces, interfaces, and thin films of complex metal oxides, in a clear and accessible manner. The order of the 16 contributions reflects the broad range of disciplines within this field, beginning with general considerations and theoretical models, continuing with film growth techniques and characterization, and concluding with material types and devices. It is fairly safe to assume that research in this area will enjoy as illustrious and long-lived a future as it has had a past. As such, it is hoped that this contribution will accurately reflect this status in the first decade of the 21st Century and long provide a reference for physicists continuing on this exciting Odyssey.

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

    SciTech Connect

    Li, D.

    1998-09-21

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

  9. X-ray absorption near-edge structure of adsorbate-induced reconstruction: (2 × 1)O on Cu(110)

    NASA Astrophysics Data System (ADS)

    Döbler, U.; Baberschke, K.; Vvedensky, D. D.; Pendry, J. B.

    1986-12-01

    We present O K-edge near-edge absorption spectra for (2 sx 1)O on Cu(110) and accompanying multiple-scattering calculations for models with an unreconstructed substrate and with missing-row and saw-tooth adsorbate-induced reconstructions. The calculated NEXAFS has been analysed to assess the importance of multiple scattering as a function of the azimuthal angle of the electric field vector, and to identify the dominant structure-sensitive multiple-scattering paths. We find strong support for an oxygen-induced reconstruction of the Cu(110) substrate, though an unequivocal resolution between the missing-row and saw-tooth models must await further measurements.

  10. Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides

    NASA Astrophysics Data System (ADS)

    Gattinoni, Chiara; Michaelides, Angelos

    2015-11-01

    The oxidation and corrosion of metals are fundamental problems in materials science and technology that have been studied using a large variety of experimental and computational techniques. Here we review some of the recent studies that have led to significant advances in our atomic-level understanding of copper oxide, one of the most studied and best understood metal oxides. We show that a good atomistic understanding of the physical characteristics of cuprous (Cu2O) and cupric (CuO) oxide and of some key processes of their formation has been obtained. Indeed, the growth of the oxide has been shown to be epitaxial with the surface and to proceed, in most cases, through the formation of oxide nano-islands which, with continuous oxygen exposure, grow and eventually coalesce. We also show how electronic structure calculations have become increasingly useful in helping to characterise the structures and energetics of various Cu oxide surfaces. However a number of challenges remain. For example, it is not clear under which conditions the oxidation of copper in air at room temperature (known as native oxidation) leads to the formation of a cuprous oxide film only, or also of a cupric overlayer. Moreover, the atomistic details of the nucleation of the oxide islands are still unknown. We close our review with a brief perspective on future work and discuss how recent advances in experimental techniques, bringing greater temporal and spatial resolution, along with improvements in the accuracy, realism and timescales achievable with computational approaches make it possible for these questions to be answered in the near future.

  11. Oxide driven strength evolution of silicon surfaces

    NASA Astrophysics Data System (ADS)

    Grutzik, Scott J.; Milosevic, Erik; Boyce, Brad L.; Zehnder, Alan T.

    2015-11-01

    Previous experiments have shown a link between oxidation and strength changes in single crystal silicon nanostructures but provided no clues as to the mechanisms leading to this relationship. Using atomic force microscope-based fracture strength experiments, molecular dynamics modeling, and measurement of oxide development with angle resolved x-ray spectroscopy we study the evolution of strength of silicon (111) surfaces as they oxidize and with fully developed oxide layers. We find that strength drops with partial oxidation but recovers when a fully developed oxide is formed and that surfaces intentionally oxidized from the start maintain their high initial strengths. MD simulations show that strength decreases with the height of atomic layer steps on the surface. These results are corroborated by a completely separate line of testing using micro-scale, polysilicon devices, and the slack chain method in which strength recovers over a long period of exposure to the atmosphere. Combining our results with insights from prior experiments we conclude that previously described strength decrease is a result of oxidation induced roughening of an initially flat silicon (1 1 1) surface and that this effect is transient, a result consistent with the observation that surfaces flatten upon full oxidation.

  12. Surface modification to prevent oxide scale spallation

    DOEpatents

    Stephens, Elizabeth V; Sun, Xin; Liu, Wenning; Stevenson, Jeffry W; Surdoval, Wayne; Khaleel, Mohammad A

    2013-07-16

    A surface modification to prevent oxide scale spallation is disclosed. The surface modification includes a ferritic stainless steel substrate having a modified surface. A cross-section of the modified surface exhibits a periodic morphology. The periodic morphology does not exceed a critical buckling length, which is equivalent to the length of a wave attribute observed in the cross section periodic morphology. The modified surface can be created using at least one of the following processes: shot peening, surface blasting and surface grinding. A coating can be applied to the modified surface.

  13. Platinum attachments on iron oxide nanoparticle surfaces

    NASA Astrophysics Data System (ADS)

    Palchoudhury, Soubantika; Xu, Yaolin; An, Wei; Turner, C. Heath; Bao, Yuping

    2010-05-01

    Platinum nanoparticles supported on metal oxide surfaces have shown great potential as heterogeneous catalysts to accelerate electrochemical processes, such as the oxygen reduction reaction in fuel cells. Recently, the use of magnetic supports has become a promising research topic for easy separation and recovery of catalysts using magnets, such as Pt nanoparticles supported on iron oxide nanoparticles. The attachment of Pt on iron oxide nanoparticles is limited by the wetting ability of the Pt (metal) on ceramic surfaces. A study of Pt nanoparticle attachment on iron oxide nanoparticle surfaces in an organic solvent is reported, which addresses the factors that promote or inhibit such attachment. It was discovered that the Pt attachment strongly depends on the capping molecules of the iron oxide seeds and the reaction temperature. For example, the attachment of Pt nanoparticles on oleic acid coated iron oxide nanoparticles was very challenging, because of the strong binding between the carboxylic groups and iron oxide surfaces. In contrast, when nanoparticles are coated with oleic acid/tri-n-octylphosphine oxide or oleic acid/oleylamine, a significant increase in Pt attachment was observed. Electronic structure calculations were then applied to estimate the binding energies between the capping molecules and iron ions, and the modeling results strongly support the experimental observations.

  14. Platinum Attachments on Iron Oxide Nanoparticle Surfaces

    SciTech Connect

    Palchoudhury, Soubantika; Xu, Yaolin; An, Wei; Turner, C. H.; Bao, Yuping

    2010-04-30

    Platinum nanoparticles supported on metal oxide surfaces have shown great potential as heterogeneous catalysts to accelerate electrochemical processes, such as the oxygen reduction reaction in fuel cells. Recently, the use of magnetic supports has become a promising research topic for easy separation and recovery of catalysts using magnets, such as Pt nanoparticles supported on iron oxide nanoparticles. The attachment of Pt on iron oxide nanoparticles is limited by the wetting ability of the Pt (metal) on ceramic surfaces. A study of Pt nanoparticle attachment on iron oxide nanoparticle surfaces in an organic solvent is reported, which addresses the factors that promote or inhibit such attachment. It was discovered that the Pt attachment strongly depends on the capping molecules of the iron oxide seeds and the reaction temperature. For example, the attachment of Pt nanoparticles on oleic acid coated iron oxide nanoparticles was very challenging, because of the strong binding between the carboxylic groups and iron oxide surfaces. In contrast, when nanoparticles are coated with oleic acid/tri-n-octylphosphine oxide or oleic acid/oleylamine, a significant increase in Pt attachment was observed. Electronic structure calculations were then applied to estimate the binding energies between the capping molecules and iron ions, and the modeling results strongly support the experimental observations.

  15. Surface Wrinkling on Polydimethylsiloxane Microspheres via Wet Surface Chemical Oxidation

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  16. Surface Wrinkling on Polydimethylsiloxane Microspheres via Wet Surface Chemical Oxidation

    PubMed Central

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

    2014-01-01

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

  17. Surface chemistry of Pu oxides

    NASA Astrophysics Data System (ADS)

    Farr, J. Douglas; Schulze, Roland K.; Neu, Mary P.

    2004-07-01

    X-ray photoelectron spectroscopy was used to examine the surface chemistry of a variety of Pu(IV) compounds, including PuO 2 and Pu(OH) 4. The Pu 4f, O 1s and C 1s binding energy regions were line shape fit to unequivocally demonstrate that multiple species are present. Surface hydroxyls were ubiquitous in all PuO 2 samples exposed to H 2O vapor or ambient air, and persisted with heating to 590 °C. Active surface sites for the reaction of H 2O and other small molecules and spectral features consistent with pure stoichiometric PuO 2 can be regenerated by thermal energy or by effects of a radiation field. Evidence of higher valence Pu species was observed in some treated samples with the formula PuO 2+ x.

  18. The surface chemistry of cerium oxide

    NASA Astrophysics Data System (ADS)

    Mullins, David R.

    2015-03-01

    This review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water-gas shift reaction. Ceria's acid-base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. Most surface science studies have been conducted on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  19. Germanium surface cleaning, passivation, and initial oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Shiyu

    Germanium (Ge) is an attractive material to be incorporated into Si-based electronic devices because of its higher intrinsic low field carrier mobility. In order to fabricate devices using Ge, it is essential to understand the Ge surface chemistry and find an effective way to clean and passivate its surface. Systematic studies of these processes had not been performed prior to this work. In this work, synchrotron radiation photoelectron spectroscopy and atomic force microscopy are used to investigate the Ge surface cleaning, passivation, morphology and initial oxidation. In addition, other materials closely related to Ge are characterized. The wet chemical cleaning and passivation of Ge surfaces are first studied. The etching mechanism determines the surface passivation. HF etching leads to rougher, hydrophobic, hydrogen passivated surfaces, and the hydrogen coverage is a function of the HF concentration. In contrast, HCl (HBr) etching results in smoother, hydrophilic, chlorine (bromine) passivated surfaces. Results from substrates with different orientations are compared, and the similarity and difference between Ge and Si are discussed. The thermal stability of passivated Ge surfaces is probed by vacuum annealing. As the annealing temperature increases, the passivation layers desorb gradually from the surfaces, and surface states are formed. The thermal stability of different passivation layers is compared, and the influence of substrate orientations is stressed. The passivated Ge surfaces are not stable in air at room temperature. Therefore, controlled experiments are performed to derive the initial oxidation mechanism. The stability of passivated surfaces relies on the coverage of the passivation layers, the size of the passivating atoms, the amount of hydroxide left on the surface after etching, and the difficulty of replacing the passivation layers. Finally, other materials closely related to Ge are characterized. Results on strained Si and Si1-xGex surfaces show that the introduced strain does not alter the Si surface chemistry significantly, while the addition of Ge changes the Si surface chemistry dramatically. Both strained Si and Si1-xGex surfaces have enhanced oxidation rates. In addition, Ge nanowires have similar surface chemistry to Ge planar wafers, and a very nonstoichiometric GeO, layer exists at the HfO2/Ge(100) interface.

  20. Alkane activation on crystalline metal oxide surfaces.

    PubMed

    Weaver, Jason F; Hakanoglu, Can; Antony, Abbin; Asthagiri, Aravind

    2014-11-21

    Advances in the fundamental understanding of alkane activation on oxide surfaces are essential for developing new catalysts that efficiently and selectively promote chemical transformations of alkanes. In this tutorial review, we discuss the current understanding of alkane activation on crystalline metal oxide surfaces, and focus mainly on summarizing our findings on alkane adsorption and C-H bond cleavage on the PdO(101) surface as determined from model ultrahigh vacuum experiments and theoretical calculations. These studies show that alkanes form strongly-bound ?-complexes on PdO(101) by datively bonding with coordinatively-unsaturated Pd atoms and that these molecularly adsorbed species serve as precursors for C-H bond activation on the oxide surface. In addition to discussing the binding and properties of alkane ?-complexes on PdO(101), we also summarize recent advances in kinetic models to predict alkane dissociation rates on solid surfaces. Lastly, we highlight computations which predict that the formation and facile C-H bond activation of alkane ?-complexes also occurs on RuO2 and IrO2 surfaces. PMID:24480977

  1. SURFACE REACTIONS OF OXIDES OF SULFUR

    EPA Science Inventory

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

  2. Surface Growth and Oxidation of Soot Particles under Flame Conditions

    NASA Astrophysics Data System (ADS)

    Schäfer, Th.; Mauß, F.; Bockhorn, H.; Fetting, F.

    1995-11-01

    Surface growth and oxidation of soot particles is investigated in premixed counter flow flames. Surface growth rates and soot oxidation rates can be evaluated from the measured appearance rates of soot and the calculated surface growth rates derived from the HACA-mechanism. The dependence of surface growth rates and soot oxidation rates on composition of the gas phase, temperature and "surface concentration" is discussed. A mechanism of soot oxidation accounting for the experimental findings is suggested.

  3. Patterning pentacene surfaces by local oxidation nanolithography.

    PubMed

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

    2010-05-01

    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 36V for 1ms. The parallel local oxidation process is performed by using a conductive and patterned stamp. Then, a voltage pulse is applied between the stamp and the pentacene surface. Patterns formed by arrays of parallel lines covering 1mm(2) regions and with a periodicity of less than 1microm have been generated in a few seconds. We also show that the patterns can be used as templates for the deposition of antibodies. PMID:20226594

  4. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    PubMed Central

    2015-01-01

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

  5. Surface Structure of Aerobically Oxidized Diamond Nanocrystals.

    PubMed

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

    2014-11-20

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

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

    E-print Network

    Ma, Xinzheng

    1995-01-01

    Surface oxidation in metal matrix composites (MMC's) is modeled by Fickian diffusion of oxygen in both the oxide layer and metal matrix. The oxidation process and the resulting immobilized oxygen at the interface is accounted for by the introduction...

  7. Structural Imaging of Surface Oxidation and Oxidation Catalysis on Ru(0001)

    SciTech Connect

    Flege, J.; Hrbek, J; Sutter, P

    2008-01-01

    Using simultaneous imaging and structural fingerprinting under reaction conditions, we probe the initial oxidation pathway and CO oxidation catalysis on Ru(0001). Oxidation beyond an initial (1 x 1)-O adlayer phase produces a heterogeneous surface, comprising a disordered trilayerlike surface oxide and an ordered RuO{sub 2}(110) thin-film oxide, which form independently and exhibit similar stability. The surface oxide and RuO{sub 2} phases both show high intrinsic catalytic activity. The oxygen adlayer is inactive in isolation but becomes active due to cooperative effects in close proximity to the surface oxide.

  8. Oxidation-driven surface dynamics on NiAl(100)

    PubMed Central

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

    2015-01-01

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

  9. Oxidation-driven surface dynamics on NiAl(100).

    PubMed

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

    2015-01-13

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

  10. Perfluorodiethoxymethane on nickel and nickel oxide surfaces

    SciTech Connect

    Jacobson, J.

    1994-03-03

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

  11. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

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

    1992-01-01

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

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

    PubMed Central

    Navrotsky, Alexandra

    2003-01-01

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

  13. Pretreatment of lubricated surfaces with sputtered cadmium oxide

    NASA Technical Reports Server (NTRS)

    Fusaro, Robert L. (inventor)

    1991-01-01

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

  14. TOPICAL REVIEW: Low-dimensional surface oxides in the oxidation of Rh particles

    NASA Astrophysics Data System (ADS)

    Mittendorfer, Florian

    2010-10-01

    The oxidation of rhodium particles leads to the formation of low-dimensional nanostructures, namely ultrathin oxide films and stripes adsorbed on the metallic surface. These structures display unique electronic and structural properties, which have been studied in detail experimentally and theoretically in recent years. In this review, the state of research on low-dimensional surface oxides formed on Rh surfaces will be discussed with a special focus on the contributions derived from computational approaches. Several points elucidating the novel properties of the surface oxides will be addressed: (i) the structural relation between the surface oxides and their bulk counterparts, (ii) the electronic properties of the low-dimensional oxide films and (iii) potential catalytic and electronic applications of the surface oxides.

  15. Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study.

    PubMed

    Hu, Xiao; Schuster, Jörg; Schulz, Stefan E; Gessner, Thomas

    2015-10-28

    Atomistic mechanisms for the atomic layer deposition using the Cu(acac)2 (acac = acetylacetonate) precursor are studied using first-principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)2 chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac-ligands. A sequential dissociation and reduction of the Cu precursor [Cu(acac)2 ? Cu(acac) ? Cu] are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)2 on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)2 on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by-products CO2 and H2O are observed during the reaction between Cu(acac)2 and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)2 follows the order H > O3 > H2O. PMID:26399423

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

    SciTech Connect

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.; Kokke, S.; Zoethout, E.

    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.

  17. Characterization and stability of thin oxide films on plutonium surfaces

    NASA Astrophysics Data System (ADS)

    Flores, H. G. García; Roussel, P.; Moore, D. P.; Pugmire, D. L.

    2011-02-01

    X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were employed to study oxide films on plutonium metal surfaces. Measurements of the relative concentrations of oxygen and plutonium, as well as the resulting oxidation states of the plutonium (Pu) species in the near-surface region are presented. The oxide product of the auto-reduction (AR) of plutonium dioxide films is evaluated and found to be an oxide species which is reduced further than what is expected. The results of this study show a much greater than anticipated extent of auto-reduction and challenge the commonly held notion of the stoichiometric stability of Pu 2O 3 thin-films. The data indicates that a sub-stoichiometric plutonium oxide (Pu 2O 3 - y ) exists at the metal-oxide interface. The level of sub-stoichiometry is shown to depend, in part, on the carbidic contamination of the metal surface.

  18. The Role of Surface Defects in CO Oxidation, Methanol Oxidation, and Oxygen Reduction on Pt,,111...

    E-print Network

    Kenis, Paul J. A.

    The Role of Surface Defects in CO Oxidation, Methanol Oxidation, and Oxygen Reduction on Pt,,111 as a model for terrace favored reactions. More complicated reactions, such as methanol oxidation, can of electronic structure, but methanol dehydrogenation is promoted only by step-type defects, as a result

  19. Chemical properties of two-dimensional oxide systems: Adsorption of (WO3)3 clusters on CuWO4

    NASA Astrophysics Data System (ADS)

    Ma, Liying; Denk, Martin; Kuhness, David; Surnev, Svetlozar; Mankad, Venu; Barcaro, Giovanni; Fortunelli, Alessandro; Netzer, Falko P.

    2015-10-01

    A two-dimensional ternary oxide layer, Cu-tungstate (CuWO4) on Cu(110), has been tested as a substrate for the adsorption of (WO3)3 cluster molecules from the gas phase. Scanning tunneling microscopy/spectroscopy and X-ray photoelectron spectroscopy have been used to characterize the adsorbed species, while density functional theory has scanned the energy landscape for stable adsorption modes. The (WO3)3 clusters adsorb in preferential adsorption sites at low temperature (85 K) as stable, only slightly perturbed units, as established both experimentally and theoretically. The preferred sites are the Cu surface rows in the [100] substrate direction, which feature elastic flexibility as a result of ultrasoft phonon modes and are a characteristic of this two-dimensional ternary oxide structure.

  20. High-Temperature Oxide Regrowth on Mechanically-Damaged Surfaces

    SciTech Connect

    Blau, Peter Julian; Lowe, Tracie M

    2008-01-01

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

  1. Surface Catalysis of Water Oxidation by the Blue Ruthenium Dimer

    SciTech Connect

    Jurss, Jonah W.; Concepcion, Javier C.; Norris, Michael R.; Templeton, Joseph L.; Meyer, Thomas J.

    2010-04-08

    Single-electron activation of multielectron catalysis has been shown to be viable in catalytic water oxidation with stepwise proton-coupled electron transfer, leading to high-energy catalytic precursors. For the blue dimer, cis,cis-[(bpy)2(H2O)RuIIIORuIII(H2O)(bpy)2]4+, the first well-defined molecular catalyst for water oxidation, stepwise 4e-/4H+ oxidation occurs to give the reactive precursor [(O)RuVORuV(O)]4+. This key intermediate is kinetically inaccessible at an unmodified metal oxide surface, where the only available redox pathway is electron transfer. We report here a remarkable surface activation of indium-tin oxide (In2O3:Sn) electrodes toward catalytic water oxidation by the blue dimer at electrodes derivatized by surface phosphonate binding of [Ru(4,4'-((HO)2P(O)CH2)2bpy)2(bpy)]2+. Surface binding dramatically improves the rate of surface oxidation of the blue dimer and induces water oxidation catalysis.

  2. Surface Oxidation and Dissolution of Metal Nanocatalysts in Acid Medium 

    E-print Network

    Callejas-Tovar, Juan

    2012-10-19

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

  3. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    NASA Astrophysics Data System (ADS)

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-08-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

  4. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    PubMed Central

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content. PMID:26269034

  5. Improve oxidation resistance at high temperature by nanocrystalline surface layer.

    PubMed

    Xia, Z X; Zhang, C; Huang, X F; Liu, W B; Yang, Z G

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content. PMID:26269034

  6. Rates of oxidative weathering on the surface of Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1992-01-01

    Implicit in the mnemonic 'MSATT' (Mars surface and atmosphere through time) is that rates of surface processes on Mars through time should be investigated, including studies of the kinetics and mechanism of oxidative weathering reactions occurring in the Martian regolith. Such measurements are described. Two major elements analyzed in the Viking Lander XRF experiment that are most vulnerable to atmospheric oxidation are iron and sulfur. Originally, they occurred as Fe(2+)-bearing silicate and sulfide minerals in basaltic rocks on the surface of Mars. However, chemical weathering reactions through time have produced ferric- and sulfate-bearing assemblages now visible in the Martian regolith. Such observations raise several question about: (1) when the oxidative weathering reactions took place on Mars; (2) whether or not the oxidized regolith is a fossilized remnant of past weathering processes; (3) deducting chemical interactions of the ancient Martian atmosphere with its surface from surviving phases; (4) possible weathering reactions still occurring in the frozen regolith; and (5) the kinetics and mechanism of past and present-day oxidative reactions on Mars. These questions may be addressed experimentally by studying reaction rates of dissolution and oxidation of basaltic minerals, and by identifying reaction products forming on the mineral surfaces. Results for the oxidation of pyrrhotite and dissolved ferrous iron are reported.

  7. Activation of aromatics on the polar surfaces of zinc oxide

    SciTech Connect

    Vohs, J.M.; Barteau, M.A. )

    1989-12-28

    The reactions of the aromatic oxygenates benzoic acid, benzaldehyde, benzyl alcohol, and phenol exhibit both strong similarities and strong differences as compared with their aliphatic analogues on the two polar surfaces of zinc oxide. The greatest similarities between aromatic and aliphatic compounds were observed on the (0001)-Zn polar surface. Benzyl alcohol and phenol reacted on the (0001)-Zn surface to form the corresponding surface alkoxide species. In sharp contrast to aliphatic alcohols, aldehydes, and carboxylic acids, toward which the (0001)-O polar surface is unreactive, the aromatic compounds reacted on the (0001)-O polar surface. These results further demonstrate the effects of surface crystallographic structure in determining the activity and reaction pathways on the metal oxide surfaces.

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

    NASA Astrophysics Data System (ADS)

    Graham, Andrew M.; Bouwer, Edward J.

    2012-04-01

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

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

    SciTech Connect

    Deng, Hui; Endo, Katsuyoshi; Yamamura, Kazuya

    2014-03-10

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

  10. MOISTURE AND SURFACE AREA MEASUREMENTS OF PLUTONIUM-BEARING OXIDES

    SciTech Connect

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

    2009-09-28

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

  11. Albumin adsorption on to aluminium oxide and polyurethane surfaces.

    PubMed

    Sharma, C P; Sunny, M C

    1990-05-01

    The changes in protein adsorption onto aluminium surfaces coated with different thicknesses of oxide layers were examined. The oxide layers on aluminium substrates were derived by the anodizing technique. Protein adsorption studies were conducted using 125I-labelled albumin and the amount of albumin adsorbed was estimated with the help of a gamma counter. An increase in albumin adsorption was observed on oxide layer coated aluminium surfaces. The effect of anti-Hageman factor on albumin and fibrinogen adsorption on to bare aluminium, oxide layer coated aluminium and bare polyether urethane urea surfaces was also investigated. It was observed that the presence of anti-Hageman factor increased the adsorption of albumin and fibrinogen on to all these substrates. PMID:2383620

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

    PubMed Central

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

    2015-01-01

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

  13. Pulmonary effects of sulfur oxides on the surface of copper oxide aerosol

    SciTech Connect

    Chen, L.C.; Peoples, S.M.; Amdur, M.O. )

    1991-05-01

    The authors have developed a system that generates copper oxide aerosol similar to the primary emissions from smelters. The surface of the ultrafine copper oxide aerosol is coated with a layer of sulfur oxides consisting of sulfate, S(VI), and sulfite, S(IV). Guinea pigs were exposed to this sulfur oxide layered copper oxide aerosol, and pulmonary mechanical functions were measured by using the Amdur-Mead method. The concentration of sulfur oxides on the aerosol was determined by using a flame photometric detector system. Although sulfuric acid was not found in this system, S(IV) at concentrations as low as 0.36 mumol/m3 delivered as a surface layer caused prolonged changes in pulmonary mechanical functions.

  14. Method of producing adherent metal oxide coatings on metallic surfaces

    DOEpatents

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

    2001-01-01

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

  15. Surface oxidation of liquid Sn Alexei Grigoriev a,*

    E-print Network

    Grigoriev, Alexei

    Review Copy 1 Surface oxidation of liquid Sn Alexei Grigoriev a,* , Oleg Shpyrko b , Christoph of SnO at the liquid-vapour interface of Sn. Our experiments reveal that the pure liquid Sn surface does not react with molecular oxygen below an activation pressure of ~5.0×10-6 Torr. Above that pressure a rough

  16. OXYANION SORPTION TO HIGH SURFACE AREA IRON AND ALUMINUM OXIDES

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  17. Effect of surface-applied reactive element oxide on the oxidation of binary alloys containing Cr

    SciTech Connect

    Hou, P.Y.; Stringer, J.

    1987-07-01

    The influence of surface-applied Ca,Ce, Hf, La, Y, and Zr nitrate-converted oxides on the oxidation behavior of Co-15 weight percent (w/o) Cr, Co-25 w/o Cr, and Ni-25 w/o Cr alloys at 1000/sup 0/ and 1100/sup 0/C in 1 atm O/sub 2/ was studied. The surface oxides were most beneficial on the established Cr/sub 2/O/sub 3/ forming alloy. Surface-applied CeO/sub 2/,Y/sub 2/O/sub 3/, and La/sub 2/O/sub 3/ were effective in reducing the growth rate of the Cr/sub 2/O/sub 3/ scale and improving the scale adhesion. The presence of these surface oxides also prevented base metal oxide formation and changed the growth direction of the scale. All of these observed effects were similar to those found when the reactive element oxides were present within the alloys. However, the presence of surface HfO/sub 2/ made the oxide scales nonadherent causing a breakaway behavior at the early stage of the oxidation process. None of the surface-applied oxides showed any effects on the non-Cr/sub 2/O/sub 3/ forming alloy, and they acted as a semibarrier on the borderline Cr/sub 2/O/sub 3/ former. Unlike the case of dispersoids present in the alloy, these surface-applied as a semibarrier on the borderline Cr/sub 2/O/sub 3/ layer at alloy Cr levels lower than those normally required to form the Cr/sub 2/O/sub 3/ scale.

  18. First-principles study of water on copper and noble metal (110) surfaces

    SciTech Connect

    Ren, Jun; Meng, Sheng

    2008-02-01

    Water structure and dissociation kinetics on a model open metal surface: Cu(110), has been investigated in detail based on first-principles electronic structure calculations. We revealed that in both monomer and overlayer forms, water adsorbs molecularly, with a high tendency for diffusion and/or desorption rather than dissociation on clean surfaces at low temperature. Studying water on other noble metal (110) surfaces confirms that Cu(110) is the borderline between intact and dissociative water adsorption, differing in energy by only 0.08 eV. This may lead to promising applications in hydrogen generation and fuel cells.

  19. The intermediate oxidation of the Pd(100) surface

    NASA Astrophysics Data System (ADS)

    Mikkelsen, A.; Lundgren, E.; Gustafson, J.; Borg, M.; Andersen, J. N.

    2003-03-01

    The formation of oxides on metal surfaces has recently received much attention. Apart from the fundamental importance of the oxidation process, the interest is driven by the observation that oxides can play an important role in catalysis1, 2. The geometric structure of surface oxides can in some cases3 not be directly inferred from known bulk oxides. The surface structures formed by oxygen on Pd(100) have been studied by Scanning Tunneling Microscopy (STM), High Resolution Core-Level Spectroscopy (HRCLS) and Low Energy Electron Diffraction (LEED). It is shown that the structure determined in a recent LEED analysis4 of the Pd(100)- (root5xroot5)-O structure formed by adsorption of 0.8 ML of oxygen is difficult to reconcile with our STM and HRCLS data. New models for this surface oxide consistent with our experimental results are suggested. [1] Y. D. Kim, A. P. Seitsonen, S. Wendt, E. Lundgren, M. Schmid, P. Varga, A. Morgante, and G. Ertl., Science 287, 1474 (2000). [2] B. L. M. Hendriksen and J. W. M. Frenken, Phys. Rev. Lett. 89, 046101 (2002). [3] E. Lundgren,, G. Kresse, C. Klein, M. Borg, J.N. Andersen, M. De Santis, Y. Gauthier, C. Konvicka, M. Schmid, and P.Varga, Phys. Rev. Lett. 88 (2002) 246103 [4] M. Saidy, O.L. Warren, P.A. Thiel, and K.A.R. Mitchell, Surf. Sci. 494, L799 (2001).

  20. Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

  1. Tribological interaction between polytetrafluoroethylene and silicon oxide surfaces

    SciTech Connect

    Uçar, A.; Çopuro?lu, M.; Suzer, S.; Baykara, M. Z.; Ar?kan, O.

    2014-10-28

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

  2. Reporting central tendencies of chamber measured surface emission and oxidation

    SciTech Connect

    Abichou, Tarek; Clark, Jeremy; Chanton, Jeffery

    2011-05-15

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

  3. Rate Law Analysis of Water Oxidation on a Hematite Surface

    PubMed Central

    2015-01-01

    Water oxidation is a key chemical reaction, central to both biological photosynthesis and artificial solar fuel synthesis strategies. Despite recent progress on the structure of the natural catalytic site, and on inorganic catalyst function, determining the mechanistic details of this multiredox reaction remains a significant challenge. We report herein a rate law analysis of the order of water oxidation as a function of surface hole density on a hematite photoanode employing photoinduced absorption spectroscopy. Our study reveals a transition from a slow, first order reaction at low accumulated hole density to a faster, third order mechanism once the surface hole density is sufficient to enable the oxidation of nearest neighbor metal atoms. This study thus provides direct evidence for the multihole catalysis of water oxidation by hematite, and demonstrates the hole accumulation level required to achieve this, leading to key insights both for reaction mechanism and strategies to enhance function. PMID:25936408

  4. Oxidation-Resistant Surfaces For Solar Reflectors

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  5. Surface Properties of Photo-Oxidized Bituminous Coals: Final report

    SciTech Connect

    1998-09-01

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

  6. Surface Science Letters Bulk-defect dependent adsorption on a metal oxide surface

    E-print Network

    Diebold, Ulrike

    Ti atoms and oxygen vacancies. At elevated temperatures (120±440°C) sulfur replaces surface oxygen atoms. Evidence was found that the reduction state of TiO2 crystals strongly aects the surface coverage tunneling microscopy; Photoelectron spectroscopy; Titanium oxide; Sulphur; Low index single crystal surfaces

  7. Chemical reactions on metal oxide surfaces investigated by vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Yuemin; Wöll, Christof

    2009-06-01

    The most successful method to unravel the microscopic mechanisms governing reactions in heterogeneous catalysis is the "surface science" approach which is based on well-controlled studies on model catalysts (usually single crystal surfaces) under ultrahigh vacuum (UHV) conditions [G. Ertl, Angew. Chem. 47 (2008) 3524]. In this review our recent vibrational spectroscopic studies on selected model reactions at various single-crystalline metal oxide surfaces are summarized. Two vibrational spectroscopic methods, high resolution electron energy loss spectroscopy (HREELS) and Fourier-transform infrared spectroscopy (FTIRS), were applied to characterize the adsorbed species and to elucidate the elementary processes of chemical reactions at oxide surfaces ranging from well-defined single crystals to modified surfaces with deliberately introduced defects. The combination of both methods allows us to extend the vibrational spectroscopic studies from ideal to complex systems.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  9. Cr(OH)?(s) Oxidation Induced by Surface Catalyzed Mn(II) Oxidation

    SciTech Connect

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

    2014-09-16

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

  10. Microwave surface impedance measurements on reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Hao, L.; Mattevi, C.; Gallop, J.; Goniszewski, S.; Xiao, Y.; Cohen, L.; Klein, N.

    2012-07-01

    Here we report a non-contact method for microwave surface impedance measurements of reduced graphene oxide samples using a high Q dielectric resonator perturbation technique, with the aim of studying the water content of graphene oxide flakes. Measurements are made before, during and after heating and cooling cycles. We have modelled plane wave propagation of microwaves perpendicular to the surface of graphene on quartz substrates, capacitively coupled to a dielectric resonator. Analytical solutions are derived for both changes in resonant frequency and microwave loss for a range of water layer thicknesses. In this way we have measured the presence of adsorbed water layers in reduced graphene oxide films. The water can be removed by low temperature annealing on both single and multilayer samples. The results indicate that water is intercalated between the layers in a multilayer sample, rather than only being adsorbed on the outer surfaces, and it can be released by applying a mild heating.

  11. Surface Chemistry and Properties of Oxides as Catalyst Supports

    SciTech Connect

    DeBusk, Melanie Moses; Narula, Chaitanya Kumar; Contescu, Cristian I

    2015-01-01

    Heterogeneous catalysis relies on metal-oxides as supports for the catalysts. Catalyst supports are an indispensable component of most heterogeneous catalysts, but the role of the support is often minimized in light of the one played by the catalytically active species it supports. The active species of supported catalysts are located on the surface of the support where their contact with liquid or gas phase reactants will be greatest. Considering that support plays a major role in distribution and stability of active species, the absorption and retention of reactive species, and in some cases in catalytic reaction, the properties and chemistry that can occur at the surface of an oxide support are important for understanding their impact on the activity of a supported catalyst. This chapter examines this rich surface chemistry and properties of oxides used as catalyst supports, and explores the influence of their interaction with the active species.

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

    NASA Astrophysics Data System (ADS)

    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. Process of forming catalytic surfaces for wet oxidation reactions

    NASA Technical Reports Server (NTRS)

    Jagow, R. B. (inventor)

    1977-01-01

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

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

    PubMed

    George, Lijin; Gupta, Aparna; Shaina, P R; Gupta, Nandita Das; 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 ?m 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. PMID:26572253

  15. Mechanical tearing of graphene on an oxidizing metal surface

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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 ?m 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 sp3-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.

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

    EPA Science Inventory

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

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

    E-print Network

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

    2008-01-01

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

  18. Silatranes for binding inorganic complexes to metal oxide surfaces.

    PubMed

    Materna, Kelly L; Brennan, Bradley J; Brudvig, Gary W

    2015-12-21

    A ruthenium complex containing silatrane functional groups has been synthesized and covalently bound to a conductive metal oxide film composed of nanoparticulate ITO (nanoITO). The silatrane-derived siloxane surface anchors were found to be stable in the examined range of pH 2 to 11 in aqueous phosphate buffer, and the ruthenium complex was found to have stable electrochemical features with repeated electrochemical cycling. The non-coordinating properties of the silatrane group to metals, which facilitates synthesis of silatrane-labeled coordination complexes, together with the facile surface-binding procedure, robustness of the surface linkages, and stability of the electrochemical properties suggest that incorporating silatrane motifs into ligands for inorganic complexes provides superior properties for attachment of catalysts to metal oxide surfaces under aqueous conditions. PMID:26506505

  19. Surface modification of nickel based alloys for improved oxidation resistance

    SciTech Connect

    Jablonski, Paul D.; Alman, David E.

    2005-02-01

    The present research is aimed at the evaluation of a surface modification treatment to enhance the high temperature stability of nickel-base superalloys. A low Coefficient Thermal Expansion (CTE ~12.5x10-6/°C) alloy based on the composition (in weight %) of Ni-22Mo-12.5Cr was produced by Vacuum Induction Melting and Vacuum Arc Melting and reduced to sheet by conventional thermal-mechanical processing. A surface treatment was devised to enhance the oxidation resistance of the alloys at high temperature. Oxidation tests (in dry and wet air; treated and untreated) were conducted 800°C to evaluate the oxidation resistance of the alloys. The results were compared to the behavior of Haynes 230 (Ni-22Cr) in the treated and untreated conditions. The treatment was not very effective for Haynes 230, as this alloy had similar oxidation behavior in both the treated and untreated conditions. However, the treatment had a significant effect on the behavior of the low CTE alloy. At 800°C, the untreated Ni-12.5Cr alloy was 5 times less oxidation resistant than Haynes 230. However, in the treated condition, the Ni-12.5Cr alloy had comparable oxidation resistance to the Haynes 230 alloy.

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

  1. Emerging applications of liquid metals featuring surface oxides.

    PubMed

    Dickey, Michael D

    2014-11-12

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

  2. Emerging Applications of Liquid Metals Featuring Surface Oxides

    PubMed Central

    2014-01-01

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

  3. Viewpoint Paper Surface oxide effects on failure of polysilicon MEMS

    E-print Network

    Ballarini, Roberto

    ]). Stress corrosion cracking of bulk sil- icon dioxide due to humidity is well documented. The strongest, which are then susceptible to moisture-assisted stress corrosion. Polysilicon MEMS devices with typical fatigue cycles, excluding stress corrosion of the surface oxide as a cause of fatigue failure. Possible

  4. Semiconducting and Piezoelectric Oxide Nanostructures Induced by Polar Surfaces**

    E-print Network

    Wang, Zhong L.

    . This article reviews our recent progress in the synthesis and characterization of polar-surface-induced ZnO transport along the nanobelt has been mea- sured.[14] Zinc oxide (ZnO) is the most typical and successful sensors and trans- ducers. Finally, ZnO is bio-safe and biocompatible, and it can be directly used

  5. The surface chemistry of multi-oxide silicates

    NASA Astrophysics Data System (ADS)

    Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

    2009-08-01

    The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

  6. Electrostatic Cooperativity of Hydroxyl Groups at Metal Oxide Surfaces

    SciTech Connect

    Boily, Jean F.; Lins, Roberto D.

    2009-09-24

    The O-H bond distribution of hydroxyl groups at the {110} goethite (R-FeOOH) surface was investigated by molecular dynamics. This distribution was strongly affected by electrostatic interactions with neighboring oxo and hydroxo groups. The effects of proton surface loading, simulated by emplacing two protons at different distances of separation, were diverse and generated several sets of O-H bond distributions. DFT calculations of a representative molecular cluster were also carried out to demonstrate the impact of these effects on the orientation of oxygen lone pairs in neighboring oxo groups. These effects should have strong repercussions on O-H stretching vibrations of metal oxide surfaces.h

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

    E-print Network

    Velev, Orlin D.

    Giant and switchable surface activity of liquid metal via surface oxidation Mohammad Rashed Khana,1 metals. Liquid metals offer new opportunities for soft, stretch- able, and shape the interfacial ten- sion of metals but either limit the shape of liquid metals to plugs (e.g., continuous

  8. Simulation of the surface structure of lithium manganese oxide spinel.

    SciTech Connect

    Benedek, R.; Thackeray, M. M.

    2011-05-31

    Simulations of the surface structure of low-index surfaces of LiMn{sub 2}O{sub 4} (LMO), a candidate Li-ion battery electrode material, have been performed within the GGA+U approximation, using the VASP code. Surfaces of (001), (110), and (111) orientation were considered, with at least two terminations treated in each case. A slab geometry was employed, with termination-layer vacancies introduced to remove the bulk dipole moment while maintaining ideal stoichiometry. To complement static-structure relaxation calculations, molecular-dynamics simulations were performed to explore the phase space of possible surface reconstructions. A reconstruction is predicted for the Mn-terminated (111) surface, in which the top layers mix in stoichiometric proportions to form an LMO termination layer with square-planar-coordinated Mn. Average surface Mn oxidation states are reduced, relative to the bulk, for all surfaces considered, as a consequence of the lower-energy cost of Jahn-Teller distortion at the surface. Threefold-coordinated surface Mn, found for two terminations, is divalent, which may enhance its vulnerability to dissolution. The Li-terminated (001) surface is lowest in energy, consistent with previous classical-potential simulations for MgAl{sub 2}O{sub 4} that showed the Mg-terminated (001) surface to be lowest in energy.

  9. H2O Dissociation-Induced Aluminum Oxide Growth on Oxidized Al(111) Surfaces.

    PubMed

    Liu, Qianqian; Tong, Xiao; Zhou, Guangwen

    2015-12-01

    The interaction of water vapor with amorphous aluminum oxide films on Al(111) is studied using X-ray photoelectron spectroscopy to elucidate the passivation mechanism of the oxidized Al(111) surfaces. Exposure of the aluminum oxide film to water vapor results in self-limiting Al2O3/Al(OH)3 bilayer film growth via counter-diffusion of both ions, Al outward and OH inward, where a thinner starting aluminum oxide film is more reactive toward H2O dissociation-induced oxide growth because of the thickness-dependent ionic transport in the aluminum oxide film. The aluminum oxide film exhibits reactivity toward H2O dissociation in both low-vapor pressure [p(H2O) = 1 × 10(-6) Torr] and intermediate-vapor pressure [p(H2O) = 5 Torr] regimes. Compared to the oxide film growth by exposure to a p(H2O) of 1 × 10(-6) Torr, the exposure to a p(H2O) of 5 Torr results in the formation of a more open structure of the inner Al(OH)3 layer and a more compact outer Al2O3 layer, demonstrating the vapor-pressure-dependent atomic structure in the passivating layer. PMID:26550986

  10. Electrochemically-Controlled Compositional Oscillations of Oxide Surfaces

    SciTech Connect

    Mutoro, Eva; Crumlin, Ethan; Pöpke, Hendrik; Luerssen, Bjoern; Amati, Matteo; Abyaneh, Majid; Biegalski, Michael D; Christen, Hans M; Gregoratti, Luca; Janek, Jürgen; Shao-Horn, Yang

    2012-01-01

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

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

    PubMed

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

    2014-09-30

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

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

    PubMed Central

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

    2014-01-01

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

  13. Mechanically reliable surface oxides for high-temperature corrosion resistance

    SciTech Connect

    Natesan, K.; Veal, B.W.; Grimsditch, M.; Renusch, D.; Paulikas, A.P.

    1995-05-01

    Corrosion is widely recognized as being important, but an understanding of the underlying phenomena involves factors such as the chemistry and physics of early stages of oxidation, chemistry and bonding at the substrate/oxide interface, role of segregants on the strength of that bond, transport processes through scale, mechanisms of residual stress generation and relief, and fracture behavior at the oxide/substrate interface. Because of this complexity a multilaboratory program has been initiated under the auspices of the DOE Center of Excellence for the Synthesis and Processing of Advanced Materials, with strong interactions and cross-leveraging with DOE Fossil Energy and US industry. Objective is to systematically generate the knowledge required to establish a scientific basis for designing and synthesizing improved protective oxide scales/coatings (slow-growing, adherent, sound) on high-temperature materials without compromising the requisite properties of the bulk materials. The objectives of program work at Argonne are to (1) correlate actual corrosion performance with stresses, voids, segregants, interface roughness, initial stages of oxidation, and microstructures; (2) study such behavior in growing or as-grown films; and (3) define prescriptive design and synthesis routes to mechanically reliable surface oxides. Several techniques, such as Auger electron spectroscopy, X-ray diffraction, X-ray grazing incidence reflectance, grazing-angle X-ray fluorescence, optical fluorescence, and Raman spectroscopy, are used in the studies. Tne project has selected Fe-25 wt.% Cr-20 wt.% Ni and Fe-Cr-Al alloys, which are chromia- and alumina-formers respectively, for the studies. This paper presents some of the results on early stages of oxidation and on surface segregation of elements.

  14. Formation, Removal, and Reformation of Surface Coatings on Various Metal Oxide Surfaces Inspired by Mussel Adhesives.

    PubMed

    Kang, Taegon; Oh, Dongyeop X; Heo, Jinhwa; Lee, Han-Koo; Choy, Seunghwan; Hawker, Craig J; Hwang, Dong Soo

    2015-11-11

    Mussels survive by strongly attaching to a variety of different surfaces, primarily subsurface rocks composed of metal oxides, through the formation of coordinative interactions driven by protein-based catechol repeating units contained within their adhesive secretions. From a chemistry perspective, catechols are known to form strong and reversible complexes with metal ions or metal oxides, with the binding affinity being dependent on the nature of the metal ion. As a result, catechol binding with metal oxides is reversible and can be broken in the presence of a free metal ion with a higher stability constant. It is proposed to exploit this competitive exchange in the design of a new strategy for the formation, removal, and reformation of surface coatings and self-assembled monolayers (SAM) based on catechols as the adhesive unit. In this study, catechol-functionalized tri(ethylene oxide) (TEO) was synthesized as a removable and recoverable self-assembled monolayer (SAM) for use on oxides surfaces. Attachment and detachment of these catechol derivatives on a variety of surfaces was shown to be reversible and controllable by exploiting the high stability constant of catechol to soluble metal ions, such as Fe(III). This tunable assembly based on catechol binding to metal oxides represents a new concept for reformable coatings with applications in fields ranging from friction/wettability control to biomolecular sensing and antifouling. PMID:26492561

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

    SciTech Connect

    Minaye Hashemi, Fatemeh Sadat; Laboratoire des Materiaux Semiconducteurs, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne ; Thombare, Shruti; Brongersma, Mark L.; Morral, Anna Fontcuberta i; McIntyre, Paul C.; Geballe Laboratory for Advanced Materials, Stanford University, Stanford, California 94305

    2013-06-24

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

  16. Study of tin oxide: Surface properties and palladium adsorption

    NASA Astrophysics Data System (ADS)

    Katsiev, Khabiboulakh

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

  17. Creating a Stable Oxide at the Surface of Black Phosphorus.

    PubMed

    Edmonds, M T; Tadich, A; Carvalho, A; Ziletti, A; O'Donnell, K M; Koenig, S P; Coker, D F; Özyilmaz, B; Neto, A H Castro; Fuhrer, M S

    2015-07-15

    The stability of the surface of in situ cleaved black phosphorus crystals upon exposure to atmosphere is investigated with synchrotron-based photoelectron spectroscopy. After 2 days atmosphere exposure a stable subnanometer layer of primarily P2O5 forms at the surface. The work function increases by 0.1 eV from 3.9 eV for as-cleaved black phosphorus to 4.0 eV after formation of the 0.4 nm thick oxide, with phosphorus core levels shifting by <0.1 eV. The results indicate minimal charge transfer, suggesting that the oxide layer is suitable for passivation or as an interface layer for further dielectric deposition. PMID:26126232

  18. Kinetics and Mechanisms of Ciprofloxacin Oxidation on Hematite Surfaces.

    PubMed

    Martin, Sébastien; Shchukarev, Andrey; Hanna, Khalil; Boily, Jean-François

    2015-10-20

    Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment. PMID:26419340

  19. Charge-transfer doping by fullerenes on oxidized Si surfaces

    SciTech Connect

    Tada, Tetsuya; Uchida, Noriyuki; Kanayama, Toshihiko; Hiura, Hidefumi; Kimoto, Kenji

    2007-10-01

    We have studied the charge transfer between various fullerenes (C{sub 60}, C{sub 78}, C{sub 84}, C{sub 60}F{sub 36}, and C{sub 60}F{sub 48}) and oxidized Si surfaces in order to evaluate their capability of charge-transfer doping to form ultrashallow junctions in Si. Although the lowest unoccupied molecular orbitals of these fullerene molecules in isolated states are higher in energy than the valence band maximum (VBM) of Si, the fullerenes C{sub 60}F{sub 36} and C{sub 60}F{sub 48}, which were deposited on oxidized Si substrates, captured electrons from the Si surfaces; this generated hole inversion layers. C{sub 60}, C{sub 78}, and C{sub 84} did not induce such electron transfer. From the densities of the generated holes, we estimated the acceptor levels of C{sub 60}F{sub 36} and C{sub 60}F{sub 48}, which were condensed on the oxidized Si surface, to be 5.6-5.7 and 5.2 eV below the vacuum level, respectively; these values are lower than the VBM of Si.

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

    SciTech Connect

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

    2005-08-25

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

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

    SciTech Connect

    Alexandridis, P.; Athanassiou, V.; Fukuda, Shinya; Hatton, T.A. )

    1994-08-01

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

  2. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Mao, Ming; Cerjan, Charlie; Kools, Jacques

    2002-05-01

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

  4. Growth and surface structure of vanadium oxide on anatase (001)

    SciTech Connect

    Gao, Weiwei; Wang, Chong M.; Wang, Huiqiong; Henrich, Victor E.; Altman, Eric I.

    2004-06-20

    Oxygen plasma assisted molecular beam epitaxy (OPA-MBE) of vanadium oxide on (1?4)-reconstructed anatase (001) thin films was studied using reflection high energy electron diffraction (RHEED), low energy electron diffraction (LEED), x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), x-ray diffraction (XRD), and transmission electron microscopy (TEM). XPS and UPS results showed that the vanadium was predominantly in the 5+ oxidation state after deposition of a monolayer at 525 K. After 1 ML of vanadia was deposited, the anatase (1?4)/(4?1) LEED and RHEED patterns were replaced by (1?1) patterns indicating that the vanadia lifts the reconstruction and suggesting that the monolayer is pseudomorphic. At 525 K, the V?? oxidation state predominated in thicker films, however, no discernible LEED or RHEED patterns were seen after a few monolayers were deposited indicating that V?O? epitaxy cannot be continued beyond 1 ML. When the growth temperature was increased to 750 K, RHEED patterns indicated no change in the surface structure after more than 20 ML of vanadia were deposited. Under these conditions, XPS peak positions were consistent with VO?. After growth at 775 K a c(2x2) LEED pattern attributed to half a monolayer of adsorbed oxygen on the VO? surface was observed. The surface characterization data all pointed towards pseudomorphic growth of VO? with a half monolayer of capping oxygen allowing the monolayer to achieve the V?O? stoichiometry while maintaining the anatase structure. Bulk XRD data, however, were consistent with VO? (B), V?O??, and rutile VO? none of which expose surfaces with the periodicity observed with RHEED and LEED. The reasons for the differences between the surface and bulk characterization are discussed.

  5. Effect of surface roughness on the texture and oxidation behavior of Zircaloy-4 cladding tube

    NASA Astrophysics Data System (ADS)

    Akhiani, Hamed; Szpunar, Jerzy A.

    2013-11-01

    Conventional pressure water reactors like CANDU use Zircaloy-4 as a fuel cladding tube. Surface roughness that arises from the manufacturing process, pilgering, may alter these tubes' properties in various ways. This paper presents a comparative study of cladding tubes with different surface conditions in order to investigate their effect on the Zircaloy-4 substrate and oxide textures as well as the oxidation kinetic. The experimental results reveal that surface roughness affects the oxidation rate and weight gain of the cladding tubes. Although surface polishing slightly changes the substrate texture, it induces no significant change in the oxide texture. Moreover, oxidation time does not significantly change the preferred orientation of the zirconium oxide.

  6. Atomistic Mechanism of Surface-Oxide Formation on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Reuter, K.; Ganduglia-Pirovano, M. V.; Scheffler, M.; Stampfl, C.

    2001-03-01

    CO-oxidation catalysis on Ruthenium is a prime example of the pressure and materials gap in the sense, that a very low activity under UHV conditions is contrasted with very high turnover rates at high pressures. A recent experimental study has connected this change in activity with the formation of RuO_2(110) patches on the surface (H. Over et al., Science 287, 1474 (2000)). In order to analyze the atomistic mechanism behind this surface oxide formation, we perform density functional theory calculations for more and more O loaded Ru(0001) surfaces. After a full monolayer coverage on the surface has been reached, O starts to penetrate into the sample. Instead of diffusing further into the bulk, oxygen agglomerates in subsurface islands between the first and second substrate layers. These islands can be characterized as a O-Ru-O trilayer ``floating'' on top of the Ru(0001) substrate. Further O incorporation leads to a successive formation of such O-Ru-O trilayers, which at first remain in a CaF2 type stacking sequence. After a critical thickness has been exceeded, we finally observe a phase transition into the experimentally seen rutile RuO_2(110) structure.

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

    NASA Technical Reports Server (NTRS)

    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.

  8. Attachment of Pathogenic Prion Protein to Model Oxide Surfaces

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  10. Reflection spectra and magnetochemistry of iron oxides and natural surfaces

    NASA Technical Reports Server (NTRS)

    Wasilewski, P.

    1978-01-01

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

  11. Using Alkali Ions to Probe the 3D Surface Potential of Cerium Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Guangzhi

    2005-03-01

    Charge exchange between low-energy alkali ions and cerium oxide (CeO2) single crystal surfaces is shown to depend on the surface local electrostatic potential (LEP). CeO2 has interesting catalytic properties, and is also a good surrogate for studies of U and Pu oxides. The surface is terminated by oxygen, and the degree of oxidation can be varied by annealing in vacuum or O2. The final charge state of alkali ions scattered from a metal surface is determined along the exit trajectory by a resonant charge transfer process, which depends on the LEP a few å's above the scattering site.^1 The neutral fractions of ^23Na^+ ions singly scattered from the Ce sites were measured with time-of-flight. The neutralization decreases for more grazing angles and increases for higher energy, in contrast to the usual expectations. This behavior directly reflects the inhomogeneity in the surface potential, and demonstrates that this technique can provide an experimental measure of the 3D shape of the potential. ^1C. B. Weare and J. A. Yarmoff, Surf. Sci. 348 (1996) 359.

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

    SciTech Connect

    Zhernokletov, D. M.; Laukkanen, P.; Dong, H.; Brennan, B.; Kim, J.; Galatage, R. V.; Yakimov, M.; Tokranov, V.; Oktyabrsky, S.; Wallace, R. M.; Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080

    2013-05-27

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

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

    E-print Network

    Chorover, Jon

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

  14. Reactions of CFCs with aluminum oxide surfaces at stratospheric temperatures

    SciTech Connect

    Robinson, G.N.; Dai, Q.; Freedman, A.

    1996-10-01

    Approximately 30 wt % of the exhaust emitted by the Space Shuttle`s solid-propellant rocket motors is composed of micron and submicron sized aluminum oxide particles. In order to assess the impact of these particles on stratospheric chemistry, we have investigated the reactions of several chlorofluorcarbons (CFCs) on {alpha}- and {gamma}-aluminum oxide powders at temperatures from 80-400 K. Using a combination of molecular beam dosing under UHV conditions, FTIR and X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD), we conclude that CFCs dissociatively chemisorb on dehydroxylated alumina surfaces at temperatures as low as 130 K. A number of temperature-dependent absorption features are observed in the infrared spectra which can be attributed to carbonate species. TPD spectra indicate that CO{sub 2} desorbs from CFC-dosed alumina at temperatures below 370 K. X-ray photoelectron spectra reveal the presence of inorganic halides at temperatures as low As 150 K. The relative reactivities of the CFCs with alumina surfaces at stratospheric temperatures ({approximately}200 K) reflect differences in the initial sticking probabilities of the molecules and in the energetics of the dissociative chemisorption process.

  15. Surface composition of solid-rocket exhausted aluminum oxide particles

    NASA Technical Reports Server (NTRS)

    Cofer, Wesley R., III; Winstead, Edward L.; Key, Lawrence E.

    1989-01-01

    Particulate samples of aluminum oxide were collected on Teflon filters from the exhaust plume of the Space Shuttle (STS-61A, October 30, 1985) over the altitude interval 4.6-7.6 km immediately after launch. These particles were analyzed using SEM, energy-dispersive X-ray analysis, electron spectroscopy for chemical analysis, X-ray fluorescent spectroscopy, and conventional wet-chemical techniques. The samples were 0.6-1.0 percent surface-chlorided (chlorided meaning predominantly aluminum chlorides and oxychlorides, possibly including other adsorbed forms of chloride) by weight. This level of chloriding is about one-third of the amount determined previously from laboratory-prepared alumina and surface site samples of solid-rocket-produced alumina (SRPA) after both had been exposed to moist HCl vapor at temperatures down to ambient. This level is equivalent to previous laboratory results with samples exposed to moist HCl at temperatures above the boiling point of water. It is suggested that the present lower chloriding levels, determined for samples from a 'dry' Shuttle exhaust cloud, underscore the importance of a liquid water/hydrochloric acid phase in governing the extent of surface chloriding of SRPA. The reduced chloriding is not trivial with respect to potential physical/chemical modification of the SRPA particle surfaces and their corresponding interaction with the atmosphere.

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

    E-print Network

    Rohrer, Gregory S.

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

  17. Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

    PubMed Central

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

    2012-01-01

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

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

    E-print Network

    Yildiz, Bilge

    Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides Wonyoung Lee segregation, a detrimental process on the surface of perovskite cathodes (1). Motivated by those results, here separation. Introduction Cation segregation on the perovskite oxide surface imposes the significant impacts

  19. Oxidation of step edges on vicinal 4H-SiC(0001) surfaces

    SciTech Connect

    Li, Wenbo; Zhu, Qiaozhi; Wang, Dejun; Zhao, Jijun

    2013-11-18

    The oxidation processes of stepped SiC(0001) surfaces are studied within the ab initio atomistic thermodynamics approach. Our calculations show that a one-dimensional -Si-O- chain structure as a precursor for oxide growth on stepped SiC surfaces is formed along the step edge, promoting further oxidation of the step edges. Following the modified Deal-Grove oxidation model, we also find that the oxidation rate at steps is higher than that at terraces by three orders of magnitude. These findings give a reasonable explanation for the oxide thickness fluctuation between the step and the terrace observed in the previous experiments.

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

    SciTech Connect

    Boffa, A B

    1994-07-01

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

  1. High surface area, electrically conductive nanocarbon-supported metal oxide

    DOEpatents

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

    2014-03-04

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

  2. High surface area, electrically conductive nanocarbon-supported metal oxide

    DOEpatents

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

    2015-07-14

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

  3. A surface science investigation of silicon carbide: Oxidation, crystal growth and surface structural analysis

    SciTech Connect

    Powers, J.M.

    1991-11-01

    For the semiconductor SiC to fulfill its potential as an electronic material, methods must be developed to produce insulating surface oxide layers in a reproducible fashion. Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) were used to investigate the oxidation of single crystal {alpha}-SiC over a wide temperature and O{sub 2} pressure range. The {alpha}-SiC surface becomes graphitic at high temperatures and low O{sub 2} pressures due to Si and SiO sublimation from the surface. Amorphous SiO{sub 2} surface layers from on {alpha}-SiC at elevated O{sub 2} pressures and temperatures. Both the graphitization and oxidation of {alpha}-SiC appears to be enhanced by surface roughness. Chemical vapor deposition (CVD) is currently the preferred method of producing single crystal SiC, although the method is slow and prone to contamination. We have attempted to produce SiC films at lower temperatures and higher deposition rates using plasma enhanced CVD with CH{sub 3}SiH{sub 3}. Scanning AES, XPS and scanning electron microscopy (SEM) were utilized to study the composition and morphology of the deposited Si{sub x}C{sub y}H{sub z} films as a function of substrate temperature, plasma power and ion flux bombardment of the film during deposition. High energy ion bombardment during deposition was found to increase film density and substrate adhesion while simultaneously reducing hydrogen and oxygen incorporation in the film. Under all deposition conditions the Si{sub x}C{sub y}H{sub z} films were found to be amorphous, with the ion bombarded films showing promise as hard protective coatings. Studies with LEED and AES have shown that {beta}-SiC (100) exhibits multiple surface reconstructions, depending on the surface composition. These surface reconstructions possess substantially different surface reactivities at elevated temperatures, which can complicate the fabrication of metal on SiC junctions.

  4. Electrospun nickel oxide nanofibers: Microstructure and surface evolution

    NASA Astrophysics Data System (ADS)

    Khalil, Abdullah; Hashaikeh, Raed

    2015-12-01

    Nickel oxide (NiO) nanofibers with controlled microstructure were synthesized through the electrospinning technique using a solution composed of nickel acetate and polyvinyl alcohol. The microstructure of NiO nanofibers was found to be highly dependent on nickel acetate concentration in the solution and the post-heat treatment. As the nickel acetate concentration increases, the crystallinity index of NiO nanofibers increases from nearly 50 percent to 90 percent and the average crystallite size in the nanofibers increases from about 20 nm to 30 nm. Further, it was found that annealing the nanofibers at 1000 °C for 2 h leads to nearly full crystallization of nanofibers with significant increase in the crystallite size to about 50 nm while maintaining the fibrous shape. For low nickel acetate concentration, and because of the small nanofibers size, the surface of the calcined nanofibers showed oxygen deficiency which promises a superior activity of these NiO nanofibers for catalytic and sensing applications.

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

    SciTech Connect

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

    2007-08-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    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.

  7. Oxygen Reduction Kinetics Enhancement on a 2 Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    SciTech Connect

    Crumlin, Ethan; Mutoro, Eva; Ahn, Sung Jin; Jose la O', Gerardo; Leonard, Donovan N; Borisevich, Albina Y; 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 {approx}85 nm thick La{sub 0.8}Sr{sub 0.2}CoO{sub 3-{delta}} (LSC{sub 113}) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced ({approx} 3-4 orders of magnitude above bulk LSC{sub 113}) by surface decorations of (La{sub 0.5}Sr{sub 0.5}){sub 2}CoO{sub 4{+-}{delta}} (LSC{sub 214}) with coverage in the range from {approx}0.1 to {approx}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 LSC{sub 113}/LSC{sub 214} regions, which were shown to be atomically sharp.

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

    PubMed

    Wibroe, Peter P; Petersen, Søren V; Bovet, Nicolas; Laursen, Bo W; Moghimi, S Moein

    2016-02-01

    Graphene oxide (GO) is believed to become applicable in biomedical products and medicine, thereby necessitating appropriate safety evaluation dependent on their applications and the route of administration. We have examined the effect of GO form (in solution versus immobilized) and oxidation state 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 of GO-based implantable devices. PMID:26646624

  9. Decontamination of U-metal Surface by an Oxidation Etching System

    SciTech Connect

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

    2000-12-18

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

  10. In-situ X-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

    SciTech Connect

    Salmeron, Miquel; Yamamoto, S.; Bluhm, H.; Andersson, K.; Ketteler, G.; Ogasawara, H.; Salmeron, M.; Nilsson, A.

    2007-10-29

    X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in-situ XPS measurements at pressures above 5 Torr. In this review, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in-situ XPS to studies of water adsorption on the surface of metals and oxides including Cu(110), Cu(111), TiO2(110) under environmental conditions of water vapor pressure. On all these surfaces we observe a general trend where hydroxyl groups form first, followed by molecular water adsorption. The importance of surface OH groups and their hydrogen bonding to water molecules in water adsorption on surfaces is discussed in detail.

  11. Abiotic formation of elemental selenium and role of iron oxide surfaces Yu-Wei Chen a

    E-print Network

    Belzile, Nelson

    Abiotic formation of elemental selenium and role of iron oxide surfaces Yu-Wei Chen a , Hoang: Elemental selenium Abiotic reduction Surface catalysis Laboratory simulation Lake sediments a b s t r a c

  12. Hydrophobic cotton textile surfaces using an amphiphilic graphene oxide (GO) coating

    NASA Astrophysics Data System (ADS)

    Tissera, Nadeeka D.; Wijesena, Ruchira N.; Perera, J. Rangana; de Silva, K. M. Nalin; Amaratunge, Gehan A. J.

    2015-01-01

    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. Microscopic characterization of the fiber surface using SEM and AFM reveals the deposition of GO sheets on the fiber surface as a conformal coating. Analysis of the fabric surface using UV-vis absorption allowed identification of the ratio of hydrophobic to hydrophilic domains present on the GO coated cotton fabric surface. Hydrophobic properties on cotton fabric are ascribed to two dimensional amphiphilic properties of deposited GO nano sheets, which successfully lower the interfacial energy of the fabric surface.

  13. Surface and sub-surface reactions during low temperature aluminium oxide atomic layer deposition on fiber-forming polymers

    E-print Network

    Khan, Saad A.

    Surface and sub-surface reactions during low temperature aluminium oxide atomic layer deposition-phase chemical precursors and high molecular weight polymers are important for polymer coating, encapsulation and surface modification. Using trimethylaluminium and water in an atomic layer deposition (ALD) exposure

  14. Study on Oxidation of Cu and Cu3Au Surfaces with Hyperthermal Oxygen Molecular Beam

    NASA Astrophysics Data System (ADS)

    Okada, Michio; Teraoka, Yuden

    Corrosion wastes more than a few percent of the world's GDP every year. The initial stage of the corrosion is one of the central topics in material science. The oxidation is one of the major corrosion processes of metals. Thus, the study of the oxidation process on metal surfaces is generally interesting in various fields of science and technology. The growth of a protective thin surface layer, which prevents further oxidation into bulk of a metal, requires the formation of a homogeneous film. One simple way for the protection of underlying metals is surface alloying, combining different substances to form multi-component surfaces. The surface alloying leads to the formation of a protective oxide layer due to the preferential oxidation of one component, possibly with surface segregation. Copper and copper alloys have wide industrial applications, and therefore are of interest for studies of oxidation mechanism, especially in the Cu2O formation. Cu forms the stable Cu2O, while Au does not form a stable oxide and is not soluble into stable Cu2O. Thus, the Cu-Au alloy system is ideal for investigating the effect of alloying on the formation of protective layer against further oxidation into bulk. Here, we introduce our recent comparative studies of the oxidation of Cu(100) and Cu3Au(100) with hyperthermal O2 molecular beam and discuss why Cu3Au(100) is protective against the oxidation.

  15. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface

    NASA Astrophysics Data System (ADS)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.

    2015-12-01

    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  16. Mechanism of the Initial Oxidation of Hydrogen andHalogen Terminated Ge(111) Surfaces in Air

    SciTech Connect

    Sun, Shiyu; Sun, Yun; Liu, Zhi; Lee, Dong-Ick; Pianetta, Piero; /SLAC, SSRL

    2006-08-23

    The initial stage of the oxidation of Ge(111) surfaces etched by HF, HCl and HBr solutions is systematically studied using synchrotron radiation photoelectron spectroscopy (SR-PES). We perform controlled experiments to differentiate the effects of different oxidation factors. SR-PES results show that both moisture and oxygen contribute to the oxidation of the surfaces; however, they play different roles in the oxidation process. Moisture effectively replaces the hydrogen and halogen termination layers with hydroxyl (OH), but hardly oxidizes the surfaces further. On the other hand, dry oxygen does not replace the termination layers, but breaks the Ge-Ge back bonds and oxidizes the substrates with the aid of moisture. In addition, room light enhances the oxidation rate significantly.

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

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  18. Investigation of Oxide Layer Structure on Niobium Surfaces using a Secondary Ion Mass Spectrometer

    SciTech Connect

    Andy T. Wu

    2005-07-10

    Oxide layer structure on the surfaces of niobium (Nb) can be studied by continuously monitoring peaks of the secondary ions of Nb and its relevant oxides as a function of time during depth profiling measurements employing a secondary ion mass spectrometer (SIMS). This is based on the fact that different oxides have different cracking patterns. This new approach is much simpler and easier for studying oxide layer structure on Nb surfaces than the conventional approach through deconvolution of oxide peaks obtained from an x-ray photoemission spectrometer. Eventually it can be developed into an in-situ tool for monitoring the oxide layer structure on Nb surfaces prepared by various procedures. Preliminary results of SIMS measurements on the surfaces of Nb samples treated by buffered electropolishing and buffered chemical polishing will be reported.

  19. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Final report

    SciTech Connect

    Doyle, F.M.

    1996-01-26

    Coal oxidation has been studies extensively in previous work. However, there is still no general agreement concerning the mechanisms of oxidation. Moreover, the oxidation behavior of coal and mineral matter have generally been regarded as separate processed. There is appreciable evidence that organic and inorganic oxidation process are actually coupled, consequently the changes in their surface properties induced by oxidation are difficult to predict. This makes the effectively of coal cleaning processes highly sensitive to the extent of weathering and oxidation that the coal has experienced. The objective of this research was to investigate the oxidation behavior of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with these surface properties that would influence the behavior in physical cleaning processes.

  20. Nitric Oxide Production from Surface Recombination of Oxygen and Nitrogen Atoms

    E-print Network

    Martín, Pino

    1 Nitric Oxide Production from Surface Recombination of Oxygen and Nitrogen Atoms Dusan A. Pejakovi;2 Abstract Experimental results are presented that support the surface-catalyzed production of nitric oxide from the recombination of oxygen and nitrogen atoms on quartz. The experiments employ two-photon laser

  1. A chemical approach to understanding oxide surfaces James A. Enterkin a,b,c

    E-print Network

    Marks, Laurence D.

    A chemical approach to understanding oxide surfaces James A. Enterkin a,b,c , Andres E. Becerra-Toledo d , Kenneth R. Poeppelmeier a,b,c , Laurence D. Marks c,d, a Chemical Sciences and Engineering Keywords: Bond valence sum Coordination Chemical bond Surface structure Metal oxide Chemical bonding has

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

    SciTech Connect

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

    2011-04-14

    By employing variable-charge molecular dynamics, surface oxide film growth on aluminum-nickel-iron alloys has been studied at 300 and 600 K. The dynamics of oxidation and oxide growth is strongly dependent on the composition of the initial alloy and the ambient temperature. Higher content of Ni and Fe in Al alloys is found to reduce the oxide growth kinetics; 15% Ni + 15% Fe Al alloy yielded 30-40% less growth at 400 ps oxygen exposure compared to pure Al. We observe dopant segregation, which disrupts the interaction between O atoms and Al atoms in the alloy, leading to a nonlinear oxide growth profile in the case of ternary Al-Ni-Fe alloy. Compared to oxidation at 300 K, 30% more oxide layer was yielded at 600 K, due to the elevated temperature. The simulated oxide kinetics indicates that the growth rate of anion surpasses the cation rate with higher sensitivity to the stoichiometry of the base metal substrate. Charge state analysis provides insights into the evolution of cation and anion species as the oxide layer grows. In particular, due to higher correlation, Fe shows a high rate of oxidation when the content is high, whereas the rate of Ni oxidation is consistently low. Density profile analysis suggests the segregation of dopant atoms below the growing ultrathin oxide layer, showing the presence of a layer-by-layer mode of oxide layer even with disordered structure. Coordination number (Z, the number of oxygen atoms around an aluminum atom) of aluminum oxide has been used to identify how the initial oxidation transitions into equilibrated states. Z = 3 is dominant in the early stages of oxidation and at the interface between oxide and bulk substrate, but it transitions quickly to Z = 4 (45%) and 5 (35%) as the oxide equilibrates and approaches its self-limiting thickness. Even though growth kinetics is dependent on the base metal stoichiometry, the composition of the oxide microstructure is not significantly affected, primarily segregating dopant elements, i.e., Ni and Fe outside of the oxide layer.

  3. Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films

    NASA Astrophysics Data System (ADS)

    Di, N.; Kubal, J.; Zeng, Z.; Greeley, J.; Maroun, F.; Allongue, P.

    2015-03-01

    We studied the influence of controlled surface-limited oxidation of electrodeposited epitaxial Co(0001)/Au(111) films on their magnetic anisotropy energy using real time in situ magneto optical Kerr effect and density functional theory (DFT) calculations. We investigated the Co first electrochemical oxidation step which we demonstrate to be completely reversible and determined the structure of this oxide layer. We show that the interface magnetic anisotropy of the Co film increases by 0.36 erg/cm2 upon Co surface oxidation. We performed DFT calculations to determine the different surface structures in a wide potential range as well as the charge transfer at the Co surface. Our results suggest that the magnetic anisotropy change is correlated with a positive charge increase of 0.54 e- for the Co surface atom upon oxidation.

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  5. Friction-induced surface activity of some hydrocarbons with clean and oxide-covered iron

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1973-01-01

    Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.

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

    DOEpatents

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

    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.

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

    DOEpatents

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

    1998-01-01

    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.

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

    SciTech Connect

    Doyle, F.M.

    1992-01-28

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical coal cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fifth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville {number sign}2 Mine, Clearfield County, Pennsylvania.

  9. Surface x-ray diffraction of complex metal oxide surfaces and interfaces--a new era

    SciTech Connect

    Schlepuetz, C. M.; Willmott, P. R.; Pauli, S. A.; Herger, R.; Martoccia, D.; Bjoerck, M.; Kumah, D.; Clarke, R.; Yacoby, Y.

    2009-01-29

    The availability of high-brilliance hard x-ray synchrotron radiation and the advent of novel photon counting area detectors have brought surface x-ray diffraction (SXRD) into a new era. It is now possible to record large numbers of structure factors with much improved reliability within reasonable beamtime durations. As a result, structural determination of the surfaces and interfaces of complex crystallographic systems and heterostructures has now become feasible, especially in conjunction with phase-retrieval methods. It is thereby hoped that detailed structural information will shed light on the unusual physical properties of these systems. Complex metal oxide systems investigated at the Materials Science beamline of the Swiss Light Source, including the surface of SrTiO{sub 3}, the interface between LaAlO{sub 3} and SrTiO{sub 3}, and the structure of YBa{sub 2}Cu{sub 3}O{sub 7} grown on NdGaO{sub 3}, SrTiO{sub 3}, and (LaSr)(AlTa)O{sub 3} will be presented as examples of what is now possible using SXRD.

  10. DIVISION S-2--SOIL CHEMISTRY Dissolution Kinetics of Nickel Surface Precipitates on Clay Mineral and Oxide Surfaces

    E-print Network

    Sparks, Donald L.

    DIVISION S-2--SOIL CHEMISTRY Dissolution Kinetics of Nickel Surface Precipitates on Clay Mineral and Oxide Surfaces Kirk G. Scheckel* and Donald L. Sparks ABSTRACT M3 are divalent and trivalent metal at pH 4 and 6. Nickel de-brucite-like hydroxide layers, (ii) Si-for-NO3 exchange in the interlay

  11. Role of RuO2(100) in surface oxidation and CO oxidation catalysis on Ru(0001).

    PubMed

    Flege, Jan Ingo; Lachnitt, Jan; Mazur, Daniel; Sutter, Peter; Falta, Jens

    2016-01-01

    We have studied the oxidation of the Ru(0001) surface by in situ microscopy during exposure to NO2, an efficient source of atomic oxygen, at elevated temperatures. In a previous investigation [Flege et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78, 165407], at O coverages exceeding 1 monolayer, using the combination of intensity-voltage (I(V)) low-energy electron microscopy (LEEM) and multiple scattering calculations for the (00) beam in the very-low-energy range (E? 50 eV) we identified three surface components during the initial Ru oxidation: a (1 × 1)-O chemisorption phase, the RuO2(110) oxide phase, and a surface oxide structure characterized by a trilayer O-Ru-O stacking. Here, we use dark-field LEEM imaging and micro-illumination low-energy electron diffraction in the range of 100 to 400 eV to show that this trilayer phase is actually a RuO2(100)-(1 × 1) phase with possibly mixed O and Ru surface terminations. This identification rationalizes the thermodynamic stability of this phase at elevated temperatures and is consistent with the observation of catalytic activity of the phase in CO oxidation. PMID:26601756

  12. Analysis of surface oxides on narrow bandgap III-V semiconductors leading towards surface leakage free IR photodetectors

    NASA Astrophysics Data System (ADS)

    Wang, Qin; Li, Xun; Zhang, Andy; Almqvist, Susanne; Karim, Amir; Noharet, Bertrand; Andersson, Jan Y.; Göthelid, Mats; Yu, Shun; Gustafsson, Oscar; Hammar, Mattias; Asplund, Carl; Göthelid, Emmanuelle

    2012-06-01

    Narrow bandgap semiconductors GaSb, InAs, and InSb are important building blocks for infrared photodetectors based on type-II InSb quantum dots or an InAs/GaSb strained layer superlattice. Understanding the surface chemical composition of these materials can provide valuable information that enables optimization of device surface passivation techniques leading towards surface leakage free IR photodetectors. We report on an investigation into Ga-, In-, Sb-, and As-oxides and other chemical species on the surface of untreated, dry etched and thermally treated GaSb, InAs and InSb samples by x-ray photoelectron spectroscopy. The experimental results reveal the presence of Sb- and Ga-oxides on the surfaces of the untreated and treated GaSb samples. Both Sb- and In-oxides were observed on the surface of all InSb samples, and especially the dry etched sample had thicker oxide layers. In the case of the InAs samples, not only In- and As-oxides XPS signals were obtained, but also AsCl species were found on the ICP dry etched sample. These results helped to analyze the dark current of our fabricated IR detectors.

  13. Formation of surface oxides and Ag2O thin films with atomic oxygen on Ag(111)

    NASA Astrophysics Data System (ADS)

    Derouin, Jonathan; Farber, Rachael G.; Heslop, Stacy L.; Killelea, Daniel R.

    2015-11-01

    The nature of the oxygen species adsorbed to silver surfaces is a key component of the heterogeneously catalyzed epoxidation of ethylene and partial oxidation of methanol over silver catalysts. We report the formation of two different silver-oxygen species depending on the flux and energy of incident gas-phase oxygen atoms on an Ag(111) surface. A combination of surface science techniques was used to characterize the oxidized surfaces. Atomic oxygen was generated with an Ir filament; lower temperatures created surface oxides previously reported. When O was deposited with a higher filament temperature, the surface became highly corrugated, little subsurface oxygen was observed, and thin layers of Ag2O were likely formed. These results show that the energy and flux of oxygen are important parameters in the chemical identity and abundance of oxygen on silver surfaces and suggest that formation of the Ag2O thin film hinders formation of subsurface oxygen.

  14. Effect of Surface Oxidation on Interfacial Water Structure at a Pyrite (100) Surface as Studied by Molecular Dynamics Simulation

    SciTech Connect

    Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.; Wick, Collin D.

    2015-06-01

    In the first part of this paper, a Scanning Electron Microscopy and contact angle study of a pyrite surface (100) is reported describing the relationship between surface oxidation and the hydrophilic surface state. In addition to these experimental results, the following simulated surface states were examined using Molecular Dynamics Simulation (MDS): fresh unoxidized (100) surface; polysulfide at the (100) surface; elemental sulfur at the (100) surface. Crystal structures for the polysulfide and elemental sulfur at the (100) surface were simulated using Density Functional Theory (DFT) quantum chemical calculations. The well known oxidation mechanism which involves formation of a metal deficient layer was also described with DFT. Our MDS results of the behavior of interfacial water at the fresh and oxidized pyrite (100) surfaces without/with the presence of ferric hydroxide include simulated contact angles, number density distribution for water, water dipole orientation, water residence time, and hydrogen-bonding considerations. The significance of the formation of ferric hydroxide islands in accounting for the corresponding hydrophilic surface state is revealed not only from experimental contact angle measurements but also from simulated contact angle measurements using MDS. The hydrophilic surface state developed at oxidized pyrite surfaces has been described by MDS, on which basis the surface state is explained based on interfacial water structure. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE funded work performed by Liem X. Dang. Battelle operates the Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

  15. UO2 surface oxidation by mixtures of water vapor and hydrogen as a function of temperature

    NASA Astrophysics Data System (ADS)

    Espriu-Gascon, A.; Llorca, J.; Domínguez, M.; Giménez, J.; Casas, I.; de Pablo, J.

    2015-12-01

    In the present work, X-Ray Photoelectron Spectroscopy (XPS) was used to study the effect of water vapor on the UO2 surface as a function of temperature. The experiments were performed in situ inside a high pressure chamber attached to the XPS instrument. UO2 samples were put in contact with either hydrogen or argon streams, saturated with water at room temperature, and the sample surface evolution was analyzed by XPS. In the case of the water vapor/argon experiments, one experiment at 350 °C was performed and, in the case of the water vapor/hydrogen experiments, the temperatures used inside the reactor were 60, 120, 200 and 350 °C. On one hand, in presence of argon, the results obtained showed that the water vapor in the argon stream oxidized 93% of the U(IV) in the sample surface. On the other hand, the degree of UO2 surface oxidation showed a different dependence on the temperature in the experiments performed in the presence of hydrogen: the maximum surface oxidation occurred at 120 °C, where 65.4% of U(IV) in the sample surface was oxidized, while at higher temperatures, the surface oxidation decreased. This observation is attributed to the increase of hydrogen reducing effect when temperature increases which prevents part of the oxidation of the UO2 surface by the water vapor.

  16. Characterization of the ''clean-up'' of the oxidized Ge(100) surface by atomic layer deposition

    SciTech Connect

    Milojevic, M.; Kim, J.; Wallace, R. M.; Contreras-Guerrero, R.; Lopez-Lopez, M.

    2009-11-23

    While the 'clean-up' effect on III-V substrates has recently been well documented interfacial reactions during atomic layer deposition (ALD) on Ge substrates are not fully explored. The 'clean-up' of Ge oxides is studied by interrupting the ALD process following individual precursor pulses for in situ monochromatic x-ray photoelectron spectroscopy analysis. Germanium oxides are found to be reduced by TMA and water, while an interfacial GeON layer is only affected by the initial TMA pulse. Oxide free germanium surfaces behave analogously to a surface with initial native oxides since they are oxidized measurably prior to the first TMA pulse due to residual oxidants in a commercial ALD chamber.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

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

    SciTech Connect

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

    2007-04-01

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

  19. Solid State, Surface and Catalytic Studies of Oxides

    SciTech Connect

    Kung, H. H.

    2004-11-23

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

  20. Surface modifications of iron oxide nanoparticles for biological applications

    E-print Network

    Insin, Numpon

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Smith, Billy

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

  2. Ozone oxidation of oleic acid surface films decreases aerosol CCN1 activity 2

    E-print Network

    Nenes, Athanasios

    1 Ozone oxidation of oleic acid surface films decreases aerosol CCN1 activity 2 3 A. N;2 Abstract24 Heterogeneous oxidation of aerosols composed of pure oleic acid (C18H34O2, an unsaturated fatty when the oleic acid is internally mixed with other electrolytes is unknown and28 addressed

  3. Electron stimulated oxidation of the Ni(111) surface: Dependence on substrate temperature and incident electron energy

    E-print Network

    Sibener, Steven

    Electron stimulated oxidation of the Ni(111) surface: Dependence on substrate temperature and incident electron energy M. J. Stirniman, Wei Li, and S. J. Sibener Department of Chemistry and The James with and without electron irradiation has been determined for temperatures between 120 and 340 K. The oxidation

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

    SciTech Connect

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

    2014-03-03

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

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

    E-print Network

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

    2014-01-01

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

  6. Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides

    E-print Network

    Lee, Wonyoung

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

  7. Surface properties of zinc oxide nanoparticles studied by inverse gas chromatography.

    PubMed

    Przybyszewska, Magdalena; Krzywania, Alicja; Zaborski, Marian; Szynkowska, Ma?gorzata Iwona

    2009-07-01

    Inverse gas chromatography (IGC) was applied in infinite dilution to evaluate the surface properties of zinc oxide nanoparticles with respect to their specific surface area, particle size and morphology (spherical, whiskers, and snowflakes). The dispersive components (gamma(S)(D)) of the free energy of zinc oxides were determined by Gray's method, whereas their tendency to undergo specific interactions was estimated based on the electron donor-acceptor approach presented by Papirer. The zinc oxide nanoparticles exhibited high surface energies that were dependent on their morphology. The highest value of gamma(S)(D) was determined for spherical zinc oxide particles with high specific surface area, which had the most structure defects. The specific interactions were characterized by the energy (DeltaG(A)(SP)) and enthalpy (DeltaH(A)(SP)) of adsorption as well as the donor and acceptor interaction parameters (K(A), K(D)). PMID:19464015

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

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

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

    SciTech Connect

    Herrera, M.N.

    1994-12-31

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

  10. Surface effects in metal oxide-based nanodevices.

    PubMed

    Lien, Der-Hsien; Durán Retamal, José Ramón; Ke, Jr-Jian; Kang, Chen-Fang; He, Jr-Hau

    2015-12-21

    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. PMID:26580674

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  12. Effect of lanthanide group REM oxides activated mechanically on the surface tension of borate melts

    NASA Astrophysics Data System (ADS)

    Istomin, S. A.; Khokhryakov, A. A.; Ivanov, A. V.; Chentsov, V. P.; Ryabov, V. V.

    2015-02-01

    Surface tension ? of boron oxide-based melts containing 1 wt % lanthanide group REM oxide activated mechanically is measured by the sessile drop method in the temperature range 800-1650 K. The temperature dependences of the surface tension are found to be linear. The temperature coefficients of the dependences are calculated. The dependence of s on the atomic number of a lanthanide obeys the series periodicity in the series of the borate melts under study.

  13. Compositional Control of Surface Oxides on Metal Alloys using Photons: Dynamic Simulations and Experiments

    SciTech Connect

    Chang, C.; Sankaranarayanan, S; Ruzmetov, D; Engelhard, M; Kaxiras, E; Ramanathan, S

    2010-01-01

    We report on the ability to modify the structure and composition of ultrathin oxides grown on Ni and Ni-Al alloy surfaces at room temperature utilizing photon illumination. We find that the nickel-oxide formation is enhanced in the case of oxidation under photo-excitation. The enhanced oxidation kinetics of nickel in 5% Ni-Al alloy is corroborated by experimental and simulation studies of natural and photon-assisted oxide growth on pure Ni(100) surfaces. In case of pure Ni substrates, combined x-ray photoelectron spectroscopy analysis, and atomic force microscope current mapping support the deterministic role of the structure of nickel passive-oxide films on their nanoscale corrosion resistance. Atomistic simulations involving dynamic charge transfer predict that the applied electric field overcomes the activation-energy barrier for ionic migration, leading to enhanced oxygen incorporation into the oxide, enabling us to tune the mixed-oxide composition at atomic length scales. Atomic scale control of ultrathin oxide structure and morphology in the case of pure substrates as well as compositional tuning of complex oxide in the case of alloys leads to excellent passivity as verified from potentiodynamic polarization experiments.

  14. Thin film lubrication of hexadecane confined by iron and iron oxide surfaces: A crucial role of surface structure

    NASA Astrophysics Data System (ADS)

    Ta, D. T.; Tieu, A. K.; Zhu, H. T.; Kosasih, B.

    2015-10-01

    A comparative analysis of thin film lubrication of hexadecane between different iron and its oxide surfaces has been carried out using classical molecular dynamic simulation. An ab initio force-field, COMPASS, was applied for n-hexadecane using explicit atom model. An effective potential derived from density functional theory calculation was utilized for the interfacial interaction between hexadecane and the tribo-surfaces. A quantitative surface parameterization was introduced to investigate the influence of surface properties on the structure, rheological properties, and tribological performance of the lubricant. The results show that although the wall-fluid attraction of hexadecane on pure iron surfaces is significantly stronger than its oxides, there is a considerable reduction of shear stress of confined n-hexadecane film between Fe(100) and Fe(110) surfaces compared with FeO(110), FeO(111), Fe2O3(001), and Fe2O3(012). It was found that, in thin film lubrication of hexadecane between smooth iron and iron oxide surfaces, the surface corrugation plays a role more important than the wall-fluid adhesion strength.

  15. Obtaining composite Zr-Al-O coating on the surface of zirconium by microplasma oxidation

    SciTech Connect

    Gubaidulina, Tatiana A. E-mail: ostk@mail2000ru; Kuzmin, Oleg S. E-mail: ostk@mail2000ru; Fedorischva, Marina V. E-mail: kmp1980@mail.ru; Kalashnikov, Mark P. E-mail: kmp1980@mail.ru; Sergeev, Viktor P.

    2014-11-14

    The paper describes the application of the microplasma oxidation for production of Zr-Al-O composition on the surface of zirconium. Certification of a new-type power supply for depositing oxide ceramic coatings by microplasma oxidation was also carried out. The growth rate of Zr-Al-O coating amounted around 0.2 nm/s, which around 10 times exceeds that for depositing similar coatings using the similar equipment. We have studied the change of surface morphology and the chemical composition of the formed ceramic coating by means of EVO 50 scanning electron microscope and X-ray spectral analysis.

  16. Interaction of carbon oxides with the surface of catalysts containing iron and nickel nanoparticles

    NASA Astrophysics Data System (ADS)

    Sheshko, T. F.; Serov, Yu. M.

    2011-05-01

    The interaction of individual carbon oxides and their mixture with the surface of monometallic catalysts that contain iron and nickel nanoparticles was investigated for the first time by thermoprogrammed desorption. It was found that both oxides are adsorbed molecularly and dissociatively. No competition between CO and CO2 was observed upon the coadsorption of these oxides. It was shown that the preadsoption of hydrogen on the surface leads to a strengthening of the Me-CO bond, raises the activation energy of desorption, assists in the dissociative chemisorption of carbon monoxide, and leads to the appearance of hydrocarbons among the products of desorption.

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

    NASA Astrophysics Data System (ADS)

    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 compounds Mg _2Sn, Mg_2Ge and Mg _2Si were detected at 29, 32, and 40 meV, respectively. The native oxide of all three show a dominant Mg-O mode at 80 meV. Probable Sn-O, Ge-O, and Si-O modes are also identified. Complete removal of the oxide layer was accomplished only on the Mg_2 Si surface but resulted in no noticeable change in the energy of the surface phonon. Results are compared to the known bulk optical properties of these compounds.

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

    SciTech Connect

    Doyle, F.M.

    1992-06-30

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

  19. Isothermal oxidation behavior and microstructure of plasma surface Ta coating on ?-TiAl

    SciTech Connect

    Song, Jian; Zhang, Ping-Ze Wei, Dong-Bo; Wei, Xiang-Fei; Wang, Ya

    2014-12-15

    The oxidation behavior of ?-TiAl with Ta surface coating fabricated by double glow plasma surface alloying technology was investigated by thermogravimetric method. Oxidation experiments were carried out at 750 °C and 850 °C in air for 100 h. The modification layer was comprised of deposition layer and diffusion layer, which metallurgically adhered to the substrate. Tantalum element decreased with the case depth. The oxidation morphology was studied by a scanning electron microscope and X-ray diffraction. The results highlighted that in the oxidizing process of the oxidation, the phase containing Ta-richer may restrain diffusing outward of the element Al in the matrix. Ti diffused outward, and formed the TiO{sub 2} scales, while the middle layer was rich in Al, and formed the continuous Al{sub 2}O{sub 3} scales after oxidation, which was effective to prevent further infiltration of oxygen atoms, and as a result the oxidation resistance increased immensely. - Highlights: • A Ta modified coating was prepared on ?-TiAl using DGP surface alloying technology. • The modification layer metallurgically adhered to the substrate. • The bonding force is about 60 N, satisfying the demands of practical use. • The oxidation resistance increased immensely at 750 °C and 850 °C.

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

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  1. Thermal oxidation of the surface of binary aluminum alloys with rare-earth metals

    NASA Astrophysics Data System (ADS)

    Akashev, L. A.; Popov, N. A.; Kuznetsov, M. V.; Shevchenko, V. G.

    2015-05-01

    The kinetics of oxidation of the surface of Al alloys with 1-2.5 at % rare-earth metals (REMs) at 400-500°C in air was studied by ellipsometry and X-ray photoelectron spectroscopy (XPS). The addition (1-2.5 at % REM) of all rare-earth metals to aluminum was shown to increase the thickness of the oxide layer. The addition of surfactant and chemically active REMs (Yb, Sm, La, and Ce) increased the rate of oxidation of solid aluminum most effectively. The oxidation can be accelerated by the polymorphic transformations of the individual REM oxides in the film. The surface activity of Sm with respect to solid Al was confirmed by XRS.

  2. Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  5. Rates of oxidative weathering on the surface of Mars

    NASA Astrophysics Data System (ADS)

    Burns, R. G.; Fisher, D. S.

    1993-02-01

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

  6. Rates of oxidative weathering on the surface of Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1993-01-01

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

  7. High Temperature Oxidation and Surface Modification of Binary Aluminide Intermetallic Compounds Using Ion Implantation of Oxygen.

    NASA Astrophysics Data System (ADS)

    Hanrahan, Robert Joseph, Jr.

    This work presents a novel approach to the modification of intermetallic compounds to achieve improved oxidation resistance. In order to bypass problems associated with the transient oxidation stage of alloys and intermetallic compounds, high-dose implants of oxygen are used to form a continuous oxygen saturated layer at room temperature. In order to study the implanted layer using secondary ion mass spectrometry ^{18}O is used as the implanted species. Three different aluminides have been investigated. With NbAl_3 it was found that oxidation at 1000^circC resulted in significantly thinner protective alumina scales on the oxygen implanted surfaces. Exposure at 760 ^circC to an atmosphere containing 50 ppm oxygen was used to induce pest. The oxygen implanted surfaces showed significantly improved resistance to pesting. The implanted surfaces were found to have much less oxygen penetration below the surface than the non-implanted surfaces. An interpretation of the controlling mechanism of pest is presented. In TiAl the as-implanted material was found to form a layer containing primarily aluminum oxide. After brief exposures at 1000^circC the implanted surfaces were found to form titanium oxide scales which were thicker than those formed on the non -implanted surfaces. Using specimens implanted with ^{20}Ne this phenomenon was shown to be due to the effect of damage to the surface. In NiAl a well-defined oxide layer was formed by the implanted oxygen after annealing at 1000 ^circC. This layer was shown to be completely stable after exposures of up to 1 hour. The oxide layer appears to recrystallize as NiAl_2 O_4 with an epitaxial relationship to the substrate. The implanted oxide layer was shown to result in significantly improved oxidation resistance under both isothermal and cyclic exposure at 1000 ^circC. This research proves the principal that oxygen implantation can be used as a technique for forming in -situ coatings on aluminide intermetallic compounds that in some cases result in significantly improved oxidation resistance by modifying the initial oxidation kinetics of the material.

  8. Surface oxidation of liquid Sn Alexei Grigoriev a,*, Oleg Shpyrko b

    E-print Network

    Pershan, Peter S.

    Surface oxidation of liquid Sn Alexei Grigoriev a,*, Oleg Shpyrko b , Christoph Steimer a , Peter S of SnO at the liquid­vapour interface of Sn. Our experiments reveal that the pure liquid Sn surface does not react with molecular oxygen below an activation pressure of $5.0 · 10À6 Torr. Above that pressure

  9. Surfactant Organic Molecules Restore Magnetism in Metal-Oxide Nanoparticle Surfaces

    E-print Network

    Pennycook, Steve

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

  10. Antibacterial Efficacy of Iron-Oxide Nanoparticles against Biofilms on Different Biomaterial Surfaces.

    PubMed

    Thukkaram, Monica; Sitaram, Soundarya; Kannaiyan, Sathish Kumar; Subbiahdoss, Guruprakash

    2014-01-01

    Biofilm growth on the implant surface is the number one cause of the failure of the implants. Biofilms on implant surfaces are hard to eliminate by antibiotics due to the protection offered by the exopolymeric substances that embed the organisms in a matrix, impenetrable for most antibiotics and immune cells. Application of metals in nanoscale is considered to resolve biofilm formation. Here we studied the effect of iron-oxide nanoparticles over biofilm formation on different biomaterial surfaces and pluronic coated surfaces. Bacterial adhesion for 30?min showed significant reduction in bacterial adhesion on pluronic coated surfaces compared to other surfaces. Subsequently, bacteria were allowed to grow for 24?h in the presence of different concentrations of iron-oxide nanoparticles. A significant reduction in biofilm growth was observed in the presence of the highest concentration of iron-oxide nanoparticles on pluronic coated surfaces compared to other surfaces. Therefore, combination of polymer brush coating and iron-oxide nanoparticles could show a significant reduction in biofilm formation. PMID:25332720

  11. Surface spectroscopic characterization of oxide thin films and bimetallic model catalysts 

    E-print Network

    Wei, Tao

    2009-05-15

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

  12. Surface Composition, Work Function, and Electrochemical Characteristics of Gallium-Doped Zinc Oxide

    SciTech Connect

    Ratcliff, E. L.; Sigdel, A. K.; Macech, M. R.; Nebesny, K.; Lee, P. A.; Ginley, D. S.; Armstrong, N. R.; Berry, J. J.

    2012-06-30

    Gallium-doped zinc oxide (GZO) possesses the electric conductivity, thermal stability, and earth abundance to be a promising transparent conductive oxide replacement for indium tin oxide electrodes in a number of molecular electronic devices, including organic solar cells and organic light emitting diodes. The surface chemistry of GZO is complex and dominated by the hydrolysis chemistry of ZnO, which influences the work function via charge transfer and band bending caused by adsorbates. A comprehensive characterization of the surface chemical composition and electrochemical properties of GZO electrodes is presented, using both solution and surface adsorbed redox probe molecules. The GZO surface is characterized using monochromatic X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy after the following pretreatments: (i) hydriodic acid etch, (ii) potassium hydroxide etch, (iii) RF oxygen plasma etching, and (iv) high-vacuum argon-ion sputtering. The O 1s spectra for the GZO electrodes have contributions from the stoichiometric oxide lattice, defects within the lattice, hydroxylated species, and carbonaceous impurities, with relative near-surface compositions varying with pretreatment. Solution etching procedures result in an increase of the work function and ionization potential of the GZO electrode, but yield different near surface Zn:Ga atomic ratios, which significantly influence charge transfer rates for a chemisorbed probe molecule. The near surface chemical composition is shown to be the dominant factor in controlling surface work function and significantly influences the rate of electron transfer to both solution and tethered probe molecules.

  13. Aqueous phase deposition of dense tin oxide films with nano-structured surfaces

    SciTech Connect

    Masuda, Yoshitake Ohji, Tatsuki; Kato, Kazumi

    2014-06-01

    Dense tin oxide films were successfully fabricated in an aqueous solution. The pH of the solutions was controlled to pH 1.3 by addition of HCl. Precise control of solution condition and crystal growth allowed us to obtain dense tin oxide films. Concave–convex surface of fluorine-doped tin oxide (FTO) substrates was entirely-covered with the continuous films. The films were about 65 nm in thickness and had nano-structured surfaces. Morphology of the films was strikingly different from our previous reported nano-sheet assembled structures. The films were not removed from the substrates by strong water flow or air blow to show strong adhesion strength. The aqueous solution process can be applied to surface coating of various materials such as nano/micro-structured surfaces, particles, fibers, polymers, metals or biomaterials. - Graphical abstract: Dense tin oxide films of 65 nm were successfully fabricated in an aqueous solution. They had nano-structured surfaces. Concave-convex substrates were entirely-covered with the continuous films. - Highlights: • Dense tin oxide films of 65 nm were successfully fabricated in an aqueous solution. • They had nano-structured surfaces. • Concave–convex substrates were entirely-covered with the continuous films.

  14. Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

    NASA Astrophysics Data System (ADS)

    Weiss, Werner; Ranke, Wolfgang

    2002-03-01

    Metal-oxide-based catalysts are used for many important synthesis reactions in the chemical industry. A better understanding of the catalyst operation can be achieved by studying elementary reaction steps on well-defined model catalyst systems. For the dehydrogenation of ethylbenzene to styrene in the presence of steam both unpromoted and potassium promoted iron-oxide catalysts are active. Here we review the work done over unpromoted single-crystalline FeO(1 1 1), Fe3O4(1 1 1) and ?- Fe2O3(0 0 0 1) films grown epitaxially on Pt(1 1 1) substrates. Their geometric and electronic surface structures were characterized by STM, LEED, electron microscopy and electron spectroscopic techniques. In an integrative approach, the interaction of water, ethylbenzene and styrene with these films was investigated mainly by thermal desorption and photoelectron emission spectroscopy. The adsorption-desorption energetics and kinetics depend on the oxide surface terminations and are correlated to the electronic structures and acid-base properties of the corresponding oxide phases, which reveal insight into the nature of the active sites and into the catalytic function of semiconducting oxides in general. Catalytic studies, using a batch-reactor arrangement at high gas pressures and post-reaction surface analysis, showed that only ?- Fe2O3(0 0 0 1) containing surface defects is catalytically active, whereas Fe3O4(1 1 1) is always inactive. This can be related to the elementary adsorption and desorption properties observed in ultrahigh vacuum, which indicates that the surface chemical properties of the iron-oxide films do not change significantly across the “pressure-gap”. A model is proposed according to which the active site involves a regular acidic surface site and a defect site next to it. The results on metal-oxide surface chemistry also have implications for other fields such as environmental science, biophysics and chemical sensors.

  15. Surface modification of alloys for improved oxidation resistance in SOFC applications

    SciTech Connect

    Alman, D.E.; Jablonski, P.D.; Kung, S.C.

    2006-11-01

    This research is aimed at improving the oxidation behavior of metallic alloys for SOFC application, by the incorporation of rare earths through surface treatments. This paper details the effect of such surface modification on the behavior of Crofer 22 APU, a ferritic steel designed specifically for SOFC application, and Type 430 stainless steel. Two pack cementation like treatments were used to incorporate Ce into the surface of the alloys. After 4000 hours of exposure at 800oC to air+3%H2O, the weight gain of Crofer 22APU samples that were Ce surface modified were less than half that of an unmodified sample, revealing the effectiveness of the treatments on enhancing oxidation resistance. For Type-430, the treatment prevented scale spalling that occurred during oxidation of the unmodified alloy.

  16. Ester oxidation on an aluminum surface using chemiluminescence

    NASA Technical Reports Server (NTRS)

    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.

  17. Intermolecular potential energy surface and thermophysical properties of ethylene oxide

    SciTech Connect

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

    2014-10-28

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

  18. Surface-functionalized monolayered nanodots of a transition metal oxide and their properties.

    PubMed

    Honda, Masashi; Oaki, Yuya; Imai, Hiroaki

    2015-12-28

    Lateral size, surface chemistry, and properties are varied in inorganic monolayers based on a transition metal-oxide. A variety of inorganic monolayers with their emergent properties have been studied in recent decades. However, it is not easy to tune the lateral size, surface chemistry, and dispersibility of monolayers by typical synthetic methods. In the present work, a new approach is developed for the simultaneous surface functionalization and exfoliation of the precursor nanocrystals in a nonpolar organic medium. We obtained monolayered nanodots of a titanium oxide less than 5 nm in lateral size with surface functionalization by an alkylamine (C14H29NH2) and dihydroxynaphthalene (DHN) in toluene. The bandgap energy of the monolayers was changed by the lateral size and surface functionalization. The present study suggests versatile potentials of the monolayers with tuned size, surface chemistry, and properties. PMID:26592924

  19. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the ? and ? channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  20. Proton binding by hydrous ferric oxide and aluminum oxide surfaces interpreted using fully optimized continuous pKa spectra.

    PubMed

    Smith, D S; Ferris, F G

    2001-12-01

    A modified regularized least squares pKa spectrum approach is proposed to determine proton stability constants and concentrations for binding sites on hydrous ferric oxide (HFO) and aluminum oxide surfaces. Acid-base titration data are fit to a continuous binding site model for the system represented as a pKa spectrum. The modified parameter fitting method optimizes simultaneously for both smoothness of the pKa spectrum and goodness-of-fit, whereas other methods optimize for goodness-of-fit given a fixed smoothness factor. The modified method is tested with aluminum oxide and recovers values consistent with theoretical values. The regularized pKa spectrum method optimized for smoothness is applied to prepared samples of two types of HFO. The prepared HFO samples differ only in the total iron concentration of the parent solution. The resultant pKa distributions are compared to proton binding constants from MUSIC model results for crystalline iron oxides. The types of binding sites in the HFO sample are consistent with theoretical binding site stability constants for crystalline iron oxides. Overall, the prepared HFO samples have binding constants most consistent with values for lepidocrocite and goethite. PMID:11770764

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

    NASA Astrophysics Data System (ADS)

    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 seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

  2. Elucidation of the reaction mechanism during the removal of copper oxide by halogen surfactant at the surface of copper plate

    NASA Astrophysics Data System (ADS)

    Yokoyama, Shun; Takahashi, Hideyuki; Itoh, Takashi; Motomiya, Kenichi; Tohji, Kazuyuki

    2013-01-01

    Although copper nanoparticles have various attractive properties, electrical applications of these was not achieved because of its surface oxide layer which prohibited electrical conduction. Thus, it can be considered that a new elimination method of the oxide on Cu surface, which simultaneously provide the resistance to re-oxidized, should be developed. In this study, the reaction between the metal oxide on Cu plate surface and halogen surfactant was introduced into development as a new elimination method of surface oxide layer. Since electrochemical and surface analysis are effective for analyzing the reaction mechanism which expected to be the reduction reaction of the oxide on metal surface, Cu electrode, which represented material of Cu nanoparticles surface, was used for the reaction mechanism analysis. The oxide is removed by controlling the temperature and selecting the optimal combination of solvents and the halogen surfactant (TIC). Results of electrochemical measurements strongly suggest that the chemical reaction between the oxides on the surface with the halogen surfactant is a substitution reaction which converts Cu oxide to Cu bromide, and continuously formed Cu bromide was dissolved into solvent. Totally, the oxide on the Cu surface was successfully eliminated.

  3. Titanium surface modification by microarc oxidation in electrolyte based on wollastonite and hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Sharkeev, Yu. P.; Sedelnikova, M. B.; Komarova, E. G.; Khlusov, I. A.

    2015-11-01

    An investigation of titanium surface modification by microarc oxidation in the electrolyte based on wollastonite and hydroxyapatite was presented. The dependences of the coating properties on the microarc oxidation parameters were found. A variation of the process parameters allowed producing wollastonite-calcium phosphate coatings with aplate-like structure, thickness 25-30 µm, roughness 2.5-5.0 µm, and adhesion strength 57 MPa. The optimum microarc oxidation parameters such as the electrical voltage of 150 V, process duration of 5-10 min, and pulse duration of 100-300 µs were revealed. The wollastonite addition to the electrolyte based on the aqueous solution of phosphoric acid and hydroxyapatite allowed us to form wollastonite-calcium phosphate coatings on the titanium surface by the microarc oxidation method with enhanced strength properties and an increased ability to osseointegration.

  4. Effect of surface oxidation on the nm-scale wear behavior of a metallic glass

    SciTech Connect

    Caron, A.; Louzguine-Luzguin, D. V.; Sharma, P.; Inoue, A.; Shluger, A.; Fecht, H.-J.

    2011-04-15

    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{sub 62}Nb{sub 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.

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

    SciTech Connect

    Doyle, F.M.

    1992-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Napier, Mary E.; Stair, Peter C.

    1992-01-01

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

  7. Initial oxidation behaviors of nitride surfaces of uranium by XPS analysis

    NASA Astrophysics Data System (ADS)

    Liu, Kezhao; Luo, Lizu; Luo, Lili; Long, Zhong; Hong, Zhanglian; Yang, Hui; Wu, Sheng

    2013-09-01

    The nitride surfaces of uranium were prepared by the surface glow plasma nitriding (SGPN) and plasma immersion ion implantation (PIII) methods. The initial oxidation behaviors of modified surfaces were studied by X-ray photoelectron spectroscopy (XPS). The SGPN on the uranium surface led to a single layer of uranium sesquinitride (U2N3), while the PIII on the surface resulted in a compound layer composed of U2N3 and uranium dioxide (UO2). The oxygen covered on these modified layers led to the formation of UO2 from U2N3 and U2N3 from UN. The oxidized nitrogen species were also observed on the two types of nitriding layers, with the discussion of the N-O coaction behaviors.

  8. Defects in oxide surfaces studied by atomic force and scanning tunneling microscopy

    PubMed Central

    König, Thomas; Simon, Georg H; Heinke, Lars; Lichtenstein, Leonid

    2011-01-01

    Summary Surfaces of thin oxide ?lms 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 classi?cation 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 ?lms beyond imaging the topography of the surface atoms. PMID:21977410

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

    SciTech Connect

    Suzuki, Satoshi; Tsuneda, Takao; Hirao, Kimihiko

    2012-01-14

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

  10. Atomic resolution non-contact atomic force microscopy of clean metal oxide surfaces.

    PubMed

    Lauritsen, J V; Reichling, M

    2010-07-01

    In the last two decades the atomic force microscope (AFM) has become the premier tool for topographical analysis of surface structures at the nanometre scale. In its ultimately sensitive implementation, namely dynamic scanning force microscopy (SFM) operated in the so-called non-contact mode (NC-AFM), this technique yields genuine atomic resolution and offers a unique tool for real space atomic-scale studies of surfaces, nanoparticles as well as thin films, single atoms and molecules on surfaces irrespective of the substrate being electrically conducting or non-conducting. Recent advances in NC-AFM have paved the way for groundbreaking atomic level insight into insulator surfaces, specifically in the most important field of metal oxides. NC-AFM imaging now strongly contributes to our understanding of the surface structure, chemical composition, defects, polarity and reactivity of metal oxide surfaces and related physical and chemical surface processes. Here we review the latest advancements in the field of NC-AFM applied to the fundamental atomic resolution studies of clean single crystal metal oxide surfaces with special focus on the representative materials Al(2)O(3)(0001), TiO(2)(110), ZnO(1000) and CeO(2)(111). PMID:21386455

  11. Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces.

    PubMed

    Hyde, Jacob T; Hanson, Kenneth; Vannucci, Aaron K; Lapides, Alexander M; Alibabaei, Leila; Norris, Michael R; Meyer, Thomas J; Harrison, Daniel P

    2015-05-13

    The oxidative stability of the molecular components of dye-sensitized photoelectrosynthesis cells for solar water splitting remains to be explored systematically. We report here the results of an electrochemical study on the oxidative stability of ruthenium(II) polypyridyl complexes surface-bound to fluorine-doped tin oxide electrodes in acidic solutions and, to a lesser extent, as a function of pH and solvent with electrochemical monitoring. Desorption occurs for the Ru(II) forms of the surface-bound complexes with oxidation to Ru(III) enhancing both desorption and decomposition. Based on the results of long-term potential hold experiments with cyclic voltammetry monitoring, electrochemical oxidation to Ru(III) results in slow decomposition of the complex by 2,2'-bipyridine ligand loss and aquation and/or anation. A similar pattern of ligand loss was also observed for a known chromophore-catalyst assembly for both electrochemical water oxidation and photoelectrochemical water splitting. Our results are significant in identifying the importance of enhancing chromophore stability, or at least transient stability, in oxidized forms in order to achieve stable performance in aqueous environments in photoelectrochemical devices. PMID:25871342

  12. Differences in the adsorption of FePc on coinage metal surfaces

    NASA Astrophysics Data System (ADS)

    Rehman, R. A.; Cai, Yi-Liang; Zhang, Han-Jie; Wu, Ke; Dou, Wei-Dong; Li, Hai-Yang; He, Pi-Mo; Bao, Shi-Ning

    2013-06-01

    A study of the electronic and structural properties of iron phthalocyanine (FePc) molecules adsorbed on coinage metal surfaces Cu (100) and Cu (110) has been conducted by means of density functional theory calculations. The strength of the molecule-substrate interactions is interpreted in terms of the lateral adsorption geometry and the site specific electronic structure of the molecule. In the case of FePc on a (100)-oriented copper surface, the benzopyrrole leg is found to be oriented at an angle of 9° or 3° from the [01-1] substrate direction. Further, an upward bend in the molecular plane ranging from 7 to 10° is also observed; giving an almost buckled shape to the molecule. However, in the case of FePc on Cu (110), neither a bend nor a sizable rotation is observed. From the knowledge of the principle structural and electronic properties, it is concluded that FePc—Cu (100) interaction is relatively stronger than FePc—Cu (110) interaction, which is further evidenced by the charge transfer, work function changes, changes in the shape of the adsorbed molecular orbitals, and the orbital shifts. Furthermore, density of states analysis shows that the valence band level shift is surface- and site-dependent.

  13. Growth morphology of thin films on metallic and oxide surfaces.

    PubMed

    Krupski, Aleksander

    2014-02-01

    In this work we briefly review recent investigations concerning the growth morphology of thin metallic films on the Mo(110) and Ni3Al(111) surfaces, and Fe and copper phthalocyanine (C32H16N8Cu) on the Al2O3/Ni3Al(111) surface. Comparison of Ag, Au, Sn, and Pb growth on the Mo(110) surface has shown a number of similarities between these adsorption systems, except that surface alloy formation has only been observed in the case of Sn and Au. In the Pb/Mo(110) and Pb/Ni3Al(111) adsorption systems selective formation of uniform Pb island heights during metal thin film growth has been observed and interpreted in terms of quantum size effects. Furthermore, our studies showed that Al2O3 on Ni3Al(111) exhibits a large superstructure in which the unit cell has a commensurate relation with the substrate lattice. In addition, copper phthalocyanine chemisorbed weakly onto an ultra-thin Al2O3 film on Ni3Al(111) and showed a poor template effect of the Al2O3/Ni3Al(111) system. In the case of iron cluster growth on Al2O3/Ni3Al(111) the nucleation sites were independent of deposition temperature, yet the cluster shape showed a dependence. In this system, Fe clusters formed a regular hexagonal lattice on the Al2O3/Ni3Al(111). PMID:24445588

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

    PubMed

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

    2015-02-21

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

  15. In situ passivation of GaAs surface with aluminum oxide with MOVPE

    NASA Astrophysics Data System (ADS)

    Terada, Yuki; Deura, Momoko; Shimogaki, Yukihiro; Sugiyama, Masakazu; Nakano, Yoshiaki

    2008-11-01

    In situ passivation of GaAs surface subsequent to the growth in a metalorganic vapor phase epitaxy (MOVPE) reactor has been made possible using trimethylaluminum (TMAl). The adsorption layer on GaAs, presumably consisting of aluminum and the decomposition product of TMAl, was oxidized upon exposure to air to form thin AlO x layer. TMAl supply of only 0.5 monolayer completely prevented the oxidation of As on the surface, as confirmed by XPS. The passivation layer mostly prevented the oxidation of As upon O 2 annealing for 5 min at 250 °C. For the successful passivation, complete desorption of excess As on the GaAs surface was essential prior to the injection of TMAl. Otherwise, AlAs layer was formed and arsenic oxide was inevitably formed. The optimum length of H 2 purge to desorb As was determined to be 2 min with in situ surface monitoring using reflectance anisotropy spectroscopy (RAS). This passivation method, combined with the succeeding deposition of Al 2O 3 as a gate dielectric in a different reactor, provides the GaAs/gate interface without As-oxide. The method is applicable to the MOVPE growth of electron channel layers containing As for III-V metal-insulator-semiconductor field effect transistors (MISFETs).

  16. Positron-electron pairs emitted from metallic and oxide surfaces

    NASA Astrophysics Data System (ADS)

    Brandt, I. S.; Wei, Z.; Schumann, F. O.; Kirschner, J.

    2015-10-01

    If a positron impacts onto a surface, it may lead to the emission of a positron-electron pair. We have commissioned a laboratory-based positron source and performed a systematic study on a variety of solid surfaces. In a symmetric emission geometry we can explore the fact that positrons and electrons are distinguishable particles. Following fundamental symmetry arguments we have to expect that the available energy is shared unequally among positrons and electrons. Experimentally we observe such a behavior for all materials studied. We find a universal feature for all materials in the sense that, on average, the positron carries a larger fraction of the available energy. A scattering model accounts qualitatively for the observed energy sharing in positron-electron pair emission. A comparison of the intensity levels from the different materials reveals a monotonic relation between the singles and pair coincidence count rates.

  17. Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals.

    PubMed

    Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

    2015-01-01

    In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

  18. Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals

    PubMed Central

    Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

    2015-01-01

    In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

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

    SciTech Connect

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

    2014-10-21

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

  1. MicroRNA functionalized microporous titanium oxide surface by lyophilization with enhanced osteogenic activity.

    PubMed

    Wu, Kaimin; Song, Wen; Zhao, Lingzhou; Liu, Mengyuan; Yan, Jun; Andersen, Morten Østergaard; Kjems, Jørgen; Gao, Shan; Zhang, Yumei

    2013-04-10

    Developing biomedical titanium (Ti) implants with high osteogenic ability and consequent rigid osseointegration is a constant requirement from the clinic. In this study, we fabricate novel miRNA functionalized microporous Ti implants by lyophilizing miRNA lipoplexes onto a microporous titanium oxide surface formed by microarc oxidation (MAO). The microporous titanium oxide surface provides a larger surface area for miRNA loading and enables spatial retention of the miRNAs within the pores until cellular delivery. The loading of lipoplexes into the micropores on the MAO Ti surface is facilitated by the superhydrophilicity and Ti-OH groups gathering of the MAO surface after UV irradiation followed by lyophilization. A high miRNA transfection efficiency was observed in mesenchymal stem cells (MSCs) seeded onto the miRNA functionalized surface with no apparent cytotoxicity. When functionalizing the Ti surface with miR-29b that enhances osteogenic activity and antimiR-138 that inhibits miR-138 inhibition of endogenous osteogenesis, clear stimulation of MSC osteogenic differentiation was observed, in terms of up-regulating osteogenic expression and enhancing alkaline phosphatase production, collagen secretion and ECM mineralization. The novel miRNA functionalized Ti implants with enhanced osteogenic activity promisingly lead to more rapid and robust osseointegration of a clinical bone implant interface. Our study implies that lyophilization may constitute a versatile method for miRNA loading to other biomaterials with the aim of controlling cellular function. PMID:23459382

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

    PubMed

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

    2015-04-13

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

  3. Nitrogen-doped hierarchical porous carbon with high surface area derived from graphene oxide/pitch oxide composite for supercapacitors.

    PubMed

    Ma, Yuan; Ma, Chang; Sheng, Jie; Zhang, Haixia; Wang, Ranran; Xie, Zhenyu; Shi, Jingli

    2016-01-01

    A nitrogen-doped hierarchical porous carbon has been prepared through one-step KOH activation of pitch oxide/graphene oxide composite. At a low weight ratio of KOH/composite (1:1), the as-prepared carbon possesses high specific surface area, rich nitrogen and oxygen, appropriate mesopore/micropore ratio and considerable small-sized mesopores. The addition of graphene oxide plays a key role in forming 4nm mesopores. The sample PO-GO-16 presents the characteristics of large surface area (2196m(2)g(-1)), high mesoporosity (47.6%), as well as rich nitrogen (1.52at.%) and oxygen (6.9at.%). As a result, PO-GO-16 electrode shows an outstanding capacitive behavior: high capacitance (296Fg(-1)) and ultrahigh-rate performance (192Fg(-1) at 10Ag(-1)) in 6M KOH aqueous electrolyte. The balanced structure characteristic, low-cost and high performance, make the porous carbon a promising electrode material for supercapacitors. PMID:26397915

  4. Surface Oxidation Effects During Low Energy BF{sub 2}{sup +} Ion Implantation

    SciTech Connect

    Kondratenko, Serguei; Hsu, P. K.; Zhao, Hongchen; Reece, Ronald N.

    2011-01-07

    We present results on silicon wafer surface oxidation observed during low energy high dose BF{sub 2}{sup +} implantation. Experiments were performed on single-crystal and pre-amorphized silicon wafers that help elucidate the surface structure impact on boron distribution profiles and dose retention. Implanters with different architectures were compared including both single wafer and batch systems. It was found that the oxidation rate depends on implanter type and design, and that the surface oxide thickness is a linear function of implantation dose and time. Surface oxidation is significantly higher for batch systems compared to single wafer tools. This is due primarily to the significantly lower beam duty cycle on the batch implanter. The oxide thicknesses estimated from SIMS oxygen profiles are in agreement with ellipsometry measurements after spike annealing, and show a similar difference between single wafer and batch implanters. SIMS boron distribution profiles after implantation were compared and used to calculate retained dose. In the medium dose range ({<=}3x10{sup 14} at/cm{sup 2}) the profiles from different implanters are well matched and the dose retention is close to 100%. For the higher dose range ({>=}3x10{sup 15} at/cm{sup 2}) retention for the batch implanter is significantly less than the single wafer tool and depends on the wafer surface structure. A higher oxidation rate results in lower dopant activation and higher Rs value after spike annealing. For high implantation doses the single wafer system allows much higher dose retention and better boron activation after annealing.

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

    SciTech Connect

    Kerr, A. J.; Chagarov, E.; Kaufman-Osborn, T.; Kummel, A. C.; Gu, S.; Wu, J.; Asbeck, P. M.; Madisetti, S.; Oktyabrsky, S.

    2014-09-14

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

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

    PubMed

    Kerr, A J; Chagarov, E; Gu, S; Kaufman-Osborn, T; Madisetti, S; Wu, J; Asbeck, P M; Oktyabrsky, S; Kummel, A C

    2014-09-14

    A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al2O3 gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge. These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001). PMID:25217942

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

    SciTech Connect

    Gopalan, Srikanth

    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. Surface oxidation of tin chalcogenide nanocrystals revealed by 119Sn-Mössbauer spectroscopy.

    PubMed

    de Kergommeaux, Antoine; Faure-Vincent, Jérôme; Pron, Adam; de Bettignies, Rémi; Malaman, Bernard; Reiss, Peter

    2012-07-18

    Narrow band gap tin(II) chalcogenide (SnS, SnSe, SnTe) nanocrystals are of high interest for optoelectronic applications such as thin film solar cells or photodetectors. However, charge transfer and charge transport processes strongly depend on nanocrystals' surface quality. Using (119)Sn-Mössbauer spectroscopy, which is the most sensitive tool for probing the Sn oxidation state, we show that SnS nanocrystals exhibit a Sn((IV))/Sn((II)) ratio of around 20:80 before and 40:60 after five minutes exposure to air. Regardless of the tin or sulfur precursors used, similar results are obtained using six different synthesis protocols. The Sn((IV)) content before air exposure arises from surface related SnS(2) and Sn(2)S(3) species as well as from surface Sn atoms bound to oleic acid ligands. The increase of the Sn((IV)) content upon air exposure results from surface oxidation. Full oxidation of the SnS nanocrystals without size change is achieved by annealing at 500 °C in air. With the goal to prevent surface oxidation, SnS nanocrystals are capped with a cadmium-phosphonate complex. A broad photoluminescence signal centered at 600 nm indicates successful capping, which however does not reduce the air sensitivity. Finally we demonstrate that SnSe nanocrystals exhibit a very similar behavior with a Sn((IV))/Sn((II)) ratio of 43:57 after air exposure. In the case of SnTe nanocrystals, the ratio of 55:45 is evidence of a more pronounced tendency for oxidation. These results demonstrate that prior to their use in optoelectronics further surface engineering of tin chalcogenide nanocrystals is required, which otherwise have to be stored and processed under inert atmosphere. PMID:22691030

  9. Effect of surface roughness on leakage current and corrosion resistance of oxide layer on AZ91 Mg alloy prepared by plasma electrolytic oxidation

    NASA Astrophysics Data System (ADS)

    Yoo, Bongyoung; Shin, Ki Ryoung; Hwang, Duck Young; Lee, Dong Heon; Shin, Dong Hyuk

    2010-09-01

    The influence of the surface roughness of Mg alloys on the electrical properties and corrosion resistance of oxide layers obtained by plasma electrolytic oxidation (PEO) were studied. The leakage current in the insulating oxide layer was enhanced by increasing the surface roughness, which is a favorable characteristic for the material when applied to hand-held electronic devices. The variation of corrosion resistance with surface roughness was also investigated. The corrosion resistance was degraded by the increasing surface roughness, which was confirmed with DC polarization and impedance spectroscopy. Pitting corrosion on the passive oxide layer was also analyzed with a salt spray test, which showed that the number of pits was not affected by the surface roughness when the spray time reached 96 h.

  10. In situ transmission infrared spectroscopy of high-kappa oxide atomic layer deposition onto silicon surfaces

    NASA Astrophysics Data System (ADS)

    Ho, Ming-Tsung

    Ultra-thin aluminum oxide (Al2O3) and hafnium oxide (HfO2) layers have been grown by atomic layer deposition (ALD) using tri-methyl-aluminum (TMA) and tetrakis-ethyl-methyl-amino-hafnium (TEMAH) respectively with heavy water (D2O) as the oxidizing agent. Several different silicon surfaces were used as substrates such as hydrogen terminated silicon (H/Si), SC2 (or RCA 2) cleaned native silicon oxide (SiO 2/Si), and silicon (oxy)nitride. In-situ transmission Fourier transform infrared spectroscopy (FTIR) has been adopted for the study of the growth mechanisms during ALD of these films. The vibrational spectra of gas phase TEMAH and its reaction byproducts with oxidants have also been investigated. Density functional theory (DFT) normal mode calculations show a good agreement with the experimental data when it is combined with linear wave-number scaling method and Fermi resonance mechanism. Ether (-C-O-C-) and tertiary alkylamine (N(R1R 2R3)) compounds are the two most dominant products of TEMAH reacting with oxygen gas and water. When ozone is used as the oxidant, gas phase CH2O, CH3NO2, CH3-N=C=O and other compounds containing -(C=O)- and --C-O-C- (or --O-C-) segments are observed. With substrate temperatures less than 400°C and 300°C for TMA and TEMAH respectively, Al oxide and Hf oxide ALD can be appropriately performed on silicon surfaces. Thin silicon (oxy)nitride thermally grown in ammonia on silicon substrate can significantly reduce silicon oxide interlayer formation during ALD and post-deposition annealing. The crystallization temperature of amorphous ALD grown HfO2 on nitridized silicon is 600°C, which is 100°C higher than on the other silicon surfaces. When HfO2 is grown on H/Si(111) at 100°C deposition temperature, minimum 5--10 ALD cycles are required for the full surface coverage. The steric effect can be seen by the evolution of the H-Si stretching mode at 2083 cm-1. The observed red shift of H-Si stretching to ˜ 2060 cm-1 can be caused by Si-H...Hf interactions or by the dielectric screening effect of as-grown high-kappa moiety. A summary of local bonding models with vibrational mode assignments of the adsorbed TMA and TEMAH on silicon surfaces is presented based on the analysis of the substructure of silicate interfacial band at 900--1100 cm-1.

  11. Reconstructing Earth's Surface Oxidation Across The Archean- Proterozoic Transition

    NASA Astrophysics Data System (ADS)

    Kaufman, A. J.; Guo, Q.; Strauss, H.; Schröder, S.; Gutzmer, J.; Wing, B. A.; Baker, M.; Bekker, A.; Jin, Q.; Kim, S.; Farquhar, J.

    2010-12-01

    The Archean-Proterozoic transition is characterized by the widespread deposition of organic-rich shale, sedimentary iron formation, glacial diamictite, and marine carbonates recording profound carbon isotope anomalies, but notably lacks bedded evaporites. All deposits reflect environmental changes in oceanic and atmospheric redox states, in part associated with Earth’s earliest ice ages. Time-series data for multiple sulfur isotopes from carbonate associated sulfate as well as sulfides in the glaciogenic Duitschland Formation of the Transvaal Supergroup, South Africa, capture the concomitant buildup of sulfate in the ocean and the loss of mass independent sulfur isotope fractionation. This is arguably associated with the atmospheric rise of oxygen (as well as the protective ozone layer) coincident with profound changes in ocean chemistry and biology. The loss of the MIF signal within the Duitschland succession is in phase with the earliest recorded positive carbon isotope anomaly, convincingly linking these environmental perturbations to the Great Oxidation Event (ca. 2.3 Ga). The emergence of cyanobacteria and oxygenic photosynthesis may be associated with a geochemical “whiff of oxygen” recorded in 2.5 Ga sediments. If true, the delay in the GOE can then be understood in terms of a finite sink for molecular oxygen - ferrous iron, which was abundant in deep Neoarchean seawater and sequestered in a worldwide episode of iron formation deposition ending shortly before accumulation of the Duitschland Formation. Insofar as early Paleoproterozoic glaciation is associated with oxygenation of a methane-rich atmosphere, we conclude that Earth’s earliest ice age(s) and the onset of a modern and far more energetic carbon cycle are directly related to the global expansion of cyanobacteria that released oxygen to the environment, and of eukaryotes that respired it.

  12. Effect of Reacting Surface Density on the Overall Graphite Oxidation Rate

    SciTech Connect

    Chang H. Oh; Eung Kim; Jong Lim; Richard Schultz; David Petti

    2009-05-01

    Graphite oxidation in an air-ingress accident is presently a very important issue for the reactor safety of the very high temperature gas cooled-reactor (VHTR), the concept of the next generation nuclear plant (NGNP) because of its potential problems such as mechanical degradation of the supporting graphite in the lower plenum of the VHTR might lead to core collapse if the countermeasure is taken carefully. The oxidation process of graphite has known to be affected by various factors, including temperature, pressure, oxygen concentration, types of graphite, graphite shape and size, flow distribution, etc. However, our recent study reveals that the internal pore characteristics play very important roles in the overall graphite oxidation rate. One of the main issues regarding graphite oxidation is the potential core collapse problem that may occur following the degradation of graphite mechanical strength. In analyzing this phenomenon, it is very important to understand the relationship between the degree of oxidization and strength degradation. In addition, the change of oxidation rate by graphite oxidation degree characterization by burn-off (ratio of the oxidized graphite density to the original density) should be quantified because graphite strength degradation is followed by graphite density decrease, which highly affects oxidation rates and patterns. Because the density change is proportional to the internal pore surface area, they should be quantified in advance. In order to understand the above issues, the following experiments were performed: (1)Experiment on the fracture of the oxidized graphite and validation of the previous correlations, (2) Experiment on the change of oxidation rate using graphite density and data collection, (3) Measure the BET surface area of the graphite. The experiments were performed using H451 (Great Lakes Carbon Corporation) and IG-110 (Toyo Tanso Co., Ltd) graphite. The reason for the use of those graphite materials is because their chemical and mechanical characteristics are well identified by the previous investigations, and therefore it was convenient for us to access the published data, and to apply and validate our new methodologies. This paper presents preliminary results of compressive strength vs. burn-off and surface area density vs. burn-off, which can be used for the nuclear graphite selection for the NGNP.

  13. A charge transport study in diamond, surface passivated by high-k dielectric oxides

    SciTech Connect

    Kovi, Kiran Kumar Majdi, Saman; Gabrysch, Markus; Isberg, Jan

    2014-11-17

    The recent progress in the growth of high-quality single-crystalline diamond films has sparked interest in the realization of efficient diamond power electronic devices. However, finding a suitable passivation is essential to improve the reliability and electrical performance of devices. In the current work, high-k dielectric materials such as aluminum oxide and hafnium oxide were deposited by atomic layer deposition on intrinsic diamond as a surface passivation layer. The hole transport properties in the diamond films were evaluated and compared to unpassivated films using the lateral time-of-flight technique. An enhancement of the near surface hole mobility in diamond films of up to 27% is observed when using aluminum oxide passivation.

  14. Oxide-free InSb (100) surfaces by molecular hydrogen cleaning

    SciTech Connect

    Tessler, R.; Saguy, C.; Klin, O.; Greenberg, S.; Weiss, E.; Akhvlediani, R.; Edrei, R.; Hoffman, A.

    2006-01-16

    We report that annealing of an oxidized InSb (100) single-crystal sample at 250 deg. C under molecular hydrogen flow [molecular hydrogen cleaning (MHC)] results in complete desorption of the surface oxides. Following this process, the surface morphology is found to be very smooth at the nanometric scale without any droplet structure and a nearly 1:1 In:Sb stoichiometry. MHC was applied to remove the native oxide of an epi-ready InSb(100) substrate used for molecular beam epitaxy growth of InSb films. These results suggest that MHC of InSb can be used as a very effective cleaning process for epitaxial film growth.

  15. Activated carbon enhanced ozonation of oxalate attributed to HO oxidation in bulk solution and surface oxidation: effect of activated carbon dosage and pH.

    PubMed

    Xing, Linlin; Xie, Yongbing; Minakata, Daisuke; Cao, Hongbin; Xiao, Jiadong; Zhang, Yi; Crittenden, John C

    2014-10-01

    Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon (AC) in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals (HO) in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol (tBA) with low dosages of AC, while it was hardly affected by tBA when the AC dosage was greater than 0.3g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05g/L, but it did not work when the AC dosage was no less than 0.1g/L. These observations indicate that HO in bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HO oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HO oxidation in basic bulk solution. A mechanism involving both HO oxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate. PMID:25288554

  16. Localized surface plasmon sensing based investigation of nanoscale metal oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Malasi, A.; Sachan, R.; Ramos, V.; Garcia, H.; Duscher, G.; Kalyanaraman, R.

    2015-05-01

    The localized surface plasmon resonance (LSPR) of nanoparticles can be a powerful and sensitive probe of chemical changes in nanoscale volumes. Here we have used the LSPR of silver (Ag) to study the oxidation kinetics of nanoscopic volumes of cobalt (Co) metal. Bimetal nanoparticles of the immiscible Co-Ag system prepared by pulsed laser dewetting were aged in ambient air and the resulting changes to the LSPR signal and bandwidth were used to probe the oxidation kinetics. Co was found to preferentially oxidize first. This resulted in a significant enhancement by a factor of 8 or more in the lifetime of stable Ag plasmons over that of pure Ag. Theoretical modeling based on optical mean field approximation was able to predict the oxidation lifetimes and could help design stable Ag-based plasmonic nanoparticles for sensing applications.

  17. Effects of oxide charge and surface recombination velocity on the excess base current of BJTs

    SciTech Connect

    Kosier, S.L.; Schrimpf, R.D.; Wei, A.; DeLaus, M.; Fleetwood, D.M.; Combs, W.E.

    1993-12-01

    The role of net positive oxide trapped charge and surface recombination velocity on excess base current in BJTs is identified. The effects of the two types of damage can be detected by plotting the excess base current versus base-emitter voltage. Differences and similarities between ionizing-radiation-induced and hot electron-induced degradation are discussed.

  18. Revisiting the Structure of the p4 4 Surface Oxide on Ag(111) J. Schnadt,1

    E-print Network

    Alavi, Ali

    relevant to corrosion and corrosion resistant materials, but they may also be the active phases to be identified in the 1970s [8,9], and indeed ever since it has been a key challenge of surface science) shows a typical image obtained with our home-built Aarhus STM [17] after oxidizing

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

    EPA Science Inventory

    The hypothesis was tested that silica and silicate dusts complex iron on their surface and that this iron increases 1) in vitro oxidant generation, and mediator release by alveolar macrophages, and 2) acute inflammatory lung injury. ilica and silicates were found to complex more ...

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

    DOEpatents

    Sugama, Toshifumi.

    1990-05-22

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

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

    DOEpatents

    Sugama, Toshifumi (Mastic Beach, NY)

    1990-01-01

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

  2. Abiotic formation of elemental selenium and role of iron oxide surfaces Yu-Wei Chen a

    E-print Network

    Belzile, Nelson

    Abiotic formation of elemental selenium and role of iron oxide surfaces Yu-Wei Chen a , Hoang Received in revised form 24 October 2008 Accepted 27 October 2008 Available online xxxx Keywords: Elemental t The possible abiotic reduction of selenite to form elemental Se was studied under controlled conditions

  3. Chemical changes in secondary electron emission during oxidation of nickel /100/ and /111/ crystal surfaces

    NASA Technical Reports Server (NTRS)

    Holloway, P. H.; Hudson, J. B.

    1975-01-01

    Changes in the secondary electron spectra (which include chemical shifts of Auger transitions) between 0-70 eV during the oxidation of both (100) and (111) nickel surfaces are reported. The reaction sequence between oxygen and nickel is also briefly described. Emission rate changes are correlated with changes in the work function of the solid.

  4. Metal/Oxide Interface Nanostructures Generated by Surface Segregation for Electrocatalysis.

    PubMed

    Weng, Zhe; Liu, Wen; Yin, Li-Chang; Fang, Ruopian; Li, Min; Altman, Eric I; Fan, Qi; Li, Feng; Cheng, Hui-Ming; Wang, Hailiang

    2015-11-11

    Strong metal/oxide interactions have been acknowledged to play prominent roles in chemical catalysis in the gas phase, but remain as an unexplored area in electrocatalysis in the liquid phase. Utilization of metal/oxide interface structures could generate high performance electrocatalysts for clean energy storage and conversion. However, building highly dispersed nanoscale metal/oxide interfaces on conductive scaffolds remains a significant challenge. Here, we report a novel strategy to create metal/oxide interface nanostructures by growing mixed metal oxide nanoparticles on carbon nanotubes (CNTs) and then selectively promoting migration of one of the metal ions to the surface of the oxide nanoparticles and simultaneous reduction to metal. Employing this strategy, we have synthesized Ni/CeO2 nanointerfaces coupled with CNTs. The Ni/CeO2 interface promotes hydrogen evolution catalysis by facilitating water dissociation and modifying the hydrogen binding energy. The Ni/CeO2-CNT hybrid material exhibits superior activity for hydrogen evolution as a result of synergistic effects including strong metal/oxide interactions, inorganic/carbon coupling, and particle size control. PMID:26509583

  5. The surface oxidation potential of human neuromelanin reveals a spherical architecture with a pheomelanin core and a eumelanin surface

    PubMed Central

    Bush, William D.; Garguilo, Jacob; Zucca, Fabio A.; Albertini, Alberto; Zecca, Luigi; Edwards, Glenn S.; Nemanich, Robert J.; Simon, John D.

    2006-01-01

    Neuromelanin (NM) isolated from the substantia nigra region of the human brain was studied by scanning probe and photoelectron emission microscopies. Atomic force microscopy reveals that NM granules are comprised of spherical structures with a diameter of ?30 nm, similar to that observed for Sepia cuttlefish, bovine eye, and human eye and hair melanosomes. Photoelectron microscopy images were collected at specific wavelengths of UV light between 248 and 413 nm, using the spontaneous-emission output from the Duke OK-4 free electron laser. Analysis of the data establishes a threshold photoionization potential for NM of 4.5 ± 0.2 eV, which corresponds to an oxidation potential of ?0.1 ± 0.2 V vs. the normal hydrogen electrode (NHE). The oxidation potential of NM is within experimental error of the oxidation potential measured for human eumelanosomes (?0.2 ± 0.2 V vs. NHE), despite the presence of a significant fraction of the red pigment, pheomelanin, which is characterized by a higher oxidation potential (+0.5 ± 0.2 V vs. NHE). Published kinetic studies on the early chemical steps of melanogenesis show that in the case of pigments containing a mixture of pheomelanin and eumelanin, of which NM is an example, pheomelanin formation occurs first with eumelanin formation predominantly occurring only after cysteine levels are depleted. Such a kinetic model would predict a structural motif with pheomelanin at the core and eumelanin at the surface, which is consistent with the measured surface oxidation potential of the ?30-nm constituents of NM granules. PMID:17001010

  6. Aqueous aggregation and surface deposition processes of engineered superparamagnetic iron oxide nanoparticles for environmental applications.

    PubMed

    Li, Wenlu; Liu, Di; Wu, Jiewei; Kim, Changwoo; Fortner, John D

    2014-10-21

    Engineered, superparamagnetic, iron oxide nanoparticles (IONPs) have significant potential as platform materials for environmental sensing, imaging and remediation due to their unique size, physicochemical and magnetic properties. To this end, controlling the size and surface chemistry of the materials is crucial for such applications in the aqueous phase, and in particular, for porous matrixes with particle-surface interaction considerations. In this study, superparamagnetic, highly monodispersed 8 nm IONPs were synthesized and transferred into water as stable suspensions (remaining monodispersed) by way of an interfacial oleic acid bilayer surface. Once stabilized and characterized, particle-particle and model surface interactions (deposition and release) were quantitatively investigated and described systematically as a function of ionic strength (IS) and type with time-resolved dynamic light scattering (DLS), zeta potential, and real-time quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The critical coagulation concentration (CCC) for oleic acid bilayer coated iron oxide nanoparticles (OA-IONPs) were determined to be 710 mM for NaCl (matching DLVO predictions) and 10.6 mM for CaCl2, respectively. For all conditions tested, surface deposition kinetics showed stronger, more favorable interactions between OA-IONPs and polystyrene surfaces compared to silica, which is hypothesized to be due to increased particle-surface hydrophobic interactions (when compared to silica surfaces). PMID:25222070

  7. Influence of substrate preparation on the shaping of the topography of the surface of nanoceramic oxide layers

    NASA Astrophysics Data System (ADS)

    Bara, Marek; Kubica, Marek

    2014-02-01

    The paper discusses the shaping mechanism and changes occurring in the structure and topography of the surface of nanoceramic oxide layers during their formation. The paper presents the influence of substrate preparation on the surface topography of oxide layers. The layers were produced via hard anodizing on the EN AW-5251 aluminum alloy. The layers obtained were subjected to microscope examinations, image and chemical composition analyses, and stereometric examinations. Heredity of substrate properties in the topography of the surface of nanoceramic oxide layers formed as a result of electrochemical oxidation has been shown.

  8. Differences in SiC thermal oxidation process between crystalline surface orientations observed by in-situ spectroscopic ellipsometry

    NASA Astrophysics Data System (ADS)

    Goto, Daisuke; Hijikata, Yasuto; Yagi, Shuhei; Yaguchi, Hiroyuki

    2015-03-01

    For a better understanding of the SiC oxidation mechanism, we investigated differences in the oxidation process for surfaces with different crystal orientations. Real-time observations of oxidation processes for (0001) Si-face, (11 2 ¯ 0) a-face, and (000 1 ¯ ) C-face substrates at various oxidation temperatures were performed using in-situ spectroscopic ellipsometry. Massoud's empirical equation, which is composed of the classical Deal-Grove equation added by an exponential term, was applied to the observed growth rates and the oxidation rate parameters were extracted by curve fitting. The SiC oxidation mechanism is discussed in terms of the oxidation temperature dependence and surface orientation dependence of the oxidation rate parameters.

  9. Biomembrane phospholipid-oxide surface interactions: crystal chemical and thermodynamic basis.

    PubMed

    Sahai, Nita

    2002-08-15

    Quartz has the least favored surface among many oxides for bacterial attachment and for lipid bilayer or micelle interactions. Tetrahedrally coordinated crystalline silica polymorphs are membranolytic toward liposomes, lysosomes, erythrocytes, and macrophages. Amorphous silica, the octahedral silica polymorph, (stishovite), and oxides such as Al2O3, Fe2 O3, and TiO2 are less cytotoxic. Existing theories for membrane rupture that invoke interactions between oxide surfaces and cell membrane phospholipids (PLs) do not adequately explain these differences in membranolytic potential of the oxides. The author presents a crystal chemical, thermodynamic model for the initial interaction of oxide surfaces with the quaternary ammonium component of the PL's polar head group. The model includes solvation energy changes and electrostatic forces during adsorption, represented by the dielectric constant of the solid and the charge-to-radius ratio of the adsorbing solute. The nature of oxide-solute interactions compared with oxide-water, solute-water, and water-water interactions determines the membranolytic activity of the oxide, where the solute is TMA+, the quaternary ammonium moeity. Significant membrane rupture, as on quartz, requires unfavorable adsorption entropy (DeltaS(ads,TMA+)<0) to maximize disruption of normal membrane structure and requires favorable Gibbs free energy of exchange between TMA+ and the ambient Na+ ions (DeltaG(exc,TMA+/Na+) = DeltaG(ads,TMA+)-DeltaG(ads,Na+)<0) to maximize the extent of membrane affected. For amorphous silica, DeltaS(ads,TMA+) >0, so disruption of structure is limited, even though G(exc,TMA+/Na+) is <0. Stishovite and other oxides have DeltaS(ads,TMA+) <0, but now DeltaG(exc,TMA+/Na+) is>0 at the acidic to circumneutral pHs of cellular and subcellular organelle fluids. The model predicts the correct sequence of membranolytic ability: quartz > or = amorphous SiO2 >Al2O3 >Fe2O3 >TiO2. The model thus explains the relatively poor adhesion of bacterial cells to quartz and the lack of quartz as a biomineral. It is proposed that one function of extracellular polymeric substances exuded by bacteria is to render mineral surfaces more hydrophilic. PMID:16290794

  10. Carbon contamination and oxidation of Au surfaces under extreme ultraviolet radiation: An x-ray photoelectron spectroscopy study

    E-print Network

    Harilal, S. S.

    Carbon contamination and oxidation of Au surfaces under extreme ultraviolet radiation: An x 2012) Extreme ultraviolet (EUV) radiation-induced carbon contamination and oxidation of Au surfaces during interaction with an ionizing radiation such as x-ray or extreme ultraviolet (EUV) light.1

  11. Interfacial interactions of polymer coatings with oxide-free phosphate films on metal surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yuqing; Sherwood, Peter M. A.

    2003-07-01

    A method for producing thin oxide-free phosphate films using an easier process than those previously reported is described. The process is carried out under ambient conditions using aqueous phosphoric acid. The chemistry of the phosphated surface prepared by the process and the interaction of this surface with a thin film of polyvinyl alcohol (PVA) are examined with the purpose of evaluating the potential of this film to serve as an adhesion promoting layer. The surface chemical changes are monitored by core and valence band x-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, with the resultant spectra compared to those from band structure calculations. Valance band photoemission interpreted by band structure calculations can be used to study the interfaces involved, and proves to be a very effective tool for conclusively identifying the surface species present. The process for forming oxide-free phosphate films forms the same surface chemistry as previously reported for other processes. PVA is found to strongly interact with the oxide-free phosphate film on aluminum metal illustrating the potential of such films as adhesion promoters.

  12. Sputtered cadmium oxide as a surface pretreatment for graphite solid-lubricant films

    NASA Technical Reports Server (NTRS)

    Fusaro, Robert L.

    1987-01-01

    Sputtered films of cadmium oxide were applied to sand blasted AISI 440C HT stainless steel disks as a surface pretreatment for the application of rubbed graphite films. Mixtures of cadmium oxide and graphite were applied to the nonpretreated sandblasted metal and evaluated. The results were compared to graphite films applied to other commercially available surface pretreatments. It is found that sputtered CdO pretreated surfaces increase the endurance lives of the graphite films and decrease the counterface steady state wear rate of the pins almost an order of magnitude compared to commercially available pretreatments. The CdO additions in general improved the tribological properties of graphite. The greatest benefit occurred when it was applied to the substrate rather than mixing it with the graphite and that sputtered films of CdO perform much better than rubbed CdO films.

  13. Experimental evaluation of the effects of quench rate and quartz surface area on homogeneous mercury oxidation

    SciTech Connect

    Andrew Fry; Brydger Cauch; Geoffrey D. Silcox; JoAnn S. Lighty; Constance L. Senior

    2007-07-01

    This paper presents a mercury oxidation data set suitable for validation of fundamental kinetic models of mercury chemistry and for mechanism development. Experimental facilities include a mercury reactor fitted with a 300-W, quartz-glass burner and a quartz reaction chamber. While operated with a temperature profile representative of a typical boiler, a residence time of 6 s was achieved. Participating reacting species (chlorine, mercury) were introduced through the burner to produce a radical pool representative of real combustion systems. Speciated mercury measurements were performed using a Tekran 2537A Analyzer coupled with a conditioning system. Homogeneous mercury reactions involving chlorine have been investigated under two different temperature profiles producing quench rates of -210 K/s and -440 K/s. The larger quench rate produced 52% greater total oxidation than the lower quench at chlorine concentrations of 200 ppm. The effect of reactor surface area on oxidation was also investigated. The quartz surfaces interacted with mercury only in the presence of chlorine and their overall effect was to weakly inhibit oxidation. The extent of oxidation was predicted using a detailed kinetic model. The model predicted the effects of quench rate and chlorine concentration shown in experimentation. 12 refs., 5 figs., 3 tabs.

  14. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    SciTech Connect

    Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger

    2004-10-22

    Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

  15. Interaction and reactivity of nitric oxide and carbon monoxide on ruthenium surfaces

    SciTech Connect

    Quick, E.E.

    1980-03-01

    A multifaceted investigation of the reduction of nitric oxide by carbon monoxide using a ruthenium (102) single crystal catalyst in the pressure range 10/sup -3/ to 10 Torr and temperature range of 300 to 475/sup 0/C has been undertaken. Kinetic and isotopic results indicate that the reaction products CO/sub 2/ and N/sub 2/ were produced via two reaction mechanisms. Using a reducing gas mixture (low P/sub NO//P/sub CO/ ratio) a two site mechanism was operative involving NO dissociation. The carbon monoxide kinetic order varied from +1 to -3 and the nitric oxide order varied from +1 to 0. The catalyst under these conditions was determined to be metallic ruthenium with oxygen bonded within the first surface layer. The oxygen was unreactive and formed a (1 x 3)-0 LEED pattern. Under oxidizing conditions (high P/sub NO//P/sub CO/ ratio) the catalyst was ruthenium dioxide and the functional mechanism under these reaction conditions yielded a nitric oxide order of +2 to -4. Inclusion of a site poisoning mechanism under reducing conditions and an RuO/sub 2/ growth mechanism involving ruthenium cation transfer under oxidizing conditions into the kinetic rate laws led to an overall rate law which could be fit to the carbon monoxide and nitric oxide order plots. Using isotopically oxygen labelled reactants, it was observed that the three possible isotopes of carbon dioxide were produced. A ..gamma..-CO surface species is postulated as an intermediate in the exchange process. The reaction was observed to be initially surface structure insensitive and the reaction kinetics were derived using a Langmuir-Hinshelwood formalism.

  16. Computational Fluid Dynamics Simulation of Flows in an Oxidation Ditch Driven by a New Surface Aerator

    PubMed Central

    Huang, Weidong; Li, Kun; Wang, Gan; Wang, Yingzhe

    2013-01-01

    Abstract In this article, we present a newly designed inverse umbrella surface aerator, and tested its performance in driving flow of an oxidation ditch. Results show that it has a better performance in driving the oxidation ditch than the original one with higher average velocity and more uniform flow field. We also present a computational fluid dynamics model for predicting the flow field in an oxidation ditch driven by a surface aerator. The improved momentum source term approach to simulate the flow field of the oxidation ditch driven by an inverse umbrella surface aerator was developed and validated through experiments. Four kinds of turbulent models were investigated with the approach, including the standard k?? model, RNG k?? model, realizable k?? model, and Reynolds stress model, and the predicted data were compared with those calculated with the multiple rotating reference frame approach (MRF) and sliding mesh approach (SM). Results of the momentum source term approach are in good agreement with the experimental data, and its prediction accuracy is better than MRF, close to SM. It is also found that the momentum source term approach has lower computational expenses, is simpler to preprocess, and is easier to use. PMID:24302850

  17. Computational Fluid Dynamics Simulation of Flows in an Oxidation Ditch Driven by a New Surface Aerator.

    PubMed

    Huang, Weidong; Li, Kun; Wang, Gan; Wang, Yingzhe

    2013-11-01

    In this article, we present a newly designed inverse umbrella surface aerator, and tested its performance in driving flow of an oxidation ditch. Results show that it has a better performance in driving the oxidation ditch than the original one with higher average velocity and more uniform flow field. We also present a computational fluid dynamics model for predicting the flow field in an oxidation ditch driven by a surface aerator. The improved momentum source term approach to simulate the flow field of the oxidation ditch driven by an inverse umbrella surface aerator was developed and validated through experiments. Four kinds of turbulent models were investigated with the approach, including the standard k-? model, RNG k-? model, realizable k-? model, and Reynolds stress model, and the predicted data were compared with those calculated with the multiple rotating reference frame approach (MRF) and sliding mesh approach (SM). Results of the momentum source term approach are in good agreement with the experimental data, and its prediction accuracy is better than MRF, close to SM. It is also found that the momentum source term approach has lower computational expenses, is simpler to preprocess, and is easier to use. PMID:24302850

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

    NASA Astrophysics Data System (ADS)

    Singh, Jagdeep

    This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups. UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure. Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shorte

  19. The growth and evolution of thin oxide films on ?-plutonium surfaces

    NASA Astrophysics Data System (ADS)

    García Flores, Harry G.; Pugmire, David L.

    2010-03-01

    The common oxides of plutonium are the dioxide (PuO2) and the sesquioxide (Pu2O3). The nature of an oxide on plutonium metal under air at room temperature is typically described as a thick PuO2 film at the gas-oxide interface with a thinner Pu2O3 film near the oxide-metal substrate interface. In a reducing environment, such as ultra high vacuum, the dioxide (Pu4+; O/Pu=2.0) readily converts to the sesquioxide (Pu3+; O/Pu=1.5) with time. In this work, the growth and evolution of thin plutonium oxide films is studied with x-ray photoelectron spectroscopy (XPS) under varying conditions. The results indicate that, like the dioxide, the sesquioxide is not stable on a clean metal substrate under reducing conditions, resulting in substoichiometric films (Pu2O3-y). The Pu2O3-y films prepared exhibit a variety of stoichiometries (y~0.2-1) as a function of preparation conditions, highlighting the fact that caution must be exercised when studying plutonium oxide surfaces under these conditions and interpreting resulting data.

  20. The growth and evolution of thin oxide films on delta-plutonium surfaces

    SciTech Connect

    Garcia Flores, Harry G; Pugmire, David L

    2009-01-01

    The common oxides of plutonium are the dioxide (PuO{sub 2}) and the sesquioxide (Pu{sub 2}O{sub 3}). The structure of an oxide on plutonium metal under air at room temperature is typically described as a thick PuO{sub 2} film at the gas-oxide interface with a thinner PuO{sub 2} film near the oxide-metal substrate interface. In a reducing environment, such as ultra high vacuum, the dioxide (Pu{sup 4+}; O/Pu = 2.0) readily converts to the sesquioxide (Pu{sup 3+}; O/Pu = 1.5) with time. In this work, the growth and evolution of thin plutonium oxide films is studied with x-ray photoelectron spectroscopy (XPS) under varying conditions. The results indicate that, like the dioxide, the sesquioxide is not stable on a very clean metal substrate under reducing conditions, resulting in substoichiometric films (Pu{sub 2}O{sub 3-y}). The Pu{sub 2}O{sub 3-y} films prepared exhibit a variety of stoichiometries (y = 0.2-1) as a function of preparation conditions, highlighting the fact that caution must be exercised when studying plutonium oxide surfaces under these conditions and interpreting resulting data.

  1. Oxygen embrittlement of vanadium alloys with and without surface oxide formation

    NASA Astrophysics Data System (ADS)

    Pint, B. A.; DiStefano, J. R.

    2002-12-01

    Specimens of V-4Cr-4Ti have been exposed to low pressure oxygen and high purity He environments from 10 5 Pa down to 10 -1 Pa in order to determine oxidation kinetics at 600-700 °C and effects on mechanical properties at 25 and 600 °C. At lower pressures ( p(O 2)?10 -5 Pa), linear reaction kinetics were measured for exposures up to 2000 h and the data was used to develop a mathematical expression for the oxidation rate as a function of temperature and oxygen pressure. At higher pressures, linear-parabolic reaction kinetics were measured associated with high oxygen uptake and the formation of an external oxide layer. Room-temperature and 600 °C tensile ductility was reduced by these exposures, but specimens which formed an external oxide retained some tensile ductility after exposure. However, similar specimens with an external oxide that were subsequently annealed for 2000 h at 700 °C were severely embrittled. These results suggest that a surface oxide on V-4Cr-4Ti can be a source of oxygen for further embrittlement and does not prevent embrittlement in extended exposures at 700 °C.

  2. Near-Field Spectroscopy of Selectively Oxidized Vertical Cavity Surface Emitting Lasers

    SciTech Connect

    KIM,J.; BOYD,J.T.; JACKSON,HOWARD E.; CHOQUETTE,KENT D.

    1999-12-09

    Selectively oxidized vertical cavity surface emitting lasers (VCSELS) have been studied by spectrally resolved near field scanning optical microscopy (NSOM). We have obtained spatially and spectrally resolved images of both subthreshold emission and lasing emission from a selectively oxidized VCSEL operating at a wavelength of 850 nm. Below threshold, highly local high gain regions, emitting local intensity maxima within the active area, were observed; these were found to serve as lasing centers just above threshold. Above threshold, the near field spatial modal distributions of low order transverse modes were identified by spectrally analyzing the emission; these were found to be complex and significantly different from those measured in the far field.

  3. Adsorption of syndiotactic and isotactic poly(2-vinylpyridine 1-oxide) on quartz surface.

    PubMed Central

    Dobreva, M; Dancheva, N; Holt, P F

    1975-01-01

    Poly(2-vinylpyridine 1-oxide) inhibits the cytotoxic effects of quartz in cell cultures but the syndiotactic polymer behaves differently from the isotactic and atactic polymers. In each case approximately 1-0 mg/m2 of the polymer represents the adsorption maximum. No difference has been found between the adsorption isotherms of the stereoisomeric polymers or the stability of the adsorbed layers. The layers are not removed by repeated washing. The observations do not support the theory that the poly(2-vinylpyridine 1-oxide) is active because it coats the quartz surface. PMID:168917

  4. Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Li, L.; Chen, Z. M.; Zhang, Y. H.; Zhu, T.; Li, J. L.; Ding, J.

    2006-06-01

    Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6-9.8)×1014 molecule cm-3] oxidation by O3 [(1.2-12)×1014 molecule cm-3] was determined to be (1.4±0.3)×10-7 using the BET area as the reactive area and (7.7±1.6)×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

  5. Hydrophobic/hydrophilic switching on zinc oxide micro-textured surface

    NASA Astrophysics Data System (ADS)

    Myint, Myo Tay Zar; Kumar, Nithin Senthur; Hornyak, Gabor Louis; Dutta, Joydeep

    2013-01-01

    Switchable wettability of zinc oxide (ZnO) microrod coated surfaces was controlled in two different ways: (1) by physical geometry (surface coverage area SA: the area covered by solid) and (2) by irradiation with ultraviolet (UV) light followed by infrared (IR) or furnace heating. In the first approach, the threshold coverage area for achieving hydrophobic surfaces was found to be <40%, which is in good agreement with predicted values in the literature leading to a metastable Cassie-Baxter regime. The transformation of hydrophobic to hydrophilic surfaces was studied by alternating cycles of 3 h exposure to ultraviolet (?peak ? 253 nm) light followed by 1 h of annealing or IR irradiation alone. Three different annealing temperatures (120 °C, 200 °C and 250 °C) were utilized. Results of this work can be applied for designing surfaces with controlled wettability.

  6. Early stages of the oxidation of metal surfaces. [photoelectron spectroscopy of zinc oxide

    NASA Technical Reports Server (NTRS)

    Gatos, H. C.; Johnson, K. H.

    1978-01-01

    Photoemission cross sections were calculated for the ZnO4(-6) cluster using the self consistent-chi alpha- scattered wave theory to display the main features of the ultraviolet and X-ray photoemission data from ZnO. A solid model is suggested for an absolute photoemission intensity comparison resulting in chi alpha intensities which are roughly 70% of the experimental values. Together with the experimental data, the calculations allow a complete determination of the electronic structure of a ZnO surface.

  7. Hydrogen Spillover between Single Gold Nanorods and Metal Oxide Supports: A Surface Plasmon Spectroscopy Study.

    PubMed

    Collins, Sean S E; Cittadini, Michela; Pecharromán, Carlos; Martucci, Alessandro; Mulvaney, Paul

    2015-08-25

    We used dark field spectroscopy to monitor the dissociation of hydrogen on single gold nanoparticles embedded in metal oxide supports. Individual gold nanorods were monitored in real time to reveal the peak position, the full width at half-maximum, and the relative intensity of the surface plasmon resonances during repeated N2-H2-N2 and air-H2-air cycles. Shifts in the spectra are shown to be due to changes in electron density and not to refractive index shifts in the environment. We demonstrate that hydrogen does not dissociate on gold nanorods (13 nm × 40 nm) at room temperature when in contact with silica and that electrons or hydrogen atoms migrate from Pt nanoparticles to Au nanoparticles through the supporting metal oxide at room temperature. However, this spillover mechanism only occurs for semiconducting oxides (anatase TiO2 and ZnO) and does not occur for Au and Pt nanoparticles embedded in silica. Finally, we show that hydrogen does dissociate directly on anatase surfaces at room temperature during air-H2-air cycles. Our results show that hydrogen spillover, surface dissociation of reactants, and surface migration of chemical intermediates can be detected and monitored in real time at the single particle level. PMID:26154166

  8. {Rb}/{?- SiC(100) } surface and catalytic oxidation of the substrate

    NASA Astrophysics Data System (ADS)

    Riehl-Chudoba, M.; Dupont, S.; Soukiassian, P.

    1995-07-01

    We investigate the {Rb}/{?- SiC(100) } surface and the subsequent promoted SiC oxidation using photoemission spectroscopy with the AlK? (1486.6 eV) and ZrM? (151.4 eV) X-ray lines at Si 2p, C 1s, O 1s and Rb 3p core levels, and work-function measurements. Clean and stoichiometric ?-SiC(100) surfaces are obtained by thermal annealing procedures only. Rb deposition on the clean ?-SiC(100) surface induces a large decrease of the work function reaching a minimum at ?? = - 3.3 eV. The Rb layer enhances the room temperature oxygen uptake by 4 orders of magnitude. Upon subsequent annealing, high silicon oxidation states are formed, leading to {SiO2}/{?- SiC(100) } interface formation with no apparent carbon atoms present on the surface and/or in the oxide layer. Further heating below 800°C removes the Rb atoms completely by thermal desorption.

  9. Ab initio modeling of the bonding of benzotriazole corrosion inhibitor to reduced and oxidized copper surfaces.

    PubMed

    Kokalj, Anton

    2015-01-01

    The bonding of benzotriazole-an outstanding corrosion inhibitor for copper-on reduced and oxidized copper surfaces is discussed on the basis of density functional theory (DFT) calculations. Calculations reveal that benzotriazole is able to bond with oxide-free and oxidized copper surfaces and on both of them it bonds significantly stronger to coordinatively unsaturated Cu sites. This suggests that benzotriazole is able to passivate the reactive under-coordinated surface sites that are plausible microscopic sites for corrosion attack. Benzotriazole can adsorb in a variety of different forms, yet it forms a strong molecule-surface bond only in deprotonated form. The bonding is even stronger when the deprotonated form is incorporated into organometallic adcomplexes. This is consistent with existing experimental evidence that benzotriazole inhibits corrosion by forming protective organometallic complexes. It is further shown that adsorption of benzotriazole considerably reduces the metal work function, which is a consequence of a large permanent molecular dipole and a properly oriented adsorption structure. It is argued that such a pronounced effect on the work function might be relevant for corrosion inhibition, because it should diminish the anodic corrosion reaction, which is consistent with existing experimental evidence that benzotriazole, although a mixed type inhibitor, predominantly affects the anodic reaction. PMID:25955130

  10. Quantitative analysis of chemical interaction and doping of the Si(111) native oxide surface with tetrafluorotetracyanoquinodimethane

    SciTech Connect

    Yoshimoto, Shinya Furuhashi, Masayuki; Koitaya, Takanori; Shiozawa, Yuichiro; Fujimaki, Kazutaka; Harada, Yosuke; Mukai, Kozo; Yoshinobu, Jun

    2014-04-14

    The charge-transfer states and the carrier concentration of the native oxide Si(111) surface adsorbed with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F{sub 4}-TCNQ) were investigated by X-ray photoelectron spectroscopy (XPS) and independently driven four-probe electrical conductivity measurements. The XPS results show that F{sub 4}-TCNQ molecules are involved in charge transfer with the SiO{sub 2}/Si(111) surface. The Si 2p XPS spectra and the surface photovoltage shift provide the evidences of (i) change in the oxidation states at the SiO{sub 2}-Si(111) interface region and (ii) formation of a p-type space charge layer (SCL) with a hole concentration of 1.7?×?10{sup 10}?cm{sup ?2}, respectively. The four-probe I–V measurements also support the formation of the p-type SCL, and the estimated hole concentration of 2.0?×?10{sup 10}?cm{sup ?2} agrees well with the XPS results. The estimated SCL hole concentrations were much smaller than the excess charge density in the F{sub 4}-TCNQ layer, of the order of 10{sup 13}?cm{sup ?2}, suggesting that most of charges were localized as the oxidation states at the SiO{sub 2}-Si(111) interface region. The present quantitative methods ensure precise determination of the doping concentration near the surface region.

  11. Excellent c-Si surface passivation by low-temperature atomic layer deposited titanium oxide

    NASA Astrophysics Data System (ADS)

    Liao, Baochen; Hoex, Bram; Aberle, Armin G.; Chi, Dongzhi; Bhatia, Charanjit S.

    2014-06-01

    In this work, we demonstrate that thermal atomic layer deposited (ALD) titanium oxide (TiOx) films are able to provide a—up to now unprecedented—level of surface passivation on undiffused low-resistivity crystalline silicon (c-Si). The surface passivation provided by the ALD TiOx films is activated by a post-deposition anneal and subsequent light soaking treatment. Ultralow effective surface recombination velocities down to 2.8 cm/s and 8.3 cm/s, respectively, are achieved on n-type and p-type float-zone c-Si wafers. Detailed analysis confirms that the TiOx films are nearly stoichiometric, have no significant level of contaminants, and are of amorphous nature. The passivation is found to be stable after storage in the dark for eight months. These results demonstrate that TiOx films are also capable of providing excellent passivation of undiffused c-Si surfaces on a comparable level to thermal silicon oxide, silicon nitride, and aluminum oxide. In addition, it is well known that TiOx has an optimal refractive index of 2.4 in the visible range for glass encapsulated solar cells, as well as a low extinction coefficient. Thus, the results presented in this work could facilitate the re-emergence of TiOx in the field of high-efficiency silicon wafer solar cells.

  12. Excellent c-Si surface passivation by low-temperature atomic layer deposited titanium oxide

    SciTech Connect

    Liao, Baochen; Hoex, Bram; Aberle, Armin G.; Bhatia, Charanjit S.; Chi, Dongzhi

    2014-06-23

    In this work, we demonstrate that thermal atomic layer deposited (ALD) titanium oxide (TiO{sub x}) films are able to provide a—up to now unprecedented—level of surface passivation on undiffused low-resistivity crystalline silicon (c-Si). The surface passivation provided by the ALD TiO{sub x} films is activated by a post-deposition anneal and subsequent light soaking treatment. Ultralow effective surface recombination velocities down to 2.8?cm/s and 8.3?cm/s, respectively, are achieved on n-type and p-type float-zone c-Si wafers. Detailed analysis confirms that the TiO{sub x} films are nearly stoichiometric, have no significant level of contaminants, and are of amorphous nature. The passivation is found to be stable after storage in the dark for eight months. These results demonstrate that TiO{sub x} films are also capable of providing excellent passivation of undiffused c-Si surfaces on a comparable level to thermal silicon oxide, silicon nitride, and aluminum oxide. In addition, it is well known that TiO{sub x} has an optimal refractive index of 2.4 in the visible range for glass encapsulated solar cells, as well as a low extinction coefficient. Thus, the results presented in this work could facilitate the re-emergence of TiO{sub x} in the field of high-efficiency silicon wafer solar cells.

  13. Effect of dew point on the formation of surface oxides of twinning-induced plasticity steel

    SciTech Connect

    Kim, Yunkyum; Lee, Joonho; Shin, Kwang-Soo; Jeon, Sun-Ho; Chin, Kwang-Geun

    2014-03-01

    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{sub 2}–N{sub 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{sub 2}O{sub 4} layer with a thickness of ? 15 nm was formed with small Mn{sub 2}SiO{sub 4} particles that measured ? 70 nm in diameter. Approximately 500 nm below the MnAl{sub 2}O{sub 4} layer, Al{sub 2}O{sub 3} was formed at the grain boundaries. On the other hand, in a gas mixture with a dew point of ? 40 °C, a MnAl{sub 2}O{sub 4} layer with a thickness of ? 5 nm was formed on most parts of the surface. On some parts of the surface, Mn{sub 2}SiO{sub 4} particles were formed irregularly up to a thickness of ? 50 nm. Approximately 200 nm below the MnAl{sub 2}O{sub 4} layer, Al{sub 2}O{sub 3} was found at the grain boundaries. Thermodynamic calculations were performed to explain the experimental results. The calculations showed that when a{sub O2} > ? 1.26 × 10{sup ?28}, MnO, MnAl{sub 2}O{sub 4}, and Mn{sub 2}SiO{sub 4} can be formed together, and the major oxide is MnO. When a{sub O2} is in the range of 1.26 × 10{sup ?28}–2.51 × 10{sup ?31}, MnO is not stable but MnAl{sub 2}O{sub 4} is the major oxide. When a{sub O2} < ? 2.51 × 10{sup ?31}, only Al{sub 2}O{sub 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.

  14. Surface oxidation of GaN(0001): Nitrogen plasma-assisted cleaning for ultrahigh vacuum applications

    SciTech Connect

    Gangopadhyay, Subhashis; Schmidt, Thomas Kruse, Carsten; Figge, Stephan; Hommel, Detlef; Falta, Jens

    2014-09-01

    The cleaning of metal-organic vapor-phase epitaxial GaN(0001) template layers grown on sapphire has been investigated. Different procedures, performed under ultrahigh vacuum conditions, including degassing and exposure to active nitrogen from a radio frequency nitrogen plasma source have been compared. For this purpose, x-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and scanning tunneling microscopy have been employed in order to assess chemical as well as structural and morphological surface properties. Initial degassing at 600?°C under ultrahigh vacuum conditions only partially eliminates the surface contaminants. In contrast to plasma assisted nitrogen cleaning at temperatures as low as 300?°C, active-nitrogen exposure at temperatures as high as 700?°C removes the majority of oxide species from the surface. However, extended high-temperature active-nitrogen cleaning leads to severe surface roughening. Optimum results regarding both the removal of surface oxides as well as the surface structural and morphological quality have been achieved for a combination of initial low-temperature plasma-assisted cleaning, followed by a rapid nitrogen plasma-assisted cleaning at high temperature.

  15. Surface Analysis of Stressed and Control Tin Oxide Thin Films on Soda Lime Glass

    SciTech Connect

    Pankow, J. W.

    2003-05-01

    Surface analysis techniques have been used to investigate tin oxide-coated soda lime glass specimens prior and subsequent to their exposure to DC bias, heat, and humidity. All specimens reported here comprise the following layered structure: tin oxide/silicon oxycarbide/glass. Depth profiling using X-ray photoelectron spectroscopy (XPS) clearly shows the interfacial regions in both control samples and samples exposed to the above-mentioned conditions (stressed). Control samples show distinct and relatively compact interfacial regions as well as an intact silicon oxycarbide diffusion barrier. Stressed films, however, show more diffuse interfacial regions and a physically and chemically altered silicon oxycarbide diffusion barrier. This deterioration of the diffusion barrier is proposed to be a pre-requisite event to enable tin oxide delamination.

  16. The Interaction of Vibrationally Excited Hydrogen with a Copper Surface

    NASA Astrophysics Data System (ADS)

    Parhikhteh, Hadi

    1995-01-01

    The survival probability of H_2 (v = 1, J = 1) scattered from a clean Cu(110) surface has been measured and compared with the survival probability of hydrogen molecules in the ground state to show the role of vibrational energy of the incident molecules. For a translational energy of 78 meV, H_2(v = 0, J = 1) had a ratio of scattered flux/incident flux = 1.01 +/-.01. The same quantity for vibrationally excited molecules was measured to be 0.74 +/- 0.13. The effect of surface coverage on the reflectivity has been studied and possible loss channels are discussed.

  17. Metallic oxide nanoparticles stimulate blood coagulation independent of their surface charge.

    PubMed

    Steuer, Heiko; Krastev, Rumen; Lembert, Nicolas

    2014-07-01

    Positively charged metallic oxides prevent blood coagulation whereas negatively charged metallic oxides are thrombogenic. This study was performed to examine whether this effect extends to metallic oxide nanoparticles. Oscillation shear rheometry was used to study the effect of zinc oxide and silicon dioxide nanoparticles on thrombus formation in human whole blood. Our data show that oscillation shear rheometry is a sensitive and robust technique to analyze thrombogenicity induced by nanoparticles. Blood without previous contact with nanoparticles had a clotting time (CT) of 16.7?±?1.0 min reaching a maximal clot strength (CS) of 16?±?14 Pa (G') after 30 min. ZnO nanoparticles (diameter 70 nm, +37 mV zeta-potential) at a concentration of 1 mg/mL prolonged CT to 20.8?±?3.6 min and provoked a weak clot (CS 1.5?±?1.0 Pa). However, at a lower concentration of 100 µg/mL the ZnO particles dramatically reduced CT to 6.0?±?0.5 min and increased CS to 171?±?63 Pa. This procoagulant effect decreased at lower concentrations reaching the detection limit at 10 ng/mL. SiO2 nanoparticles (diameter 232 nm, -28 mV zeta-potential) at high concentrations (1 mg/mL) reduced CT (2.1?±?0.2 min) and stimulated CS (249?±?59 Pa). Similar to ZnO particles, this procoagulant effect reached a detection limit at 10 ng/mL. Nanoparticles in high concentrations reproduce the surface charge effects on blood coagulation previously observed with large particles or solid metal oxides. However, nanoparticles with different surface charges equally well stimulate coagulation at lower concentrations. This stimulation may be an effect which is not directly related to the surface charge. PMID:24347269

  18. Compositional Tuning of Ultrathin Surface Oxides on Metal and Alloy Substrates Using Photons: Dynamic Simulations and Experiments

    SciTech Connect

    Chang, Chia-Lin; Sankaranarayanan, Subramanian; Ruzmetov, Dmitry; Engelhard, Mark H.; Kaxiras, Efthimios; Ramanathan, Shriram

    2010-02-02

    Oxide synthesis with controlled functional properties is desirable for a plethora of applications but is elusive due to oxide growth kinetics. Here, we report on the ability to modify the structure and composition of ultra-thin oxides grown on Ni-Al alloy surfaces at room temperature utilizing photon illumination. Atomistic simulations that take into account dynamic charge transfer predict that the electric field produced across an oxide film in photon-assisted synthesis overcomes the activation energy barrier for ionic migration, leading to enhanced oxidation kinetics and oxygen incorporation into the oxide, enabling us to control the oxide composition at atomic length scales. Experiments (near-edge x-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy) indicate that the native oxide on 5%Ni-Al alloy is primarily composed of aluminum oxide with no nickel oxide whereas the photon-assisted oxide comprises of both aluminum oxide and nickel oxide. The ability to tune the composition at the atomic scale of the ultra-thin oxide films leads to excellent passivity as verified from polarization experiments.

  19. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    NASA Astrophysics Data System (ADS)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  20. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, [September--December 1991

    SciTech Connect

    Doyle, F.M.

    1992-01-28

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical coal cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the fifth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville {number_sign}2 Mine, Clearfield County, Pennsylvania.

  1. The Performance of Ce Surface Treated Ferritic Stainless Steels for Solid Oxide Fuel Cell Interconnects

    SciTech Connect

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

    2007-09-01

    This research deals with the effect of a Ce surface treatment on the behavior of Fe-Cr-Mn ferritic stainless steels which may have application in SOFC technology. This treatment consisted of applying a slurry of CeO2 and a halide activator to the surface of coupons. After the slurry dried the coupons were heated to 900C in a controlled atmosphere furnace for 12 hours. The effectiveness of the treatment on commercial (Type 409 (12Cr), Type 430 (18Cr), Crofer 22APU (22Cr), Type 446(26Cr)) and experimental (NETL F9 (12Cr) and NETL F5 (22Cr)) alloys as a function of Cr content will be presented. The oxidation behavior of the alloys was assessed by exposing coupons (untreated and treated) to moist air at 800C. Area specific resistance (ASR) was measured at 800C. In general, the rare earth treatment effectively reduced the oxidation rate, resulting in thinner oxide scales and less internal oxidation.

  2. Energy dependence of the trapping of uranium atoms by aluminum oxide surfaces

    NASA Technical Reports Server (NTRS)

    Librecht, K. G.

    1979-01-01

    The energy dependence of the trapping probability for sputtered U-235 atoms striking an oxidized aluminum collector surface at energies between 1 eV and 184 eV was measured. At the lowest energies, approximately 10% of the uranium atoms are not trapped, while above 10 eV essentially all of them stick. Trapping probabilities averaged over the sputtered energy distribution for uranium incident on gold and mica are also presented.

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

    E-print Network

    Sparks, Donald L.

    INFLUENCE OF TEMPERATURE ON NICKEL SORPTION ON CLAY MINERAL AND OXIDE SURFACES. K. G. Scheckel1 by applying the Ey- ring equation k = (kbT / h) e -G / RT = (kbT / h) e -S / R e - H / RT . Materials to the thermodynamic solubility product of -Ni(OH)2 [4], was reacted with a 10 g/L suspension of each of the minerals

  4. Oxidation mechanism of the ammonium-fluoride-treated Si(100) surface

    SciTech Connect

    Kluth, G.J.; Maboudian, R.

    1996-11-01

    High-resolution electron energy loss (HREEL) spectroscopy, Auger electron spectroscopy, and low-energy electron diffraction have been employed to examine the initial oxidation stage of ammonium-fluoride-treated Si(100) surfaces exposed to air. The NH{sub 4}F treatment results in a hydrogen-terminated surface, as shown by the presence of the Si{endash}H stretch (2100 cm{sup {minus}1}), SiH{sub 2} scissor (910 cm{sup {minus}1}), and SiH bend (650 cm{sup {minus}1}) in the HREEL spectra. Initial oxidation on this surface occurs through oxygen insertion in the silicon backbonds, as indicated by the presence of the asymmetric bridge-bonded oxygen stretch in the region between 1060 and 1160 cm{sup {minus}1}. Oxygen is observed in both surface and bulk bridge-bonding sites for even the shortest air exposures, suggesting that initial oxygen uptake is not taking place in a layer-by-layer fashion. Auger electron spectroscopy shows a slow uptake of oxygen over the first few days of air exposure, followed by more rapid oxidation. Over the first two weeks of air exposure, the Si{endash}H stretch at 2100 cm{sup {minus}1} gradually disappears, accompanied by the appearance of oxygen backbonded Si{endash}H peaks around 2250 cm{sup {minus}1}. This behavior indicates that, despite the increase in oxygen uptake, the hydrogen termination remains intact, and further confirms that oxygen uptake occurs through insertion in the silicon backbonds. Water is found to play a significant role in the initial oxidation. {copyright} {ital 1996 American Institute of Physics.}

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

    SciTech Connect

    Doyle, F.M.

    1992-01-01

    During the ninth quarter, electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania. Scanning electron microscopy and energy dispersive X-ray analysis were done to characterize the morphology and composition of the surface of as-received coal, oxidized coal and coal pyrite. In addition, electrokinetic tests were done on Upper Freeport coal pyrite.

  6. Surface conductivity of the single crystal aluminum oxide in vacuum and caesium vapors

    SciTech Connect

    Vasilchenko, A.V.; Izhvanov, O.L.

    1996-03-01

    Results of measurements of surface conductivity of single-crystal aluminum oxide samples in vacuum and cesium vapors at T=620{endash}830 K and P{sub Cs}=0.13{endash}2 Pa are shown in the paper. Analysis of caesium vapor influence is carried out and ultimate characteristics of samples conductivity under operation conditions in thermionic nuclear power system (NPP) TFE are estimated. {copyright} {ital 1996 American Institute of Physics.}

  7. ANRV408-PC61-07 ARI 14 October 2009 17:16 Oxide Surface Science

    E-print Network

    Diebold, Ulrike

    the stability of oxide surfaces and is discussed using ZnO as an example. This review also highlights the role Universit¨at Wien, A-1040 Vienna, Austria Annu. Rev. Phys. Chem. 2010. 61:129­48 The Annual Review.physchem.012809.103254 Copyright c 2010 by Annual Reviews. All rights reserved 0066-426X/10/0505-0001$20.00 Key

  8. Effects of electron-beam irradiation on surface oxidation of polymer composites

    NASA Astrophysics Data System (ADS)

    ?enkiewicz, Marian; Rauchfleisz, Marta; Czupry?ska, Joanna; Pola?ski, Julian; Karasiewicz, Tomasz; Engelgard, W?odzimierz

    2007-09-01

    The aim of this article was to show the effects of an electron radiation dose and presence of a compatibilizer on the oxidation of composites made of blends of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate) (PET) as well as of blends of LDPE, HDPE, and PP. As the compatibilizers, the styrene-ethylene/butylene-styrene elastomer grafted with maleic anhydride (SEBS- g-MA) and trimethylol propane trimethylacrylate (TMPTA) were used; they were added in the amounts of 5, 10, and 15 wt% and 1, 2, and 3 wt%, respectively. The oxidation of the surface layer (SL) was investigated by the X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). It was found that the extent of the composite oxidation increased with the increasing dose of the electron radiation. The addition of the compatibilizers enhanced the oxidation of the SL but hindered the oxidation of the bulk of the material.

  9. Ion beam deposition and surface characterization of thin multi-component oxide films during growth.

    SciTech Connect

    Krauss, A.R.; Im, J.; Smentkowski, V.; Schultz, J.A.; Auciello, O.; Gruen, D.M.; Holocek, J.; Chang, R.P.H.

    1998-01-13

    Ion beam deposition of either elemental targets in a chemically active gas such as oxygen or nitrogen, or of the appropriate oxide or nitride target, usually with an additional amount of ambient oxygen or nitrogen present, is an effective means of depositing high quality oxide and nitride films. However, there are a number of phenomena which can occur, especially during the production of multicomponent films such as the ferroelectric perovskites or high temperature superconducting oxides, which make it desirable to monitor the composition and structure of the growing film in situ. These phenomena include thermodynamic (Gibbsian), and oxidation or nitridation-driven segregation, enhanced oxidation or nitridation through production of a highly reactive gas phase species such as atomic oxygen or ozone via interaction of the ion beam with the target, and changes in the film composition due to preferential sputtering of the substrate via primary ion backscattering and secondary sputtering of the film. Ion beam deposition provides a relatively low background pressure of the sputtering gas, but the ambient oxygen or nitrogen required to produce the desired phase, along with the gas burden produced by the ion source, result in a background pressure which is too high by several orders of magnitude to perform in situ surface analysis by conventional means. Similarly, diamond is normally grown in the presence of a hydrogen atmosphere to inhibit the formation of the graphitic phase.

  10. Surface Binding and Organization of Sensitizing Dyes on Metal Oxide Single Crystal Surfaces

    SciTech Connect

    Parkinson, Bruce

    2010-06-04

    Even though investigations of dye-sensitized nanocrystalline semiconductors in solar cells has dominated research on dye-sensitized semiconductors over the past two decades. Single crystal electrodes represent far simpler model systems for studying the sensitization process with a continuing train of studies dating back more than forty years. Even today single crystal surfaces prove to be more controlled experimental models for the study of dye-sensitized semiconductors than the nanocrystalline substrates. We analyzed the scientific advances in the model sensitized single crystal systems that preceded the introduction of nanocrystalline semiconductor electrodes. It then follows the single crystal research to the present, illustrating both their striking simplicity of use and clarity of interpretation relative to nanocrystalline electrodes. Researchers have employed many electrochemical, photochemical and scanning probe techniques for studying monolayer quantities of sensitizing dyes at specific crystallographic faces of different semiconductors. These methods include photochronocoulometry, electronic spectroscopy and flash photolysis of dyes at potential-controlled semiconductor electrodes and the use of total internal reflection methods. In addition, we describe the preparation of surfaces of single crystal SnS2 and TiO2 electrodes to serve as reproducible model systems for charge separation at dye sensitized solar cells. This process involves cleaving the SnS2 electrodes and a photoelectrochemical surface treatment for TiO2 that produces clean surfaces for sensitization (as verified by AFM) resulting in near unity yields for electron transfer from the molecular excited dyes into the conduction band.

  11. Further studies of oxidation processes on filter surfaces: Evidence for oxidation products and the influence of time in service

    NASA Astrophysics Data System (ADS)

    Bekö, Gabriel; Clausen, Geo; Weschler, Charles J.

    The sensory pollutants emitted by loaded ventilation filters are assumed to include products formed via oxidation of organics associated with captured particles. In this study, experiments were performed that used either particle production or ozone removal as probes to further improve our understanding of such processes. The measured ratio of downstream to upstream submicron particle concentrations increased when ozone was added to air passing through samples from loaded particle filters. Such an observation is consistent with low volatility oxidation products desorbing from the filter and subsequently partitioning between the gas phase and the surface of particles that have passed through the filter, including particles that were previously too small (<20 nm) to be detected by the instrument used in these studies. A related set of experiments conducted with unused filters and filters that had been in service from 2 to 16 weeks found that ozone removal efficiencies changed in a manner that indicated at least two different removal mechanisms—reactions with compounds present on the filter media following manufacturing and reactions with compounds associated with captured particles. The contribution from the former varies with the type and manufacturer of the filter, while that of the latter varies with the duration of service and nature of the captured particles. In complimentary experiments, a filter sample protected from ozone during its 9 weeks of service had higher ozone removal efficiencies than an identical filter not protected from ozone during the same 9 weeks of service filtering the same air. This result indicates that a filter's exposure history subsequently influences the quantity of oxidation products generated when ozone-containing air flows through it.

  12. Molecular adsorption and methanol synthesis on the oxidized Cu/ZnO(0001) surface

    NASA Astrophysics Data System (ADS)

    Lyle, Matthew J.; Warschkow, Oliver; Delley, Bernard; Stampfl, Catherine

    2015-11-01

    Cu/ZnO is an important catalyst used in the industrial synthesis of methanol from syngas. Many aspects of the functional synergy between the Cu and ZnO components in this system require further understanding. This work uses density functional theory calculations to examine the adsorption of various reactants of methanol synthesis to a recently proposed copper-oxide overlayer reconstruction on the ZnO(0001) surface. We identify the preferred binding configurations as a function of adsorbate coverage and compare the energetics of adsorption to that on the clean ZnO(0001) surface. The relevance of our results to methanol synthesis is discussed.

  13. A study on measurement of the surface charge accumulation using anodic aluminum oxide template

    NASA Astrophysics Data System (ADS)

    Oh, Seung-Ju; Lee, Hyo-Chang; Moon, Jun-Hyeon; Chung*, Chin-Wook; Kwon, Soon-Ho; Lee, Jung-Joong; Koo, Il-Gyo; Lee, Soo-Jin; Seong, Kyo-Seong; Plasma Surface Engineering Lab Collaboration; Semes Collaboration

    2013-09-01

    As the critical dimension of the nano-device shrinks, an undesired etch profile resulting from the local electric field by the surface charge accumulation is made on the plasma processing. To understand and monitor the surface charge accumulation, the measurement of the voltage difference between top electrode and bottom electrode on the anodic aluminum oxide (AAO) which has high aspect structure is performed in inductively coupled plasma. The voltage difference is changed with external discharge conditions, such as gas pressure, input power, and gas species, and the result is analyzed with the measured plasma parameters. This work was supported by SEMES cooperative research project.

  14. Surface nanostructuring by ion-induced localized plasma expansion in zinc oxide

    SciTech Connect

    El-Said, A. S. E-mail: a.s.el-said@hzdr.de; Moslem, W. M.; Djebli, M.

    2014-06-09

    Creation of hillock-like nanostructures on the surface of zinc oxide single crystals by irradiation with slow highly charged ions is reported. At constant kinetic energy, the nanostructures were only observed after irradiation with ions of potential energies above a threshold between 19.1?keV and 23.3?keV. The size of the nanostructures increases as a function of potential energy. A plasma expansion approach is used to explain the nanostructures creation. The calculations showed that the surface nanostructures became taller with the increase of ionic temperature. The influence of charged cluster formation and the relevance of their polarity are discussed.

  15. Interactions of water, methanol and diethyl ether molecules with the surface of oxidized activated carbon

    NASA Astrophysics Data System (ADS)

    Salame, Issa I.; Bandosz, Teresa J.

    Two samples of oxidized activated carbon of wood origin were used as adsorbents of water, methanol, and diethyl ether. Structural and chemical characteristics of the samples' surfaces were obtained using adsorption of nitrogen and Boehm titration. The adsorption isotherms of water and methanol were measured using a volumetric apparatus whereas the adsorption of diethyl ether was studied by means of inverse gas chromatography at finite concentration. Then the isotherms at three different temperatures were used to calculate the isosteric heats of adsorption. The results showed that the strength of interaction depends on the porosity of the sample and its surface chemistry. The effect of surface chemistry and the presence of oxygenated groups are predominant in the case of water and the least important in the case of diethyl ether. This is the result of the chemical nature of the molecules, their sizes, and the relative strengths of the dispersive interactions in small pores in comparison with hydrogen bonding to surface functional groups.

  16. Plastic deformation of a magnesium oxide 001-plane surface produced by cavitation

    NASA Technical Reports Server (NTRS)

    Hattori, S.; Miyoshi, K.; Buckley, D. H.; Okada, T.

    1986-01-01

    An investigation was conducted to examine plastic deformation of a cleaved single-crystal magnesium oxide 001-plane surface exposed to cavitation. Cavitation damage experiments were carried out in distilled water at 25 C by using a magnetostrictive oscillator in close proximity (2 mm) to the surface of the cleaved specimen. The dislocation-etch-pit patterns induced by cavitation were examined and compared with that of microhardness indentations. The results revealed that dislocation-etch-pit patterns around hardness indentations contain both screw and edge dislocations, while the etch-pit patterns on the surface exposed to cavitation contain only screw dislocations. During cavitation, deformation occurred in a thin surface layer, accompanied by work-hardening of the ceramic. The row of screw dislocations underwent a stable growth, which was analyzed crystallographically.

  17. Solubility and Surface Adsorption Characteristics of Metal Oxides to High Temperature

    SciTech Connect

    D.J. Wesolowski; M.L. Machesky; S.E. Ziemniak; C. Xiao; D.A. Palmer; L.M. Anovitz; P. Benezeth

    2001-05-04

    The interaction of high temperature aqueous solutions with mineral surfaces plays a key role in many aspects of fossil, geothermal and nuclear energy production. This is an area of study in which the subsurface geochemical processes that determine brine composition, porosity and permeability changes, reservoir integrity, and fluid flow rates overlap with the industrial processes associated with corrosion of metal parts and deposition of solids in pipes and on heat exchanger surfaces. The sorption of ions on mineral surfaces is also of great interest in both the subsurface and ''above ground'' regimes of power production, playing a key role in subsurface migration of contaminants (nuclear waste disposal, geothermal brine re-injection, etc.) and in plant operations (corrosion mitigation, migration of radioactive metals from reactor core to heat exchanger, etc.). In this paper, results of the solubility and surface chemistry of metal oxides relevant to both regimes are summarized.

  18. Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications

    NASA Astrophysics Data System (ADS)

    Wu, Wei; Wu, Zhaohui; Yu, Taekyung; Jiang, Changzhong; Kim, Woo-Sik

    2015-04-01

    This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed.

  19. Raman Spectroscopy as a Probe of Surface Oxides and Hydrides on Niobium

    SciTech Connect

    J. Zasadzinski, B. Albee, S. Bishnoi, C. Cao, G. Ciovati, L.D. Cooley, D.C. Ford, Th. Proslier

    2011-07-01

    Raman microscopy/spectroscopy has been used in conjunction with AFM, tunneling and magnetic susceptibility to identify surface oxides and hydrides on annealed, recrystallized foils of high purity Nb and on single crystals of cavity grade Nb. Cold worked regions of the Nb foil as well as rough regions near grain boundaries showed clear evidence of ordered hydride phases which were identified by VASP phonon calculations. Cold worked regions also displayed enhanced surface paramagnetism. Surface enhanced Raman spectra have also been obtained using 1.0 nm Au depositon. The SERS spectra reveal hydride molecular species which are not observable by conventional Raman. These results indicate that Raman is a useful probe of Nb surfaces relevant for cavity performance

  20. Adsorption of antimony(V) onto Mn(II)-enriched surfaces of manganese-oxide and FeMn binary oxide.

    PubMed

    Liu, Ruiping; Xu, Wei; He, Zan; Lan, Huachun; Liu, Huijuan; Qu, Jiuhui; Prasai, Tista

    2015-11-01

    Manganese(IV) oxide [Mn(IV)] potentially oxidizes antimony(III) [Sb(III)] to antimony(V) [Sb(V)] and improves Sb removal by FeMn binary oxide (FMBO) through an oxidation-adsorption mechanism. This study focused on the effect of Mn(IV) reductive dissolution by potassium sulfite (K2SO3) on Sb(V) adsorption onto manganese oxide (Mn-oxide) and FMBO. The maximum Sb(V) adsorption (Qmax,Sb(V)) increased from 1.0 to 1.1 mmol g(-1) for FMBO and from 0.4 to 0.6 mmol g(-1) for Mn-oxide after pretreatment with 10 mmol L(-1) K2SO3. The addition of 2.5 mmol L(-1) Mn(2+) also significantly improved Sb(V) adsorption, and the observed Qmax,Sb(V) increased to 1.4 and 1.0 mmol g(-1) for FMBO and Mn-oxide, respectively, with pre-adsorbed Mn(2+). Neither K2SO3 nor Mn(2+) addition had any effect on Sb(V) adsorption onto iron oxide (Fe-oxide). Mn(2+) introduced by either Mn(IV) dissolution or addition tended to form outer-sphere surface complexes with hydroxyl groups on Mn-oxide surfaces (MnOOH). Mn(2+) at 2.5 mmol L(-1) shifted the isoelectric point (pHiep) from 7.5 to 10.2 for FMBO and from 4.8 to 9.2 for Mn-oxide and hence benefited Sb(V) adsorption. The adsorption of Sb(V) onto Mn(2+)-enriched surfaces contributed to the release of Mn(2+), and the X-ray photoelectron spectra also indicated increased binding energy of Mn 2p3/2 after the adsorption of Sb(V) onto K2SO3-pretreated FMBO and Mn-oxide. Sb(V) adsorption involved the formation of inner-sphere complexes and contributed to the release of Mn(2+). In the removal of Sb(III) by Mn-based oxides, the oxidation of Sb(III) to Sb(V) by Mn(IV) oxides had an effect; however, Mn(IV) dissolution and Mn(2+)-enrichment also played an important role. PMID:26218341

  1. Sexithiophene films on clean and oxidized Si(111) surfaces: Growth and electronic structure

    NASA Astrophysics Data System (ADS)

    Ivanco, J.; Krenn, J. R.; Ramsey, M. G.; Netzer, F. P.; Haber, T.; Resel, R.; Haase, A.; Stadlober, B.; Jakopic, G.

    2004-09-01

    The growth and the electronic properties of sexithiophene thin films on silicon surfaces have been studied by angle resolved ultraviolet photoelectron spectroscopy while morphology and crystalline order have been assessed by atomic force microscopy and x-ray diffraction. The influence of the surface modification of the substrate as well as of the growth temperature and the growth rate were investigated in ultrahigh vacuum through controlled multistep growth sequences ranging from (sub)monolayer coverage up to thick films. Depending on the preparation, two electronically distinct sexithiophene (6T) films could be produced, as revealed by their ionization potentials which differed by ˜0.7eV. The evolution of the electronic energy levels with film thickness is considered in terms of the concepts of interface dipole and band bending, with the latter being argued to be inappropriate. Irrespective of substrate or growth conditions the thick 6T films were found to all have the same work function of ˜0.4eV, which is related to near vertically oriented molecules on the films surface. Against general expectations 6T grown at a low rate on the reactive Si(111) substrate and those grown at high rates on the oxide surface produces films that are more uniform and crystalline than those grown at low rates on the passive oxidized Si surfaces. The latter promotes the formation of small three-dimensional crystallites and a much poorer morphology for planar devices.

  2. Chemical identification of point defects and adsorbates on a metal oxide surface by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Lauritsen, Jeppe V.; Foster, Adam S.; Olesen, Georg H.; Christensen, Mona C.; Kühnle, Angelika; Helveg, Stig; Rostrup-Nielsen, Jens R.; Clausen, Bjerne S.; Reichling, Michael; Besenbacher, Flemming

    2006-07-01

    Atomic force microscopy in the non-contact mode (nc-AFM) can provide atom-resolved images of the surface of, in principle, any material independent of its conductivity. Due to the complex mechanisms involved in the contrast formation in nc-AFM imaging, it is, however, far from trivial to identify individual surface atoms or adsorbates from AFM images. In this work, we successfully demonstrate how to extract detailed information about defects and the chemical identity of adsorbates on a metal oxide surface from nc-AFM images. We make use of the observation that the apex of the AFM tip can be altered to expose either a positive or negative tip termination. The complementary set of images recorded with the two tip terminations unambiguously define the ionic sub-lattices and reveal the exact positions of oxygen vacancies and hydroxyl (OH) defects on a TiO2 surface. Chemical specificity is extracted by comparing the characteristic contrast patterns of the defects with results from comprehensive AFM simulations. Our methodology of analysis is generally applicable and may be pivotal for uncovering surface defects and adsorbates on other transition metal oxides designed for heterogeneous catalysis, photo-electrolysis or biocompatibility.

  3. Recent advances in surface chemistry strategies for the fabrication of functional iron oxide based magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Turcheniuk, Kostiantyn; Tarasevych, Arkadii V.; Kukhar, Valeriy P.; Boukherroub, Rabah; Szunerits, Sabine

    2013-10-01

    The synthesis of superparamagnetic nanostructures, especially iron-oxide based nanoparticles (IONPs), with appropriate surface functional groups has been intensively researched for many high-technological applications, including high density data storage, biosensing and biomedicine. In medicine, IONPs are nowadays widely used as contrast agents for magnetic resonance imaging (MRI), in hyperthermia therapy, but are also exploited for drug and gene delivery, detoxification of biological fluids or immunoassays, as they are relatively non-toxic. The use of magnetic particles in vivo requires IONPs to have high magnetization values, diameters below 100 nm with overall narrow size distribution and long time stability in biological fluids. Due to the high surface energies of IONPs agglomeration over time is often encountered. It is thus of prime importance to modify their surface to prevent aggregation and to limit non-specific adsorption of biomolecules onto their surface. Such chemical modifications result in IONPs being well-dispersed and biocompatible, and allow for targeted delivery and specific interactions. The chemical nature of IONPs thus determines not only the overall size of the colloid, but also plays a significant role for in vivo and in vitro applications. This review discusses the different concepts currently used for the surface functionalization and coating of iron oxide nanoparticles. The diverse strategies for the covalent linking of drugs, proteins, enzymes, antibodies, and nucleotides will be discussed and the chemically relevant steps will be explained in detail.

  4. Assembly of Linear Nano-Chains from Iron Oxide Nanospheres with Asymmetric Surface Chemistry

    PubMed Central

    Peiris, Pubudu M.; Schmidt, Erik; Calabrese, Michael; Karathanasis, Efstathios

    2011-01-01

    Besides the multifunctionality, another equally important aspect of nanoparticles is their engineerability to control the geometrical and chemical properties during fabrication. In this work, we exploited this aspect to define asymmetric surface chemistry of an iron oxide nanosphere by controlling the topology of ligand expression on its surface resulting in a particle with two faces, one displaying only amines and the other only thiols. Specifically, amine-functionalized iron oxide nanospheres were attached on a solid support via a crosslinker containing a disulfide bridge. Liberation of the nanosphere using thiolytic cleavage created thiols on the portion of the particle's surface that interacted with the solid support. Employing a solid-phase strategy and a step-by-step addition of particles, the two unique faces on the same nanosphere served as fittings to assemble them into linear nano-chains. Assembly of chains with various lengths and aspect ratios was controlled by the size and number of the added nanospheres. The characteristics of those chains showed a high degree of uniformity indicating the exceptional control of the synthetic process. Notably, one of the unique properties of the iron oxide nano-chains was an increased magnetic relaxivity, indicating their potential use as contrast agents for magnetic resonance imaging. PMID:21253600

  5. The surface oxidation potential of melanosomes measured by free electron laser-photoelectron emission microscopy.

    PubMed

    Garguilo, Jacob; Hong, Lian; Edwards, Glenn S; Nemanich, Robert J; Simon, John D

    2007-01-01

    A technique for measuring the photoionization spectrum and the photoelectron emission threshold of a microscopic structured material is presented. The theoretical underpinning of the experiment and the accuracy of the measurements are discussed. The technique is applied to titanium silicide nanostructures and melanosomes isolated from human hair, human and bovine retinal pigment epithelium cells, and the ink sac of Sepia officinalis. A common photothreshold of 4.5 +/- 0.2 eV is found for this set of melanosomes and is attributed to the photoionization of the eumelanin pigment. The relationship between the photoionization threshold and the electrochemical potential referenced to the normal hydrogen electrode is used to quantify the surface oxidation potential of the melanosome. The developed technique is used to examine the effect of iron chelation on the surface oxidation potential of Sepia melanosomes. The surface oxidation potential is insensitive to bound Fe(III) up to saturation, suggesting that the metal is bound to the interior of the granule. This result is discussed in relation to the age-dependent accumulation of iron in human melanosomes in both the eye and brain. PMID:17007561

  6. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states.

    PubMed

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-01-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (?-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce(3+) sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce(3+) sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials. PMID:26489858

  7. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

    NASA Astrophysics Data System (ADS)

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-10-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (?-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials.

  8. Nonenzymatic Reactions above Phospholipid Surfaces of Biological Membranes: Reactivity of Phospholipids and Their Oxidation Derivatives

    PubMed Central

    Solís-Calero, Christian; Ortega-Castro, Joaquín; Frau, Juan; Muñoz, Francisco

    2015-01-01

    Phospholipids play multiple and essential roles in cells, as components of biological membranes. Although phospholipid bilayers provide the supporting matrix and surface for many enzymatic reactions, their inherent reactivity and possible catalytic role have not been highlighted. As other biomolecules, phospholipids are frequent targets of nonenzymatic modifications by reactive substances including oxidants and glycating agents which conduct to the formation of advanced lipoxidation end products (ALEs) and advanced glycation end products (AGEs). There are some theoretical studies about the mechanisms of reactions related to these processes on phosphatidylethanolamine surfaces, which hypothesize that cell membrane phospholipids surface environment could enhance some reactions through a catalyst effect. On the other hand, the phospholipid bilayers are susceptible to oxidative damage by oxidant agents as reactive oxygen species (ROS). Molecular dynamics simulations performed on phospholipid bilayers models, which include modified phospholipids by these reactions and subsequent reactions that conduct to formation of ALEs and AGEs, have revealed changes in the molecular interactions and biophysical properties of these bilayers as consequence of these reactions. Then, more studies are desirable which could correlate the biophysics of modified phospholipids with metabolism in processes such as aging and diseases such as diabetes, atherosclerosis, and Alzheimer's disease. PMID:25977746

  9. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

    PubMed Central

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-01-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (?-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials. PMID:26489858

  10. Surface-Directed Synthesis of Erbium-Doped Yttrium Oxide Nanoparticles within Organosilane Zeptoliter Containers

    PubMed Central

    2015-01-01

    We introduce an approach to synthesize rare earth oxide nanoparticles using high temperature without aggregation of the nanoparticles. The dispersity of the nanoparticles is controlled at the nanoscale by using small organosilane molds as reaction containers. Zeptoliter reaction vessels prepared from organosilane self-assembled monolayers (SAMs) were used for the surface-directed synthesis of rare earth oxide (REO) nanoparticles. Nanopores of octadecyltrichlorosilane were prepared on Si(111) using particle lithography with immersion steps. The nanopores were filled with a precursor solution of erbium and yttrium salts to confine the crystallization step to occur within individual zeptoliter-sized organosilane reaction vessels. Areas between the nanopores were separated by a matrix film of octadecyltrichlorosilane. With heating, the organosilane template was removed by calcination to generate a surface array of erbium-doped yttria nanoparticles. Nanoparticles synthesized by the surface-directed approach retain the periodic arrangement of the nanopores formed from mesoparticle masks. While bulk rare earth oxides can be readily prepared by solid state methods at high temperature (>900 °C), approaches for preparing REO nanoparticles are limited. Conventional wet chemistry methods are limited to low temperatures according to the boiling points of the solvents used for synthesis. To achieve crystallinity of REO nanoparticles requires steps for high-temperature processing of samples, which can cause self-aggregation and dispersity in sample diameters. The facile steps for particle lithography address the problems of aggregation and the requirement for high-temperature synthesis. PMID:25163977

  11. Thermal and Photochemical Reactions of NO2 on a Chromium (III) Oxide Surface

    NASA Astrophysics Data System (ADS)

    Nishino, N.; Finlayson-Pitts, B. J.

    2011-12-01

    Chromium oxide (Cr2O3) is a major component of the oxide layer on stainless steel surfaces. It is also widely used as pigment in paints and roofs and as a protective coating on various surfaces. While many studies have focused on the catalytic activity of Cr2O3 surfaces for selective catalytic reduction (SCR), less attention has been paid to its surface chemistry involving atmospherically important species such as NO2 under atmospheric conditions. In this study, we have investigated thermal and photochemical reactions of NO2 in the presence and the absence of water vapor, using a thin layer of Cr2O3 as a model for the surface of stainless steel as well as other similarly coated surfaces in the boundary layer. A 30 nm thick Cr2O3 film was deposited on a germanium attenuated total reflectance (ATR) crystal, and the changes in the surface species were monitored by Fourier Transform Infrared (FTIR) spectroscopy. Upon NO2 adsorption, nitrate (NO3-) ions appeared likely coordinated to Cr3+ ion(s). The NO3- peaks reversibly shifted when water vapor was added, suggesting that NO3- become solvated. Irradiation at 311 nm led to a decrease in NO3- ions under both dry and humid conditions. The major gas-phase species formed by the irradiation was NO under dry conditions, while NO2 was mainly formed in the presence of H2O. Possible mechanisms and the implications for heterogeneous NO2 chemistry in the boundary layer will be discussed. The results will also be compared to similar chemistry on other surfaces.

  12. First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment

    SciTech Connect

    Piccinin, Simone; Stampfl, Catherine; Scheffler, Matthias

    2008-02-15

    In this paper, we investigate by means of first-principles density functional theory calculations the (111) surface of the Ag-Cu alloy under varying conditions of pressure of the surrounding oxygen atmosphere and temperature. This alloy has been recently proposed as a catalyst with improved selectivity for ethylene epoxidation with respect to pure silver, the catalyst commonly used in industrial applications. Here, we show that the presence of oxygen leads to copper segregation to the surface. Considering the surface free energy as a function of the surface composition, we construct the convex hull to investigate the stability of various surface structures. By including the dependence of the free surface energy on the oxygen chemical potential, we are able compute the phase diagram of the alloy as a function of temperature, pressure, and surface composition. We find that, at temperature and pressure, typically used in ethylene epoxidation, a number of structures can be present on the surface of the alloy, including clean Ag(111), thin layers of copper oxide, and thick oxidelike structures. These results are consistent with, and help explain, recent experimental results.

  13. As(V) and As(III) reactions on pristine pyrite and on surface-oxidized pyrite.

    PubMed

    Sun, Fenglong; Dempsey, Brian A; Osseo-Asare, Kwadwo A

    2012-12-15

    Reactions of As(III) and As(V) with pyrite were investigated using pristine pyrite (produced and reacted in a rigorously anoxic environment with P(O2)<10(-8)atm) and using surface-oxidized pyrite (produced under anoxic conditions, exposed to air, then stored and reacted under rigorously anoxic conditions). Results with surface-oxidized pyrite were similar to previously reported arsenic-pyrite results. However As(III) adsorbed over a broader pH range on pristine pyrite than on surface-oxidized pyrite, As(V) adsorbed over a narrower pH range on pristine pyrite than on surface-oxidized pyrite, and adsorbed As(V) on pristine pyrite was reduced to As(III) but adsorbed As(V) was not reduced with surface-oxidized pyrite. Reduction of As(V) with pristine pyrite was first-order in total As(V), Fe(II) was released, and sulfur was oxidized. The proposed mechanism for pyrite oxidation by As(V) was similar to the published mechanism for oxidation by O(2) and rates were compared. The results can be used to predict the removals of As(V) and As(III) on pyrite in continuously anoxic environments or on pyrite in intermittently oxic/anoxic environments. Rigorous cleanup and continuous maintenance of strictly anoxic conditions are required if commercial or produced pyrites are to be used as surrogates for pristine pyrite. PMID:23000211

  14. Anaerobic methane oxidation may be more prevalent in surface soils than was originally thought

    NASA Astrophysics Data System (ADS)

    Gauthier, Mathieu; Bradley, Robert L.; Šimek, Miloslav

    2013-04-01

    Anaerobic oxidation of methane (CH4) (AOM) is a process that was first reported to occur in deep anoxic marine sediments. In this environment, CH4 is oxidized with sulphate (SO42-) as the terminal electron acceptor. It is mediated by a syntrophic consortium formed by SO42- reducing bacteria and anaerobic CH4 oxidizing Archaea, or by the latter alone. Since this landmark discovery, AOM was found to occur in other environments including freshwater lake sediments and water columns, mud volcanoes, landfill leachate, deep buried Holocene sediments and hydrocarbon contaminated aquifers. All of these situations are very specific and point to AOM as being primarily occurring in highly reducing conditions. Thus, observations of AOM in surface soils with fluctuating REDOX conditions are relatively scarce, although a few independent studies have reported AOM in surface peatlands as well as in a forest soil. Furthermore, AOM may follow different pathways, such as via the coupled oxidation of CH4 and reduction of manganese (Mn(IV)) or iron (Fe(III)), or by a lone denitrifying species that converts nitrite to nitric oxide in order to generate O2 that is then used internally to oxidize CH4. Thus, the goal of our study was to determine whether AOM is more prevalent than was thought in hydromorphic surface soils across different environments, and whether the addition of NO3- or SO4= as alternative electron acceptors may stimulate the process. We collected samples from 3 peatland soils in Scotland, 2 acid-sulphate soils in Finland, and shore sediments of 15 drained fish ponds in the Czech Republic. Subsamples were incubated in the absence of O2 and amended with either NO3-, SO42-, or left unamended (control). The net flux of CH4 and CO2 were assessed by gas chromatography after 2, 20, 40 and 60 days. We also used a 13C-CH4 isotope dilution technique to determine gross production and consumption rates of CH4. We detected AOM in all of our soils, with oxidation rates ranging between 0.001 and 37.28 nmol g-1 day-1, suggesting that AOM may be more ubiquitous than was originally thought. On the other hand, no clear patterns emerged as to the effects of NO3- or SO42- amendments on this process.

  15. Formation, stability, and solubility of metal oxide nanoparticles: Surface entropy, enthalpy, and free energy of ferrihydrite

    NASA Astrophysics Data System (ADS)

    Hiemstra, Tjisse

    2015-06-01

    Ferrihydrite (Fh) is an excellent model for understanding nanoparticle behavior in general. Moreover, Fh is one of the most important Fe (hydr) oxides in nature. Fh particles can be extremely small leading to a very high reactive surface area that changes its chemical potential, strongly affecting the solubility, nucleation, and stability. These characteristics can be coupled to the interfacial Gibbs free energy, being ? = 0.186 ± 0.01 J m-2 for Fh. The surface free energy has a relatively large contribution of surface entropy (-TSsurf = +0.079 ± 0.01 J m-2). The surface entropy is primarily related to the formation of surface groups by chemisorption of water (-17.1 J mol-1 K-1), for Fh equivalent with +0.064 ± 0.002 J m-2 at a surface loading NH2O = 12.6 ?mol m-2. The entropy contribution of physisorbed water has been estimated by analyzing, as model, the surface enthalpy, entropy, and Gibbs free energy of the principal interfaces of H2O, i.e. ice-water-gas. It is about 20% of the contribution of chemisorbed water. The surface enthalpy of Fh is exceptionally low (Hsurf = +0.107 ± 0.01 J m-2), which can be explained by surface depletion (SD) of relatively unstable Fe polyhedra, or similarly, by additional surface loading of the non-depleted mineral core with specific Fe polyhedra for stabilization. The experimental enthalpy of Fh formation varies linearly with the surface area and correctly predicts the enthalpy value for the mineral core (-405.2 ± 1.2 kJ mol FeO3/2), being similar to the literature value for Fh as virtual bulk material (-406.7 ± 1.5 kJ mol FeO3/2) obtained with MO/DFT computations. The thermochemical quantities of the mineral core and surface are essentially the same for the entire range of Fh samples, in line with the SD model. The solubility of Fh suspensions as a whole may differ from the behavior of individual particles due to polydispersity. For 2-line Fh, the overall solubility is log Kso ? -38.5 ± 0.1 and for prolongedly aged 6-line Fh, log Kso ? -39.5 ± 0.1. The smallest Fh particles in a suspension react according to the Ostwald-Freundlich equation (RT?lnKso = 2/3 ?A), but the suspension as a whole apparently reacts according to the Ostwald equation (RT?lnKso = ?A). This difference can be explained by the observed linear relation between the minimum (dmin) and mean (dmean) particle size (dmin = 2/3 dmean) in Fh suspensions. With best estimates for the surface entropy of goethite, hematite, and lepidocrocite, predictions show that Fh becomes thermodynamically unstable above a diameter of ?8.0 nm at 298 K, allowing formation of nano-goethite and nano-hematite, as experienced experimentally at Ostwald ripening. More generally, one observes that metal (hydr) oxides with the highest chemical stability also have the highest mean surface Gibbs free energy, which can be considered as the scientific explanation of the empirical rule of Ostwald-Lussac. In addition, it is shown that the surface Gibbs free energies of metal (hydr) oxides increase with the mean metal coordination number of oxygen in the lattices following the order: oxides > oxyhydroxides > hydroxides.

  16. Electric double layer at metal oxide surfaces: Static properties of the cassiterite - Water Interface

    SciTech Connect

    Vlcek, Lukas; Zhang, Zhan; Machesky, Michael L.; Wesolowski, David J

    2007-04-01

    The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively charged variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).

  17. Electric double layer at metal oxide surfaces:static properties of the cassiterite-water interface.

    SciTech Connect

    Vlcek, L.; Zhang, Z.; Machesky, M .L.; Fenter, P.; Rosenqvist, J.; Wesolowski, D. J.; Anovitz, L. M.; Predota, M.; Cummings, P. T.; Vanderbilt Univ.; ORNL; Univ. of South Bohimia; Illinois State Water Survey

    2007-03-24

    The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively charged variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).

  18. CO-oxidation on surface hematite in hot atmospheres of rocky planets

    NASA Astrophysics Data System (ADS)

    Grenfell, John Lee; Stock, Joachim W.; Patzer, A. Beate C.

    2013-08-01

    Hematite surface minerals can play a key role for the stability in hot, CO2 exoplanetary atmospheres. In a previous work we applied a heterogeneous mechanism for the oxidation of atmospheric CO(g) into CO2(g) occurring on the surface of hematite to planetary atmospheres. In that work we calculated CO2(g) production rates via this "hematite mechanism" for specific planetary atmospheric scenarios both in and out of the Solar System. We perform a general parameter study of the hematite mechanism in which we change key initial variables (CO and O2 gas-phase abundances) and temperature, pressure covering the diverse range of conditions for terrestrial planetary atmospheres; we investigate the response of the CO(g) oxidation rate and hence discuss the implications for the atmospheric CO2(g) budget. We apply a numerical integration scheme based on the Gear method to a system of seven chemical equations to investigate the rate of CO(g) oxidation via the hematite mechanism. Results suggest the mechanism has a potentially important influence on the evolution of hot atmospheres of terrestrial-type planets, especially for temperatures above about 550 K. The abundance of CO(g) was found to be not important for the rate of CO oxidation, whereas the abundance of O2(g) begins to play a role above about 10-5 volume mixing ratio. Above about 550 K, the efficiency of CO(g) oxidation increases because the rate determining step involving CO2 desorption is faster. Subsequently switching off the rather uncertain rate of diffusion of O atoms from the crystal bulk to the surface led to a strong lowering in reaction rates and a stronger dependency of the CO(g) oxidation rate upon O2(g). For example, on increasing the volume mixing ratio of O2(g) from 10-5 to 10-4 for a scenario without diffusion (with Venus-like surface conditions) the percentage conversion of initial CO(g) into CO2(g) increased from ~30% up to ~60%.

  19. Surface Oxide Net Charge of a Titanium Alloy; Comparison Between Effects of Treatment With Heat or Radiofrequency Plasma Glow Discharge

    PubMed Central

    MacDonald, Daniel E.; Rapuano, Bruce E.; Schniepp, Hannes C.

    2010-01-01

    In the current study, we have compared the effects of heat and radiofrequency plasma glow discharge (RFGD) treatment of a Ti6Al4V alloy on the physico-chemical properties of the alloy’s surface oxide. Titanium alloy (Ti6Al4V) disks were passivated alone, heated to 600 °C, or RFGD plasma treated in pure oxygen. RFGD treatment did not alter the roughness, topography, elemental composition or thickness of the alloy’s surface oxide layer. In contrast, heat treatment altered oxide topography by creating a pattern of oxide elevations approximately 50–100 nm in diameter. These nanostructures exhibited a three-fold increase in roughness compared to untreated surfaces when RMS roughness was calculated after applying a spatial high-pass filter with a 200 nm cutoff wavelength. Heat treatment also produced a surface enrichment in aluminum and vanadium oxides. Both RFGD and heat treatment produced similar increases in oxide wettability. Atomic force microscopy (AFM) measurements of metal surface oxide net charge signified by a long range force of attraction to or repulsion from a (negatively charged) silicon nitride AFM probe were also obtained for all three experimental groups. Force measurements showed that the RFGD-treated Ti6Al4V samples demonstrated a higher net positive surface charge at pH values below 6 and a higher net negative surface charge at physiological pH (pH values between 7 and 8) compared to control and heat-treated samples These findings suggest that RFGD treatment of metallic implant materials can be used to study the role of negatively charged surface oxide functional groups in protein bioactivity, osteogenic cell behavior and osseointegration independently of oxide topography. PMID:20880672

  20. Homogeneous surface oxidation of organosilicates by controlled combustion of adsorbed fuels: a facile method for low-temperature processing.

    PubMed

    Feller, Bob E; Deline, Vaughn R; Bass, John; Knoesen, André; Miller, Robert D

    2013-09-25

    We have developed a method for the oxidation of organosilicate materials at temperatures considerably lower than those typically required for uncatalyzed oxidation. The process utilizes a combustible fuel delivered to the surface in an oxidizing environment to locally oxidize materials with carbon-silicon bonds. It also provides a level of control that cannot be achieved through standard high-energy top-to-bottom oxidative procedures such as UV-ozone and O2 plasmas. While the latter processes attack the outer interface, local oxidation can be achieved using our process by manipulating the distribution of the combustible fuel. We use this technique to generate oxidized porous organosilicate films with either a sharp oxidation front or uniform oxidation where the relative carbon content can be controlled through the film thickness depending on processing conditions. Further, we show that this process can also be used to seal bulk interconnected microporosity in films (<1 nm) without substantially changing the refractive index of the material. For both the nominally dense and porous films, the surface oxidation is accompanied by an increase in the Young's modulus and the oxidized films can be readily functionalized using standard silane chemistry to provide a variety of chemical functionalities. PMID:24040934

  1. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. [Quarterly] technical progress report, April--June 1993

    SciTech Connect

    Doyle, F.M.

    1993-06-30

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the eleventh quarter, dry thermal oxidation tests were done on coal samples from the Pennsylvania State Coal Bank. As-received and oxidized coal samples were studied by ion-exchange methods to determine the carboxylate and phenolic group concentrations. Film flotation tests were done to characterize the flotability of as-received and oxidized coals. In addition, electrokinetic tests were done on different coals, to obtain information pertinent to the selection of flotation reagents. DRIFT analysis was done to characterize the structure of coals.

  2. Cell-surface protein disulfide isomerase catalyzes transnitrosation and regulates intracellular transfer of nitric oxide

    PubMed Central

    Zai, Adrian; Rudd, M. Audrey; Scribner, Anne Ward; Loscalzo, Joseph

    1999-01-01

    Since thiols can undergo nitrosation and the cell membrane is rich in thiol-containing proteins, we considered the possibility that membrane surface thiols may regulate cellular entry of NO. Recently, protein disulfide isomerase (PDI), a protein that catalyzes thio–disulfide exchange reactions, has been found on the cell-surface membrane. We hypothesized that cell-surface PDI reacts with NO, catalyzes S-nitrosation reactions, and facilitates NO transfer from the extracellular to intracellular compartment. We observed that PDI catalyzes the S-nitrosothiol–dependent oxidation of the heme group of myoglobin (15-fold increase in the rate of oxidation compared with control), and that NO reduces the activity of PDI by 73.1 ± 21.8% (P < 0.005). To assess the role of PDI in the cellular action of NO, we inhibited human erythroleukemia (HEL) cell-surface PDI expression using an antisense phosphorothioate oligodeoxynucleotide directed against PDI mRNA. This oligodeoxynucleotide decreased cell-surface PDI content by 74.1 ± 9.3% and PDI folding activity by 46.6 ± 3.5% compared with untreated or “scrambled” phosphorothioate oligodeoxynucleotide–treated cells (P < 0.0001). This decrease in cell-surface PDI was associated with a significant decrease in cyclic guanosine monophosphate (cGMP) generation after S-nitrosothiol exposure (65.4 ± 26.7% reduction compared with control; P < 0.05), with no effect on cyclic adenosine monophosphate (cAMP) generation after prostaglandin E1 exposure. These data demonstrate that the cellular entry of NO involves a transnitrosation mechanism catalyzed by cell-surface PDI. These observations suggest a unique mechanism by which extracellular NO gains access to the intracellular environment. PMID:9927500

  3. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

    SciTech Connect

    Khan, Sami; Varanasi, Kripa K.; Azimi, Gisele; Yildiz, Bilge

    2015-02-09

    Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ?3 and a water contact angle of ?15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (?2.2) and becomes hydrophobic (contact angle of ?104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

  4. Toxicity Assessment of Silica Coated Iron Oxide Nanoparticles and Biocompatibility Improvement by Surface Engineering

    PubMed Central

    Malvindi, Maria Ada; De Matteis, Valeria; Galeone, Antonio; Brunetti, Virgilio; Anyfantis, George C.; Athanassiou, Athanassia; Cingolani, Roberto; Pompa, Pier Paolo

    2014-01-01

    We have studied in vitro toxicity of iron oxide nanoparticles (NPs) coated with a thin silica shell (Fe3O4/SiO2 NPs) on A549 and HeLa cells. We compared bare and surface passivated Fe3O4/SiO2 NPs to evaluate the effects of the coating on the particle stability and toxicity. NPs cytotoxicity was investigated by cell viability, membrane integrity, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) assays, and their genotoxicity by comet assay. Our results show that NPs surface passivation reduces the oxidative stress and alteration of iron homeostasis and, consequently, the overall toxicity, despite bare and passivated NPs show similar cell internalization efficiency. We found that the higher toxicity of bare NPs is due to their stronger in-situ degradation, with larger intracellular release of iron ions, as compared to surface passivated NPs. Our results indicate that surface engineering of Fe3O4/SiO2 NPs plays a key role in improving particles stability in biological environments reducing both cytotoxic and genotoxic effects. PMID:24465736

  5. A molecular beacon biosensor based on the nanostructured aluminum oxide surface.

    PubMed

    Che, Xiangchen; He, Yuan; Yin, Haocheng; Que, Long

    2015-10-15

    A new class of molecular beacon biosensors based on the nanostructured aluminum oxide or anodic aluminum oxide (AAO) surface is reported. In this type of sensor, the AAO surface is used to enhance the fluorescent signals of the fluorophore-labeled hairpin DNA. When a target DNA with a complementary sequence to that of the hairpin DNA is applied on the sensor, the fluorophores are forced to move away from the AAO surface due to the hybridization between the hairpin DNA and the target DNA, resulting in the significant decrease of the fluorescent signals. The observed signal reduction is sufficient to achieve a demonstrated detection limit of 10nM, which could be further improved by optimizing the AAO surface. The control experiments have also demonstrated that the bioassay used in the experiments has excellent specificity and selectivity, indicating the great promise of this type of sensor for diagnostic applications. Since the arrayed AAO micropatterns can be fabricated on a single chip in a cost-effective manner, the arrayed sensors could provide an ideal technical platform for studying fundamental biological process and monitoring disease biomarkers. PMID:25988788

  6. The structures of hexadecylamine films adsorbed on iron-oxide surfaces in dodecane and hexadecane.

    PubMed

    Doig, Michael; Camp, Philip J

    2015-02-21

    Molecular-dynamics simulations are used to gain insights on recent sum-frequency spectroscopy and polarised neutron reflectometry measurements of the structure of hexadecylamine films adsorbed on iron-oxide surfaces in dodecane and hexadecane. Simulations were carried out under quiescent and high-shear conditions. Mass-density profiles, molecular-height and molecular-orientation probability distribution functions, and in-layer radial distribution functions were calculated. The simulation results show that at high surface coverage, the film thickness is about 15 Å, and that the molecules are mainly pointing upwards from the surface at an angle of 40-50°. The results are compared critically against published experimental results, and the agreement is found to be good. The in-layer ordering of the hexadecylamine head-group atoms is found to be dictated by the crystalline structure of the iron-oxide surface, but this influence rapidly diminishes along the molecular backbone. The tail-group atoms show almost no positional ordering. Finally, an example calculation of the kinetic friction coefficient under high-shear conditions is presented. The lateral (friction) force is measured as a function of the normal (applied) force, and the kinetic friction coefficient is determined to be about 0.09, which is typical for this kind of system. PMID:25607715

  7. Spectra investigation on surface characteristics of graphene oxide nanosheets treated with tartaric, malic and oxalic acids

    NASA Astrophysics Data System (ADS)

    Teng, Xiyao; Yan, Manqing; Bi, Hong

    2014-01-01

    The surface characteristics of graphene oxide nanosheets (GO) treated respectively with tartaric acid, malic acid and oxalic acid, have been investigated by mainly using optical spectroscopic methods including Fourier transform infrared spectroscopy (FT-IR), Ultraviolet-visible (UV-Vis) absorption and Raman spectroscopy. Additionally, the electrochemical property of the products has also been studied. The data revealed that oxygen-containing groups such as sbnd OH, sbnd COOH and sbnd Cdbnd O on the GO surface have been almost removed and thus reduced graphene oxide nanosheets (RGN) were obtained. Interestingly, the number of sp2 domains of RGN increases as treated by tartaric acid < malic acid < oxalic acid whereas the steric hindrance (SH) decreases and the ionization constant (IC) differs among these three acids. Furthermore, the specific capacitances (Cs) of GO have been greatly promoted from 2.4 F g-1 to 100.8, 112.4, and 147 F g-1 after treated with tartaric, malic and oxalic acids, respectively. This finding agrees well with the spectra result of the tendency of surface conjugated degree alteration. We claim that the difference in both SH and IC among these acids is the main reason for the diverse surface characteristics as well as the improved Cs of the RGN.

  8. Phenol oxidation on the surface of granular activated carbon under water-treatment conditions

    SciTech Connect

    Chin, L.S.

    1989-01-01

    Chemical activity of granular activated carbon (GAC) toward adsorbed phenol were investigated in a fixed bed column. After adsorption from aqueous solution, phenol was oxidized to carbon-carbon (C-C) and carbon-oxygen (C-0) bonded dimers as well as an oxidized compound of uncertain structure (molecular weight 276) as major products. This phenol coupling oxidation was observed on several types of commercial GAC. Various experimental parameters were tested to further characterize the coupling reaction of phenol on F400 GAC. Total product yields (based on adsorbed phenol) were determined based on the amount of phenol removed by GAC, not the initial concentration of input phenol. The ratio of C-C dimer to C-0 dimer increased with the increase of the amount of phenol adsorbed. Also, total product yield was dependent on reaction pH which influenced phenol adsorption onto GAC from aqueous solution. Phenol oxidations on GAC surfaces were also studied in a series of experiments under conditions similar to those commonly met in water treatment. The presence of humic substances from soil or groundwater inhibited phenol oxidation and favored the formation of the C-0 dimer relative to the C-C dimer. The lower total product yield was partially due to the competitive adsorption on active sit and partially to the free radical quenching activity of humic substances. The mechanism of the inhibition of humic substance h been discussed according to the results from syringic acid as a model compound of humic substances and ascorbic acid as a hydrophilic free radical scavenger, which were applied along with phenol onto GAC separately. Free chlorine-oxidized GAC showed less capacity for phenol adsorption than virgin GAC. The lower degree of phenol uptake resulted in lower formation of phenol coupling products on the GAC.

  9. Ozone oxidation of oleic acid surface films decreases aerosol cloud condensation nuclei activity

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Sareen, N.; Lathem, T. L.; Nenes, A.; McNeill, V. F.

    2011-08-01

    Heterogeneous oxidation of aerosols composed of pure oleic acid (C18H34O2, an unsaturated fatty acid commonly found in continental and marine aerosol) by gas-phase O3 is known to increase aerosol hygroscopicity and activity as cloud condensation nuclei (CCN). Whether this trend is preserved when the oleic acid is internally mixed with other electrolytes is unknown and addressed in this study. We quantify the CCN activity of sodium salt aerosols (NaCl and Na2SO4) internally mixed with sodium oleate (SO) and oleic acid (OA). We find that particles containing roughly one monolayer of SO/OA show similar CCN activity to pure salt particles, whereas a tenfold increase in organic concentration slightly depresses CCN activity. O3 oxidation of these multicomponent aerosols has little effect on the critical diameter for CCN activation for unacidified particles at all conditions studied, and the activation kinetics of the CCN are similar in each case to those of pure salts. SO-containing particles which are acidified to atmospherically relevant pH before analysis in order to form oleic acid, however, show depressed CCN activity upon oxidation. This effect is more pronounced at higher organic concentrations. The behavior after oxidation is consistent with the disappearance of the organic surface film, supported by Köhler Theory Analysis (KTA). The ?-Köhler calculations show a small decrease in hygroscopicity after oxidation. The important implication of this finding is that oxidative aging may not always enhance the hygroscopicity of internally mixed inorganic-organic aerosols.

  10. Investigations of adsorption sites on oxide surfaces using solid-state NMR and TPD-IGC

    NASA Astrophysics Data System (ADS)

    Golombeck, Rebecca A.

    The number and chemical identity of reactive sites on surfaces of glass affects the processing, reliability, and lifetime of a number of important commercial products. Surface site densities, distributions, and structural identities are closely tied to the formation and processing of the glass surface, and exert a direct influence on strength and coating performance. The surface of a glass sample may vary markedly from the composition and chemistry of the bulk glass. We are taking a physicochemical approach to understanding adsorption sites on pristine multicomponent glass fibers surfaces, directly addressing the effect of processing on surface reactivity. This project aimed to understand the energy distributions of surface adsorption sites, the chemical/structural identity of those sites, and the relationship of these glasses to glass composition, thermal history, and in future work, surface coatings. We have studied the bulk and surface structure as well as the surface reactivity of the glass fibers with solid-state nuclear magnetic resonance (NMR) spectroscopy, inverse gas chromatography (IGC), and computational chemistry methods. These methods, solid-state NMR and IGC, typically require high surface area materials; however, by using probe molecules for NMR experiments or packing a column at high density for IGC measurements, lower surface area materials, such as glass fibers, can be investigated. The glasses used within this study were chosen as representative specimens of fibers with potentially different reactive sites on their surfaces. The two glass compositions were centered around a nominal E-glass, which contains very little alkali cations and mainly alkaline earth cations, and wool glass, which contains an abundance of alkali cations. The concentration of boron was varied from 0 to 8 mole % in both fiber compositions. Fibers were drawn from each composition at a variety of temperatures and draw speeds to provide a range of glass samples with varying diameters and thermal histories. The bulk structural features in both compositions of glass fibers were identified using high-resolution 29Si, 27Al, and 11B magic-angle spinning (MAS) NMR spectroscopic measurements. In multi-component glasses, the determination of silicon, aluminum, and boron distributions becomes difficult due to the competitive nature of the network-modifying oxides among the network-forming oxides. In pure silicates, 29Si MAS NMR can often resolve resonances arising from silicate tetrahedron having varying numbers of bridging oxygens. In aluminoborosilicate glasses, aluminum is present in four-, five-, and six- coordination with oxygen as neighbors. The speciation of the aluminum can be determined using 27Al MAS NMR. The fraction of tetrahedral boron species in the glass fibers were measured using 11B MAS NMR, which is typically used to study the short-range structure of borate containing glasses such as alkali borate, borosilicate, and aluminoborosilicate glasses. While solid-state NMR is a powerful tool for elucidating bonding environments and coordination changes in the glass structure, it cannot quantitatively probe low to moderate surface area samples due to insufficient spins. Chemical probes either physisorbed or chemisorbed to the fiber's surface can increase the surface selectivity of NMR for analysis of samples with low surface areas and provide information about the local molecular structure of the reactive surface site. Common chemical probe molecules contain NMR active nuclei such as 19F or may be enriched with 13C. A silyating agent, (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), reacts with reactive surface hydroxyls, which can be quantified by utilizing the NMR active nucleus (19F) contained in the probe molecule. The observed 19F MAS NMR peak area is integrated and compared against a standard of known fluorine spins (concentration), allowing the number of reactive hydroxyl sites to be quantified. IGC is a method used to study the surface properties of a material by examining the retention behavior of a probe molecule. The I

  11. Chemisorption and anodic oxidation of aromatic molecules on Pd electrode surfaces: studies by UHV-EC-STM 

    E-print Network

    Chen, Xiaole

    2006-04-12

    The chemisorption and anodic oxidation of hydroquinone (H2Q) and benzoquinone (BQ) at palladium electrode surfaces was studied by a combination of electrochemistry (EC), Auger electron spectroscopy (AES), high-resolution electron...

  12. Effects of prior surface damage on high-temperature oxidation of Fe-, Ni-, and Co-based alloys

    SciTech Connect

    Blau, Peter Julian; Lowe, Tracie M; Pint, Bruce A

    2009-01-01

    Multi-component metallic alloys have been developed to withstand high-temperature service in corrosive environments. Some of these applications, like exhaust valve seats in internal combustion engines, must also resist sliding, impact, and abrasion. The conjoint effects of temperature, oxidation, and mechanical contact can result in accelerated wear and the formation of complex surface layers whose properties differ from those of the base metal and the oxide scale that forms in the absence of mechanical contact. The authors have investigated the effects of prior surface damage, produced by scratch tests, on the localized reformation of oxide layers. Three high-performance commercial alloys, based on iron, nickel, and cobalt, were used as model materials. Thermogravimetric analysis (TGA) was used to determine their static oxidation rates at elevated temperature (850o C). A micro-abrasion, ball-cratering technique was used to measure oxide layer thickness and to compare it with TGA results. By using taper-sectioning techniques and energy-dispersive elemental mapping, a comparison was made between oxide compositions grown on non-damaged surfaces and oxides that formed on grooves produced by a diamond stylus. Microindentation and scratch hardness data revealed the effects of high temperature exposure on both the substrate hardness and the nature of oxide scale disruption. There were significant differences in elemental distribution between statically-formed oxides and those that formed on scratched regions

  13. Oxidation pretreatment to reduce corrosion of 20%Cr-25%Ni-Nb stainless steel. II. Surface morphology and oxide characterization

    SciTech Connect

    Tempest, P.A.; Wild, R.K.

    1988-10-01

    Improved corrosion behavior of 20%Cr-25%Ni-Nb steel resulting from a low pressure oxidation pretreatment in CO/sub 2/ has been related to changes in elemental composition and distribution in the oxide scale. Auger electron spectroscopy, secondary ion mass spectroscopy, electron microprobe, and X-ray diffraction techniques have been used to investigate the properties of the oxide scale formed on both untreated and pretreated specimens when oxidized at 823 K and 923 K in a CO/sub 2/-1%CO atmosphere. A sputter ion plating technique has been used to separate the oxide from the metal and the incorporation of chromium and silicon at the metal-oxide interface has been investigated at grain centers and grain boundaries by depth profiling. The improvement in oxide adhesion and oxidation rates, using data from Parts I and II of this study, is assessed in terms of oxide formation by solid-state displacement reactions.

  14. The Dependence of the Oxidation Enhancement of InP(100) Surface on the Coverage of the Adsorbed Cs

    SciTech Connect

    Sun, Yun

    2010-06-07

    We report the oxidation of the InP(100) surface promoted by adsorbed Cs by synchrotron radiation photoemission. Oxygen exposure causes reduction of the charge transferred to the InP substrate from Cs and the growth of indium oxide and phosphorous oxide. The oxide growth displays a clear dependence on the Cs coverage. The oxidation of phosphorous is negligible up to 1000 L of O{sub 2} exposure when the Cs coverage is less than half a monolayer (ML), but the formation of the second half monolayer of Cs greatly accelerates the oxidation. This different enhancement of the InP oxidation by the first and the second half monolayer of Cs is due to the double layer structure of the adsorbed Cs atoms, and consequently the higher 6s electron density in the Cs atoms when Cs coverage is larger than 0.5 ML.

  15. Surface Decoration of MgO Nanocubes with Sulfur Oxides: Experiment and Theory

    PubMed Central

    2013-01-01

    We investigated the effect of surface sulfate formation on the structure and spectroscopic properties of MgO nanocubes using X-ray diffraction, electron microscopy, several spectroscopic techniques, and ab initio calculations. After CS2 adsorption and oxidative treatment at elevated temperatures the MgO particles remain cubic and retain their average size of ?6 nm. Their low coordinated surface elements (corners and edges) were found to bind sulfite and sulfate groups even after annealing up to 1173 K. The absence of MgO corner specific photoluminescence emission bands at 3.4 and 3.2 eV substantiates that sulfur modifies the electronic properties of characteristic surface structures, which we attribute to the formation of (SO3)2– and (SO4)2– groups at corners and edges. Ab initio calculations support these conclusions and provide insight into the local atomic structures and spectroscopic properties of these groups. PMID:23616910

  16. Surface diffusion control of the photocatalytic oxidation in air/TiO2 heterogeneous reactors

    E-print Network

    Tsekov, R

    2015-01-01

    The diffusion of superoxide radical anions on the surface of TiO2 catalysts is theoretically considered as an important step in the kinetics of photocatalytic oxidation of toxic pollutants. A detailed analysis is performed to discriminate the effects of rotation, anion and adsorption bonds vibrations on the diffusion coefficient. A resonant dependence of the diffusivity on the lattice parameters of the TiO2 surface is discovered showing that the most rapid diffusion takes place when the lattice parameters are twice larger than the bond length of the superoxide radical anions. Whereas the rotation and vibrations normal to the catalyst surface are important, the anion bond vibrations do not affect the diffusivity due to their low amplitudes as compared to the lattice parameters.

  17. Nanostructured sapphire vicinal surfaces as templates for the growth of self-organized oxide nanostructures

    NASA Astrophysics Data System (ADS)

    Thune, E.; Boulle, A.; Babonneau, D.; Pailloux, F.; Hamd, W.; Guinebretière, R.

    2009-11-01

    Vicinal substrates of sapphire with miscut angle of 10° from the (0 0 1) planes towards the [1 1 0] direction have been annealed in air in the range from 1000 to 1500 °C. The behaviour of these surfaces has been characterized as a function of the temperature and the thermal treatment time by Atomic Force Microscopy observations. A thermal treatment at 1250 °C allows to stabilize a surface made of periodically spaced nanosized step-bunches. Such stepped surfaces were used as template to grow self-patterned epitaxial oxide nanoparticles by thermal annealing of yttria-stabilized zirconia thin films produced by sol-gel dip-coating. Grazing Incidence Small Angle X-ray Scattering and High-Resolution Transmission Electron Microscopy were used to study the morphology of the nanoparticles and their epitaxial relationships with the substrate.

  18. Significant electrical control of amorphous oxide thin film transistors by an ultrathin Ti surface polarity modifier

    SciTech Connect

    Cho, Byungsu; Choi, Yonghyuk; Shin, Seokyoon; Jeon, Heeyoung; Seo, Hyungtak; Jeon, Hyeongtag

    2014-01-27

    We demonstrate an enhanced electrical stability through a Ti oxide (TiO{sub x}) layer on the amorphous InGaZnO (a-IGZO) back-channel; this layer acts as a surface polarity modifier. Ultrathin Ti deposited on the a-IGZO existed as a TiO{sub x} thin film, resulting in oxygen cross-binding with a-IGZO surface. The electrical properties of a-IGZO thin film transistors (TFTs) with TiO{sub x} depend on the surface polarity change and electronic band structure evolution. This result indicates that TiO{sub x} on the back-channel serves as not only a passivation layer protecting the channel from ambient molecules or process variables but also a control layer of TFT device parameters.

  19. Low temperature formation of electrode having electrically conductive metal oxide surface

    DOEpatents

    Anders, Simone (Albany, CA); Anders, Andre (Albany, CA); Brown, Ian G. (Berkeley, CA); McLarnon, Frank R. (Orinda, CA); Kong, Fanping (Berkeley, CA)

    1998-01-01

    A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

  20. Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process

    SciTech Connect

    Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young

    2012-11-15

    The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

  1. Surface Structure of Silver Nanoparticles as a Model for Understanding the Oxidative Dissolution of Silver Ions.

    PubMed

    Molleman, Bastiaan; Hiemstra, Tjisse

    2015-12-15

    The toxicity of silver nanoparticles (AgNPs) has been related to the release of ionic silver. This process is influenced by a large variety of factors and is poorly understood. The key to understanding Ag(+) release by AgNPs is its subvalency. This is a fundamental property of Ag that can be elucidated by analyzing the crystal structures of a specific class of Ag materials as well as MO/DFT (molecular orbital/density functional theory)-optimized Ag13(OH)4 clusters, being precursors of AgNPs. Semimetallic silver at the (111) faces of AgNPs has a subvalency of +(1)/3 v.u., forming ?Ag3OH(0) surface groups with a maximum site density of 4.7 sites/nm(2). Oxidative dissolution may remove these groups with the simultaneous formation of oxygen radicals that may further interact with the surface via different pathways. Reactive oxygen species (ROS) can create a circular process with the dissolution of ?Ag3OH(0), exposure of new metallic sites at the underlying lattice, and subsequent oxidation to ?Ag3OH(0). This regeneration process is interrupted by the penetration of O(•) radicals into the lattice, forming highly stable Ag6O octahedra with subvalent silver that protects the AgNP from further oxidation. A thermodynamic model has been developed that quantitatively describes the equilibrium condition between ?Ag3OH(0) and ?Ag6O(0) and explains a large variety of collectively observed phenomena. PMID:26595806

  2. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  3. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  4. Stability and Transport of Graphene Oxide Nanoparticles in Groundwater and Surface Water

    PubMed Central

    Lanphere, Jacob D.; Rogers, Brandon; Luth, Corey; Bolster, Carl H.; Walker, Sharon L.

    2014-01-01

    Abstract The effects of groundwater and surface water constituents (i.e., natural organic matter [NOM] and the presence of a complex assortment of ions) on graphene oxide nanoparticles (GONPs) were investigated to provide additional insight into the factors contributing to fate and the mechanisms involved in their transport in soil, groundwater, and surface water environments. The stability and transport of GONPs was investigated using dynamic light scattering, electrokinetic characterization, and packed bed column experiments. Stability results showed that the hydrodynamic diameter of the GONPs at a similar ionic strength (2.1±1.1?mM) was 10 times greater in groundwater environments compared with surface water and NaCl and MgCl2 suspensions. Transport results confirmed that in groundwater, GONPs are less stable and are more likely to be removed during transport in porous media. In surface water and MgCl2 and NaCl suspensions, the relative recovery was 94%±3% indicating that GONPs will be very mobile in surface waters. Additional experiments were carried out in monovalent (KCl) and divalent (CaCl2) salts across an environmentally relevant concentration range (0.1–10?mg/L) of NOM using Suwannee River humic acid. Overall, the transport and stability of GONPs was increased in the presence of NOM. This study confirms that planar “carbonaceous-oxide” materials follow traditional theory for stability and transport, both due to their response to ionic strength, valence, and NOM presence and is the first to look at GONP transport across a wide range of representative conditions found in surface and groundwater environments. PMID:25053876

  5. Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification

    NASA Astrophysics Data System (ADS)

    Bahl, Sumit; Shreyas, P.; Trishul, M. A.; Suwas, Satyam; Chatterjee, Kaushik

    2015-04-01

    Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

  6. Effects of surface oxide layer on nanocavity formation and silver gettering in hydrogen ion implanted silicon

    SciTech Connect

    Naczas, Sebastian; Huang Mengbing; Yaqoob, Faisal

    2013-07-14

    We have made an investigation of the surface oxide effects on nanocavity formation in hydrogen implanted silicon and the influence of resultant nanocavities on diffusion and gettering of implanted silver atoms. A wafer with a 200-nm SiO{sub 2} surface layer was implanted with 22.5 keV H ions to a dose of 1 Multiplication-Sign 10{sup 17} cm{sup -2}, yielding the concentration peak of implanted H ions at {approx}140 nm below the SiO{sub 2}/Si interface. Subsequently, two sets of Si samples were prepared, depending on whether the oxide layer was etched off before (Group-A) or after (Group-B) post-H-implantation annealing. As evidenced by transmission electron microscopy, Group-A samples exhibited an array of large-sized nanocavities in hexagon-like shape, extending from the surface to the depth {approx}140 nm, whereas a narrow band of sphere-shaped nanocavities of small size was present around 140 nm below the surface in Group-B samples. These Si samples with pre-existing nanocavities were further implanted with Ag ions in the surface region ({approx}40 nm projected range) and post-Ag-implantation annealing was conducted in the temperature range between 600 and 900 Degree-Sign C. Measurements based on Rutherford backscattering spectroscopy revealed much different behaviors for Ag redistribution and defect accumulation in these two sets of samples. Compared to the case for Group-B Si, Group-A Si exhibited a lower concentration of residual defects and a slower kinetics in Ag diffusion as well. We discuss the role of thick surface oxide in point defect generation and recombination, and the consequence on nanocavity formation and defect retention in Si. The properties of nanocavities, e.g., their depth distribution, size, and even shape, are believed to be responsible for the observed disparities between these samples, including an interesting contrast of surface vs. bulk diffusion phenomena for implanted Ag atoms.

  7. Surface analysis of a nano-sized oxide formed on alloy 600 in a high temperature/pressure aqueous solution.

    PubMed

    Kim, Dong-jin; Lim, Yun Soo; Kwon, Hyuk Chul; Hwang, Seong Sik; Kim, Hong Pyo

    2010-01-01

    Even though nickel based Alloy 600 (Ni 75 wt%, Cr 15 wt% and Fe 10 wt%) shows superior corrosion and mechanical properties, numerous corrosion problems, caused by a long time exposure of more than 30 years under a high temperature and high pressure water chemical environment have occurred. Especially, a lead induced stress corrosion cracking (SCC) has been a very important issue. A SCC is deeply related to a nano-sized oxide properties, formed on an Alloy 600 surface, because a crack initiates and propagates through a breakdown and modification of a thin surface oxide formed naturally on Alloy 600 in an aqueous solution. Therefore an investigation of an oxide properties would provide key information to elucidate the mechanism of a SCC and to establish a countermeasure. In the present work, a surface oxide film formed on Alloy 600 in an aqueous solution at 315 degrees C without/with a lead oxide and nickel boride as a SCC accelerator and an inhibitor, respectively, was analyzed by using a transmission electron microscopy, equipped with an energy dispersive X-ray spectroscopy and an X-ray photoelectron spectroscopy, equipped with an ion sputter for a depth profiling. In both the ammonia solutions without/with NiB, a duplex oxide layer was formed, i.e., a porous outer oxide mainly composed of NiO and Ni(OH)2 and a relatively dense inner Cr2O3 layer. Lead was incorporated into the oxide layer leading to a Cr depletion in the oxide layer and a passivity degradation. The passivity of the surface oxide was increased when NiB was added into a solution with PbO, which was in accordance with the increase of the SCC resistance. Passivity degradation by lead and the inhibitive mechanism of nickel boride were explained by a defect chemistry in an oxide semiconductor and an adhesion preference as a function of the wetting angle, respectively. PMID:20352815

  8. Oxidation states of GaAs surface and their effects on neutral beam etching during nanopillar fabrication

    NASA Astrophysics Data System (ADS)

    Thomas, C.; Tamura, Y.; Syazwan, M. E.; Higo, A.; Samukawa, S.

    2014-05-01

    We have investigated a new process for fabricating GaAs sub-20 nm nanopillars that uses a top-down combination of a bio-template and damage-free neutral beam etching. A two-dimensional array of nanoparticles composed of a protein shell embedded with a metal oxide core was formed on the top of a GaAs surface treated by neutral beam oxidation. Because of device requirements, three low-temperature oxygen techniques were investigated for removing the protein shell prior to the etching process: oxygen radical, oxygen neutral beam, and low-temperature oxygen annealing in vacuum (LT-OAV). X-ray photoelectron spectroscopy was used to monitor the effects of the different treatments on the GaAs surface. While the three processes could efficiently remove a protein shell, subsequent oxidation of the GaAs surface showed some differences in the oxide layer composition. Therefore, LT-OAV was selected considering its lower gallium oxide formation. A hydrogen radical process was then performed at temperatures lower than 400 °C to remove the oxide layer prior to etching. This process completely removed arsenide oxide and only residual gallium oxide was found on the surface afterwards. Etching was performed using a pure chlorine neutral beam of GaAs samples with metal oxide core etching masks. We found that control of the Ga-oxide amount on the surface is the key parameter for controlling the diameter and the density of nanopillars. Finally, high-aspect ratio nanopillars using stacked layers of GaAs and AlGaAs were obtained and showed no damage layer.

  9. Surface engineering on CeO2 nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation

    NASA Astrophysics Data System (ADS)

    Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-07-01

    Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c

  10. Near-field spectroscopy of selectively oxidized vertical cavity surface emitting lasers

    SciTech Connect

    Kim, J.; Boyd, J. T.; Jackson, Howard E.; Choquette, K. D.

    2000-01-31

    Selectively oxidized vertical cavity surface emitting lasers (VCSELs) have been studied by spectrally resolved near-field scanning optical microscopy. We have obtained spatially and spectrally resolved images of both subthreshold emission and lasing emission from a selectively oxidized VCSEL operating at a wavelength of 850 nm. Below threshold, highly local high gain regions, emitting local intensity maxima within the active area, were observed; these were found to serve as lasing centers just above threshold. Above threshold, the near-field spatial modal distributions of low order transverse modes were identified by spectrally analyzing the emission; these were found to be complex and somewhat different from those measured in the far field. (c) 2000 American Institute of Physics.

  11. Preparation, characterization and dissolution of passive oxide film on the 400 series stainless steel surfaces

    NASA Astrophysics Data System (ADS)

    Sathyaseelan, V. S.; Rufus, A. L.; Chandramohan, P.; Subramanian, H.; Velmurugan, S.

    2015-12-01

    Full system decontamination of Primary Heat Transport (PHT) system of Pressurised Heavy Water Reactors (PHWRs) resulted in low decontamination factors (DF) on stainless steel (SS) surfaces. Hence, studies were carried out with 403 SS and 410 SS that are the material of construction of "End-Fitting body" and "End-Fitting Liner tubes". Three formulations were evaluated for the dissolution of passive films formed over these alloys viz., i) Two-step process consisting of oxidation and reduction reactions, ii) Dilute Chemical Decontamination (DCD) and iii) High Temperature Process. The two-step and high temperature processes could dissolve the oxide completely while the DCD process could remove only 60%. Various techniques like XRD, Raman spectroscopy and SEM-EDX were used for assessing the dissolution process. The two-step process is time consuming, laborious while the high temperature process is less time consuming and is recommended for SS decontamination.

  12. Electronic structure of nitinol surfaces oxidized by low-energy ion bombardment

    SciTech Connect

    Petravic, M. Varasanec, M.; Peter, R.; Kavre, I.; Metikos-Hukovic, M.; Yang, Y.-W.

    2014-06-28

    We have studied the electronic structure of nitinol exposed to low-energy oxygen-ion bombardment, using x-ray photoemission spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. XPS spectra reveal a gradual transformation of nitinol surfaces into TiO{sub 2} with increased dose of implanted oxygen. No oxidation of Ni atoms has been detected. NEXAFS spectra around O K-edge and Ti L{sub 2,3}-edge, reflecting the element-specific partial density of empty electronic states, exhibit features, which can be attributed to the creation of molecular orbitals, crystal field splitting, and the absence of long-range order, characteristic of the amorphous TiO{sub 2}. Based on these results, we discuss the oxidation kinetics of nitinol under low-energy oxygen-ion bombardment.

  13. Nanoscale Surface Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing Voltage Fade.

    PubMed

    Zheng, Fenghua; Yang, Chenghao; Xiong, Xunhui; Xiong, Jiawen; Hu, Renzong; Chen, Yu; Liu, Meilin

    2015-10-26

    Lithium-rich layered oxides are promising cathode materials for lithium-ion batteries and exhibit a high reversible capacity exceeding 250?mAh?g(-1) . However, voltage fade is the major problem that needs to be overcome before they can find practical applications. Here, Li1.2 Mn0.54 Ni0.13 Co0.13 O2 (LLMO) oxides are subjected to nanoscale LiFePO4 (LFP) surface modification. The resulting materials combine the advantages of both bulk doping and surface coating as the LLMO crystal structure is stabilized through cationic doping, and the LLMO cathode materials are protected from corrosion induced by organic electrolytes. An LLMO cathode modified with 5?wt?% LFP (LLMO-LFP5) demonstrated suppressed voltage fade and a discharge capacity of 282.8?mAh?g(-1) at 0.1?C with a capacity retention of 98.1?% after 120 cycles. Moreover, the nanoscale LFP layers incorporated into the LLMO surfaces can effectively maintain the lithium-ion and charge transport channels, and the LLMO-LFP5 cathode demonstrated an excellent rate capacity. PMID:26335589

  14. Structure and surface and catalytic properties of Mg-Al basic oxides

    SciTech Connect

    Cosimo, J.I.D.; Diez, V.K.; Apesteguia, C.R.; Xu, M.; Iglesia, E.

    1998-09-10

    Mg-Al mixed oxides with Mg/Al molar ratios of 0.5--9.0 were obtained by thermal decomposition of precipitated hydrotalcite precursors. The effect of composition on structure and surface and catalytic properties was studied by combining several characterization methods with ethanol conversion reactions. The nature, density, and strength of surface basic sites depended on the Al content. The catalyst activity and selectivity of Mg-Al mixed oxides in ethanol conversion reactions depended on composition. The dehydrogenation of ethanol to acetaldehyde and the aldol condensation to n-butanol both involved the initial surface ethoxide formation on a Lewis acid-strong base pair. The dehydration of ethanol to ethylene, and the coupling and dehydration to diethyl ether increased with Al content, probably reflecting the density increase of both Al{sup 3+}-O{sup 2{minus}} pairs and low- and medium-strength basic sites. Pure Al{sub 2}O{sub 3} displayed the highest dehydration activity.

  15. Surface-Related States in Oxidized Silicon Nanocrystals Enhance Carrier Relaxation and Inhibit Auger Recombination

    PubMed Central

    2008-01-01

    We have studied ultrafast carrier dynamics in oxidized silicon nanocrystals (NCs) and the role that surface-related states play in the various relaxation mechanisms over a broad range of photon excitation energy corresponding to energy levels below and above the direct bandgap of the formed NCs. Transient photoinduced absorption techniques have been employed to investigate the effects of surface-related states on the relaxation dynamics of photogenerated carriers in 2.8 nm oxidized silicon NCs. Independent of the excitation photon energy, non-degenerate measurements reveal several distinct relaxation regions corresponding to relaxation of photoexcited carriers from the initial excited states, the lowest indirect states and the surface-related states. Furthermore, degenerate and non-degenerate measurements at difference excitation fluences reveal a linear dependence of the maximum of the photoinduced absorption (PA) signal and an identical decay, suggesting that Auger recombination does not play a significant role in these nanostructures even for fluence generating up to 20 carriers/NC.

  16. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  17. Strontium oxide segregation at SrLaAlO4 surfaces A.E. Becerra-Toledo , L.D. Marks

    E-print Network

    Marks, Laurence D.

    Strontium oxide segregation at SrLaAlO4 surfaces A.E. Becerra-Toledo , L.D. Marks Northwestern surfaces We report observable segregation of strontium oxide at the surface of strontium lanthanum-dispersive X-ray spectroscopy showed that Sr and O segregation occurs on strontium lanthanum aluminate surfaces

  18. Initial Backbond Oxidation at an Unpaired Dangling Bond Site on a Hydrogen-Terminated Si(100)2×1 Surface

    NASA Astrophysics Data System (ADS)

    Kajiyama, Hiroshi; Heike, Seiji; Hitosugi, Taro; Hashizume, Tomihiro

    1998-11-01

    The oxidation reaction at an unpaired dangling bond (DB) site on a hydrogen-terminated Si(100)2×1 surface was studied using an ultrahigh-vacuum scanning tunneling microscope. The surface image was observed in situ during the exposure to O2 molecules at room temperature. During exposure, the unpaired DBs induced structural changes around themselves, and they were mostly localized on one side of a Si dimer bond. We conclude that the backbonds near an unpaired DB were preferentially oxidized, following the dissociation of O2 molecules at the unpaired DB site. Based on high-resolution measurements, models of backbond-oxidized-structure were proposed.

  19. Method and apparatus for detecting the presence and thickness of carbon and oxide layers on EUV reflective surfaces

    DOEpatents

    Malinowski, Michael E.

    2005-01-25

    The characteristics of radiation that is reflected from carbon deposits and oxidation formations on highly reflective surfaces such as Mo/Si mirrors can be quantified and employed to detect and measure the presence of such impurities on optics. Specifically, it has been shown that carbon deposits on a Mo/Si multilayer mirror decreases the intensity of reflected HeNe laser (632.8 nm) light. In contrast, oxide layers formed on the mirror should cause an increase in HeNe power reflection. Both static measurements and real-time monitoring of carbon and oxide surface impurities on optical elements in lithography tools should be achievable.

  20. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, [March--May 1992

    SciTech Connect

    Doyle, F.M.

    1992-06-30

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

  1. Photo-driven oxidation of water on ?-Fe2O3 surfaces: an ab initio study.

    PubMed

    Nguyen, Manh-Thuong; Seriani, Nicola; Piccinin, Simone; Gebauer, Ralph

    2014-02-14

    Adopting the theoretical scheme developed by the Nørskov group [see, for example, Nørskov et al., J. Phys. Chem. B 108, 17886 (2004)], we conducted a density functional theory study of photo-driven oxidation processes of water on various terminations of the clean hematite (?-Fe2O3) (0001) surface, explicitly taking into account the strong correlation among the 3d states of iron through the Hubbard U parameter. Six best-known terminations, namely, Fe?Fe?O3? (we call S1), O?Fe?Fe?(S2), O2?Fe?Fe?(S3), O3?Fe?Fe? (S4), Fe?O3?Fe? (S5), and O?Fe?O3?(S6), are first exposed to water, the stability of resulting surfaces is investigated under photoelectrochemical conditions by considering different chemical reactions (and their reaction free energies) that lead to surfaces covered by O atoms or/and OH groups. Assuming that the water splitting reaction is driven by the redox potential for photogenerated holes with respect to the normal hydrogen electrode, UVB, at voltage larger than UVB, most 3-oxygen terminated substrates are stable. These results thus suggest that the surface, hydroxylated in the dark, should release protons under illumination. Considering the surface free energy of all the possible terminations shows that O3–S5 and O3–S1 are the most thermodynamically stable. While water oxidation process on the former requires an overpotential of 1.22 V, only 0.84 V is needed on the latter. PMID:24527933

  2. Formation of paramagnetic defects in oxide glasses during the bombardment of their surface with charged particles

    SciTech Connect

    Bogomolova, L.D.; Stefanovsky, S.V.; Teplyakov, Y.G.; Dmitriev, S.A.

    1997-12-31

    In the present work some results of EPR study of point defects formed in silicate, borate, borosilicate, phosphate and other oxide glasses irradiated with different charge particles (C, N, O, Ar, Mn, Cu, Pb) at energy E = 150 keV and large total fluence of ions (up to 10{sup 17} cm{sup {minus}2}) are reported. Electron paramagnetic resonance (EPR) is a very sensitive technique which gives information on the structure of point defects and their content. It is shown that in some cases (for example, in borate glasses) the oxygen hole centers similar to ones observed in {gamma}-irradiated glasses are formed after ion bombardment. However, in the majority of cases new defects which are not typical of {gamma}-irradiated oxide glasses were found. They were large molecular oxygen ions (O{sub 2}{sup {minus}}, O{sub 3}{sup {minus}}, O{sub 4}{sup {minus}}) located in the cavities formed under ion bombardment in the near surface layer of glass. It should be noted that the relative content of these defects is of the order of several tens per 1,000 incident ions. This content decreases with increasing fluence and atomic mass of incident ions. It indicates indirectly that point defects are clustered when the damage of the near surface layer becomes strong. The formation of gaseous oxygen is possible in cavities of the damage surface layer. It was found that some elements (for example C, N and transition metals) form chemical compounds with oxygen. The migration of alkali ions promotes the formation of such compounds since the chemical compounds were detected by means EPR in glasses rich in alkali oxides.

  3. Vibrational spectra of CO adsorbed on oxide thin films: A tool to probe the surface defects and phase changes of oxide thin films

    SciTech Connect

    Savara, Aditya

    2014-03-15

    Thin films of iron oxide were grown on Pt(111) single crystals using cycles of physical vapor deposition of iron followed by oxidative annealing in an ultrahigh vacuum apparatus. Two procedures were utilized for film growth of ?15–30 ML thick films, where both procedures involved sequential deposition+oxidation cycles. In procedure 1, the iron oxide film was fully grown via sequential deposition+oxidation cycles, and then the fully grown film was exposed to a CO flux equivalent to 8 × 10{sup ?7} millibars, and a vibrational spectrum of adsorbed CO was obtained using infrared reflection-absorption spectroscopy. The vibrational spectra of adsorbed CO from multiple preparations using procedure 1 show changes in the film termination structure and/or chemical nature of the surface defects—some of which are correlated with another phase that forms (“phase B”), even before enough of phase B has formed to be easily detected using low energy electron diffraction (LEED). During procedure 2, CO vibrational spectra were obtained between deposition+oxidation cycles, and these spectra show that the film termination structure and/or chemical nature of the surface defects changed as a function of sequential deposition+oxidation cycles. The authors conclude that measurement of vibrational spectra of adsorbed CO on oxide thin films provides a sensitive tool to probe chemical changes of defects on the surface and can thus complement LEED techniques by probing changes not visible by LEED. Increased use of vibrational spectra of adsorbed CO on thin films would enable better comparisons between films grown with different procedures and by different groups.

  4. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    SciTech Connect

    Sato, Soshi Honjo, Hiroaki; Niwa, Masaaki; Ikeda, Shoji; Ohno, Hideo; Endoh, Tetsuo

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400?°C for 1?h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1?nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

  5. Adsorption and reaction of NO on oxidized and reduced SrTiO3(100) surfaces

    NASA Astrophysics Data System (ADS)

    Azad, S.; Szanyi, J.; Peden, C. H. F.; Wang, L.-Q.

    2003-07-01

    Adsorption and reaction of NO on oxidized and reduced SrTiO3(100) surfaces have been studied using temperature programmed desorption (TPD). Major desorption peaks for NO from the fully oxidized surface are found at 140 and 260 K, along with a long tail that continues up to 500 K. The desorption features at 140 and 260 K correspond to activation energies of 36 and 66 kJ/mol, respectively, using a simple Redhead analysis. NO reacts nondissociatively on the fully oxidized surface. Reactivity of reduced SrTiO3(100) is relatively higher than that of the fully oxidized surface and is influenced by the adsorption temperature of the NO molecules on the surface. NO and N2O are the major desorption products following adsorption of NO on the reduced surface at 110 K. Desorption of N2O from significantly reduced SrTiO3(100) indicates that the oxygen atoms of the adsorbed NO molecules are preferentially extracted by the surface oxygen vacancy sites, whereas the surface oxidizes as a result of the deoxygenation of the adsorbates. Adsorption of NO on the reduced surface at 297 K is followed by breakage of the N-O bond producing adsorbed N and O atoms and recombination of these adspecies results in desorption of NO and N2 from this surface. Adsorption of NO on the significantly reduced surface at 200 K is followed by desorption of NO, N2, and N2O as TPD products and the reactivity of this surface at 200 K presumably is a composite of the behavior observed for NO adsorption at 110 and 297 K.

  6. Adsorption and Reaction of NO on Oxidized and Reduced SrTiO{sub 3} (100) Surfaces

    SciTech Connect

    Azad, Samina; Szanyi, Janos; Peden, Charles HF.; Wang, Li Q.

    2003-07-01

    Adsorption and reaction of NO on oxidized and reduced SrTiO{sub 3}(100) surfaces have been studied using temperature programmed desorption (TPD). Major desorption peaks for NO from the fully oxidized surface as found at 140 and 260 K, along with a long tail that continues up to 500 K. The desorption features at 140 and 260 K correspond to activation energies of 36 and 66 kJ/mol, respectively, using a simple Redhead analysis. NO reacts non-dissociatively on the fully oxidized surface. Reactivity of reduced SrTiO{sub 3}(100) is relatively higher than that of the fully oxidized surface and is influenced by the adsorption temperature of the NO molecules on the surface. NO and N{sub 2}O are the major desorption products following adsorption of NO on the reduced surface at 110 K. Desorption of N{sub 2}O from significantly reduced SrTiO{sub 3}(100) indicates that the oxygen atoms of the adsorbed NO molecules are preferentially extracted by the surface oxygen vacancy sites whereas the surface oxidizes as a result of the de-oxygenation of the adsorbates. Adsorption of NO on the reduced surface at 297 K is followed by breakage of the N-O bond producing adsorbed N and O atoms and recombination of these ad-species results in desorption of NO and N{sub 2} from this surface. Adsorption of NO on the significantly reduced surface at 200 K is followed by desorption of NO, N{sub 2} and N{sub 2}O as TPD products and the reactivity of this surface at 200 K presumable is a composite of the behavior observed for NO adsorption at 110 and 297 K.

  7. Surface analysis of Pu oxide powders: thermal dehydration/water vapor rehydration studies

    NASA Astrophysics Data System (ADS)

    Farr, J. Douglas; Schulze, Roland K.; Neu, Mary P.; Morales, Luis A.

    2000-07-01

    This work investigates the chemical nature of the surfaces of Pu oxide powders, primarily to help address issues that are critical for plutonium stabilization and 50-year storage. The interface between solid PuO2 particles, adsorbed materials and the surrounding vapor phase plays a dominant role in determining reactions which affect the chemistry of the resultant atmosphere surrounding the solids. Understanding the chemistry at this interface, particularly with respect to reactions with water and water vapor, is crucial for predicting the storage behavior of these powders.

  8. A critical study of the role of the surface oxide layer in titanium bonding

    NASA Technical Reports Server (NTRS)

    Dias, S.; Wightman, J. P.

    1983-01-01

    Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

  9. Characterization of the surface changes during the activation of erbium/erbium oxide for hydrogen storage.

    SciTech Connect

    Zavadil, Kevin Robert; Snow, Clark Sheldon; Brumbach, Michael Todd

    2010-09-01

    Erbium is known to effectively load with hydrogen when held at high temperature in a hydrogen atmosphere. To make the storage of hydrogen kinetically feasible, a thermal activation step is required. Activation is a routine practice, but very little is known about the physical, chemical, and/or electronic processes that occur during Activation. This work presents in situ characterization of erbium Activation using variable energy photoelectron spectroscopy at various stages of the Activation process. Modification of the passive surface oxide plays a significant role in Activation. The chemical and electronic changes observed from core-level and valence band spectra will be discussed along with corroborating ion scattering spectroscopy measurements.

  10. Surface enhanced Raman scattering of biospecies on anodized aluminum oxide films

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Smirnov, A. I.; Hahn, D.; Grebel, H.

    2007-06-01

    Traditionally, aluminum and anodized aluminum oxide films (AAO) are not the platforms of choice for surface-enhanced raman scattering (SERS) experiments despite of the aluminum's large negative permittivity value. Here we examine the usefulness of aluminum and nanoporous alumina platforms for detecting soft biospecies ranging from bacterial spores to protein markers. We used these flat platforms to examine SERS of a model protein (cytochrome c from bovine heart tissue) and bacterial cells (spores of Bacillus subtilis ATCC13933 used as Anthrax simulant) and demonstrated clear Raman amplification.

  11. Effect of oxidation temperature on microstructure, mechanical behaviors and surface morphology of nanocomposite Ti-Cx-Ny thin films

    NASA Astrophysics Data System (ADS)

    Lu, Y. H.; Wang, J. P.; Shen, Y. G.

    2011-01-01

    Two nanocomposite Ti-Cx-Ny thin films, TiC0.95N0.60 and TiC2.35N0.68, as well as one pure TiN, were deposited at 500 °C on Si(1 0 0) substrate by reactive unbalanced dc-magnetron sputtering. Oxidation experiments of these films were carried out in air at fixed temperatures in a regime of 250-600 °C with an interval of 50 °C. As-deposited and oxidized films were characterized and analyzed using X-ray diffraction (XRD), microindentation, Newton's ring methods and atomic force microscopy (AFM). It was found that the starting oxidation temperature of nanocomposite Ti-Cx-Ny thin films was 300 °C irrespective of the carbon content; however their oxidation rate strongly depended on their carbon content. Higher carbon content caused more serious oxidation. After oxidation, the film hardness value remained up to the starting oxidation temperature, followed by fast decrease with increasing heating temperature. The residual compressive stress did not show a similar trend with the hardness. Its value was first increased with increase of heating temperature, and got its maximum at the starting oxidation temperature. A decrease in residual stress was followed when heating temperature was further increased. The film surface roughness value was slightly increased with heating temperature till the starting oxidation temperature, a great decrease in surface roughness was followed with further increase of heating temperature.

  12. CO Oxidation at the Interface of Au Nanoclusters and the Stepped-CeO2(111) Surface

    SciTech Connect

    Kim H. Y.; Henkelman, G.

    2013-01-14

    To reveal the richer chemistry of CO oxidation by CeO2 supported Au Nanoclusters NCs)/Nanoparticles, we design a Au12 supported on a stepped-CeO2 model (Au/CeO2-step) and study various kinds of CO oxidation mechanisms at the interface of the Au/CeO2-step: oxygen spillover from the CeO2 to the Au NCs;2 CO oxidation by the O2 bound to the Au-Ce3+ interface;3 and CO oxidation by the Mars-van Krevelen (M-vK) mechanism.4 DFT+U calculations show that lattice oxygen at the CeO2 step edge oxidizes CO bound to Au NCs by the M-vK mechanism. CO2 desorption determines the rate of CO oxidation and the vacancy formation energy (Evac) is a reactivity descriptor for CO oxidation. The maximum Evac that insures spontaneous CO2 production is higher for the Au/CeO2-step than the Au/CeO2-surface suggesting that the CeO2-step is a better supporting material than the CeO2-surface for CO oxidation by the Au/CeO2. Our results also suggest that for CO oxidation by Au NCs supported on nano- or meso-structured CeO2, which is the case of industrial catalysts, the M-vK mechanism accounts for a large portion of the total activity.

  13. Biomass Oxidation: Formyl C-H Bond Activation by the Surface Lattice Oxygen of Regenerative CuO Nanoleaves.

    PubMed

    Amaniampong, Prince N; Trinh, Quang Thang; Wang, Bo; Borgna, Armando; Yang, Yanhui; Mushrif, Samir H

    2015-07-27

    An integrated experimental and computational investigation reveals that surface lattice oxygen of copper oxide (CuO) nanoleaves activates the formyl C-H bond in glucose and incorporates itself into the glucose molecule to oxidize it to gluconic acid. The reduced CuO catalyst regains its structure, morphology, and activity upon reoxidation. The activity of lattice oxygen is shown to be superior to that of the chemisorbed oxygen on the metal surface and the hydrogen abstraction ability of the catalyst is correlated with the adsorption energy. Based on the present investigation, it is suggested that surface lattice oxygen is critical for the oxidation of glucose to gluconic acid, without further breaking down the glucose molecule into smaller fragments, because of C-C cleavage. Using CuO nanoleaves as catalyst, an excellent yield of gluconic acid is also obtained for the direct oxidation of cellobiose and polymeric cellulose, as biomass substrates. PMID:26119659

  14. Optical Property and the Relationship between Resistivity and Surface Roughness of Indium Tin Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Tang, Wu; Chao, Yipeng; Weng, Xiaolong; Deng, Longjiang; Xu, Kewei

    Indium tin oxide (ITO) films with high visible transmittance were fabricated on polymethyl methacrylate (PMMA) flexible substrate at room temperature by radio frequency (RF) magnetron sputtering. The deposition rate, microstructure, surface roughness, electrical and optical properties of these films have been investigated as a function of Ar partial pressure from 0.2- 1.4 Pa. The microstructure and surface morphology of ITO films were studied using X-ray diffraction (XRD) and atomic force microscopy (AFM), the resistivity was investigated by four-point probe technology, and the optical transmittance was determined by UV-Vis spectrophotometer. The results show that the resistivity of the ITO film decreases with increasing Ar partial pressure from 0.2 Pa to 0.8 Pa, and then increases with increasing Ar partial pressure from 0.8 Pa to 1.4 Pa. The resistivity varied from 1.25×10-3 ?.cm to 2.33 ×10-3 ?.cm and the average transmission in the visible range was 90%. It was also found that the microstructure is amorphous and the surface roughness decreases from 1.438 nm to 0.813 nm with increasing Ar partial pressure to 1.1 Pa. The most interesting fact is that the resistivity increases with the increasing surface roughness, which indicates that the surface roughness also plays an important role in electrical properties of the ITO films.

  15. Surface stress relaxation of oxide glasses: The effects on mechanical strength

    NASA Astrophysics Data System (ADS)

    Lezzi, Peter Joseph

    A new glass strengthening mechanism based upon surface compressive stress formation by surface stress relaxation of glasses that were held under a tensile stress, at a temperature lower than the glass transition temperature, in low water vapor pressure, has been demonstrated. Although glass fibers are traditionally known to become mechanically weaker when heat-treated at a temperature lower than the glass transition temperature in the presence of water vapor, the strength was found to become greater than the as-received fiber strength when fibers were subjected to a sub-critical tensile stress during heat-treatment. The observed strengthening was attributed to surface compressive residual stress formation through surface stress relaxation during the sub-critical tensile stress application in the atmosphere containing water vapor. Surface stress relaxation of the same glass fibers was shown to take place under conditions identical to those experienced by the strengthened mechanical test specimens by observing permanent bending of the fiber. Furthermore, the magnitude and presence of the residual stresses formed during bending or tensile heat-treatments were confirmed by FTIR, fiber etching, and fiber slicing methods. The method can in principle be used to strengthen any oxide glass and is not subjected to the constraints of traditional strengthening methods such as a minimum thickness for tempering, or a glass containing alkali ions for ion-exchange. Thus far, the method has been successful in strengthening silica glass, E-glass, and soda-lime silicate glass by approximately 20-30%.

  16. Surface morphology of ultrathin graphene oxide films obtained by the SAW atomization

    NASA Astrophysics Data System (ADS)

    Balachova, Olga V.; Balashov, Sergey M.; Costa, Carlos A. R.; Pavani Filho, A.

    2015-08-01

    Lately, graphene oxide (GO) thin films have attracted much attention: they can be used as humidity-sensitive coatings in the surface acoustic wave (SAW) sensors; being functionalized, they can be used in optoelectronic or biodevices, etc. In this research we study surface morphology of small-area thin GO films obtained on Si and quartz substrates by deposition of very small amounts of H2O-GO aerosols produced by the SAW atomizer. An important feature of this method is the ability to work with submicrovolumes of liquids during deposition that provides relatively good control over the film thickness and quality, in particular, minimization of the coffee ring effect. The obtained films were examined using AFM and electron microscopy. Image analysis showed that the films consist of GO sheets of different geometry and sizes and may form discrete or continuous coatings at the surface of the substrates with the minimum thickness of 1.0-1.8 nm which corresponds to one or two monolayers of GO. The thickness and quality of the deposited films depend on the parameters of the SAW atomization (number of atomized droplets, a volume of the initial droplet, etc.) and on sample surface preparation (activation in oxygen plasma). We discuss the structure of the obtained films, uniformity and the surface coverage as a function of parameters of the film deposition process and sample preparation. Qualitative analysis of adhesion of GO films is made by rinsing the samples in DI water and subsequent evaluation of morphology of the remained films.

  17. Effect of atomic layer deposition coatings on the surface structure of anodic aluminum oxide membranes.

    PubMed

    Xiong, Guang; Elam, Jeffrey W; Feng, Hao; Han, Catherine Y; Wang, Hsien-Hau; Iton, Lennox E; Curtiss, Larry A; Pellin, Michael J; Kung, Mayfair; Kung, Harold; Stair, Peter C

    2005-07-28

    Anodic aluminum oxide (AAO) membranes were characterized by UV Raman and FT-IR spectroscopies before and after coating the entire surface (including the interior pore walls) of the AAO membranes by atomic layer deposition (ALD). UV Raman reveals the presence of aluminum oxalate in bulk AAO, both before and after ALD coating with Al2O3, because of acid anion incorporation during the anodization process used to produce AAO membranes. The aluminum oxalate in AAO exhibits remarkable thermal stability, not totally decomposing in air until exposed to a temperature >900 degrees C. ALD was used to cover the surface of AAO with either Al2O3 or TiO2. Uncoated AAO have FT-IR spectra with two separate types of OH stretches that can be assigned to isolated OH groups and hydrogen-bonded surface OH groups, respectively. In contrast, AAO surfaces coated by ALD with Al2O3 display a single, broad band of hydrogen-bonded OH groups. AAO substrates coated with TiO2 show a more complicated behavior. UV Raman results show that very thin TiO2 coatings (1 nm) are not stable upon annealing to 500 degrees C. In contrast, thicker coatings can totally cover the contaminated alumina surface and are stable at temperatures in excess of 500 degrees C. PMID:16852765

  18. Natural Oxidation of Black Carbon in Soils: Changes in Molecular Form and Surface Charge along a Climosequence

    SciTech Connect

    Cheng, Chih-hsin; Lehmann, Johannes C.; Engelhard, Mark H.

    2008-03-15

    The aim of this work was to investigate changes in molecular form and surface charge of black carbon (BC) due to longtermnatural oxidation and to examine how climatic and soil factors affect BC oxidation. Black C was collected from 11 historical charcoal blast furnace sites with a geographic distribution from Quebec, Canada, to Georgia, USA, and compared to BC that was newly produced (new BC) using rebuilt historical kilns. The results showed that the historical BC samples were substantially oxidized after 130 years in soils as compared to new BC or BC incubated for one year. The major alterations by natural oxidation of BC included: (1) changes in elemental composition with increases in oxygen (O) from 7.2% in new BC to 24.8% in historical BC and decreases in C from 90.8% to 70.5%; (2) formation of oxygen-containing functional groups, particularly carboxylic and phenolic functional groups, and (3) disappearance of surface positive charge and evolution of surface negative charge after 12 months of incubation. Although time of exposure significantly increased natural oxidation of BC, a significant positive relationship between mean annual temperature (MAT) and BC oxidation (O/C ratio with r = 0.83;P < 0.01) explained that BC oxidation was increased by 87 mmole kg C?1 per unit Celsius increase in MAT. This long-term oxidation was more pronounced on BC surfaces than for entire particles, and responded 7-fold stronger to increases in MAT. Our results also indicated that oxidation of BC was more important than adsorption of non-BC. Thus, natural oxidation of BC may play an important role in the effects of BC on soil biogeochemistry.

  19. Natural oxidation of black carbon in soils: Changes in molecular form and surface charge along a climosequence

    NASA Astrophysics Data System (ADS)

    Cheng, Chih-Hsin; Lehmann, Johannes; Engelhard, Mark H.

    2008-03-01

    The aim of this work was to investigate changes in molecular form and surface charge of black carbon (BC) due to long-term natural oxidation and to examine how climatic and soil factors affect BC oxidation. Black C was collected from 11 historical charcoal blast furnace sites with a geographic distribution from Quebec, Canada, to Georgia, USA, and compared to BC that was newly produced (new BC) using rebuilt historical kilns. The results showed that the historical BC samples were substantially oxidized after 130 years in soils as compared to new BC or BC incubated for one year. The major alterations by natural oxidation of BC included: (1) changes in elemental composition with increases in oxygen (O) from 7.2% in new BC to 24.8% in historical BC and decreases in C from 90.8% to 70.5%; (2) formation of oxygen-containing functional groups, particularly carboxylic and phenolic functional groups, and (3) disappearance of surface positive charge and evolution of surface negative charge after 12 months of incubation. Although time of exposure significantly increased natural oxidation of BC, a significant positive relationship between mean annual temperature (MAT) and BC oxidation (O/C ratio with r = 0.83; P < 0.01) explained that BC oxidation was increased by 87 mmole kg C -1 per unit Celsius increase in MAT. This long-term oxidation was more pronounced on BC surfaces than for entire particles, and responded 7-fold stronger to increases in MAT. Our results also indicated that oxidation of BC was more important than adsorption of non-BC. Thus, natural oxidation of BC may play an important role in the effects of BC on soil biogeochemistry.

  20. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  1. Effect of Surface Preparation on the 815°C Oxidation of Single-Crystal Nickel-Based Superalloys

    NASA Astrophysics Data System (ADS)

    Sudbrack, Chantal K.; Beckett, Devon L.; MacKay, Rebecca A.

    2015-09-01

    A primary application for single-crystal superalloys has been jet engine turbine blades, where operation temperatures reach well above 1000°C. The NASA Glenn Research Center is considering use of single-crystal alloys for future, lower temperature application in the rims of jet engine turbine disks. Mechanical and environmental properties required for potential disk rim operation at 815°C are being examined, including the oxidation and corrosion behavior, where there is little documentation at intermediate temperatures. In this study, single-crystal superalloys, LDS-1101+Hf and CMSX-4+Y, were prepared with different surface finishes and compared after isothermal and cyclic oxidation exposures. Surface finish has a clear effect on oxide formation at 815°C. Machined low-stress ground surfaces after exposure for 440 h produce thin Al2O3 external scales, which is consistent with higher temperature oxidation, whereas polished surfaces with a mirror finish yield much thicker NiO external scales with subscale of Cr2O3-spinel-Al2O3, which may offer less reliable oxidation resistance. Additional experiments separate the roles of cold-work, localized deformation, and the extent of polishing and surface roughness on oxide formation.

  2. Effect of Surface Preparation on the 815°C Oxidation of Single-Crystal Nickel-Based Superalloys

    NASA Astrophysics Data System (ADS)

    Sudbrack, Chantal K.; Beckett, Devon L.; MacKay, Rebecca A.

    2015-11-01

    A primary application for single-crystal superalloys has been jet engine turbine blades, where operation temperatures reach well above 1000°C. The NASA Glenn Research Center is considering use of single-crystal alloys for future, lower temperature application in the rims of jet engine turbine disks. Mechanical and environmental properties required for potential disk rim operation at 815°C are being examined, including the oxidation and corrosion behavior, where there is little documentation at intermediate temperatures. In this study, single-crystal superalloys, LDS-1101+Hf and CMSX-4+Y, were prepared with different surface finishes and compared after isothermal and cyclic oxidation exposures. Surface finish has a clear effect on oxide formation at 815°C. Machined low-stress ground surfaces after exposure for 440 h produce thin Al2O3 external scales, which is consistent with higher temperature oxidation, whereas polished surfaces with a mirror finish yield much thicker NiO external scales with subscale of Cr2O3-spinel-Al2O3, which may offer less reliable oxidation resistance. Additional experiments separate the roles of cold-work, localized deformation, and the extent of polishing and surface roughness on oxide formation.

  3. Manganese-Cobalt Mixed Spinel Oxides as Surface Modifiers for Stainless Steel Interconnects of Solid Oxide Fuel Cells

    SciTech Connect

    Xia, Gordon; Yang, Z Gary; Stevenson, Jeffry W.

    2006-11-06

    Ferritic stainless steels are promising candidates for interconnect applications in low- and mid-temperature solid oxide fuel cells (SOFCs). A couple of issues however remain for the particular application, including the chromium poisoning due to chromia evaporation, and long-term surface and electrical stability of the scale grown on these steels. Application of a manganese colbaltite spinel protection layer on the steels appears to be an effective approach to solve the issues. For an optimized performance, Mn{sub 1+x}Co{sub 2-x}O{sub 4} (-1 {le} x {le} 2) spinels were investigated against properties relative for protection coating applications on ferritic SOFC interconnects. Overall it appears that the spinels with x around 0.5 demonstrate a good CTE match to ceramic cell components, a relative high electrical conductivity, and a good thermal stability up to 1,250 C. This was confirmed by a long-term test on the Mn{sub 1.5}Co{sub 1.5}O{sub 4} protection layer that was thermally grown on Crofer22 APU, indicating the spinel protection layer not only significantly decreased the contact resistance between a LSF cathode and the stainless steel interconnects, but also inhibited the sub-scale growth on the stainless steels.

  4. The role of chemical structural conversions on solid surfaces in the formation of singlet oxygen and its participation in the catalytic oxidation of napthalene

    SciTech Connect

    Zav'yalov, S.A.; Mysnikov, I.A.; Zav'yalova, L.M.

    1986-03-01

    This paper elucidates the role of structural changes in the catalyst surface in some heterogeneous catalytic oxidations, using as an example the oxidation of naphthalene to phthalic anhydride over freshly ground quartz and a vanadium oxide catalyst. The oxidation of partly reduced vanadium oxide is accompanied by /sup 1/O/sub 2/ emission, which stops when the oxide is completely oxidized. These results are evidence that certain nonequilibrium processes in the solid cause the emission of singlet oxygen. There is reason to assume that the emission results from changes in chemical structure in the layers near the catalyst surface. Data are presented on which such a conclusion is based.

  5. Surface Potential Control on Thin Oxide Films with Respect to Electron Stimulated Desorption Studies

    NASA Astrophysics Data System (ADS)

    Bernheim, Marc; Rousse, Gilles

    1995-09-01

    These experiments deal with the study of desorption of negative ions stimulated by low energy electron collisions on insulating surfaces covered with various adsorbates. For such investigation a careful control of the sample surface potential is required to set the incident electron energy accurately as well as to identify the desorbed species by mass spectrometry. Most of the reported experiments concern this surface potential control. We show that, for very thin SiO2 films thermally grown on silicon substrates, a tunnel conduction might set the surface potential accurately. This assertion mainly relies on recording the intensity of electrons transmitted through thin oxides as well as the intensity of backscattered and secondary electrons re-emitted from the surface. A direct comparison of the O^- ion energy distributions confirms the correct control of the surface potential for a large range of incident electron energies. In such condition we noticed that the O^- desorption yields just swiftly varied with incident electron energy. In particular no modification could be detected as the incident electron energy passed the various Auger excitation levels. The discrepancy between this last result and the published data is discussed in the last part of this paper. Des collisions électroniques sur des surfaces peuvent provoquer une éjection d'ions négatifs formés à partir des molécules adsorbées suivant un processus résonnant à très basse énergie. Pour étendre ces études expérimentales aux surfaces isolantes, un contrôle précis du potentiel superficiel devient indispensable tant pour fixer l'énergie finale des électrons sur la surface que pour effectuer la spectrométrie des ions désorbés. L'examen de surfaces de silice en couche mince montre comment une conduction tunnel intervient pour fixer le potentiel des surfaces examinées. Ces travaux expérimentaux effectués dans une configuration de miroir électrostatique reposent principalement sur l'enregistrement des variations de l'intensité des électrons transmis au travers de l'oxyde et de celle des électrons rétrodiffusés par la surface lorsque les potentiels appliqués sont modifiés. La comparaison des distributions énergétiques des ions O^- émis par l'oxyde fournit un contrôle direct de ces résultats. Ces ions résultent d'une décomposition de la silice provoquée par le bombardement électronique. Mais notre montage n'a nullement permis de reproduire les variations rapides de rendement de “désorption” au voisinage des seuils d'excitation Auger du silicium rapportés par d'autres auteurs. A notre avis, différents artefacts expérimentaux ont très vraisemblablement perturbé leurs investigations.

  6. Experimental Oxidation of Iron Sulphides from Intertidal Surface Sediments: Stable Isotope Effects (S, O, C)

    NASA Astrophysics Data System (ADS)

    Ebersbach, F.; Böttcher, M. E.; Al-Raei, A. M.; Segl, M.

    2009-04-01

    Top intertidal sediments show a pronounced zone of activities of sulphate-reducing bacteria. Iron sulfides may be formed, but a substantial part is reoxidized to sulfate. Microbial or chemical reoxidation can be further enhanced by a resuspension of surface sediments by tidal currents or storms. The rates of the different processes depend on the site-secific sedimentological properties (e.g., grain size, iron and sulphur contents etc.). In the present study 3 different areas of the German Wadden Sea were studied: a mud flat in the Jade Bay, and sandy sediments in the intertidals of Spiekeroog and Sylt islands. The latter site is part of an in-situ lugworm-exclusion experiment. The goal was the experimental and field investigation of the fate of iron sulfides and the formation of sulphate upon resuspension of intertidal surface sediments in oxygenated seawater. All sites were geochemically analyzed for dissolved and solid phase iron, manganese, sulphur and carbon phases/species, and sulphate reduction rates were measured using radiotracers. Dissolved chloride and grain sizes analysis where additionally carried out. TOC, S and metal phase contents were higher in mud compared to sandy sediments. Field results demonstrate gross but only minor net sulphide production and a downcore increases in FeS contents, due to intense sulphide oxidation at the surface. Pyrite, on the other hand, was abundant through the sediments due to continuous sediment reworking. The fate of iron-sulphides and accumulation of sulphate as a function of time was followed in batch experiments using dark suspensions of surface sediments in site-bottom waters at room temperature. During the experiments, each sample was shaken continuously under exposition to oxygen, and sub-samples were taken at the beginning and after discrete time intervalls. A very fast oxidation rate of AVS led to a complete exhaustion within a day, whereas Cr(II)-reducible sulfur was inititially built up and then decreased. This observation can be explained by a formation of S° and FeOOH, followed by the oxidation of pyrite. The dissolved species (SO4/Cl ratios) reflected the continuous accumulation of sulphate as an oxidation product. Dissolved inorganic carbonate (DIC) concentrations decreased upon reaction progress, due to the liberation of protons upon iron sulphide oxidation and degassing of carbon dioxide. The 13C/12C ratio of the residual DIC increased due to the preferential desorption of 12CO2. 34S and 18O contents of dissolved sulphate further show process specific isotope discrimination. The experiments demonstrate the importance of oxidation on the fate of FeS , but less pyrite and the formation of sulphate from resuspended intertidal surface sediments. Acknowledgements: The authors gratefully acknowledge discussions and field advice by N. Volkenborn, and financial support from Deutsche Forschungsgemeinschaft during DFG-SPP ‚BioGeoChemistry of the Wadden Sea' (JO 307/4, BO 1584/4), Max Planck Society, and Leibniz-IO Warnemünde.

  7. Bioactive surface modification of metal oxides via catechol-bearing modular peptides: multivalent-binding, surface retention, and peptide bioactivity.

    PubMed

    Tang, Wen; Policastro, Gina M; Hua, Geng; Guo, Kai; Zhou, Jinjun; Wesdemiotis, Chrys; Doll, Gary L; Becker, Matthew L

    2014-11-19

    A series of multivalent dendrons containing a bioactive osteogenic growth peptide (OGP) domain and surface-binding catechol domains were obtained through solid phase synthesis, and their binding affinity to hydroxyapatite, TiO2, ZrO2, CeO2, Fe3O4 and gold was characterized using a quartz crystal microbalance with dissipation (QCM-d). Using the distinct difference in binding affinity of the bioconjugate to the metal oxides, TiO2-coated glass slides were selectively patterned with bioactive peptides. Cell culture studies demonstrated the bioavailability of the OGP and that OGP remained on the surface for at least 2 weeks under in vitro cell culture conditions. Bone sialoprotein (BSP) and osteocalcein (OCN) markers were upregulated 3-fold and 60-fold, respectively, relative to controls at 21 days. Similarly, 3-fold more calcium was deposited using the OGP tethered dendron compared to TiO2. These catechol-bearing dendrons provide a fast and efficient method to functionalize a wide range of inorganic materials with bioactive peptides and have the potential to be used in coating orthopaedic implants and fixation devices. PMID:25343707

  8. Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

    NASA Technical Reports Server (NTRS)

    Manthiram, Arumugam (Inventor); Wu, Yan (Inventor)

    2010-01-01

    The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

  9. X-ray photoelectron spectroscopy of surface-treated indium-tin oxide thin films

    NASA Astrophysics Data System (ADS)

    Kim, J. S.; Ho, P. K. H.; Thomas, D. S.; Friend, R. H.; Cacialli, F.; Bao, G.-W.; Li, S. F. Y.

    1999-12-01

    Angle-resolved X-ray photoelectron spectroscopy and photothermal deflection spectroscopy are used to study the oxygen-plasma or aquaregia treated indium-tin oxide (ITO) anodes for organic light-emitting diodes. Detailed analysis of the O1s core-level spectra and their dependence on photoemission angle was performed. The results indicate the presence of different chemical forms of oxygen atoms (two types of O 2-, OH -, organic oxygens and H 2O) which evolve with surface treatment. We find that the treatments lead to a modification of the surface chemical states and therefore of the physico-chemical properties of ITO, which in turn control the performance of organic light-emitting diodes.

  10. Preparation, characterization and properties of novel covalently surface-functionalized zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Sato, Moriyuki; Harada, Hajime; Morito, Shigekazu; Fujita, Yasuhisa; Shimosaki, Shunsuke; Urano, Takeshi; Nakamura, Morihiko

    2010-05-01

    Novel covalently surface-modified zinc oxide (ZnO) nanoparticles (NP) (ZHIE) were successfully prepared, which have organic chains composed of hydrophilic amide and urethane linkages, and terminal amino groups on the surfaces, using zinc acetate monohydrate. FTIR spectroscopy, X-ray analysis and TEM observation suggested that the resultant ZHIE NPs have the mean sizes of about 10 nm in diameters, the organic chains linking the amino groups in the terminals and wurtzite crystal structure. UV-vis absorption spectrum of the ZHIE NPs in methanol showed maximum absorption band at 348 nm, supporting the TEM observations. Photoluminescent spectrum measurements depicted that the ZHIE NPs show broad visible emission band on the basis of trapped-electron emission. Cytotoxicity and phagocytosis assays suggested that the ZHIE NPs are noncytotoxic, and the ZHIE-labeled zymosan particles derived by conjugation of the ZHIE NPs with zymosan are internalized into the cells and generate fluorescence based on the ZHIE NPs.

  11. Pattern formation during the CO oxidation on Pt(110) surfaces under global coupling

    NASA Astrophysics Data System (ADS)

    Falcke, M.; Engel, H.

    1994-10-01

    A reaction-diffusion model for CO oxidation on Pt(110) single crystals proposed by Krischer, Eiswirth, and Ertl is supplemented by an equation for the balance of CO partial pressure in the gas phase. This allows us to study the interaction of local and global coupling with the dynamics of the reaction in the oscillatory regime. In absence of global coupling a stability analysis of the homogeneous oscillatory state predicts parameter regions with negative values of the phase diffusion coefficient indicating the possibility of phase turbulence. In the globally coupled system without diffusion we observe the formation of phase-locked clusters of oscillators and irregular behavior. If both surface diffusion and global coupling through the gas phase are taken into account depending on the range of external parameters we get the following types of structures: phase flips, standing waves, spatially irregular coverage pattern, and the uniformly oscillating surface.

  12. Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

    DOEpatents

    Manthiram, Arumugam (Austin, TX); Wu, Yan (Austin, TX)

    2010-03-16

    The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

  13. Correlation between surface chemistry and ion energy dependence of the etch yield in multicomponent oxides etching

    SciTech Connect

    Berube, P.-M.; Poirier, J.-S.; Margot, J.; Stafford, L.; Ndione, P. F.; Chaker, M.; Morandotti, R.

    2009-09-15

    The influence of surface chemistry in plasma etching of multicomponent oxides was investigated through measurements of the ion energy dependence of the etch yield. Using pulsed-laser-deposited Ca{sub x}Ba{sub (1-x)}Nb{sub 2}O{sub 6} (CBN) and SrTiO{sub 3} thin films as examples, it was found that the etching energy threshold shifts toward values larger or smaller than the sputtering threshold depending on whether or not ion-assisted chemical etching is the dominant etching pathway and whether surface chemistry is enhancing or inhibiting desorption of the film atoms. In the case of CBN films etched in an inductively coupled Cl{sub 2} plasma, it is found that the chlorine uptake is inhibiting the etching reaction, with the desorption of nonvolatile NbCl{sub 2} and BaCl{sub 2} compounds being the rate-limiting step.

  14. Resolving the two-dimensional self-assembly of iron oxide nanoparticles on a liquid surface

    NASA Astrophysics Data System (ADS)

    Hu, Jiayang; Zhang, Datong; Lu, Chenguang; Lee, Seung Whan; Ye, Fan; Herman, Irving P.

    2015-03-01

    In situ small-angle X-ray scattering (SAXS) is used to monitor the self-assembly of iron oxide nanoparticles (NPs) dispersed in alkanes that are drop-cast on a diethylene glycol liquid surface. We found that the surface separations of NP cores in 2D superlattices (SLs) are generally farther apart than in 3D SLs with corresponding NPs. At these separations, the van der Waals (vdW) energy is smaller than the Brownian motion energy and so the previous 3D vdW force driven self-assembly models fail to explain the stable closed-packed structure. Strong ligand-ligand interactions likely bind the structure after the upper solvent dries. Entropy effects are found not to be the likely driving force for the observed close packing structures.

  15. Natural oxidation of black carbon in soils: Changes in molecular form and surface charge along a climosequence

    E-print Network

    Lehmann, Johannes

    Natural oxidation of black carbon in soils: Changes in molecular form and surface charge along was to investigate changes in molecular form and surface charge of black carbon (BC) due to long- term natural. All rights reserved. 1. INTRODUCTION Black carbon (BC) is the residue of incomplete combus- tion

  16. Tuning the Electron Gas at an Oxide Heterointerface via Free Surface Charges

    SciTech Connect

    Bell, Christopher

    2011-08-11

    Oxide heterointerfaces are emerging as one of the most exciting materials systems in condensed matter science. One remarkable example is the LaAlO{sub 3}/SrTiO{sub 3} (LAO/STO) interface, a model system in which a highly mobile electron gas forms between two band insulators, exhibiting two dimensional superconductivity and unusual magnetotransport properties. An ideal tool to tune such an electron gas is the electrostatic field effect. In principle, the electrostatic field can be generated by bound charges due to polarization (as in the normal and ferroelectric field effects) or by adding excess free charge. In previous studies, a large modulation of the carrier density and mobility of the LAO/STO interface has been achieved using the normal field effect. However, little attention has been paid to the field effect generated by free charges. This issue is scarcely addressed, even in conventional semiconductor devices, since the free charges are typically not stable. Here, we demonstrate an unambiguous tuning of the LAO/STO interface conductivity via free surface charges written using conducting atomic force microscopy (AFM). The modulation of the carrier density was found to be reversible, nonvolatile and surprisingly large, {approx}3 x 10{sup 13} cm{sup -2}, comparable to the maximum modulation by the normal field effect. Our finding reveal the efficiency of free charges in controlling the conductivity of this oxide interface, and suggest that this technique may be extended more generally to other oxide systems.

  17. Oxidation resistant peroxide cross-linked UHMWPE produced by blending and surface diffusion

    NASA Astrophysics Data System (ADS)

    Gul, Rizwan M.; Oral, Ebru; Muratoglu, Orhun K.

    2014-06-01

    Ultra-high molecular weight polyethylene (UHMWPE) has been widely used as acetabular cup in total hip replacement (THR) and tibial component in total knee replacement (TKR). Crosslinking of UHMWPE has been successful used to improve its wear performance leading to longer life of orthopedic implants. Crosslinking can be performed by radiation or organic peroxides. Peroxide crosslinking is a convenient process as it does not require specialized equipment and the level of crosslinking can be manipulated by changing the amount of peroxide added. However, there is concern about the long-term stability of these materials due to possible presence of by-products. Vitamin E has been successfully used to promote long-term oxidative stability of UHMWPE. In this study, UHMWPE has been crosslinked using organic peroxide in the presence of Vitamin E to produce an oxidation resistant peroxide crosslinked material. Crosslinking was performed both in bulk by mixing peroxide and resin, and only on the surface using diffusion of peroxides.The results show that UHMWPE can be crosslinked using organic peroxides in the presence of vitamin E by both methods. However, the level of crosslinking decreases with the increase in vitamin E content. The wear resistance increases with the increase in crosslink density, and oxidation resistance significantly increases due to the presence of vitamin E.

  18. Ultimate modulation bandwidth of 850 nm oxide-confined vertical-cavity surface-emitting lasers

    NASA Astrophysics Data System (ADS)

    Bobrov, M. A.; Blokhin, S. A.; Maleev, N. A.; Kuzmenkov, A. G.; Blokhin, A. A.; Zadiranov, Yu M.; Troshkov, S. I.; Ledentsov, N. N.; Ustinov, V. M.

    2015-11-01

    Complex influence of photon lifetime (controlled by the mirror loss) and aperture size on the performance of 850 nm InGaAlAs oxide-confined vertical-cavity surface-emitting lasers (VCSELs) with fully doped AlGaAs-based distributed Bragg reflectors (DBR) was investigated. We find a tradeoff between photon lifetime and gain nonlinearity for maximizing the optical bandwidth, leading to the optimum aperture size close to 4-6 ?m. In spite of the reduced photon lifetime (from 4 ps to 1 ps), the excess damping caused by the current-induced self-heating limits the ultimate modulation bandwidth for the given VCSELs design at 24-25 GHz. Further improvement in high frequency characteristics can be facilitated by decrease of the heat generation and improvement of the heat removal from the active region as well as by proper engineering of the scattering loss at the oxide aperture while keeping the low capacitance optimizing design of the oxide aperture.

  19. Study of Interfacial Interactions Using Thing Film Surface Modification: Radiation and Oxidation Effects in Materials

    SciTech Connect

    Sridharan, Kumar; Zhang, Jinsuo

    2014-01-09

    Interfaces play a key role in dictating the long-term stability of materials under the influence of radiation and high temperatures. For example, grain boundaries affect corrosion by way of providing kinetically favorable paths for elemental diffusion, but they can also act as sinks for defects and helium generated during irradiation. Likewise, the retention of high-temperature strength in nanostructured, oxide-dispersion strengthened steels depends strongly on the stoichiometric and physical stability of the (Y, Ti)-oxide particles/matrix interface under radiation and high temperatures. An understanding of these interfacial effects at a fundamental level is important for the development of materials for extreme environments of nuclear reactors. The goal of this project is to develop an understanding stability of interfaces by depositing thin films of materials on substrates followed by ion irradiation of the film-substrate system at elevated temperatures followed by post-irradiation oxidation treatments. Specifically, the research will be performed by depositing thin films of yttrium and titanium (~500 nm) on Fe-12%Cr binary alloy substrate. Y and Ti have been selected as thin-film materials because they form highly stable protective oxides layers. The Fe-12%Cr binary alloy has been selected because it is representative of ferritic steels that are widely used in nuclear systems. The absence of other alloying elements in this binary alloy would allow for a clearer examination of structures and compositions that evolve during high-temperature irradiations and oxidation treatments. The research is divided into four specific tasks: (1) sputter deposition of 500 nm thick films of Y and Ti on Fe-12%Cr alloy substrates, (2) ion irradiation of the film-substrate system with 2MeV protons to a dose of 2 dpa at temperatures of 300°C, 500°C, and 700°C, (3) oxidation of as-deposited and ion-irradiated samples in a controlled oxygen environment at 500°C and 700°C, (4) multi-scale computational modeling involving first- principle molecular dynamics (FPMD) and coarse-grained dissipative particle dynamics (DPD) approaches to develop theories underlying the evolution and stability of structures and phases. Samples from Tasks 1 to 3 (above) will be rigorously characterized and analyzed using scanning electron microscopy, Auger electron microscopy, x-ray diffraction, Rutherford back scatter spectroscopy, and transmission electron microscopy. Expected outcomes of the experimental work include a quantitative understanding film-substrate interface mixing, evolution of defects and other phases at the interface, interaction of interfaces with defects, and the ability of the Y and Ti films to mitigate irradiation-assisted oxidation.The aforementioned experimental work will be closely coupled with multi-scale molecular dynamics (MD) modeling to understand the reactions at the surface, the transport of oxidant through the thin film, and the stabilities of the deposited thin films under radiation and oxidation. Simulations of materials property changes under conditions of radiation and oxidation require multiple size domains and a different simulation scheme for each of these domains. This will be achieved by coupling the FPMD and coarse-grained kinetic Monte Carlo (KMC). This will enable the comparison of the results of each simulation approach with the experimental results.

  20. Final Report for DOE Support of 5th the International Workshop on Oxide Surfaces (IWOX-V)

    SciTech Connect

    Charles T. Campbell

    2007-02-02

    The 5th International Workshop on Oxide Surfaces (IWOX-V) was held at Granlibakken Conference center in Lake Tahoe, CA, January 7-12. The total attendance was ~90. The breakdown of attendees by country is as follows: USA 41 Germany 18 Japan 7 UK 5 Italy 5 France 4 Austria 3 Denmark 3 Cech. Repub. 1 Ireland 1 New Zealand 1 India 1 The technical program included oral sessions on the electronic and magnetic properties of oxide surfaces, surface and interface structure, advances in theory, surface defects, thin film oxides on metals and on oxides, thin film metals on oxides, surface photochemistry, surface reactivity, and interactions with water. Two evening poster sessions had similar themes. As in previous years, the program stimulated significant interest and discussion among the attendees. The local expenses (food and lodging, $918 per person) for eight foreign invited speakers were covered by BES funds. In addition, partial reimbursement for travel ($328 per person) was supported by BES funds for two more foreign invited speakers.

  1. Nitrate reduction coupled with pyrite oxidation in the surface sediments of a sulfide-rich ecosystem

    NASA Astrophysics Data System (ADS)

    Hayakawa, Atsushi; Hatakeyama, Mizuho; Asano, Ryoki; Ishikawa, Yuichi; Hidaka, Shin

    2013-06-01

    studies of denitrification have focused on organic carbon as an electron donor, but reduced sulfur can also support denitrification. Few studies have reported nitrate (NO3-) reduction coupled with pyrite oxidation and its stoichiometry in surface sediments, especially without experimental pyrite addition. In this study, we evaluated NO3- reduction coupled with sulfur oxidation by long-term incubation of surface sediments from a sulfide-rich ecosystem in Akita Prefecture, Japan. The surface sediments were sampled from a mud pool and a riverbed. Fresh sediments and water were incubated under anoxic conditions (and one oxic condition) at 20°C. NO3- addition increased the SO42- concentration and decreased the NO3- concentration. SO42- production (?SO42-) was strongly and linearly correlated with NO3- consumption (?NO3-) during the incubation period (R2 = 0.983, P < 0.01, and n = 8), and the slope of the regression (?NO3-/?SO42-) and the stoichiometry indicated sulfur-driven NO3- reduction by indigenous autotrophic denitrifying bacteria. Framboidal pyrite and marcasite (both FeS2) were present in the sediments and functioned as the electron donors for autotrophic denitrification. Both ?NO3- and ?SO42- were higher in the riverbed sediment than in the mud pool sediment, likely because of the higher amount of easily oxidizable S (pyrite) in the riverbed sediment. Consistently low ammonium (NH4+) concentrations indicated that NO3- reduction by dissimilatory NO3- reduction to NH4+ was small but could not be disregarded. Our results demonstrate that sulfide-rich ecosystems with easily oxidizable metal-bound sulfides such as FeS2 near the ground surface may act as denitrification hot spots.

  2. Surface properties of photo-oxidized bituminous coals. Technical progress report, July--September 1995

    SciTech Connect

    Mitchell, G.; Polat, H.; Davis, A.; Chander, S.

    1995-11-01

    During this report period, a new whole-seam channel sample (Ohio {number_sign}4a) was collected and analyzed, together with the Upper Banner and Splash Dam samples obtained last quarter. These additions bring to seven the number of coals obtained for this project and that range in rank from hvCb to mvb. Polished blocks of each coal containing 3-4 mm wide vitrain bands were prepared for contact angle measurements of fresh and photo-oxidized surfaces. An advancing-drop technique was used to measure contact angle. In this test a droplet of distilled water is grown initially on fresh surfaces and then moved across those irradiated in blue-light for 1, 5, and 10 minutes. The sequence of growth was recorded on video tape, and the change in contact angle measured relative to position at the air/water/surface interface. Contact angles were measured on five of the coals collected for this study, namely the Illinois {number_sign}6, Ohio {number_sign}4a, Lower Kittanning (PSOC-1563), Pittsburgh and Splash Dam seams. Preliminary results show that both coal rank and irradiation time influence surface wettability as measured by contact angle. With one exception, contact angle values decreased and remained low when the droplet advanced into an irradiated area. In most cases, one minute of irradiation resulted in only a slight decrease in contact angle, whereas after 5 and 10 minutes a more significant decrease was observed. The magnitude of change in contact angle values with degree of photo-oxidation decreased as rank increased, such that lower rank bituminous coals show the greatest change and medium volatile coal the least.

  3. The effect of surface characteristics of reduced graphene oxide on the performance of a pseudocapacitor

    NASA Astrophysics Data System (ADS)

    Chang, M. S.; Kim, T.; Kang, J. H.; Park, J.; Park, C. R.

    2015-03-01

    In this research, we have analyzed the electrochemical characteristics of the different rGO/Co3O4 composites prepared by controlling the rGO surface characteristics and its relationship between the growth of Co3O4 nanoparticles and the performance of the pseudocapacitor. Reduced graphene oxide/cobalt oxide (rGO/Co3O4) nanocomposites of different morphologies were prepared through the simple hydrothermal method. First, different kinds of graphite precursors, crumpled and planar with different properties, were used to determine the most suitable substrate to grow Co3O4 nanoparticles. As a result, rGO/Co3O4 composite synthesized from planar graphite shows a higher specific capacitance of 207.2, 170.1, and 141.5 Fg-1 at 1, 2, and 5 Ag-1 than the one prepared from crumpled graphite. In the second part, planar graphite, confirmed to be the most suitable substrate from the previous part, was oxidized under various oxidation conditions to increase the oxygen functional groups attached on the GO surfaces and observed to see how it affects the growth of Co3O4 nanoparticles and its influence on the electrochemical performance of the rGO/Co3O4 pseudocapacitor. As a result, the one with the largest amount of functional groups had the Co3O4 nanoparticles well dispersed and grown on the rGO substrate in small nanoparticle sizes, as small as 5.9 nm, leading to an improved electrochemical performance. Thus, the specific capacitance with the least amount of oxygen functional groups are 207.2, 170.1, and 141.5 Fg-1 and for the largest amount of functional groups are 411.5, 371.4, and 292.7 Fg-1, at 1, 2, and 5 Ag-1 respectively. This approach could become a guideline for the ideal fabrication of rGO/metal oxide composite for further research involving rGO based pseudocapacitors.

  4. Aluminium metallisation of argon and oxygen plasma-modified polycarbonate thin film surfaces

    NASA Astrophysics Data System (ADS)

    Rastomjee, C. S.; Keil, M.; Sotobayashi, H.; Bradshaw, A. M.; Lamont, C. L. A.; Gador, D.; Umbach, E.

    1998-12-01

    The influence of plasma treatment on the metallisation of polycarbonate surfaces was studied using X-ray absorption spectroscopy (XAFS) and core level X-ray photoelectron spectroscopy (XPS). Thin films of two different molecules were chosen: bis-phenol-A polycarbonate with phenol endgroups (P-PC) prepared ex situ by the spin-coating technique onto MoTe 2{0001}surfaces, and the model compound bis-phenol-A polycarbonate ( n=1) with tert-butyl phenyl endgroups (tBP-PC) evaporated in situ in UHV onto Cu{110}, Ag{100} and Ag{111} surfaces with film thicknesses of up to several monolayers. Surfaces of untreated samples and of samples which were pre-treated with either an inert argon or a reactive oxygen microwave plasma were metallised with Al (evaporated by electron beam heating) at film thicknesses ranging from the sub-monolayer region up to several monolayers. For the untreated surface, XAFS and XPS spectra suggest that the Al reacts with the carbonate groups leading to a breaking of the C?O double bonds (and/or a reduction in bond order) as well as formation of Al oxide, Al hydroxide and Al-O-C linkages. A study of the time-dependent oxidation of the evaporated Al leads to the conclusion that Al slowly diffuses to the reactive sites in the first few subsurface layers of the polymer. Argon plasma treatment of samples leads to a reduction in the number of carbonyl groups in the near surface region. After metal deposition a higher ratio of metallic, non-reacted, Al was observed covering the polycarbonate surface and the diffusion rate into the polymer bulk seems to be higher than in the case of the untreated surface. Oxygen plasma treatment leads to the creation of additional C?O containing species which also react with the Al in the subsequent metallisation process. Here, the ratio of oxidised Al on the polymer surface is higher than observed for untreated and argon plasma pre-treated polymer surfaces.

  5. Water-Gas Shift Activity of Cu Surfaces and Cu Nanoparticles Supported on Metal Oxides

    SciTech Connect

    Rodriguez, J.; Liu, P; Wang, X; Wen, W; Hanson, J; Hrbek, J; Perez, M; Evans, J

    2009-01-01

    Oxide supported Cu catalysts show significant activity for the water-gas shift reaction (WGS, CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) but their performance is not fully understood and is highly dependent on the synthesis conditions or the nature of the oxide support. This article describes a series of new studies examining the water-gas shift activity of Cu/MgO(1 0 0) surfaces and compares it to the activities found for pure copper systems, Cu nanoparticles in contact with well-defined surfaces of TiO{sub 2}, ZnO, MoO{sub 2} and CeO{sub 2}, and Cu cations present in mixed-metal oxides. Catalytic tests performed over CuFe{sub 2}O{sub 4}, Ce{sub 1-x}Cu{sub x}O{sub 2} or CuMoO{sub 4} show significant WGS activity only when the Cu cations in the mixed-metal oxide are reduced to metallic copper. Thus, Cu nanoparticles were deposited on different oxide surfaces and their WGS activity was measured in a batch reactor (P{sub CO} = 20 Torr; P{sub H{sub 2}O} = 10 Torr; T = 575-650 K). The WGS activity of the Cu nanoparticles supported on MgO(1 0 0) was 2-3 times larger than that of Cu(1 0 0). Even better WGS catalysts were obtained when Cu was deposited on CeO{sub 2}(1 1 1) or TiO{sub 2}(1 1 0). An apparent activation energy of 13.8 kcal/mol was found for the WGS on Cu/MgO(1 0 0). This is smaller than the value of 15.2 kcal/mol observed on Cu(1 0 0), and substantially larger than the values of 7-9 kcal/mol seen for the apparent activation energies of the Cu/CeO2(1 1 1) and Cu/TiO2(1 1 0) catalysts. Post-reaction surface characterization pointed to the lack of O vacancies in the Cu/MgO(1 0 0) catalysts. This is in contrast to results found for Cu/CeO{sub 2}(1 1 1) and Cu/TiO{sub 2}(1 1 0), where the oxide support exhibits a significant concentration of O vacancies as a consequence of the WGS reaction. The oxygen vacancies present in Cu/CeO{sub 2}(1 1 1) and Cu/TiO{sub 2}(1 1 0) help in the dissociation of the water molecule and reduce the apparent activation energy for the WGS process. Such a phenomenon cannot occur on the Cu/MgO(0 0 1) catalysts, and the main steps of the WGS probably take place on the Cu nanoparticles.

  6. Nitric oxide-flux dependent bacterial adhesion and viability at fibrinogen-coated surfaces

    PubMed Central

    Nichols, Scott P.; Schoenfisch, Mark H.

    2013-01-01

    Nitric oxide (NO) is an endogenous antibacterial agent produced by immune cells in response to pathogens. Herein, the NO fluxes necessary to reduce bacterial adhesion of different bacteria (S. aureus, methicillin-resistant S. aureus, S. epidermidis, E. faecalis, E. coli, and P. aeruginosa) were investigated to ascertain the sensitivity of these bacteria to NO. S-nitrosothiol NO donor-modified xerogels were selected as a model NO-release surface due to their extended NO-release kinetics relative to other NO donor systems. The xerogels were coated with poly(vinyl chloride) (PVC) to achieve consistent surface energy between NO-releasing and control substrates. Fibrinogen was pre-adsorbed to these materials to more accurately mimic conditions encountered in blood and promote bacteria adhesion. Nitric oxide fluxes ranging from 20–50 pmol cm?2 s?1 universally inhibited the bacterial adhesion by >80% for each strain studied. Maximum bacteria killing activity (reduced viability by 85–98%) was observed at the greatest NO payload (1700 nmol cm?2). PMID:24288588

  7. Photo-Catalytic Oxidation of Gaseous Mercury over Titanium Dioxide Surface

    NASA Astrophysics Data System (ADS)

    Snider, G.; Ariya, P.

    2009-12-01

    Hg0(g) is photocatalytically oxidized by TiO2 under a mercury lamp. In our experiments we have seen this effect can be produced in 1L chambers. Photocatalysis done on a 1 ?m layer of TiO2 on quartz glass radiated by a mercury lamp. Gaseous mercury was measured by gas chromatography coupled to mass spectrometry (GC-MS) through single ion monitoring (SIM). Our data fits well with the Langmuir-Hinshelwood rate loss equation. We report a LH adsorption constant of K(Hg) = 3.8±4.5 ×10-14 cm3 molec-1 and an apparent surface deposition rate of 5±3 × 1014 molec min-1 cm-2 under experimental conditions. We demonstrate that UV-irradiated (320 ? ? ? 400 nm) TiO2 can lead to the removal of gaseous mercury even at room temperature. We have also studied the same reactions in presence of common industrial mercury co-pollutants such as ozone and sulfur dioxide. We did not observe a significant alteration of mercury loss rate on photo-activated titanium oxide surfaces, in presence of SO2, O3, outside experimental uncertainties. We describe the possible applications of our results.

  8. The Effects Of Micro Arc Oxidation Of Gamma Titanium Aluminide Surfaces On Osteoblast Adhesion And Differentiation

    PubMed Central

    Santiago-Medina, Pricilla; Sundaram, Paul A.; Diffoot-Carlo, Nanette

    2014-01-01

    The adhesion and proliferation of human fetal osteoblasts, hFOB 1.19, on micro arc oxidized (MAO) gamma titanium aluminide (?TiAl) surfaces were examined in vitro. Cells were seeded on MAO treated ?TiAl disks and incubated for 3 days at 33.5°C and subsequently for 7 days at 39.5°C. Samples were then analyzed by Scanning Electron Microscopy (SEM) and the Alkaline Phosphatase Assay (ALP) to evaluate cell adhesion and differentiation, respectively. Similar Ti-6Al-4V alloy samples were used for comparison. Untreated ?TiAl and Ti-6Al-4V disks, to study the effect of micro arc oxidation and glass coverslips as cell growth controls were also incubated concurrently. The ALP Assay results, at 10 days post seeding, showed significant differences in cell differentiation, with p values < 0.05 between MAO ?TiAl and MAO Ti-6Al-4V with respect to the corresponding untreated alloys. While SEM images showed that hFOB 1.19 cells adhered and proliferated on all MAO and untreated surfaces, as well as on glass coverslips at 10 days post seeding, cell differentiation, determined by the ALP assay, was significantly higher for the MAO alloys. PMID:24577944

  9. Adsorption of CO on oxide and water ice surfaces - Implications for the Martian atmosphere

    NASA Technical Reports Server (NTRS)

    Leu, M.-T.; Blamont, J. E.; Anbar, A. D.; Keyser, L. F.; Sander, S. P.

    1992-01-01

    The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.

  10. Removing of Disinfection By-Product Precursors from Surface Water by Using Magnetic Graphene Oxide

    PubMed Central

    Liu, Zhongmou; Wang, Xianze; Luo, Zhen; Huo, Mingxin; Wu, Jinghui

    2015-01-01

    The magnetic graphene oxide (MGO) was successfully synthesised by the in situ chemical co-precipitation method with Fe3+, Fe2+ and graphene oxide (GO) in laboratory and, was used as an adsorbent for disinfection by-product (DBP) precursors removing from four natural surface water samples. The results indicate that various DBPs formation significantly decreased by 7–19% to 78–98% for the four samples after MGO treatment and, the treatment process was rapidly reached equilibrium within 20 minutes. The DBP precursors removal efficiency decreased with the increasing pH value from 4 to 10. Hydrophobic compounds (humic acid and fulvic acid) are more sensitive to MGO, whereas hydrophilic and nitrogenous compounds (aromatic proteins) are more insensitive. MGO could be regenerated by using 20% (v/v) ethanol and, the DBP precursors removal efficiency can stay stable after five cycles. These results indicate that MGO can be utilized as a promising adsorbent for the removal of DBP precursors from natural surface water. PMID:26623652

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Thermal oxidation of 6 nm aerosolized silicon nanoparticles: size and surface chemistry changes.

    PubMed

    Holm, Jason; Roberts, Jeffrey T

    2007-10-23

    The earliest stages of thermal oxidation of 6 nm diameter silicon nanoparticles by molecular oxygen are examined using a tandem differential mobility analysis (TDMA) apparatus, Fourier-transform infrared (FTIR) spectroscopy, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). Particles are synthesized in and then extracted from a nonthermal RF plasma operating at approximately 20 Torr into the atmospheric pressure TDMA apparatus. The TDMA apparatus was used to measure oxidation-induced size changes over a broad range of temperature settings and N2-O2 carrier gas composition. Surface chemistry changes are evaluated in situ with an FTIR spectrometer and a hybrid flow-through cell, and ex situ with ToF-SIMS and XPS. Particle size measurements show that, at temperatures less than approximately 500 degrees C, particles shrink regardless of the carrier gas oxygen concentration, while FTIR and ToF-SIMS spectra demonstrate a loss of hydrogen from the particles and minimal oxide formation. At higher temperatures, FTIR and XPS spectra indicate that an oxide forms which tends toward, but does not fully reach, stoichiometric SiO2 with increasing temperature. Between 500 and 800 degrees C, size measurements show a small increase in particle diameter with increasing carrier gas oxygen content and temperature. Above 800 degrees C, particle growth rapidly reaches a plateau while FTIR and XPS spectra change little. ToF-SIMS signals associated with O-Si species also show an increase in intensity at 800 degrees C. PMID:17910484

  13. Low Pressure Radio-Frequency Oxygen Plasma Induced Oxidation of Titanium – Surface Characteristics and Biological Effects

    PubMed Central

    Tseng, Wan-Yu; Hsu, Sheng-Hao; Huang, Chieh-Hsiun; Tu, Yu-Chieh; Tseng, Shao-Chin; Chen, Hsuen-Li; Chen, Min-Huey; Su, Wei-Fang; Lin, Li-Deh

    2013-01-01

    Objective This research was designed to investigate the effects of low pressure radio-frequency (RF) oxygen plasma treatment (OPT) on the surface of commercially pure titanium (CP-Ti) and Ti6Al4V. Surface topography, elemental composition, water contact angle, cell viability, and cell morphology were surveyed to evaluate the biocompatibility of titanium samples with different lengths of OP treating time. Materials and Methods CP-Ti and Ti6Al4V discs were both classified into 4 groups: untreated, treated with OP generated by using oxygen (99.98%) for 5, 10, and 30 min, respectively. After OPT on CP-Ti and Ti6Al4V samples, scanning probe microscopy, X-ray photoelectron spectrometry (XPS), and contact angle tests were conducted to determine the surface topography, elemental composition and hydrophilicity, respectively. The change of surface morphology was further studied using sputtered titanium on silicon wafers. 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) assay and F-actin immunofluorescence stain were performed to investigate the viability and spreading behavior of cultivated MG-63 cells on the samples. Results The surface roughness was most prominent after 5 min OPT in both CP-Ti and Ti6Al4V, and the surface morphology of sputtered Ti sharpened after the 5 min treatment. From the XPS results, the intensity of Ti°, Ti2+, and Ti3+ of the samples’ surface decreased indicating the oxidation of titanium after OPT. The water contact angles of both CP-Ti and Ti6Al4V were increased after 5 min OPT. The results of MTT assay demonstrated MG-63 cells proliferated best on the 5 min OP treated titanium sample. The F-actin immunofluorescence stain revealed the cultivated cell number of 5 min treated CP-Ti/Ti6Al4V was greater than other groups and most of the cultivated cells were spindle-shaped. Conclusions Low pressure RF oxygen plasma modified both the composition and the morphology of titanium samples’ surface. The CP-Ti/Ti6Al4V treated with 5 min OPT displayed the roughest surface, sharpest surface profile and best biocompatibility. PMID:24386433

  14. Theoretical study of the amphoteric oxide nanoparticle surface charge during multi-particle interactions in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Alfimov, A. V.; Aryslanova, E. M.; Chivilikhin, S. A.

    2015-11-01

    Nanoparticle surface charge plays an important role in many biological applications. In this study, an analytical surface charging model for the amphoteric oxide nanoparticles has been presented. The model accounts for the particle's electric double layer self-action on the charging process and the charge regulation during multi-particle interactions in aqueous solutions. The employment of the model allows to explicitly describe the nanoparticle agglomeration process and the accompanying agglomerate surface charge variation.

  15. Effect of surface modification and UVA photoactivation on antibacterial bioactivity of zinc oxide powder

    NASA Astrophysics Data System (ADS)

    Ann, Ling Chuo; Mahmud, Shahrom; Bakhori, Siti Khadijah Mohd; Sirelkhatim, Amna; Mohamad, Dasmawati; Hasan, Habsah; Seeni, Azman; Rahman, Rosliza Abdul

    2014-02-01

    The effects of surface modification of zinc oxide (ZnO) powder and UVA illumination on the powder towards Escherichia coli and Staphylococcus aureus were investigated. FESEM-EDS results showed that oxygen annealing increased the O:Zn ratio on the surface of ZnO-rod and ZnO-plate samples. Surface conductances of ZnO-rod and ZnO-plate pellets were reduced from 1.05 nS to 0.15 nS and 1.34 nS to 0.23 nS, respectively. Meanwhile, UVA illumination on the surface of the ZnO-rod and ZnO-plate samples was found to improve surface conductance to 7.08 nS and 6.51 nS, respectively, due to the release of charge carrier. Photoluminescence results revealed that oxygen annealing halved the UV emission intensity and green emission intensity, presumably caused by oxygen absorption in the ZnO lattice. The antibacterial results showed that oxygen-treated ZnO exhibited slightly higher growth inhibition on E. coli and S. aureus compared with unannealed ZnO. UVA illumination on ZnO causes the greatest inhibition toward E. coli and S. aureus. Under the UVA excitation, the inhibition of E. coli increased by 18% (ZnO-rod) and 13% (ZnO-plate) while the inhibition of S. aureus increased by 22% (ZnO-rod) and 21% (ZnO-plate). Release of reactive oxygen species were proposed in antibacterial mechanisms, which were aided by surface modification and UVA photoactivation. The reactive oxygen species disrupted the DNA and protein synthesis of the bacterial cell, causing bacteriostatic effects toward E. coli and S. aureus.

  16. Osseointegration improvement by plasma electrolytic oxidation of modified titanium alloys surfaces.

    PubMed

    Echeverry-Rendón, Mónica; Galvis, Oscar; Quintero Giraldo, David; Pavón, Juan; López-Lacomba, José Luis; Jiménez-Piqué, Emilio; Anglada, Marc; Robledo, Sara M; Castaño, Juan G; Echeverría, Félix

    2015-02-01

    Titanium (Ti) is a material frequently used in orthopedic applications, due to its good mechanical properties and high corrosion resistance. However, formation of a non-adherent fibrous tissue between material and bone drastically could affect the osseointegration process and, therefore, the mechanical stability of the implant. Modifications of topography and configuration of the tissue/material interface is one of the mechanisms to improve that process by manipulating parameters such as morphology and roughness. There are different techniques that can be used to modify the titanium surface; plasma electrolytic oxidation (PEO) is one of those alternatives, which consists of obtaining porous anodic coatings by controlling parameters such as voltage, current, anodizing solution and time of the reaction. From all of the above factors, and based on previous studies that demonstrated that bone cells sense substrates features to grow new tissue, in this work commercially pure Ti (c.p Ti) and Ti6Al4V alloy samples were modified at their surface by PEO in different anodizing solutions composed of H2SO4 and H3PO4 mixtures. Treated surfaces were characterized and used as platforms to grow osteoblasts; subsequently, cell behavior parameters like adhesion, proliferation and differentiation were also studied. Although the results showed no significant differences in proliferation, differentiation and cell biological activity, overall results showed an important influence of topography of the modified surfaces compared with polished untreated surfaces. Finally, this study offers an alternative protocol to modify surfaces of Ti and their alloys in a controlled and reproducible way in which biocompatibility of the material is not compromised and osseointegration would be improved. PMID:25631270

  17. Influence of surface chemical properties on the toxicity of engineered zinc oxide nanoparticles to embryonic zebrafish

    PubMed Central

    Zhou, Zitao; Son, Jino; Harper, Bryan; Zhou, Zheng

    2015-01-01

    Summary Zinc oxide nanoparticles (ZnO NPs) are widely used in a variety of products, thus understanding their health and environmental impacts is necessary to appropriately manage their risks. To keep pace with the rapid increase in products utilizing engineered ZnO NPs, rapid in silico toxicity test methods based on knowledge of comprehensive in vivo and in vitro toxic responses are beneficial in determining potential nanoparticle impacts. To achieve or enhance their desired function, chemical modifications are often performed on the NPs surface; however, the roles of these alterations play in determining the toxicity of ZnO NPs are still not well understood. As such, we investigated the toxicity of 17 diverse ZnO NPs varying in both size and surface chemistry to developing zebrafish (exposure concentrations ranging from 0.016 to 250 mg/L). Despite assessing a suite of 19 different developmental, behavioural and morphological endpoints in addition to mortality in this study, mortality was the most common endpoint observed for all of the ZnO NP types tested. ZnO NPs with surface chemical modification, regardless of the type, resulted in mortality at 24 hours post-fertilization (hpf) while uncoated particles did not induce significant mortality until 120 hpf. Using eight intrinsic chemical properties that relate to the outermost surface chemistry of the engineered ZnO nanoparticles, the highly dimensional toxicity data were converted to a 2-dimensional data set through principal component analysis (PCA). Euclidean distance was used to partition different NPs into several groups based on converted data (score) which were directly related to changes in the outermost surface chemistry. Kriging estimations were then used to develop a contour map based on mortality data as a response. This study illustrates how the intrinsic properties of NPs, including surface chemical modifications and capping agents, are useful to separate and identify ZnO NP toxicity to zebrafish (Danio rerio). PMID:26425408

  18. Black-carbon-surface oxidation and organic composition of beech-wood soot aerosols

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Lohmann, U.; Sierau, B.; Keller, A.; Burtscher, H.; Mensah, A. A.

    2015-03-01

    Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The SP-AMS provided information on the OM, BC, and surface composition of the soot. The OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis, and was only present in large amounts when new wood was added to the stove. BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C+1-5), oxygenated surface groups (CO+1-2), potassium (K+) and water (H+2O and related fragments). The C+4 : C+3 ratio, but not the C+1 : C+3 ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO+1-2 signals likely originated from BC surface groups: upon aging, both CO+ and CO+2 increased relative to C+1-3 while CO+2 simultaneously increased relative to CO+. Factor analysis (PMF) of SP-AMS and AMS data, using a new error model to account for peak-integration uncertainties, indicated that the surface composition of the BC was approximately constant across all stages of combustion for both fresh and aged samples. These results represent the first time-resolved measurements of in-situ BC-surface aging and suggest that the surface of beech-wood BC may be modelled as a single chemical species.

  19. Importance of indium tin oxide surface acido basicity for charge injection into organic materials based light emitting diodes

    NASA Astrophysics Data System (ADS)

    Nüesch, F.; Forsythe, E. W.; Le, Q. T.; Gao, Y.; Rothberg, L. J.

    2000-06-01

    The influence of the indium tin oxide (ITO) electrode surface acido basicity on organic electroluminescent device characteristics is studied. As measured by photoelectron spectroscopy, acid and base treatments produce large work function shifts of the oxide compared to standard ITO treated by an oxygen plasma or water. The current onsets for triphenyldiamine (TPD) single layer diodes sandwiched between ITO and a silver electrode are in qualitative agreement with the work function of the hole injecting oxide electrode. However, saturated photovoltage measurements on single layer diodes built on acid and water treated ITO disagree with the work function obtained from photoelectron experiments. This is explained by protonation of the diamine layer close to the electrode surface producing a charged double layer. It suggests that even acidic surface hydroxyl groups of the oxide electrode are able to protonate the diamine layer, explaining the importance of plasma cleaning to remove surface hydroxyls. The same ITO treatments are investigated in tris(8-hydroxyquinoline) (Alq) aluminum single layer diodes as well as hybrid TPD/Alq light emitting devices. Implications of metal-oxide surface acido basicity on electrode treatment and molecular material design are discussed.

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

    PubMed

    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. PMID:25635269

  1. Micro-arc oxidation as a tool to develop multifunctional calcium-rich surfaces for dental implant applications.

    PubMed

    Ribeiro, A R; Oliveira, F; Boldrini, L C; Leite, P E; Falagan-Lotsch, P; Linhares, A B R; Zambuzzi, W F; Fragneaud, B; Campos, A P C; Gouvêa, C P; Archanjo, B S; Achete, C A; Marcantonio, E; Rocha, L A; Granjeiro, J M

    2015-09-01

    Titanium (Ti) is commonly used in dental implant applications. Surface modification strategies are being followed in last years in order to build Ti oxide-based surfaces that can fulfill, simultaneously, the following requirements: induced cell attachment and adhesion, while providing a superior corrosion and tribocorrosion performance. In this work micro-arc oxidation (MAO) was used as a tool for the growth of a nanostructured bioactive titanium oxide layer aimed to enhance cell attachment and adhesion for dental implant applications. Characterization of the surfaces was performed, in terms of morphology, topography, chemical composition and crystalline structure. Primary human osteoblast adhesion on the developed surfaces was investigated in detail by electronic and atomic force microscopy as well as immunocytochemistry. Also an investigation on the early cytokine production was performed. Results show that a relatively thick hybrid and graded oxide layer was produced on the Ti surface, being constituted by a mixture of anatase, rutile and amorphous phases where calcium (Ca) and phosphorous (P) were incorporated. An outermost nanometric-thick amorphous oxide layer rich in Ca was present in the film. This amorphous layer, rich in Ca, improved fibroblast viability and metabolic activity as well as osteoblast adhesion. High-resolution techniques allowed to understand that osteoblasts adhered less in the crystalline-rich regions while they preferentially adhere and spread over in the Ca-rich amorphous oxide layer. Also, these surfaces induce higher amounts of IFN-? cytokine secretion, which is known to regulate inflammatory responses, bone microarchitecture as well as cytoskeleton reorganization and cellular spreading. These surfaces are promising in the context of dental implants, since they might lead to faster osseointegration. PMID:26046283

  2. Surface morphology, microstructure, raman characterization and magnetic ordering of oxidized Fe-sputtered films on silicon substrate

    NASA Astrophysics Data System (ADS)

    Jasmin, A.; Rillera, H.; Semblante, O.; Sarmago, R.

    2012-09-01

    Iron oxide (Fe2O3) nanostructures are synthesized by thermal oxidation of Fe-sputtered films in a carbon-rich environment. Nanocrystals and nanoparticle networks are observed to grow on oxidized Fe thin films. Xray diffraction (XRD) characterization of samples reveals the existence of rhombohedral Fe2O3 crystal structure. Raman spectroscopy of annealed films shows the existence of Fe3O4 phase on network like structures which is brought about by the surface stress between the two iron oxide phases. Atomic force microscope (AFM) phase image of the Fe2O3 film shows a large scale magnetic ordering which does not depend on the surface morphology of the sample.

  3. The effects of pre-oxidation heating rate on bio-based carbon fibers and its surface repair

    NASA Astrophysics Data System (ADS)

    Wu, H.; Cheng, L. F.; Fan, S. W.; Yuan, X. W.; Bhattacharyya, D.

    2015-03-01

    Low-cost carbon fibers (CFs) are fabricated from jute fibers after pre-oxidation, carbonization and surface repair. This paper investigates the effects of pre-oxidation heating rate on jute fibers, and explores a repair method for surface defects of CFs in C/C composite. The results show the reaction mechanism of jute fibers in air is not changed at higher pre-oxidation heating rates while a low heating rate is still required as the oxidation of jute fibers cannot be fully achieved under rapid heating. The tensile strength of CFs increases after repair with a 5% phenolic resin solution. Jute-based CFs play a positive role in C/C composite performance through crack bridging and deflection.

  4. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, September 30, 1992

    SciTech Connect

    Doyle, F.M.

    1992-12-31

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

  5. Surface activation of air oxidation of hydrazine on kaolinite. 2. Consideration of oxidizing/reducing entities in relationship to other compositional, structural, and energetic factors

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Summers, D. P.

    1991-01-01

    The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

  6. Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

    PubMed

    Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

    2014-06-15

    In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. PMID:24794812

  7. Chemical Bath Deposition of Aluminum Oxide Buffer on Curved Surfaces for Growing Aligned Carbon Nanotube Arrays.

    PubMed

    Wang, Haitao; Na, Chongzheng

    2015-07-01

    Direct growth of vertically aligned carbon nanotube (CNT) arrays on substrates requires the deposition of an aluminum oxide buffer (AOB) layer to prevent the diffusion and coalescence of catalyst nanoparticles. Although AOB layers can be readily created on flat substrates using a variety of physical and chemical methods, the preparation of AOB layers on substrates with highly curved surfaces remains challenging. Here, we report a new solution-based method for preparing uniform layers of AOB on highly curved surfaces by the chemical bath deposition of basic aluminum sulfate and annealing. We show that the thickness of AOB layer can be increased by extending the immersion time of a substrate in the chemical bath, following the classical Johnson-Mehl-Avrami-Kolmogorov crystallization kinetics. The increase of AOB thickness in turn leads to the increase of CNT length and the reduction of CNT curviness. Using this method, we have successfully synthesized dense aligned CNT arrays of micrometers in length on substrates with highly curved surfaces including glass fibers, stainless steel mesh, and porous ceramic foam. PMID:26053766

  8. Tantalum oxide/silicon nitride: A negatively charged surface passivation stack for silicon solar cells

    SciTech Connect

    Wan, Yimao Bullock, James; Cuevas, Andres

    2015-05-18

    This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited tantalum oxide (Ta{sub 2}O{sub 5}) underneath plasma enhanced chemical vapour deposited silicon nitride (SiN{sub x}). Cross-sectional transmission electron microscopy imaging shows an approximately 2?nm thick interfacial layer between Ta{sub 2}O{sub 5} and c-Si. Surface recombination velocities as low as 5.0?cm/s and 3.2?cm/s are attained on p-type 0.8 ?·cm and n-type 1.0 ?·cm c-Si wafers, respectively. Recombination current densities of 25 fA/cm{sup 2} and 68 fA/cm{sup 2} are measured on 150??/sq boron-diffused p{sup +} and 120??/sq phosphorus-diffused n{sup +} c-Si, respectively. Capacitance–voltage measurements reveal a negative fixed insulator charge density of ?1.8?×?10{sup 12?}cm{sup ?2} for the Ta{sub 2}O{sub 5} film and ?1.0?×?10{sup 12?}cm{sup ?2} for the Ta{sub 2}O{sub 5}/SiN{sub x} stack. The Ta{sub 2}O{sub 5}/SiN{sub x} stack is demonstrated to be an excellent candidate for surface passivation of high efficiency silicon solar cells.

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

    PubMed

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Ding, Kunlun; Yang, Xiaoyun; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-08-12

    We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts. PMID:26222267

  10. Ultrahigh vacuum and low-temperature cleaning of oxide surfaces using a low-concentration ozone beam

    SciTech Connect

    Pratt, A.; Graziosi, P.; Bergenti, I.; Dediu, A.; Prezioso, M.; Yamauchi, Y.

    2014-07-15

    We present a novel method of delivering a low-concentration (<15%) ozone beam to an ultra-high vacuum environment for the purpose of cleaning and dosing experimental samples through oxidation processing. The system described is safe, low-cost, and practical and overcomes the limitations of ozone transport in the molecular flow environment of high or ultrahigh vacuum whilst circumventing the use of pure ozone gas which is potentially highly explosive. The effectiveness of this method in removing surface contamination is demonstrated through comparison of high-temperature annealing of a simple oxide (MgO) in ozone and oxygen environments as monitored using quadrupole mass spectroscopy and Auger electron spectroscopy. Additionally, we demonstrate the potential of ozone for obtaining clean complex oxide surfaces without the need for high-temperature annealing which may significantly alter surface structure.

  11. Density functional theory study of heterogeneous CO oxidation over an oxygen-enriched yttria-stabilized zirconia surface

    NASA Astrophysics Data System (ADS)

    Yurkiv, Vitaliy; Gorski, Alexandr; Bessler, Wolfgang G.; Volpp, Hans-Robert

    2012-08-01

    The reaction mechanism of heterogeneous CO oxidation on yttria-stabilized zirconia (YSZ), frequently used as electrolyte in solid oxide fuel cell (SOFC) composite anodes, was investigated employing density functional theory (DFT). The results demonstrate the possibility for an Eley-Rideal type CO oxidation reaction on the electrolyte surface without the need for a metallic catalyst if the vacant sites of YSZ are filled by externally supplied oxygen, either by dissociative adsorption of gaseous O2 or via bulk oxygen atoms delivered by the SOFC cathode. Our results are consistent with the findings of recent experiments [J. Electrochem. Soc. 158 (2011) B5].

  12. New surface radiolabeling schemes of super paramagnetic iron oxide nanoparticles (SPIONs) for biodistribution studies

    NASA Astrophysics Data System (ADS)

    Nallathamby, Prakash D.; Mortensen, Ninell P.; Palko, Heather A.; Malfatti, Mike; Smith, Catherine; Sonnett, James; Doktycz, Mitchel J.; Gu, Baohua; Roeder, Ryan K.; Wang, Wei; Retterer, Scott T.

    2015-04-01

    Nanomaterial based drug delivery systems allow for the independent tuning of the surface chemical and physical properties that affect their biodistribution in vivo and the therapeutic payloads that they are intended to deliver. Additionally, the added therapeutic and diagnostic value of their inherent material properties often provides extra functionality. Iron based nanomaterials with their magnetic properties and easily tailorable surface chemistry are of particular interest as model systems. In this study the core radius of the iron oxide nanoparticles (NPs) was 14.08 +/- 3.92 nm while the hydrodynamic radius of the NPs, as determined by Dynamic Light Scattering (DLS), was between 90-110 nm. In this study, different approaches were explored to create radiolabeled NPs that are stable in solution. The NPs were functionalized with polycarboxylate or polyamine surface functional groups. Polycarboxylate functionalized NPs had a zeta potential of -35 mV and polyamine functionalized NPs had a zeta potential of +40 mV. The polycarboxylate functionalized NPs were chosen for in vivo biodistribution studies and hence were radiolabeled with 14C, with a final activity of 0.097 nCi mg-1 of NPs. In chronic studies, the biodistribution profile is tracked using low level radiolabeled proxies of the nanoparticles of interest. Conventionally, these radiolabeled proxies are chemically similar but not chemically identical to the non-radiolabeled NPs of interest. This study is novel as different approaches were explored to create radiolabeled NPs that are stable, possess a hydrodynamic radius of <100 nm and most importantly they exhibit an identical surface chemical functionality as their non-radiolabeled counterparts. Identical chemical functionality of the radiolabeled probes to the non-radiolabeled probes was an important consideration to generate statistically similar biodistribution data sets using multiple imaging and detection techniques. The radiolabeling approach described here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials.Nanomaterial based drug delivery systems allow for the independent tuning of the surface chemical and physical properties that affect their biodistribution in vivo and the therapeutic payloads that they are intended to deliver. Additionally, the added therapeutic and diagnostic value of their inherent material properties often provides extra functionality. Iron based nanomaterials with their magnetic properties and easily tailorable surface chemistry are of particular interest as model systems. In this study the core radius of the iron oxide nanoparticles (NPs) was 14.08 +/- 3.92 nm while the hydrodynamic radius of the NPs, as determined by Dynamic Light Scattering (DLS), was between 90-110 nm. In this study, different approaches were explored to create radiolabeled NPs that are stable in solution. The NPs were functionalized with polycarboxylate or polyamine surface functional groups. Polycarboxylate functionalized NPs had a zeta potential of -35 mV and polyamine functionalized NPs had a zeta potential of +40 mV. The polycarboxylate functionalized NPs were chosen for in vivo biodistribution studies and hence were radiolabeled with 14C, with a final activity of 0.097 nCi mg-1 of NPs. In chronic studies, the biodistribution profile is tracked using low level radiolabeled proxies of the nanoparticles of interest. Conventionally, these radiolabeled proxies are chemically similar but not chemically identical to the non-radiolabeled NPs of interest. This study is novel as different approaches were explored to create radiolabeled NPs that are stable, possess a hydrodynamic radius of <100 nm and most importantly they exhibit an identical surface chemical functionality as their non-radiolabeled counterparts. Identical chemical functionality of t

  13. Surface engineering on CeO? nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation.

    PubMed

    Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-07-21

    Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce(3+) fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. PMID:26098593

  14. Heterogeneous oxidation of sulfur dioxide by ozone on the surface of sodium chloride and its mixtures with other components

    NASA Astrophysics Data System (ADS)

    Li, L.; Chen, Z. M.; Zhang, Y. H.; Zhu, T.; Li, S.; Li, H. J.; Zhu, L. H.; Xu, B. Y.

    2007-09-01

    The heterogeneous oxidation of SO2 by O3 on NaCl particles has been studied using diffuse reflectance infrared Fourier transform spectroscopy. The formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in the oxidation processes were determined. The results showed that in the presence of O3, SO2 could be oxidized to sulfate on the surface of NaCl particles. The reaction is first order in O3 and zero order in SO2. The initial reactive uptake coefficient for SO2 [(0.6-9.8) × 1014 molecule cm-3] oxidation by O3 [(1.2-12) × 1014 molecule cm-3] was determined to be (4.8-0.7) × 10-8 using the Brunauer-Emmett-Teller area as the reactive area and (9.8-1.4) × 10-5 using the geometric area at 40% relative humidity. A three-stage mechanism that involves the adsorption of O3 results in an alkalescent surface, the adsorption of SO2 followed by O3 oxidation is proposed, and the adsorption of O3 on the NaCl surface is the rate-determining step. The proposed mechanism can well explain the experiment results. Furthermore, the surface oxidation on mixtures of NaCl with other components such as CaCO3, Al2O3, TiO2, MgCl2 6H2O, MgO, elemental carbon, and soot were studied. The reactivity of mixtures can be predicted from the reactivity of the single component with each component weighted by its abundance in the mixture. The catalytic and basic additives could enhance the production of sulfate on the NaCl surface.

  15. Electrochemical oxidation of landfill leachate in a flow reactor: optimization using response surface methodology.

    PubMed

    Silveira, Jefferson E; Zazo, Juan A; Pliego, Gema; Bidóia, Edério D; Moraes, Peterson B

    2015-04-01

    Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99% of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested. PMID:25339535

  16. Colloidally stable surface-modified iron oxide nanoparticles: Preparation, characterization and anti-tumor activity

    NASA Astrophysics Data System (ADS)

    Macková, Hana; Horák, Daniel; Donchenko, Georgiy Viktorovich; Andriyaka, Vadim Ivanovich; Palyvoda, Olga Mikhailovna; Chernishov, Vladimir Ivanovich; Chekhun, Vasyl Fedorovich; Todor, Igor Nikolaevich; Kuzmenko, Oleksandr Ivanovich

    2015-04-01

    Maghemite (?-Fe2O3) nanoparticles were obtained by co-precipitation of Fe(II) and Fe(III) chlorides and subsequent oxidation with sodium hypochlorite and coated with poly(N,N-dimethylacrylamide-co-acrylic acid) [P(DMAAm-AA)]. They were characterized by a range of methods including transmission electron microscopy (TEM), elemental analysis, dynamic light scattering (DLS) and zeta potential measurements. The effect of superparamagnetic P(DMAAm-AA)-?-Fe2O3 nanoparticles on oxidation of blood lipids, glutathione and proteins in blood serum was detected using 2-thiobarbituric acid and the ThioGlo fluorophore. Finally, mice received magnetic nanoparticles administered per os and the antitumor activity of the particles was tested on Lewis lung carcinoma (LLC) in male mice line C57BL/6 as an experimental in vivo metastatic tumor model; the tumor size was measured and the number of metastases in lungs was determined. Surface-modified ?-Fe2O3 nanoparticles showed higher antitumor and antimetastatic activities than commercial CuFe2O4 particles and the conventional antitumor agent cisplatin.

  17. Silver nanoaggregates on chitosan functionalized graphene oxide for high-performance surface-enhanced Raman scattering.

    PubMed

    Wan, Mingming; Liu, Zhiming; Li, Shaoxin; Yang, Biwen; Zhang, Wen; Qin, Xiaochu; Guo, Zhouyi

    2013-07-01

    Herein we describe a self-assembly synthesis of graphene oxide/Ag nanoparticles nano-composites (GO/CS/AgNPs) by non-covalent attachment of AgNPs to chitosan (CS) functionalized graphene oxide (GO) sheets. The negatively charged AgNPs are prone to form aggregates on GO/CS via electrostatic interaction, which is extremely beneficial to the surface-enhanced Raman scattering (SERS) detection of aromatic molecules. Taking advantage of the enrichment of target molecules on GO, the obtained hybrids exhibit strong SERS activity to aromatic molecules (trypan blue and methylene blue). Furthermore, SERS signals of a negatively charged molecule (trypan blue) are stronger than signals of a positively charged molecule (methylene blue) due to the different adsorption capacity of GO/CS/AgNPs for the two opposite charged molecules through electrostatic interaction. Moreover, GO/CS/AgNPs remarkably enhance the main peaks of l-phenylalanine, in comparison with the silver nanoparticles, showing great potential for biomedical applications. PMID:23816129

  18. Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology.

    PubMed

    Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

    2015-09-01

    To achieve the maximum H2 yield (GYH2), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GYH2, CR and TRE were established with Box-Behnken design. GYH2, CR and TRE reached up to 14.32mmol·gTOC(-1), 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO2 and H2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH3 has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient. PMID:26028557

  19. Supercapacitors based on highly dispersed polypyrrole-reduced graphene oxide composite with a folded surface

    NASA Astrophysics Data System (ADS)

    Wang, Anqi; Zhou, Xi; Qian, Tao; Yu, Chenfei; Wu, Shishan; Shen, Jian

    2015-08-01

    Highly dispersed polypyrrole particles were decorated on reduced graphene oxide sheets using a facile in situ synthesis route. The prepared composite, which obtained a folded surface, shows remarkable performance as the electrode material of supercapacitors. The specific capacitance reaches 564.1 F g-1 at a current density of 1 A g-1 and maintains 86.4 % after 1000 charging-discharging cycles at a current density of 20 A g-1, which indicates a good cycling stability. Furthermore, the prepared supercapacitor demonstrates an ultrahigh energy density of 50.13 Wh kg-1 at power density of 0.40 kW kg-1, and remains of 45.33 Wh kg-1 even at high power density of 8.00 kW kg-1, which demonstrate that the hybrid supercapacitor can be a promising energy storage system for fast and efficient energy storage in the future.

  20. Correlation of electrical and optical characteristics of selectively oxidized vertical-cavity surface-emitting lasers

    SciTech Connect

    Li, J.; Seurin, J.; Chuang, S.L.; Choquette, K.D.; Geib, K.M.; Hou, H.Q.

    1997-04-01

    We investigate the correlation between the electrical and optical characteristics of selectively oxidized vertical-cavity surface-emitting lasers (VCSELs). Electrical derivative analysis is used on VCSELs to study the electrical performance and its correlation with the polarization-resolved optical powers and spectra. Characteristic features are shown in the IdV/dI curves near major transition points of VCSEL operation. From the IdV/dI curve we are able to precisely identify important operating currents such as the lasing threshold, the higher-order mode lasing current, and the cut-off current. Five operation regions are defined in the polarization-resolved L{minus}I curves based on these currents and their temperature dependences are also studied. {copyright} {ital 1997 American Institute of Physics.}

  1. In Situ X-Ray Probing Reveals Fingerprints of Surface Platinum Oxide

    SciTech Connect

    Friebel, Daniel

    2011-08-24

    In situ x-ray absorption spectroscopy (XAS) at the Pt L{sub 3} edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard x-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF8 code and complementary extended x-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  2. Oxidation of Hydrocarbons on the Surface of Tin Dioxide Chemical Sensors

    PubMed Central

    Teterycz, Helena; Halek, Patryk; Wi?niewski, Kamil; Halek, Grzegorz; Ko?lecki, Tomasz; Polowczyk, Izabela

    2011-01-01

    The paper presents the results of our investigation on the effect of the molecular structure of organic vapors on the characteristics of resistive chemical gas sensors. The sensors were based on tin dioxide and prepared by means of thick film technology. The electrical and catalytic examinations showed that the abstraction of two hydrogen atoms from the organic molecule and formation of a water in result of reaction with a chemisorbed oxygen ion, determine the rate of oxidation reactions, and thus the sensor performance. The rate of the process depends on the order of carbon atoms and Lewis acidity of the molecule. Therefore, any modification of the surface centers of a sensor material, modifies not only the sensor sensitivity, but also its selectivity. PMID:22163855

  3. Ab initio intermolecular potential energy surface and thermophysical properties of nitrous oxide

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    We present an analytical intermolecular potential energy surface (PES) for two rigid nitrous oxide (N2O) molecules derived from high-level quantum-chemical ab initio calculations. Interaction energies for 2018 N2O-N2O configurations were computed utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory using basis sets up to aug-cc-pVQZ supplemented with bond functions. A site-site potential function with seven sites per N2O molecule was fitted to the pair interaction energies. We validated our PES by computing the second virial coefficient as well as shear viscosity and thermal conductivity in the dilute-gas limit. The values of these properties are substantiated by the best experimental data.

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

    PubMed

    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. PMID:15045328

  5. A simple breathing rate-sensing method exploiting a temporarily condensed water layer formed on an oxidized surface

    NASA Astrophysics Data System (ADS)

    Seo, Min-Ho; Yang, Hyun-Ho; Choi, Kwang-Wook; Lee, Jae-Shin; Yoon, Jun-Bo

    2015-02-01

    We describe a very simple breathing rate-sensing method that detects a significant electric current change between two metal electrodes on an oxidized surface. The current change is caused by the formation of a water layer from exhaled breath. We discovered that breathing onto the oxidized surface causes instant water condensation, and it generates 20 times increased current than that measured in the inhalation period. The condensed water quickly evaporates, enabling us to detect dynamic human breathing in real time. We also investigated the breathing rate sensor by varying the relative humidity, temperature, and breathing frequency and confirmed its potential for practical applications.

  6. The fabrication of tunable nanoporous oxide surfaces by block copolymer lithography and atomic layer deposition.

    PubMed

    Andreozzi, A; Lamagna, L; Seguini, G; Fanciulli, M; Schamm-Chardon, S; Castro, C; Perego, M

    2011-08-19

    Patterned nanoscale materials with controllable characteristic feature sizes and periodicity are of considerable interest in a wide range of fields, with various possible applications ranging from biomedical to nanoelectronic devices. Block-copolymer (BC)-based lithography is a powerful tool for the fabrication of uniform, densely spaced nanometer-scale features over large areas. Following this bottom-up approach, nanoporous polymeric films can be deposited on any type of substrate. The nanoporous periodic template can be transferred to the underlying substrate by dry anisotropic etching. Nevertheless the physical sizes of the polymeric mask represent an important limitation in the implementation of suitable lithographic protocols based on BC technology, since the diameter and the center-to-center distance of the pores cannot be varied independently in this class of materials. This problem could be overcome by combining block copolymer technology with atomic layer deposition (ALD): by means of BC-based lithography a nanoporous SiO2 template, with well-reproducible characteristic dimensions, can be fabricated and subsequently used as a backbone for the growth of perfectly conformal thin oxide films by ALD. In this work polystyrene-b-poly(methylmethacrylate) (PS-b-PMMA) BC and reactive ion etching are used to fabricate hexagonally packed 23 nm wide nanopores in a 50 nm thick SiO2 matrix. By ALD deposition of Al2O3 thin films onto the nanoporous SiO2 templates, nanostructured Al2O3 surfaces are obtained. By properly adjusting the thickness of the Al2O3 film the dimension of the pores in the oxide films is progressively reduced, with nanometer precision, from the original size down to complete filling of the pores, thus providing a simple and fast strategy for the fabrication of nanoporous Al2O3 surfaces with well-controllable feature size. PMID:21795768

  7. Effects of surface chemistry and size on iron oxide nanoparticle delivery of oligonucleotides

    NASA Astrophysics Data System (ADS)

    Shen, Christopher

    The discovery of RNA interference and the increasing understanding of disease genetics have created a new class of potential therapeutics based on oligonucleotides. This therapeutic class includes antisense molecules, small interfering RNA (siRNA), and microRNA modulators such as antagomirs (antisense directed against microRNA) and microRNA mimics, all of which function by altering gene expression at the translational level. While these molecules have the promise of treating a host of diseases from neurological disorders to cancer, a major hurdle is their inability to enter cells on their own, where they may render therapeutic effect. Nanotechnology is the engineering of materials at the nanometer scale and has gained significant interest for nucleic acid delivery due to its biologically relevant length-scale and amenability to multifunctionality. While a number of nanoparticle vehicles have shown promise for oligonucleotide delivery, there remains a lack of understanding of how nanoparticle coating and size affect these delivery processes. This dissertation seeks to elucidate some of these factors by evaluating oligonucleotide delivery efficiencies of a panel of iron oxide nanoparticles with varying cationic coatings and sizes. A panel of uniformly-sized nanoparticles was prepared with surface coatings comprised of various amine groups representing high and low pKas. A separate panel of nanoparticles with sizes of 40, 80, 150, and 200 nm but with the same cationic coating was also prepared. Results indicated that both nanoparticle surface coating and nanoparticle hydrodynamic size affect transfection efficiency. Specific particle coatings and sizes were identified that gave superior performance. The intracellular fate of iron oxide nanoparticles was also tracked by electron microscopy and suggests that they function via the proton sponge effect. The research presented in this dissertation may aid in the rational design of improved nanoparticle delivery vectors for nucleic acid-based therapy.

  8. Theoretical prediction of single-site surface-protonation equilibrium constants for oxides and silicates in water

    NASA Astrophysics Data System (ADS)

    Sverjensky, Dimitri A.; Sahai, Nita

    1996-10-01

    The equilibrium constants for surface protonation of solid oxides and silicates can be estimated from theoretical considerations and known properties of the solids for use in the constant capacitance, diffuse double layer or triple layer models of surface complexation. The theoretical considerations take into account Born solvation theory for the adsorbing proton, electrostatic interactions of the adsorbing proton with a surface oxygen and an underlying metal, and an intrinsic binding of the proton to the surface. As a consequence, the equilibrium constants for the ?th ( ? = 1 or 2) surface protonation reaction on the kth solid can be expressed in terms of the inverse of the dielectric constant of the solid (1/ ? k) and an average Pauling bond strength per angstrom (s/r M-OH) for the solid according to log K = (1/?)-B(s/r)+log Kii, v, where the coefficients M ?, B ?, and Kii, ?? are constants characteristic of all oxides and silicates for each surface complexation model. Evaluation of these constants using experimental data for TiO 2, ?-alumina, Al 2O 3, FeOOH, Fe(OH) 3, silica, quartz, and kaolinite permits widespread prediction of surface protonation equilibrium constants from the known bulk structure properties 1/ ? ? and s/r M-OH. Such predictions should replace attempts to estimate surface protonation equilibrium constants for solids from empirical correlations with aqueous equilibrium constants. Surface protonation constants should also not be estimated from correlations with only the Pauling bond strength because these neglect specific treatment of solvation. Each individual oxide or silicate is expected to have its own unique surface characteristics, depending on the bonding in the bulk crystal structure connected to the surface. It follows that the bonding in surface protonated species is probably far more analogous to that in the bulk crystal structure than to the bonding in protonated aqueous species.

  9. Black carbon surface oxidation and organic composition of beech-wood soot aerosols

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Lohmann, U.; Sierau, B.; Keller, A.; Burtscher, H.; Mensah, A. A.

    2015-10-01

    Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The dual-vaporizer SP-AMS provided information on the OM and BC components of the soot as well as on refractory components internally mixed with BC. By switching the SP-AMS laser vaporizer off and using only the AMS thermal vaporizer (at 600 °C), information on the OM component only was obtained. In both modes, OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis and was only present in large amounts when new wood was added to the stove. In SP-AMS mode, BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C1-5+), oxygenated carbonaceous ions (CO1-2+), potassium (K+), and water (H2O+ and related fragments). The C4+ : C3+ ratio, but not the C1+ : C3+ ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO1-2+ signals likely originated from BC surface groups: upon aging, both CO+ and CO2+ increased relative to C1-3+ while CO2+ simultaneously increased relative to CO+. Factor analysis (positive matrix factorization) of SP-AMS and AMS data, using a modified error model to address peak-integration uncertainties, indicated that the surface composition of the BC was approximately constant across all stages of combustion for both fresh and aged samples. These results represent the first time-resolved measurements of in situ BC surface aging and suggest that the surface of beech-wood BC may be modelled as a single chemical species.

  10. Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures.

    SciTech Connect

    Palmer, Donald; Machesky, Michael L.; Benezeth, Pascale; Wesolowski, David J

    2009-07-01

    Surface titrations were carried out on suspensions of monoclinic ZrO{sub 2} from 25 to 290 C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol {center_dot} kg{sup -1}(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li{sup +}, Na{sup +}, K{sup +} and (CH{sub 3}){sub 4}N{sup +}, and the magnitude of their association with the surface. The combined results were treated with a 1-pK{sub a} MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pH{sub zpc}, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250 C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO{sub 2} particles from 200 to 360 C. At 350 and 360 C, Li{sup +} and OH{sup -} ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO{sub 2} surfaces at near-neutral pH conditions as indicated in earlier publications.

  11. Catalytic oxidation of cinnamyl alcohol using Au-Ag nanotubes investigated by surface-enhanced Raman spectroscopy.

    PubMed

    Costa, Jean Claudio Santos; Corio, Paola; Rossi, Liane Marcia

    2015-05-14

    Surface-enhanced Raman spectroscopy (SERS) enables ultrasensitive detection of adsorbed species at the catalyst surface. However, it is quite difficult to combine catalytic and SERS activities on the same material. Here we report the application of well-defined Au-Ag nanotubes as both SERS substrates and catalysts for the oxidation of cinnamyl alcohol. The species adsorbed on the catalyst surfaces at different reaction times were analyzed by SERS. The bimetallic nanotubes prepared via a simple galvanic replacement reaction are highly active in the oxidation of cinnamyl alcohol, but do not avoid a radical-chain reaction and the cleavage of the carbon-carbon double bond. A comparison between changes in bulk composition and the nature of adsorbed species at the surface of the catalyst over time suggests that cinnamaldehyde is formed on the catalyst surface (metal-catalyzed oxidation) and benzaldehyde is probably formed in the bulk solution via a radical-chain pathway. In the presence of 2,6-di-tert-butyl-4-methylphenol, the radical-chain reaction is suppressed and the oxidation reaction produces cinnamaldehyde. PMID:25895522

  12. Generation of Chloride Active Defects at the Aluminum Oxide Surface for the Study of Localized Corrosion Initiation

    SciTech Connect

    Barbour, J.C.; Missert, N.; Son, K.-A; Wall, F.D.; Zavadil, K.R.

    1998-12-07

    The generation of surface defects on electron cyclotron resonance (ECR) plasma derived aluminum oxide films has been studied. We find that Cl active O vacancies can be generated using electron and ion irradiation yielding surface concentrations of 3 xl 013 to 1X1014 sites"cm-2. These values correspond to surface defect concentrations of 3 to 10% when compared to ordered, crystalline u-alumina. The vacancies appear to be responsible for increased surface O concentrations when immersed in water. Anodic polarization of irradiated films yields a decrease in the stable pitting potential which correlates with electron dose.

  13. Fabrication of super slippery sheet-layered and porous anodic aluminium oxide surfaces and its anticorrosion property

    NASA Astrophysics Data System (ADS)

    Song, Tingting; Liu, Qi; Liu, Jingyuan; Yang, Wanlu; Chen, Rongrong; Jing, Xiaoyan; Takahashi, Kazunobu; Wang, Jun

    2015-11-01

    Inspired by natural plants such as Nepenthes pitcher plants, super slippery surfaces have been developed to improve the attributes of repellent surfaces. In this report, super slippery porous anodic aluminium oxide (AAO) surfaces have fabricated by a simple and reproducible method. Firstly, the aluminium substrates were treated by an anodic process producing micro-nano structured sheet-layered pores, and then immersed in Methyl Silicone Oil, Fluororalkylsilane (FAS) and DuPont Krytox, respectively, generating super slippery surfaces. Such a good material with excellent anti-corrosion property through a simple and repeatable method may be potential candidates for metallic application in anti-corrosion and extreme environment.

  14. The Golden Crown: A Single Au Atom that Boosts the CO Oxidation Catalyzed by a Palladium Cluster on Titania Surfaces

    SciTech Connect

    Zhang, Jin; Alexandrova, Anastassia N.

    2013-07-18

    We show that at the subnano scale, the catalytic properties of surface-supported clusters can be majorly impacted by strategic doping and the choice for the supporting surface. This is a first-principles investigation of CO oxidation catalyzed by two subnanoclusters, Pd4Au and Pd5, deposited on rutile TiO2(110) surfaces. The titania surface was found to participate in the reaction directly via providing additional reaction pathways. The bimetallic cluster Pd4Au shows enhanced catalytic activity, whereas the monometallic Pd5 is poisoned and deactivated in the presence of CO and oxygen, and this trend is reversed from that in the gas phase.

  15. Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Mariner, R.; Rice, A.

    1991-01-01

    Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

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

    E-print Network

    2004-01-01

    Colloids and Surfaces B: Biointerfaces 36 (2004) 81­90 Bacterial adhesion to glass and metalM, respectively) to 11 different surfaces and examined adhesion as a function of charge, hydrophobicity (water contact angle) and surface energy. Inorganic surfaces included three uncoated glass surfaces and eight

  17. Thermo-Oxidative Stability of Graphite/PMR-15 Composites: Effect of Fiber Surface Modification on Composite Shear Properties

    NASA Technical Reports Server (NTRS)

    Madhukar, Madhu S.; Bowles, Kenneth J.; Papadopolous, Demetrios S.

    1994-01-01

    Experiments were conducted to establish a correlation between the weight loss of a polyimide (PMR- 15) matrix and graphite fibers and the in-plane shear properties of their unidirectional composites subjected to different isothermal aging times up to 1000 hr at 316 C. The role of fiber surface treatment on the composite degradation during the thermo-oxidative aging was investigated by using A4 graphite fibers with three surface modifications: untreated (AU-4), surface treated (AS-4), and surface treated and sized with an epoxy-compatible sizing (AS-4G). The weight loss of the matrix fibers, and composites was determined during the aging. The effect of thermal aging was seen in all the fiber samples in terms of weight loss and reduction in fiber diameter. Calculated values of weight loss fluxes for different surfaces of rectangular unidirectional composite plates showed that the largest weight loss occurred at those cut surfaces where fibers were perpendicular to the surface. Consequently, the largest amount of damage was also noted on these cut surfaces. Optical observation of the neat matrix and composite plates subjected to different aging times revealed that the degradation (such as matrix microcracking and void growth) occurred in a thin surface layer near the specimen edges. The in-plane shear modulus of the composites was unaffected by the fiber surface treatment and the thermal aging. The shear strength of the composites with the untreated fibers was the lowest and it decreased with aging. A fracture surface examination of the composites with untreated fibers suggested that the weak interface allowed the oxidation reaction to proceed along the interface and thus expose the inner material to further oxidation. The results indicated that the fiber-matrix interface affected the composite degradation process during its thermal aging and that the the weak interface accelerated the composite degradation.

  18. Nitric oxide therapies for local inhibition of platelets' activitation on blood-contacting surfaces

    NASA Astrophysics Data System (ADS)

    Amoako, Kagya Agyeman

    Blood-contacting devices interact with blood during their function much like the endothelium that modulates hemostasis. The surfaces of these devices however, lack endothelial-like properties, and consequently, upon blood contact, activate clotting factors to form clots. Systemic heparinization for inhibiting clot formation can cause bleeding and surface coatings show insignificant benefits. This research investigated nitric oxide (NO) production mimicry of the endothehum on artificial lungs (ALs) and pediatric catheters. Their surfaces were functionalized either by (1) entrapping NO donors inside their bulk, (2) incorporating catalysts to generate NO from NO-donors or (3) supplementing NO into sweep gas of artificial lungs. Pediatric catheters functionalized with NO-donor thin coats using method 1 is limited by short NO release duration. Method 2 has not been applied to large surface-area, low-flow devices like the AL. In this work NO-generating silicone membranes were synthesized and characterized to determine the relationship between surface properties, NO flux, and blood clotting time. These outcomes helped develop and optimize NO-generating gas-exchange silicone fibers that represent the majority of ALs surface area. The first NO-generating AL prototypes, using those fibers, were manufactured, incorporated into NO-generating circuits and tested for their non-thrombogenicity. To test for NO-release duration and non-thrombogenicity, catheters were fabricated to incorporate NO-donors inside their walls, characterized for NO flux and release duration by chemilumincscence, and tested for patency using a thrombogenicity model in rabbits. Methods 1-2 involve material modification using complicated and expensive chemical formulations and/or manufacturing. Method 3 however, functionalizes ALs by only adding NO into sweep gas. Decade-long anti-clotting testing using a wide range of NO concentrations has been conducted without knowledge of what concentration yields endothelial NO flux levels in the AL. This concentration was determined for the MC3 Biolung and the Terumo capiox rx25 ALs in vitro. All these ideas have shown positive results in short-term studies, and each may play a necessary role in inhibiting clot formation in future ALs. The sufficiency however, of each idea or of a combination for clot inhibition in long-term ALs remains to be determined.

  19. Surface charges of oxides and wettability: Application to TiO2-SiO2 composite films

    NASA Astrophysics Data System (ADS)

    Joud, J.-C.; Houmard, M.; Berthomé, G.

    2013-12-01

    The super-hydrophilicity which can exist at the interface between oxides and aqueous solutions is able to sustain industrial and domestic applications. Several experimental results obtained on TiO2-SiO2 composite thin films via a sol-gel route have confirmed a natural and persistent super hydrophilicity under standard atmosphere. This property can be easily photo-regenerated after a long aging period in ambient atmosphere using a short UV illumination. The electrochemical double layer which classically exists between oxide surfaces and aqueous solution is unfavorable to high wettability properties of ideal flat surfaces. The present study indicates how the surface rugosity and the disjoining pressure caused by surface charges are able to explain the stability of a prewetting film. This film can withstand to vaporization in a weakly under saturated atmosphere, having a protective action despite a carbon contamination brought by standard atmosphere.

  20. Nickel-Oxide-Modified SrTiO3(110)-(4 × 1) Surfaces and Their Interaction with Water

    PubMed Central

    2015-01-01

    Nickel oxide (NiO), deposited onto the strontium titanate (SrTiO3) (110)-(4 × 1) surface, was studied using photoemission spectroscopy (PES), X-ray absorption near edge structure (XANES), and low-energy He+ ion scattering (LEIS), as well as scanning tunneling microscopy (STM). The main motivation for studying this system comes from the prominent role it plays in photocatalysis. The (4 × 1) reconstructed SrTiO3(110) surface was previously found to be remarkably inert toward water adsorption under ultrahigh-vacuum conditions. Nickel oxide grows on this surface as patches without any apparent ordered structure. PES and LEIS reveal an upward band bending, a reduction of the band gap, and reactivity toward water adsorption upon deposition of NiO. Spectroscopic results are discussed with respect to the enhanced reactivity toward water of the NiO-loaded surface. PMID:26617682

  1. O-(carboxymethyl)-chitosan nanofiltration membrane surface functionalized with graphene oxide nanosheets for enhanced desalting properties.

    PubMed

    Wang, Jiali; Gao, Xueli; Wang, Jian; Wei, Yi; Li, Zhaokui; Gao, Congjie

    2015-02-25

    A novel O-(carboxymethyl)-chitosan (OCMC) nanofiltration (NF) membrane is developed via surface functionalization with graphene oxide (GO) nanosheets to enhance desalting properties. Using ring-opening polymerization between epoxy groups of GO nanosheets and amino groups of OCMC active layer, GO nanosheets are irreversibly bound to the membrane. The OCMC NF membranes surface-functionalized with GO nanosheets are characterized by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, contact angle analyzer, and zeta potential analyzer. The membranes exhibit not only higher permeability but also better salt rejections than the pristine membranes and the commercial NF membranes; besides, the desalting properties are enhanced with the concentration of GO nanosheets increasing. Furthermore, the transport mechanism of GO-OCMC NF membranes reveals that the nanoporous structure of GO-OCMC functional layer and size exclusion and electrostatic repulsion of water nanochannels formed by GO nanosheets lead to the membranes possessing enhanced desalting properties. PMID:25635511

  2. Zinc oxide nanolevel surface transformation for liquid crystal orientation by ion bombardment

    SciTech Connect

    Oh, Byeong-Yun; Lee, Won-Kyu; Kim, Young-Hwan; Seo, Dae-Shik

    2009-03-01

    This paper introduces the characteristics of the zinc oxide (ZnO) inorganic film deposited by radio-frequency magnetron sputtering as an alternative alignment layer for liquid crystal display (LCD) applications. The crystalline structure related to the texture formation of ZnO (1013) was observed with a tilt angle of approximately 28.1 deg. to the ZnO (0001) plane, leading to a smooth surface and high-density structure. Ion beam (IB) bombardment at various incident angles was used to induce liquid crystal (LC) alignment and cause the measured pretilt angle on ZnO films to assume a triangular contour. The orientation order of liquid crystal molecules was due to the van der Waals force for the vertical alignment of LCs with selective breaking of O-Zn bonds by IB bombardment. The contact angle contour as a function of the IB incident angle resembled the behavior of the pretilt angle. The pretilt angle is controllable by adjusting the surface features on ZnO films with IB bombardment. The electro-optic characteristics of vertically aligned (VA)-LCD based on ZnO film were comparable to those of VA-LCD based on polyimide, showing good potential of ZnO film as a LC alignment layer.

  3. Effect of magnetic iron oxide nanoparticles in surface water treatment: trace minerals and microbes.

    PubMed

    Lakshmanan, Ramnath; Okoli, Chuka; Boutonnet, Magali; Järås, Sven; Rajarao, Gunaratna K

    2013-02-01

    The existing water treatment process often uses chemicals, which is of high health and environmental concern. The present study focused on the efficiency of microemulsion prepared magnetic iron oxide nanoparticles (ME-MIONs) and protein-functionalized nanoparticles (MOCP+ME-MIONs) in water treatment. Their influence on mineral ions and microorganisms present in the surface water from lake Brunnsviken and Örlången, Sweden were investigated. Ion analysis of water samples before and after treatment with nanoparticles was performed. Microbial content was analyzed by colony forming units (CFU/ml). The results impart that ME-MIONs could reduce the water turbidity even in low turbid water samples. Reduction of microbial content (98%) was observed at 37°C and more than 90% reduction was seen at RT and 30 °C when compared to untreated samples from lake Örlången. The investigated surface water treatment method with ME-MIONs was not significantly affecting the mineral ion composition, which implies their potential complement in the existing treatment process. PMID:23337539

  4. High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

    SciTech Connect

    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 NH? gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g?¹), high electrical conductivity (1532S m?¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg?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, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorption fine-structure spectroscopy evidenced the recover of ?-conjugation in the carbon networks with the removal of oxygenated groups and revealed the 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.

  5. High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

    DOE PAGESBeta

    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 NH? gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g?¹), high electrical conductivity (1532S m?¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg?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, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorptionmore »fine-structure spectroscopy evidenced the recover of ?-conjugation in the carbon networks with the removal of oxygenated groups and revealed the 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.« less

  6. Electronic passivation of silicon surfaces by thin films of atomic layer deposited gallium oxide

    SciTech Connect

    Allen, T. G. Cuevas, A.

    2014-07-21

    This paper proposes the application of gallium oxide (Ga{sub 2}O{sub 3}) thin films to crystalline silicon solar cells. Effective passivation of n- and p-type crystalline silicon surfaces has been achieved by the application of very thin Ga{sub 2}O{sub 3} films prepared by atomic layer deposition using trimethylgallium (TMGa) and ozone (O{sub 3}) as the reactants. Surface recombination velocities as low as 6.1?cm/s have been recorded with films less than 4.5?nm thick. A range of deposition parameters has been explored, with growth rates of approximately 0.2?Å/cycle providing optimum passivation. The thermal activation energy for passivation of the Si-Ga{sub 2}O{sub 3} interface has been found to be approximately 0.5?eV. Depassivation of the interface was observed for prolonged annealing at increased temperatures. The activation energy for depassivation was measured to be 1.9?eV.

  7. Surfactant-monomer interactions: Towards oxidative surface polymerization of transparent conducting polymers

    NASA Astrophysics Data System (ADS)

    Mukherjee, Smita; Kumar, Anshu; Sikder, Bikash K.; Kumar, Anil

    2013-02-01

    Surface pressure-molecular area (?-A) isotherms of mixed Langmuir monolayers of stearic acid (StA) and monomers based on 3,4-alkylenedioxythiophene (ADOTs), have been studied. Preliminary results show less (more) increase in A than expected, with increase in molar concentration for monomer M1 viz. 3,4-ethylenedioxythiophene (EDOT) (its long chain counterpart, M2). Presence of ferric chloride in subphase causes A to increase considerably for M1, but has no effect on M2. Moreover, unlike in M1, systematic decrease in slope m of `liquid' L2, L2' phases and `solid' S phase with increase in concentration of M2 indicate decreased complexity of system compared to StA. Again, in presence of ferric chloride, m was found to decrease in M1, but remain unchanged in M2. Results indicate strong interplay of hydrophobic and hydrophilic interactions at air-water interface, mediated through probable interaction with subphase ions and hydrocarbon chains. Findings are a first step towards understanding structural changes occurring during oxidative surface polymerization of oriented transparent conducting polymers (TCPs).

  8. Surface chemistry of coated lithium manganese nickel oxide thin film cathodes studied by XPS

    SciTech Connect

    Baggetto, Loic; Dudney, Nancy J; Veith, Gabriel M

    2013-01-01

    The effect of coating high voltage LiMn1.5Ni0.5O4 spinel cathode thin films with three metal oxide thin layers is discussed. The changes in surface chemistry of the electrodes are measured by X-ray photoelectron spectroscopy. ZnO is found to decompose during the first charge whereas Al2O3 and ZrO2 are stable for more than 100 cycles. ZrO2, however, importantly limits the available Li storage capacity of the electrochemical reaction due to poorer kinetics. Al2O3 offers the best results in term of capacity retention. Upon cycling, the evidence of a signal at 75.4 eV in the Al2p binding energy spectrum indicates the partial conversion of Al2O3 into Al2O2F2. Moreover, the continuous formation of PEO , esters and LixPOyFz compounds on the surface of the electrodes is found for all coating materials.

  9. High Performance Carbon Nanotube Yarn Supercapacitors with a Surface-Oxidized Copper Current Collector.

    PubMed

    Zhang, Daohong; Wu, Yunlong; Li, Ting; Huang, Yin; Zhang, Aiqing; Miao, Menghe

    2015-11-25

    Threadlike linear supercapacitors have demonstrated high potential for constructing fabrics to power electronic textiles (eTextiles). To improve the cyclic electrochemical performance and to produce power fabrics large enough for practical applications, a current collector has been introduced into the linear supercapcitors to transport charges produced by active materials along the length of the supercapacitor with high efficiency. Here, we first screened six candidate metal filaments (Pt, Au, Ag, AuAg, PtCu, and Cu) as current collectors for carbon nanotube (CNT) yarn-based linear supercapacitors. Although all of the metal filaments significantly improved the electrochemical performance of the linear supercapacitor, two supercapacitors constructed from Cu and PtCu filaments, respectively, demonstrate far better electrochemical performance than the other four supercapacitors. Further investigation shows that the surfaces of the two Cu-containing filaments are oxidized by the surrounding polymer electrolyte in the electrode. While the unoxidized core of the Cu-containing filaments remains highly conductive and functions as a current collector, the resulting CuO on the surface is an electrochemically active material. The linear supercapacitor architecture incorporating dual active materials CNT + Cu extends the potential window from 1.0 to 1.4 V, leading to significant improvement to the energy density and power density. PMID:26523943

  10. Surface ligand dependent toxicity of zinc oxide nanoparticles in HepG2 cell model

    NASA Astrophysics Data System (ADS)

    Bartczak, D.; Baradez, M.-O.; Merson, S.; Goenaga-Infante, H.; Marshall, D.

    2013-04-01

    Physicochemical properties of nanoparticles (NP) strongly affect their influence on cell behaviour, but can be significantly distorted by interactions with the proteins present in biological solutions. In this study we show how different surface functionalities of zinc oxide (ZnO) NP lead to changes in the size distribution and dissolution of the NP in serum containing cell culture media and how this impacts on NP toxicity. NPs capped with weakly bound large proteins undergo substantial transformations due to the exchange of the original surface ligands to the components of the cell culture media. Conversely, NP capped with a tight monolayer of small organic molecules or with covalently conjugated proteins show significantly higher stability. These differences in ligand exchange also affect the toxicity of the NP to the HepG2 liver cell model, with the NP capped with small organic molecules being more toxic than those capped with large proteins. This study highlights the importance of characterising NPs in biological media and the effect the media has during in-vitro analysis.

  11. High-Surface-Area Nitrogen-Doped Reduced Graphene Oxide for Electric Double-Layer Capacitors.

    PubMed

    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

    2015-06-01

    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 ? 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. PMID:25916491

  12. Optimization of Ni-YSZ solid oxide fuel cell anodes by surface laser melting

    NASA Astrophysics Data System (ADS)

    Cubero, A.; Peña, J. I.; Laguna-Bercero, M. A.

    2015-04-01

    A cermet composed of a metallic component (nickel) and a ceramic matrix (yttria stabilized zirconia) is commonly used as the anode for solid oxide fuel cells (SOFC). In the present work we intend to improve the performance of Ni-YSZ anodes by surface laser melting. Symmetrical cells, consisting of two NiO-YSZ anodes (?20 ?m thickness) separated by a relatively thin YSZ electrolyte (?500 ?m) were fabricated by convectional ceramic techniques. Subsequently, laser melting treatments of both anodes were performed using a CO2 laser system, producing a NiO-YSZ eutectic lamellar microstructure. Laser power of 100 W and processing rates of 1 mm s-1 were determined as the optimum processing conditions. Symmetrical processed plates (eutectic sample) were electrically characterized by impedance spectroscopy (EIS), and the results were compared with non-processed plates (ceramic sample). Preliminary EIS results showed that the polarization resistance at higher temperatures (in the range of 900 °C) is about 0.5 ? cm2 for both the eutectic and the ceramic sample. However, at lower temperatures (in the range of 800 °C) the polarization resistance for both samples differs considerably (2.9 and 1.6 ? cm2 for the ceramic and eutectic sample, respectively). These experiments confirmed that optimization of the microstructure by laser surface treatment plays a crucial role in the electrochemical properties of the anode cermets.

  13. An unusual surface peroxiredoxin protects invasive Entamoeba histolytica from oxidant attack.

    PubMed

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

    2005-09-01

    Peroxiredoxins are an important class of antioxidant enzymes found from Archaea to humans, which reduce and thereby detoxify peroxides and peroxynitrites. The major thiol-containing surface antigen of the invasive ameba, Entamoeba histolytica, is a peroxiredoxin and is likely to be important during the transition from the anaerobic environment of the large intestine to human tissues. The closely related species, Entamoeba dispar, is incapable of invasion and more sensitive to hydrogen peroxide, yet also has a peroxiredoxin. We cloned and expressed the two active recombinant enzymes and found that their activity was similar by a fluorometric stopped-flow assay, giving a Km of <10 microM for hydrogen peroxide. Three monoclonal antibodies produced to recombinant E. histolytica peroxiredoxin cross-reacted with Entamoeba dispar.E. histolytica contains as much as 50 times more peroxiredoxin than E. dispar as demonstrated by a sensitive capture ELISA. In addition, the peroxiredoxin is present largely on the outer surface of the cell, in contrast to E. dispar. This unusual peroxiredoxin localizes to the site of parasite-host cell contact where it can effectively counteract oxidants generated by host cells, thus facilitating invasion. PMID:15996766

  14. Nanopore formation on the surface oxide of commercially pure titanium grade 4 using a pulsed anodization method in sulfuric acid.

    PubMed

    Williamson, R S; Disegi, J; Griggs, J A; Roach, M D

    2013-10-01

    Titanium and its alloys form a thin amorphous protective surface oxide when exposed to an oxygen environment. The properties of this oxide layer are thought to be responsible for titanium and its alloys biocompatibility, chemical inertness, and corrosion resistance. Surface oxide crystallinity and pore size are regarded to be two of the more important properties in establishing successful osseointegration. Anodization is an electrochemical method of surface modification used for colorization marking and improved bioactivity on orthopedic and dental titanium implants. Research on titanium anodization using sulphuric acid has been reported in t