974 resultados para Oxygen vacancy formation


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A technique to quantify in real time the microstructural changes occurring during mechanical nanoscale fatigue of ultrathin surface coatings has been developed. Cyclic nanoscale loading, with amplitudes less than 100 nm, is achieved with a mechanical probe miniaturized to fit inside a transmission electron microscope (TEM). The TEM tribological probe can be used for nanofriction and nanofatigue testing, with 3D control of the loading direction and simultaneous TEM imaging of the nano-objects. It is demonstrated that fracture of 10-20 nm thick amorphous carbon films on sharp gold asperities, by a single nanoscale shear impact, results in the formation of < 10 nm diameter amorphous carbon filaments. Failure of the same carbon films after cyclic nanofatigue, however, results in the formation of carbon nanostructures with a significant degree of graphitic ordering, including a carbon onion.

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The compounds Pb2PtO4 and PbPt2O4 were synthesized from an intimate mixture of yellow PbO and Pt metal powders by heating under pure oxygen gas at 973 K for periods up to 600 ks with intermediate grinding and recompacting. Both compounds were found to decompose on heating in pure oxygen to PbO and Pt, apparently in conflict with the requirements for equilibrium phase relations in the ternary system Pb–Pt–O. The oxygen chemical potential corresponding to the three-phase mixtures, Pb2PtO4 + PbO + Pt and PbPt2O4 + PbO + Pt were measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas at 0.1 MPa pressure as the reference electrode. The standard Gibbs free energies of formation of the ternary oxides were derived from the measurements. Analysis of the results indicated that the equilibrium involving three condensed phases Pb2PtO4 + PbO + Pt is metastable. Under equilibrium conditions, Pb2PtO4 should have decomposed to a mixture of PbO and PbPt2O4. Measurement of the oxygen potential corresponding to this equilibrium decomposition as a function of temperature indicated that decomposition temperature in pure oxygen is 1014(±2) K. This was further confirmed by direct determination of phase relations in the ternary Pb–Pt–O by equilibrating several compositions at 1023 K for periods up to 850 ks and phase identification of quenched samples using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Only one ternary oxide PbPt2O4 was stable at 1023 K under equilibrium conditions. Alloys and intermetallic compounds along the Pb–Pt binary were in equilibrium with PbO.

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This study highlights the formation of an artifact designed to mediate exploratory collaboration. The data for this study was collected during a Finnish adaptation of the thinking together approach. The aim of the approach is to teach pulps how to engage in educationally beneficial form of joint discussion, namely exploratory talk. At the heart of the approach lies a set of conversational ground rules aimed to promote the use of exploratory talk. The theoretical framework of the study is based on a sociocultural perspective on learning. A central argument in the framework is that physical and psychological tools play a crucial role in human action and learning. With the help of tools humans can escape the direct stimulus of the outside world and learn to control ourselves by using tools. During the implementation of the approach, the classroom community negotiates a set of six rules, which this study conceptualizes as an artifact that mediates exploratory collaboration. Prior research done about the thinking together approach has not extensively researched the formation of the rules, which give ample reason to conduct this study. The specific research questions asked were: What kind of negotiation trajectories did the ground rules form during the intervention? What meanings were negotiated for the ground rules during the intervention The methodological framework of the study is based on discourse analysis, which has been specified by adapting the social construction of intertextuality to analyze the meanings negotiated for the created rules. The study has town units of analysis: thematic episode and negotiation trajectory. A thematic episode is a stretch of talk-in-interaction where the participants talk about a certain ground rule or a theme relating to it. A negotiation trajectory is a chronological representation of the negotiation process of a certain ground rule during the intervention and is constructed of thematic episodes. Thematic episodes were analyzed with the adapted intertextuality analysis. A contrastive analysis was done on the trajectories. Lastly, the meanings negotiated for the created rules were compared to the guidelines provided by the approach. The main result of the study is the observation, that the meanings of the created rules were more aligned with the ground rules of cumulative talk, rather than exploratory talk. Although meanings relating also to exploratory talk were negotiated, they clearly were not the dominant form. In addition, the study observed that the trajectories of the rules were non identical. Despite connecting dimensions (symmetry, composition, continuity and explicitness) none of the trajectories shared exactly the same features as the others.

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Industry acceptance of alternative sulphite treatments for preventing blackspot in prawns is limited. This study demonstrated that dipping prawns (Penaeus monodon and Fenneropenaeus merguiensis) in a less concentrated solution for longer times provides better control of blackspot formation than the recommended 2 minute dip in 50 mg/L 4-hexylresorcinol. Protection improved as modified dipping times and solution concentrations increased. Blackspot protection provided by most of the modified dip methods was more effective than a 1 minute dip in 1% sodium metabisulphite. The recommended 2 minute dip method should be limited to 125 kg when used on consecutive 25-kg batches of prawns. Yields increased by less than 10% even after 72-hour exposure in the modified dip. The new dipping method meets most international residue standards when applying the modified treatments evaluated.

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EELS and XPS studies show the presence of both adsorbed atomic and molecular oxygen at low temperatures. The nature of the oxide layer formed on the surface has been characterized by angular dependent and variable temperature EELS. A loss peak around 550 cm−1 is assigned to an electronic transition.

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EELS studies provide definitive evidence for the hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces on interaction with proton donor molecules such as H2O, CH3OH, HCOOH, NH3 and (CH3)2NH. The occurrence of surface hydroxylation is unambigouusly shown by a study of the interaction of H2S and HCl with an oxygen covered Cu(110) surface.

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From a temperature programmed desorption study employing a quadrupole mass spectrometer, the superconducting oxide YBa2Cu3O7−δ (δ = 0.05) showed two distinct oxygen desorption peaks, one below and one above 470°C. The activation energy of oxygen desorption of the superconducting oxide was 28 Kcals/mole and that of non-superconducting oxide (YBa2Cu3O6.5) was 54 Kcals/mole. No impurity peaks due to H2O, CO and CO2 from the bulk or adsorbed on surfaces could be observed when a well prepared superconducting oxide was heated up to 650°C.

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A pin-on-disc test configuration has been used to examine the formation of the strain-hardened projection, or wear lips, especially at the trailing edge of the pin during dry sliding of aluminium alloys against steel discs. The mechanism of formation of such wear lips is studied with the aid of optical and electron microscopes. The plastic deformation of the pin, growth and eventual removal of the wear lip as wear debris are elucidated. The size and shape of the wear lips in pins of different shapes, i.e. square, rectangular, triangular and circular cross-sections, are described.

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Electron energy loss spectroscopy (EELS) has been employed to monitor surface conductivity changes in YBa2Cu3O7 as a function of temperature. Concomitant use of x-ray photoelectron spectroscopy (XPS) establishes that the formation of oxygen dimers with lowering of temperature is accompanied by a simultaneous increase of surface conductivity.

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The phenomenological theory of hemispherical growth is generalised to time-dependent nucleation and growth-rates. Special cases, which include models with diffusion-controlled rates, are analysed. Expressions are obtained for small and large time behaviour and peak characteristics of potentiostatic transients, and their use in model parameter estimation is discussed. Two earlier equations are corrected. Numerically calculated transients which are presented exhibit some interesting features such as a maximum preceding the steady state, oscillations and shoulder.

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A general theory is evolved for a class of macrogrowth models which possess two independent growth-rates. Relations connecting growth-rates to growth geometry are established and some new growth forms are shown to result for models with passivation or diffusion-controlled rates. The corresponding potentiostatic responses, their small and large time behaviours and peak characteristics are obtained. Numerical transients are also presented. An empirical equation is derived as a special case and an earlier equation is corrected. An interesting stochastic result pertaining to nucleation events in the successive layers is proved.

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X-ray photoelectron and Auger spectroscopic techniques have been employed to study surface segregation and oxidation of Cu-1 at%Sn, Cu-9at%Pd and Cu-25at%Pd alloys. Both Cu-Pd(9%) and Cu-Pd(25%) alloys show segregation of Cu when heated above 500 K. The Pd concentration was reduced by 50% at 750 K compared to the bulk composition; the enthalpy of segregation of Cu is around - 6kJ/mol. Sn segregation is seen from 470 to 650 K in the Cu-Sn(1%) alloy, and a saturation plateau of Sn concentration above 650 K is observed. Surface oxidation of Cu-Sn(1%) and Cu-Pd(9%) alloys at 500 K showed the formation of Cu2O on the surface with total suppression of Sn or Pd on the respective alloy surfaces. On vacuum annealing the oxidised Cu-Sn alloy surface at 550 K, a displacement reaction 2Cu2O+Sn→4Cu+SnO2 was observed. However, under similar annealing of the oxidised Cu-Pd(9%) alloy surface at 500 K, oxide oxygen was totally desorbed leaving the Cu-Pd alloy surface clean. In the case of the Cu-Pd(25%) alloy, only dissociatively chemisorbed oxygen was seen at 500 K which desorbed at the same temperature. Oxygen spill-over from copper to palladium is suggested as the mechanism of oxygen desorption from the oxidised Cu-Pd alloy surfaces.