Mixture of Azolium Tetraphenylborate with Isopropylthioxanthone: A New Class of N-Heterocyclic Carbene (NHC) Photogenerator for Polyurethane,Polyester, and ROMP Polymers Synthesis

In the search of smarter routes to control the conditions of N-heterocyclic carbene (NHCs) formation, a two-component air-stable NHC photogenerating system is reported. It relies on the irradiation at 365 nm of a mixture of 2-isopropylthioxanthone (ITX) with 1,3-bis(mesityl)imidazoli(ni)um tetraphenylborate. The photoinduced liberation of NHC is evidenced by reaction with a mesitoyl radical to form an NHC-radical adduct detectable by electron spin resonance spectroscopy. The NHC yield can be determined by ¹H NMR spectroscopy through the formation of a soluble and stable NHC–carbodiimide adduct. To deprotonate the azolium salt and liberate the NHC, a mechanism is proposed in which the role of base is played by ITX radical anion formed in situ by a primary photoinduced electron-transfer reaction between electronically excited ITX (oxidant) and BPh₄⁻ (reductant). An NHC yield as high as 70 % is achieved upon starting with a stoichiometric ratio of ITX and azolium salt. Three different photoNHC-mediated polymerizations are described: synthesis of polyurethane and polyester by organocatalyzed step-growth polymerization and ring-opening copolymerization, respectively, and generation of polynorbornene by ring-opening metathesis polymerization using an NHC-coordinated Ru catalyst formed in situ.     

Nonlocal damage-viscoplastic model for high temperature creep of single crystal superalloys

A new nonlocal damage-viscoplastic model for high temperature creep of single crystal superalloys is developed. It is based on the variational formulation consisting of free energy, plastic and damage dissipation potentials. Evolution equations for plastic strain and damage variables are derived from the minimum principle for dissipation potentials [1]. The model is capable of describing different stages of creep in a unified way. The evolution of dislocation densities of gamma and gamma prime phases in superalloys incorporates plastic deformation. It results in the time-dependence of the creep rate in primary and secondary creep. Tertiary creep is taken into account by introducing local and nonlocal damage variables. Herein the nonlocal one is considered as numerical treatment to remove mesh-dependence. Numerical results and comparisons with experimental data of the single crystal superalloy LEK94 are shown. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On gradient projection methods for strongly pseudomonotone variational inequalities without Lipschitz continuity

In this paper, we propose two new self-adaptive algorithms for solving strongly pseudomonotone variational inequalities. Our algorithms use dynamic step-si     

Decorrelation Estimates for a 1D Tight Binding Model in the Localized Regime

In this article, we prove decorrelation estimates for the eigenvalues of a 1D discrete tight-binding model near two distinct energies in the localized regime. Consequently, for any integer n ≥ 2, the asymptotic independence for local level statistics near n distinct energies is obtained.     

FEM Shakedown of uncertain structures by chance constrained programming

We present a new primal-dual numerical algorithm of the shakedown problem under uncertainty in which the material strength is considered as a normally distributed random variable. Using chance constrained programming, we obtain deterministic equivalent formulations based on upper bound and lower bound theorems which are dual to each other. The proposed algorithm is tested in numerical examples which are applied to civil engineering structures. The obtained solutions show good performance. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile‐Based Electrolytes in Lithium Metal Batteries

The resurgence of the lithium metal battery requires innovations in technology, including the use of non‐conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (?3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile‐based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF₆ in acetonitrile.     

Local deformation in photo‐crosslinked polymer blends monitored by Mach‐Zehnder interferometry

Local deformation of a polymer mixture crosslinked by irradiation with ultraviolet light was in situ monitored by using a Mach‐Zehnder interferometer. In combination with the refractive index data obtained from independent measurements, the deformation in the nanometer scales of the crosslinked blends was calculated by using the difference in optical path length of the blend measured before and after irradiation. Upon varying the crosslink density of the blend by changing the light intensity, it was found that the local deformation well correlates with the crosslink density obtained from the reaction kinetics experiments. Furthermore, the strain relaxation of the blends was also monitored in situ and analyzed after irradiation over different time intervals. The results obtained in this study reveal the possibility of monitoring the nanometer‐scale deformation in polymers during radiation curing. These data also provide important information on the correlations between the irradiation‐induced elastic strain and the resulting morphology of reacting polymer blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2898–2913, 2005     

New flavan and unusual chalcone glycosides from Drypetes parvifolia

Two new compounds 7-hydroxy-5-O-（β-D-glucopyranoside） flavan （1） and （Z）-4＇,6＇-dihydroxy-2＇-O-（β-D-glucopyranoside） chalcone （2）, along with eight known compounds, were isolated from the stem bark of Drypetes parvifolia （Euphorbiaceae）. Their structures were established on the basis of spectroscopic analysis and chemical evidence.     

Effective Diffusivity Tensors of Point-Like Molecules in Anisotropic Porous Media by Monte Carlo Simulation

Monte Carlo simulations of random walks in anisotropic structured media are performed to determine the dependence of effective diffusivities on geometrical properties. The anisotropic media used in this study are periodic systems, which are generated by extending primitive, face-centered, and body-centered unit cells indefinitely in all axial directions. Results of simulations compare well with published experimental data and the calculations by the volume averaging method. In addition, these results suggest that if the 2D media with percolation thresholds subtantially differ from those of 3D, 2D approximations of 3D media are not satisfactory. When percolation thresholds are the same, the effective diffusivity tensors depend solely on the porosity. This fact has been suggested for isotropic media and it seems to hold for anisotropic media.