17 research outputs found

    Prediction of fretting fatigue behaviour using finite element method and machine learning

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    Study on Near-Net Forming Technology for Stepped Shaft by Cross-Wedge Rolling Based on Variable Cone Angle Billets

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    Considering problems about concaves at the stepped shaft ends, this paper established the plastic flow kinetic theories about metal deforming during the cross-wedge rolling (CWR) process. By means of the DEFORM-3D finite element software and the point tracing method, the forming process of stepped shafts and the forming mechanism of concaves at shaft ends were studied. Based on the forming features of stepped shafts, rolling pieces were designed using variable cone angle billets. Single-factor tests were conducted to analyze the influence law of the shape parameters of billet with variable cone angle on end concaves, and rolling experiments were performed for verification. According to the results, during the rolling process of stepped shafts, concaves will come into being in stages, and the increasing tendency of its depth is due to the wave mode, the parameters of cone angle α, the first cone section length n. Furthermore, the total cone section length m has an increasingly weaker influence on the end concaves. Specifically, cone angle α has the most significant influence on the quality of shaft ends, which is about twice the influence of the total cone section length m. The concave depth will decrease at the beginning, and then increase with the increasing of the cone angle α and the first cone section length n, and it will decrease with the increasing of the total cone section length m. Finite element numerical analysis results are perfectly consistent with experimental results, with the error ratio being lower than 5%. The results provide a reliable theoretical basis for effectively disposing of end concave problems during CWR, rationally confirming the shape parameters of billets with a variable cone angle, improving the quality of stepped shaft ends, and realizing the near-net forming process of cross-wedge rolling without a stub bar

    B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>‑Catalyzed (Convergent) Disproportionation Reaction of Indoles

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    A metal-free B­(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-catalyzed approach is developed for the disproportionation reaction of a series of indoles with various hydrosilanes, without any additives such as base and production of any small molecule such as dihydrogen. This boron catalyst system also exhibits excellent catalytic performance for practical application, such as catalyst loading as low as 0.01 mol % under solvent-free conditions, and a long-life catalytic performance highlighted by a constant catalytic activity being maintained and excellent yields being achieved for the desired products over 10 sequential additions of starting materials. On the basis of characterization of key intermediates through a series of in situ NMR reactions and detailed experimental data, we proposed a reaction mechanism which illustrated pathways for the formation of different products, including both major products and byproducts. Additional control experiments were conducted to support our proposed mechanism. Understanding the mechanism enables us to successfully suppress side reactions by choosing appropriate substrates and hydrosilanes. More importantly, the use of an elevated reaction temperature for continuous oxidation of the resulting indoline to indole makes the convergent disproportionation reaction an ideal atom-economical process. Near-quantitative conversions and up to 99% yields of C3-silylated indoles were achieved for various indoles with trisubstituted silanes, Ph<sub>3</sub>SiH (<b>2b</b>) or Ph<sub>2</sub>MeSiH (<b>2d</b>)

    B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>‑Catalyzed C3-Selective C–H Borylation of Indoles: Synthesis, Intermediates, and Reaction Mechanism

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    Without the addition of any additives and production of any small molecules, C3-borylated indoles and transfer hydrogenated indolines have been simultaneously achieved by a B­(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-catalyzed disproportionation reaction of a broad range of indoles with catecholborane. This catalyst system exhibits excellent catalytic performance for practical applications, such as easy scale-up under solvent-free conditions and long catalytic lifetime over ten sequential additions of starting materials. A combined mechanistic study, including isolation and characterization of key reaction intermediates, analysis of the disproportionation nature of the reaction, in situ NMR of the reaction, and analysis of detailed experimental data, has led to a possible reaction mechanism which illustrates pathways for the formation of both major products and byproducts. Understanding the reaction mechanism enables us to successfully suppress side reactions by choosing appropriate substrates and adjusting the amount of catecholborane needed. More importantly, with an elevated reaction temperature, we could achieve the convergent disproportionation reaction of indoles, in which indolines were continuously oxidized to indoles for the next disproportionation catalytic cycle. Near quantitative conversions and up to 98% yields of various C3-selective borylated indoles were achieved, without any additives or H<sub>2</sub> acceptors
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