Controlling thermomechanical behavior of semicrystalline hydrogenated polynorbornene through the cis- to trans-cyclopentylene ratio

Though polynorbornene synthesized by ring-opening metathesis polymerization has an intrinsically all-cis configuration of the cyclopentylene backbone rings, a fraction of these rings can be epimerized to the trans configuration during hydrogenation over suitable catalysts. By varying the method of hydrogenation, semicrystalline hydrogenated polynorbornenes (hPNs) with trans levels between 0 and 36% were obtained. With increasing trans content, the glass transition temperature, melting point, and enthalpy of melting decrease modestly. By contrast, the temperature at which the hPN crystal transitions into a rotationally disordered polymorph varies strongly with trans content, ranging from 126 °C (all-cis) to 71 °C at 27% trans; at trans contents of 34% and above, no rotationally-ordered phase is observed at any temperature. The room-temperature Young's modulus shows no dependence on trans content, while the yield stress drops by 20% at 1% trans content and slowly decreases further with additional epimerization. The temperature dependence of the Young's modulus differs for trans-containing versus all-cis polymers, while the temperature dependence of the yield stress is set by the polymorph type (rotationally ordered vs. disordered).     

基于应变梯度理论的微尺度蜂窝等效模量计算方法

本文提出了一种新的能够计及尺度效应的微纳米蜂窝等效模量的计算方法。将一种单参数应变梯度理论引入到本构方程当中,并基于能量等效原理推导了蜂窝面内等效模量地计算公式。算例分析表明,本文方法能够有效地计及尺度效应对蜂窝等效模量的影响。尺度效应与胞壁厚度和长度的值都有关,当胞壁厚度较小时,尺度效应显著,本文方法预测的模量会明显高于传统方法;而当胞壁厚度较大时,尺度效应变得微弱乃至可以忽略不计。但如果胞壁的长度/厚度比很大,则面内等效模量会趋近于0,此时是否考虑尺度效应意义不大。     

The existence and stability of bulk nanobubbles:a long-standing dispute on the experimentally observed mesoscopic inhomogeneities in aqueous solutions

In theory,nanobubbles can stably exist with a lifetime of microseconds at most,but numerous experimental observations demonstrate that nanobubbles in bulk solution can be stable from hours to weeks.Although various conjectures on the stability mechanism of bulk nanobubbles,such as the contaminant mechanism,skin mechanism,surface zeta potential mechanism,are proposed,there has not yet been a unified conclusion.Since bulk nanobubbles show great potential in a wide spectrum of applications and are relevant to a number of unsolved questions on cavitation and nucleation,the debate over their stability mechanisms has been active.In the past,extensive studies have been carried out to understand the mechanism of nanobubble stability,and important insights have already been provided.This paper will provide a brief overview of our current understanding of the unexpected stability of bulk nanobubbles.     

Approximation by Gamma type operators

In this study, we introduce newly defined Gamma operators which preserve constants and e^2μ·, μ>0 functions. In accordance with this purpose, we focus on their approximation properties such as uniform convergence, rate of convergence, asymptotic formula, and saturation results. Superior properties of introduced operators have been tested both theoretically and numerically in certain senses to highlight the performance of the new constructions of Gamma operators.     

Baskakov-Durrmeyer type operators involving generalized Appell Polynomials

In this paper, we define the Baskakov-Durrmeyer type operators based on generalized Appell polynomials. Here, we establish moment estimates, an estimate via weighted modulus of continuity and a Voronovoskaya type asymptotic result. Further, we study a quantitative-Voronovoskaya-type theorem and Grüss Voronovskaya-type theorem. Lastly, we give the approximation result for functions having derivatives of bounded variation.     

闪长岩单轴加载过程中声发射和弹性波速度变化规律的研究

为研究闪长岩在单轴加载过程中的声发射和各向波速变化规律,在单轴阶段加载和循环阶段加载条件下,对闪长岩岩样破裂过程中的声发射累计数、不同应力水平不同方向的波速、切线模量、轴向应变速率进行了研究。实验结果表明:(1)随着应力水平的增高,声发射事件数不断增加,在高应力水平(约80%峰值强度)时,声发射累计数急剧增多,随后切线模量出现震荡变化。(2)在加载过程中,压密程度及裂纹扩展方向对波速产生了巨大的影响,导致不同方向波速在不同的应力水平呈现出不同的变化规律,由此可以推测破裂面位置和破裂模式。在较高应力水平下(约60%峰值强度),平行于加载方向的波速趋于稳定,而垂直于加载方向的波速则持续下降,故用垂直于加载方向传播的波速预测岩石的破坏更具可靠性。(3)随着应力的增加,应变速率有逐渐减小的趋势,但临近岩石破裂时无异常变化出现,说明利用变形观测难以预测此类岩石的破坏。以上研究表明,根据纵波波速、声发射累计数和切线模量的变化可以有效预测岩石的破坏。     

Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules

Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057     

Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Behavior of poly(ε-caprolactone)-based diblock copolymers in a bulk state and in solution

Abstract

A series of amphiphilic MOPEO-b-PCL copolymers (DBCs), based on biocompatible methoxypoly(ethylene oxide) with M_n=4.5?kDa and poly(ε-caprolactone) of a variable chain length, was synthesized by an anionic ring-opening block copolymerization. The structural investigations, performed by DSC and WAXS methods, revealed the microphase separation in DBC bulk structure and the existence of separate amorphous regions and microcrystalline domains of MOPEO and PCL blocks. Spectrophotometry and SLS were used to study the self-assembling of DBC macromolecules in selective dioxane/aqueous solution and to determine the main micellization parameters (CMC and -ΔG°). The DBC micelles morphology and their specific aggregation in mixed solvent were shown.     

Weighted Approximation of Functions by Meyer–König and Zeller Operators of Max-Product Type

In this paper, we study the uniform approximation of functions by Meyer–König and Zeller operators of max-product type in some weighted spaces. We estimate the rate of approximation in terms of a suitable modulus of continuity.