Regioselective semihydrogenation of dienes

A one-pot, three-step strategy for the regioselective semihydrogenation of dienes is described. This procedure uses 9-BBN-H as a temporary protective group for alkenes. Yields range from 55% to 95%, and the reaction is tolerant of a variety of common functional groups. Additionally, the final elimination step of the sequence can be replaced with a peroxide-mediated alkylborane oxidation, generating regioselectively semihydrogenated product alcohols.     

Wavelet improvement in turning point detection using a hidden Markov model: from the aspects of cyclical identification and outlier correction

The hidden Markov model (HMM) has been widely used in regime classification and turning point detection for econometric series after the decisive paper by Hamilton (Econometrica 57(2):357–384, 1989). The present paper will show that when using HMM to detect the turning point in cyclical series, the accuracy of the detection will be influenced when the data are exposed to high volatilities or combine multiple types of cycles that have different frequency bands. Moreover, outliers will be frequently misidentified as turning points. The present paper shows that these issues can be resolved by wavelet multi-resolution analysis based methods. By providing both frequency and time resolutions, the wavelet power spectrum can identify the process dynamics at various resolution levels. We apply a Monte Carlo experiment to show that the detection accuracy of HMMs is highly improved when combined with the wavelet approach. Further simulations demonstrate the excellent accuracy of this improved HMM method relative to another two change point detection algorithms. Two empirical examples illustrate how the wavelet method can be applied to improve turning point detection in practice.     

Thermal Properties of Polymers at Low Temperatures

Abstract

The existing measurements and theories of the low-temperature thermal properties, heat capacity, and thermal conductivity of polymers are reviewed with particular attention paid to the differences between partly crystalline and amorphous polymers. The most striking feature of the low-temperature heat capacity of polymers is that in the liquid helium temperature range the heat capacity does not depend upon the cube of the temperature as for other solids. Further, only well below 1°K does the heat capacity approach the value predicted on the basis of the sound velocity. This behavior indicates the presence of a small number of low-frequency modes of vibration in the frequency spectrum. The fact that such anomalous behavior seems linearly related to the crystallinity implies that this behavior is associated with the amorphous structure, perhaps with motions of pendent groups within cavities formed in the amorphous structure. The thermal conductivity of semicrystalline and amorphous polymers differs considerably. Semicrystalline polymers display a temperature dependence of the thermal conductivity similar to that obtained from highly imperfect crystals, the thermal conductivity having a maximum in the temperature range near 100°K which moves to lower temperatures and higher thermal conductivities as the crystallinity is increased. Amorphous polymers display a temperature dependence similar to that obtained for glasses with no maximum but a significant plateau region in the range between 5 and 15°K. The theoretical interpretation of the thermal conductivity of these materials is considered.     

A regularized damage-plasticity model: micromorphic formulation and numerical aspects

A gradient-extended damage-plasticity model is discussed which is based on a micromorphic approach according to Forest [1]. Damage and plasticity are treated as independent but strongly coupled dissipative phenomena by considering separate yield and damage loading functions to describe the onset of plastic flow and / or damage evolution. A numerical benchmark test conducted in the study reveals that the model is able to essentially cure the well-known mesh-dependence issue which is known from finite element simulations involving conventional (i. e. ‘local’) damage material models. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Prediction of fracture in grain boundaries of nano-coatings using cohesive zone elements

A cohesive zone element technique (CZ) is applied to study grain boundary fracture in nano coating layers (see [1]). This goes along with the investigations of the delamination and fracture behavior of the coatings and the substrate interface. The main motivation is to investigate antiadhesive and wear resistant properties of coatings made of ceramics produced by the High Power Pulsed Magnetron Sputtering (HPPMS) technique [2]. Different physical conditions in HPPMS result into different grain morphologies with different mechanical properties. Therefore prediction of fracture and damage in such systems can lead to the optimum choice of process parameters in order to gain the best fracture resistance properties for the coatings. To illustrate the applicability of the model, several simulations with different mechanical and structural properties are performed. The developed CZ element model is capable of modeling the separation, the contact and also the irreversible reloading conditions in different directions [3]. The model is further developed to be applicable for geometrically complex interfaces including different bonding behaviors, with a high robustness. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Generalized Interface Models With Damage in Gradient Plasticity

Gradient plasticity can account for experimentally observed size effects. Here, a previously developed gradient plasticity model is extended to account for interface delamination processes. The crystal plasticity model is based on the gradient of an equivalent plastic strain measure. A modification of the related boundary conditions allows for the formulation of a generalized cohezive zone model which can take into account the effect of interface delamination on the gradient plasticity solution. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of an elastoplastic material model coupled to nonlocal damage in an implicit-gradient framework

In this work, an elastoplastic material model coupled to nonlocal damage is discussed which is based on an implicit gradient-enhanced approach. Combined nonlinear isotropic and kinematic hardening as well as continuum damage of Lemaitre-type are considered. The model is a direct nonlocal extension of a corresponding local model which was presented earlier (see e. g. [1], [2], [3]). Conclusions drawn from a numerical benchmark test performed in this study demonstrate that the nonlocal damage model is suitable to provide mesh-independent solutions in finite element simulations. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase-field modeling of martensitic phase transformations in polycrystals coupled with crystal plasticity – A spectral-based approach

The purpose of this work is the phase-field modeling of fcc-to-bcc martensitic phase transformations in polycrystals and the coupling with crystal plasticity. Assuming microscopic periodic fields, Green-function- and fast Fourier transform (FFT)-methods are used to solve the quasi-static balance of linear momentum. The Allen-Cahn evolution equation is discretized based on a semi-implicit time integration scheme in Fourier space. Two-dimensional results are presented and the interplay between martensitic phase transformation and plastic slip is studied at different stages of the deformation. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)