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91.
The roughening of interfaces as a function of layer thickness and magneto transport properties have been investigated on sputter-deposited Fe/Ni75B25 multilayer films. X-ray reflectivity data were recorded for Ni75B25(72 nm) film and for [Fe(2 nm)/Ni75B25(2 nm)]16 and [Fe(4 nm)/Ni75B25(4 nm)]8 multilayer films. A power law dependence of the interfacial width of growing Fe/Ni75B25 interfaces was observed. The resulting growth exponents β were found to be in the range of 0.55–0.58 in the initial growth stage of the multilayer with lower Fe/Ni75B25 repetition thickness and at approximately 0.34 for multilayer with higher repetition thickness. The growth exponents were compared with theoretical calculations. High resolution electron microscopy revealed the columnar growth of the Fe/Ni75B25 multilayer. Additionally, an increase of magnetoresistance was observed by the multilayering of Ni75B25 films with Fe interlayers.  相似文献   
92.
Photoacoustic effect and scanning near field microscopy have been applied to characterise the thermal properties of diamond crystallites which were coated by a Cu film, a Cr-film and a Cr-Cu film. The Cu-coated diamond exhibits a considerable thermal barrier at the Cu-diamond interface which had disappeared for the crystallites with a thin bond Cr-layer between diamond and Cu. The local inspection of the thermal conductivity with a thermal nano-probe operated in the 3ω-mode reveals slight local variations of the thermal conductivity of the Cr-coated crystallite.  相似文献   
93.
Based on the geodesic equation in a static spherically symmetric metric we discuss the rotation curve and gravitational lensing. The rotation curve determines one function in the metric without assuming Einstein’s equations. Then lensing is considered in the weak field approximation of general relativity. From the null geodesics we derive the lensing equation. The gravitational potential U(r) which determines the lensing is directly give by the rotation curve U(r) = −v 2(r). This allows to test general relativity on the scale of galaxies where dark matter is relevant.  相似文献   
94.
Using a coarse-grained molecular dynamics (CMD) approach we study the apparent nonlinear dynamics of water molecules filling or emptying carbon nanotubes as a function of system parameters. Different levels of the pore hydrophobicity give rise to tubes that are empty, water-filled, or fluctuate between these two long-lived metastable states. The corresponding coarse-grained free-energy surfaces and their hysteretic parameter dependence are explored by linking MD to continuum fixed point and bifurcation algorithms. The results are validated through equilibrium MD simulations.  相似文献   
95.
Sulphate and chloride concentrations in the shallow Pleistocene aquifer systems in the lower Jordan valley area indicate a general trend of increasing salinity eastward and southward. This study was conducted in one of the important sub-basins feeding the Pleo–Pleistocene aquifer in the Jericho area in the southern part of the valley using S and O isotopes of dissolved sulphate. The results show that sulphate has mainly two contributions to the groundwater. One is the surface seepage, which is present as a salty leachate form with the positive δ34Ssulphate values of primary gypsum in Lisan and Samara formations, and the second is the upwelling saline water which was in contact with a deep secondary gypsum, aragonites and salty rocks and rose up under heavy abstraction with depleted 34S in sulphate and relatively high sulphate and chloride content. The latest was clearly shown in the Arab Project wells to the east that is undergoing a continuous heavy abstraction. The isotopic signatures of S and O in these wells to the east show that this depleted 34S and highly concentrated sulphate might also indicate a dissolved sulphate originating from pyrite oxidation that results from the interaction with a pyrite-rich aquifer, which can well up with salty water under heavy abstraction and is oxidised in the upper aerobic shallow aquifer.  相似文献   
96.
Radiotracer diffusion studies of severely deformed, ultra-fine grained materials have revealed the presence of ultra-fast transport paths, which include “non-equilibrium” grain boundaries and free volume. Under some experimental conditions, percolating porosity is produced even in pure copper. Micro-cracks may form in metals, if the local maximum shear stress exceeds the shear yield stress. However, their growth and propagation is postponed till late in the deformation process owing to the ductility of metals, the hydrostatic component of the stress system and/or dynamic recovery/recrystallization. In other words, crack growth and propagation is present only when the scope for further deformation is highly restricted. Using this approach, the load required for equal channel angular pressing, the change in the slope of the Hall–Petch plot with decreasing grain size and the theoretical limit for the smallest grain size attainable in a metal in a severe plastic deformation process are predicted and validated by experimental results. Experimentally successful prevention of percolated crack formation by the superposition of a hydrostatic pressure is also accounted for using this model.  相似文献   
97.
98.
Zusammenfassung Die Elektronenstrukturen von Bis-durochinon-nickel(0) und der Komplexe vom Typ Olefin-Ni(0)-Chinon werden im Rahmen der LCAO-MO-Näherung diskutiert und zur Deutung der Absorptionsspektren herangezogen. Den im freien Durochmon auftretenden Übergängen lassen sich in den Komplexspektren jeweils nur wenig verschobene Banden zuordnen. Darüber hinaus wird eine intensive Charge-Transfer-Bande beobachtet, die einem Übergang vom höchsten besetzten Nickelzustand zum tiefsten unbesetzten Chinon-Orbital entspricht. Aus der Intensität der Bande, die im freien Chinon dem b 3g 2b 2 g-Übergang zugeordnet wird, ergibt sich für das gelöste Bis-durochinon-nickel(0)-Molekül die Symmetrie D 2h . Während die Komplexe mit Durochinon in Übereinstimmung mit der Theorie diamagnetisch sind, weisen die analogen Verbindungen der Dimethylchinone magnetische Momente von 1,52 bzw. 2,75 B. M. auf, woraus auf eine Mitbeteiligung polarer Strukturen am Grundzustand dieser Komplexe geschlossen wird.
The electronic structures of bis-duroquinone-nickel(0) and complexes of the type olefine-Ni(0)-quinone are discussed in the MO-LCAO approximation and used for an interpretation of the absorption spectra. The transitions of the free duroquinone can be correlated with transitions of the complexes at nearly the same wavelengths. In addition, an intense charge transfer band is observed which corresponds to a transition from the highest occupied nickel orbital to the lowest unoccupied quinone orbital. From the intensity of the band which corresponds to b 3g 2b2g in the free quinone, the symmetry D 2h for the dissolved bis-duroquinone-nickel(0) molecule is deduced. Whereas the duroquinone complexes are diamagnetic in agreement with theory, analogous compounds of the diméthylquinones exhibit magnetic momenta of 1.52 and 2.75 B. M. suggesting the participation of polar structures in the ground state of these complexes.

Résumé Les structures électroniques du bis-duroquinone-nickel(0) et des complexes du type oléfine-Ni(0)-quinone sont discutées dans le cadre del'approximationMO-LCAO et utilisées pour l'interprétation des spectres d'absorption. Aux transitions de la duroquinone libre peuvent être attribuées des bandes peu déplacées dans les spectres des complexes. En outre on observe une bande intense correspondant à une transition de la plus haute orbitale occupée du nickel à la plus basse orbitale libre de la quinone. L'intensité de la bande nommée b 3g 2b 2g dans la quinone libre indique la symétrie D 2h pour la molécule dissoute du bis-duroquinone-nickel(0). Tandis que les complexes de la duroquinone sont diamagnétiques en accord avec la théorie, des composés analogues des diméthylquinones présentent des moments magnétiques de 1,52 et de 2,75 B. M. d'où l'on infère la participation de structures polaires à l'état fondamental de ces complexes.


6. Mitteilung über Komplexe vom Typ des Bis-durochinon-nickel(0). 5. Mitt. vgl. [11].  相似文献   
99.
100.
Abstract

Thioäther, Sulfoxide, Sulfone, organische Selenide und Telluride (R – Y – R': R, R', = Alkyl, Aryl, Y=S, SO, SO2, Se, Te) werden an der Grenzfläche von Raney-Nickel hydrogenolysiert. Als Spaltprodukte entstehen die Verbindungen RH und R'H sowie eine Grenzflächenverbindung (Raney-Nickel-Y) (Y=S, Se, Te; S auch aus Sulfoxiden und Sulfonen. Letztere entbinden ebenfalls mit Mineralsäuren YH2).

Die Größe und ‘Struktur’ der Oberfläche des Raney-Nickels entscheidet über die Hydrogenolysekapazität. Bei einer technischen Raney-Nickel-Probe liegt bei Diphenylsulfid die Sättigungsausbeute an Benzol bei 1,1 mmol/g Raney-Nickel. Die Sättigungskapazität hängt ab von der Struktur von R bzw. R' und dem Heteroatom Y. (Auch Benzylether können–wenn auch langsamer als Thioether–zu Toluol aufgespalten werden). Auf Grund bekannter Daten werden Vorstellungen entwickelt, die ein Bild über den topochemischen Verlauf der Hydrogenolyse von R–Y–R' vermitteln sollen.

Vergiftetes Raney-Nickel ist im Gegensatz zum aktivierten Raney-Nickel nicht mehr oder nur stark vermindert zur Isomerisierung, Disproportionierung und zum H-D-Austausch befähigt. Bei diesen Prozessen spielt offenbar der im Nickel strukturgebundene Wasserstoff eine wichtige Rolle.

Some thioethers, sulphoxides, sulphones, organoselenium and tellurium compounds (R–Y–R' R, R'= Alkyl, Aryl, Y?S, SO, SO2, Se, Te) have been reductively cleaved on the surface of Raney-nickel. The products comprise RH and R'H, and a surface bound material (Raney-nickel-Y) (Y?S, also from sulphoxides and sulphones, Se, Te. The latter may be released as YH2 on treatment with mineral acids).

The area and ‘structure’ of the surface determines the hydrogenolysis capacity of the catalyst. For technical quality Raney-nickel, the limiting yield of benzene from diphenylsulphide is 1.1 mmol/g. The limiting yield is dependent on the structure of R and R' and also the nature of Y. (Benzyl ethers may also be reduced to toluene, if somewhat slower than the corresponding thioether).

Proposal for the processes possibly involved at the surface during hydrogenolysis of R–Y–R' are put forward in the basis of consideration of the available experimental data.

Poisoned Raney-nickel (in contrast to the activated catalyst) is practically inactive as agent for isomerization, disproportionation, or H–D exchange, and hence surface bound hydrogen clearly plays an important role in these processes.  相似文献   
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