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Organisationseinheit der BAM
Nanocrystalline particles of high temperature pretreated titania, zirconia or hafnium oxide, embedded in a carbon matrix, have been found to catalyze the aromatization of n-octane into ethylbenzene (EB) and o-xylene (OX) with high selectivity. The carbon matrix itself is catalytically not active, but seems to co-operate with the transition metal oxides in such a way that the various metal oxide/carbon composite materials exhibit equal selectivity patterns. In detail, the carbon component stabilizes a high dispersion of the oxides during the high temperature pretreatment procedure. This thermal treatment results in a destruction of surface acidity of the oxides, which would otherwise be responsible for undesirable consecutive and parallel reactions. Moreover, the carbon component is involved in the deep dehydrogenation of alkanes to multiple unsaturated alkenes. This is explained by the ability of surface carbon atoms to interact with hydrogen. The bulk and surface structure of the catalysts have been characterized by XRD, specific surface area measurements, XPS, UPS, Raman spectroscopy, in situ ESR and DRIFT spectroscopy.
A new setup is presented which enables simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) and Raman spectroscopic experiments during the synthesis of Mo-based mixed oxide catalyst precursors at the µ-spot beamline at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung (BESSY). Furthermore, we report about the separate monitoring of the same reactions under comparable conditions by simultaneous combined ATR/UVvis/Raman spectroscopic measurements. For testing the performance of both experimental setups two syntheses were described comprising the precipitation of metal molybdates by mixing solutions of metal nitrates and ammonium heptamolybdate. Additionally, the effect of H3PO4 admixture on precipitation was investigated. The combined evaluation of spectroscopic and WAXS/SAXS data allows the discrimination between different molybdate species appearing in solution and precipitate. Furthermore, these molybdate species could be assigned to separate phases of different crystallinity.
Iron-based catalysts are employed in CO2-FTS due to their ability to convert CO2 into CO in a first step and their selectivity towards higher hydrocarbons in a second CO hydrogenation step. According to the literature, iron carbides represent the active phase for hydrocarbon formation and are claimed to emerge in the presence of CO. We propose nanostructured FeOx films as model systems to assess information about the complex phase transformations during CO2-FTS. Mesoporous hematite, ferrihydrite, maghemite, maghemite/magnetite films were exposed to CO2-FTS atmospheres at 20 bar and 300°C. Up to three distinct phases were observed depending on the timeon-stream (TOS): a sintered maghemite/magnetite phase, a carbidic core-shell structure, and a low-crystalline, needle-type oxide phase. Our findings indicate that the formation of an intermediary maghemite/magnetite phase, predominant after short TOS (30 h), precedes the evolution of the carbide phase.
Yet, even after prolonged TOS (185 h), no full conversion into a bulk carbide is observed.
Monometallic Cu and bimetallic Cu/Au-TiO2 catalysts were prepared by impregnation (IM) and reductive precipitation (RP)methods in sequential (SP) and simultaneous mode (CP) and tested for photocatalytic H2 generation from H2O/Methanol mixtures with visible (400–700 nm) and UV/Vis light (320– 500 nm). Comprehensive studies by high-resolution (HR)-STEM, X-ray photoelectron spectroscopy (XPS), and different in situ methods (X-ray Absorption near-edge structure (XANES), UV/Vis, and EPR spectroscopy) revealed that IM leads to dispersed surface Cu species with no clear particle formation, which is poorly active under visible light, whereas plasmonic Cu0 nanoparticles formed by RP are about three times more active under the same conditions. In Cu/Au-TiO2 catalysts prepared by RP-SP, highly dispersed Cu surface species boost H2 production under UV/Vis light, owing to the effective separation within TiO2 and electron trapping by Cu, whereas small Cu0 and Au0 particles remain widely separated. When Cu/Au-TiO2 catalysts are prepared by RP-CP, mixed Cu/Au particles of uniform size (4–8 nm) provide the highest H2 evolution rates under visible light, owing to effective surface plasmon resonance absorption.
Influence of Sb on the structure and performance of Pd-based catalysts: An X-ray spectroscopic study
(2017)
Combined X-ray photoelectron and absorption fine spectroscopy (XAFS) investigations on 10 wt % Pd–16 wt % Sb/TiO2 catalyst allow new insight into the impact of the co-component Sb on the active Pd species, which catalyzes the gas-phase acetoxylation of toluene to benzyl acetate. Ex situ Pd 3d XPS and Pd L-edge XANES studies indicate the presence of an excess electron charge on metallic Pd species (more 4d electrons than in Pd metal) formed after several hours of stream. This observation was explained by the electron transfer from metallic Sb incorporated into the Pd bulk to the neighboring Pd atoms. TEM-EDX analysis confirms the presence of intermixed Pd–Sb particles with an atomic ratio of between 5 and 6 in the most active catalysts and of 3 in deactivated samples. In situ Sb-K-edge XAFS investigations provide evidence that the Pd–Sb interaction is more pronounced under reaction feed than in the ex situ samples.
Moiré fringes for misfit measurements at incoherent y/y'-interfaces of nickel-base superalloys
(1998)
Aluminas with Fe2O3 particles finely divided in the Al2O3 matrix were prepared via a crystalline precursor derived from ammonium dawsonite and its calcination. The precursors with Fe content between 1 and 10 wt% were synthesized by reaction of ammonium hydrogen carbonate with mixtures containing aluminium ammonium sulfate and ferric ammonium sulfate. The characterization of the as-synthesized and calcined products by chemical analysis, XRD, EPR, Mössbauer, TEM and adsorption measurements shows that all the Fe3+ ions are incorporated into the structure of dawsonite when the Fe content is low and that the calcined materials with micropores and mesopores (maximum 3040 Å) also contain very small Fe2O3 particles (<10 nm) at higher Fe contents.
α(1 0 0) Dislocations are observed in nickel-base superalloys after creep deformation at high temperatures and low stresses. They are formed in the γ/γ´ interfaces by a three step mechanism. First, primary dislocations with Burgers vector α/2(1 0 1) and 60° character are left behind in the interfaces when dislocation loops glide through the γ channels. The 60° dislocations move into edge orientation and react forming secondary dislocations α/2(1 1 0). In the third step, new primary dislocations are knit into the already existing meshes of primary and secondary dislocations, which results in hexagonal misfit dislocation networks consisting of secondary dislocations α/2(1 1 0) and tertiary dislocations α(1 0 0), both of edge type. This self-organisation process is explained by dislocation theory and crystallography.
Creep deformation accelerates when the α(1 0 0) interfacial dislocations enter the γ´ phase. During their climb towards the opposite interface, they attain a characteristic rectangular shape. This shape and the importance of the α(1 0 0) super dislocations for creep deformation are discussed.
The slip-rolling resistances of hard and stiff thin films under high Hertzian contact pressures can be improved by optimizing the 'coating/substrate systems'. It is known from former investigations that the so-called 'egg-shell' effect is no general hindrance for high slip-rolling resistance of thin hard coatings. The coating stability depends more on specific deposition process and coating/substrate interface design. In this article it is experimentally shown, that pure amorphous carbon thin films with hardness between 15 and 63 GPa can be slip-rolling resistant several million load cycles under a maximum Hertzian contact pressures of up to 3.0 GPa. Whereas all coatings were stable up to 10 million load cycles in paraffin oil at room temperature, reduced coating lifetime was found in SAE 0W-30 engine oil at 120°C. It was shown how the coating hardness and the initial coating surface roughness influence the running-in process and coating lifetime. No clear correlation between coating hardness and coating lifetime could be observed, but friction coefficients seem to be reduced with higher coating hardness. Very low friction down to ~0.03 in unmodified engine oils was found for the hardest ta-C film.------------------------------------------------------------------------------------------------------------------------------------------------
Die Wälzbeständigkeit von harten und steifen Dünnschichten unter hohen Hertzschen Kontaktpressungen kann durch die Optimierung des 'Beschichtung/Substrat Systems' deutlich verbessert werden. Aus vorangegangenen Untersuchungen ist bekannt, dass der so genannte 'Eierschaleneffekt' kein generelles Hindernis für eine hohe Wälzbeständigkeit für harte Dünnschichten darstellen muss. Die Stabilität der Beschichtungen hängt vielmehr von dem spezifischen Prozessparametern und dem Schicht/Substrat Grenzflächendesign ab. In diesem Artikel wird experimentell nachgewiesen, dass reine amorphe Kohlenstoffdünnschichten mit Härtewerten zwischen 15 und 63 GPa für mehrere Millionen Lastzyklen unter maximalen Hertzschen Kontaktpressungen bis 3.0 GPa überrollbeständig sein können. Während alle Beschichtungen bis 10 Millionen Lastzyklen in Paraffinöl bei Raumtemperatur keine Defekte aufweisen wurde unter Verwendung eines SAE 0W-30 Motorenöls bei 120°C eine Verringerung der Überrollbeständigkeit nachgewiesen. Es wurde nachgewiesen, wie die Schichthärte und ursprüngliche Oberflächenrauheit der Beschichtung den Einlaufprozess und die Lebensdauer beeinflussen. Es konnte keine offensichtliche Korrelation zwischen Schichthärte und Lebensdauer festgestellt werden, allerdings wurde eine scheinbare Reduktion des Reibwertes mit steigender Schichthärte beobachtet werden. Dabei zeigte die härteste ta-C Schicht unter Verwendung des Motorenöls sehr geringe Reibwerte mit ~0.03.