6,332 publications from this institution
Abstract Die Umsetzung der Titanverbindung (I) mit der Di‐Li‐Verbindung (II) in der Kälte in Diäthyläther unter Stickstoff‐ oder Argonatmosphäre führt zu dem nur unter ‐30°C stabilen Tetramethylen‐Ti‐Produkt (III), dessen Thermolyse Buten‐(l) und Äthylen ergibt.
Abstract To explore the range of substrates accepted by L‐LDH at a rate useful in organic synthesis, kinetic parameters for the reduction of about 20 α‐keto acids such as (I) by L‐LDH are determined.
This Article compares the ability of self-assembled monolayers (SAMs) of alkanethiolates with ferrocene (Fc) head groups (SC(11)Fc), and SAMs of alkanethiolates lacking the Fc moiety (SC(10)CH(3) and SC(14)CH(3)), to conduct charge. Ultraflat surfaces of template-stripped silver (Ag(TS)) supported these SAMs, and a eutectic alloy of gallium and indium (EGaIn), covered with a skin of gallium oxide (presumably Ga(2)O(3)), formed electrical top-contacts with them. EGaIn is a liquid at room temperature, but its spontaneously formed surface oxide skin gives it apparent non-Newtonian properties and allows it to be molded into conically shaped tips; these tips formed soft electrical contacts with SAMs and formed stable SAM-based tunneling junctions in high (70-90%) yields. Measurements of current density, J, versus applied voltage, V, showed that tunneling junctions composed of SAMs of SC(11)Fc rectify current with a rectification ratio R approximately 1.0 x 10(2) (R = |J(-V)|/|J(V)| at +/-1 V and with a log-standard deviation of 3.0). In contrast, junctions lacking the Fc moiety, that is, junctions composed of SAMs of SC(n-1)CH(3) (with n = 11 or 15 and presenting terminal CH(3) groups), showed only slight rectification (R = 1.5 (1.4) and 2.1 (2.5), respectively). A statistical analysis of large numbers (N = 300-1000) of data gave detailed information about the spread in values and the statistical significance of the rectification ratios and demonstrated the ability of the experimental techniques described here to generate SAM-based junctions in high yield useful in physical-organic studies.
Coatings subject to residual compression eventually fail by buckle-driven delamination. The phenomenon is most vivid in thermal barrier coatings (TBCs) used in gas turbines. The failure evolution commences with the formation of a large number of small cracks at geometric imperfections near the interface. These cracks spread upon thermal exposure, particularly upon thermal cycling, because of the formation of a thermally grown oxide (TGO) beneath the TBC, which introduces normal and shear stress near the interface. Experimental observations indicate that some of these cracks coalesce to form large-scale delaminations susceptible to buckling. The mechanics governing crack coalescence and the consequent failure are addressed in the present analysis. A model is introduced that simulates stresses induced in the TBC by spatial variations in TGO growth. Energy release rates for cracks evolving in this stress field are determined. Two related scenarios are considered, which differ in the way the TGO shape evolves. In both, contact between the crack faces and the consequent wedging action is responsible for ultimate coalescence. The wedging force induces a mode I stress intensity that becomes infinite as the cracks coalesce. The consequence is that, for some TGO shapes, the energy release rate is always non-zero, with a minimum at a characteristic crack length. This minimum establishes a criterion for crack coalescence and failure. Based on these insights, finite element simulations have been used to predict cyclic crack growth rates in a TBC system that correlate well with experimental observations.
Recent experimental measurements have revealed that the amplitudes of undulations in the thermally grown oxide (TGO) formed on a bond coat subject to cyclic thermal histories depend on the bond coat thickness, h bc, and exhibit a maximum when h bc ≈100μm. The existing rumpling model does not predict the maximum. To account for this effect, the model has been extended to include finite substrate thickness. The embellished code predicts the maximum and demonstrates close correspondence between calculated and measured undulation amplitudes (provided that all of the strain misfits between the bond coat and substrate are included: thermal expansion, martensite transformation and swelling). The presence of the maximum is attributed to two opposing effects. When thin, the bond coat is unable to deform to the extent needed to accommodate the undulations in the TGO. Conversely, when it has finite thickness relative to the substrate, the strains induced in the substrate reduce the constraint imposed on the bond coat, again reducing its ability to accommodate the undulations.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNuclear Magnetic Resonance Spectroscopy. The Configurational Stability of Primary Grignard Reagents. Structure and Medium Effects1George M. Whitesides and John D. RobertsCite this: J. Am. Chem. Soc. 1965, 87, 21, 4878–4888Publication Date (Print):November 1, 1965Publication History Published online1 May 2002Published inissue 1 November 1965https://doi.org/10.1021/ja00949a035Request reuse permissionsArticle Views370Altmetric-Citations46LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alertsclose Get e-Alerts