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Stage-I fatigue cracks are commonly described by the model of Bilby, Cottrell and Swinden (BCS model). However, since several experimental investigations have shown a dislocation-free zone (DFZ) in front of crack-tips, it is necessary to validate the new DFZ model and to examine the deviations to the BCS model. Therefore, the dislocation density distribution is derived from height profiles of slip lines in front of stage-I fatigue cracks in CMSX4® single crystals measured by contact-mode atomic force microscopy. This is possible, because the cracks are initiated at notches milled by focused ion beam technique directly on slip planes with a high Schmid factor. Consequently, the directions of the Burgers vectors are well known; it is possible to calculate the dislocation density distributions from the height profiles. The measured distributions are compared to the calculated distribution function of the DFZ model proposed by Chang et al. The additionally measured microscopic friction stress of the dislocations is then used to calculate the influence of grain boundaries on the dislocation density distribution in front of stage-I cracks. The calculation is done by the extended DFZ model of Shiue et al. and compared with the measured distribution function in polycrystalline specimens. Finally, the crack-tip sliding displacement as a measure for the crack propagation rate is compared for the DFZ model and the BCS model with the experimentally revealed values. The important result: the often used BCS model does not reflect the experimental measurements. On the contrary, the DFZ model reflects the measurements at stage-I cracks qualitatively and quantitatively. 相似文献
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Is PdII‐Promoted σ‐Bond Metathesis Mechanism Operative for the PdPEPPSI Complex‐Catalyzed Amination of Chlorobenzene with Aniline? Experiment and Theory 下载免费PDF全文
Feiqun Wang Lei Zhu Yunfei Zhou Prof. Xiaoguang Bao Prof. Henry F. Schaefer III 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):4153-4161
Reduction of the Pd?PEPPSI precatalyst to a Pd0 species is generally thought to be essential to drive Buchwald–Hartwig amination reactions through the well‐ documented Pd0/PdII catalytic cycle and little attention has been paid to other possible mechanisms. Considered here is the Pd?PEPPSI‐catalyzed aryl amination of chlorobenzene with aniline. A neat reaction system was used in new experiments, from which the potentially reductive roles of the solvent and labile ligand of the PEPPSI complex in leading to Pd0 species are ruled out. Computational results demonstrate that anilido‐containing PdII intermediates involving σ‐bond metathesis in pathways leading to the diphenylamine product have relatively low barriers. Such pathways are more favorable energetically than the corresponding reductive elimination reactions resulting in Pd0 species and other putative routes, such as the PdII/PdIV mechanism, single electron transfer mechanism, and halide atom transfer mechanism. In some special cases, if reactants/additives are inadequate to reduce a PdII precatalyst, a PdII‐involved σ‐bond metathesis mechanism might be feasible to drive the Buchwald–Hartwig amination reactions. 相似文献
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The strain-rate-dependent behavior of a toughened matrix composite (IM7/8552) was characterized under quasi-static and dynamic loading conditions. Unidirectional and off-axis composite specimens were tested at strain rates ranging from 10?4 to 103 s?1 using a servo-hydraulic testing machine and split Hopkinson pressure bar apparatus. The nonlinear response and failure were analyzed and evaluated based on classical failure criteria and the Northwestern (NU) failure theory. The predictive NU theory was shown to be in excellent agreement with experimental results and to accurately predict the strain-rate-dependent failure of the composite system based on measured average lamina properties. 相似文献
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The impact of blood on liver metabolite profiling – a combined metabolomic and proteomic approach 下载免费PDF全文
Saray Ly‐Verdú Alexander Schaefer Melanie Kahle Thomas Groeger Susanne Neschen Jose M. Arteaga‐Salas Marius Ueffing Martin Hrabe de Angelis Ralf Zimmermann 《Biomedical chromatography : BMC》2014,28(2):231-240
Metabolomics has entered the well‐established omic sciences as it is an indispensable information resource to achieve a global picture of biological systems. The aim of the present study was to estimate the influence of blood removal from mice liver as part of sample preparation for metabolomic and proteomic studies. For this purpose, perfused mice liver tissue (i.e. with blood removed) and unperfused mice liver tissue (i.e. containing blood) were compared by two‐dimensional gas chromatography time of flight mass spectrometry (GC × GC‐TOFMS) for the metabolomic part, and by liquid chromatography tandem mass spectrometry (LC‐MS/MS) for the proteomic part. Our data showed significant differences between the unperfused and perfused liver tissue samples. Furthermore, we also observed an overlap of blood and tissue metabolite profiles in our data, suggesting that the perfusion of liver tissue prior to analysis is beneficial for an accurate metabolic profile of this organ. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Steven S. Wesolowski Edward F. Valeev Rollin A. King Victor Baranovski Henry F. Schaefer III 《Molecular physics》2013,111(16):1227-1231
Atomic natural orbital (ANO) basis sets for calcium may produce surprisingly poor atomic and molecular properties and energetics. The weaknesses in these basis sets may be traced primarily to deficiencies within the sets of d functions which are incapable of effectively correlating the 3s and 3p electrons. Examples are given which show that addition of tight d functions to the ANO basis is required to achieve qualitatively correct energetics and structures for conventionally bonded calcium compounds. 相似文献
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