Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL]₀/[-OH]₀=5, 10, 15). Molecular weights were determined by both ¹H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/I(q) vs q² with I(q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Crystallization and thermoelectric behavior of conductive-filler-filled poly(ε-caprolactone)/poly(vinyl butyral)/montmorillonite nanocomposites

Crystallization and thermoelectric properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB)/montmorillonite (MMT) nanocomposites containing carbon black (CB) have been studied as a functions of a small amount of amorphous PVB content and a wide range of molecular weight of PVB. X-ray diffraction data of PCL/PVB/MMT nanocomposites indicates most of the swellable silicate layers are exfoliated and randomly dispersed into PCL/PVB system. The band spacings of PCL spherulites in PCL/PVB/MMT nanocomposites decrease with increasing PVB content, and this indicates that increasing the PVB content greatly shortens the period of lamellar twisting. The presence of 1 wt% MMT and higher molecular weight of PVB also shorten the period of PCL lamellar twisting. Nucleation and crystallization parameters, such as growth rate G and Avrami exponent n, can be determined by using POM and DSC isothermally crystallized at 41 °C. For samples with the same CB content, the intensity of positive temperature coefficient (PTC) (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the nanocomposites was increased as the content and the molecular weight of PVB increases. The change of the PTC property related to the morphological difference (i.e. period of lamellar twisting) in the nanocomposites can be discussed.     

高风电渗透率下考虑需求侧管理策略的智能微电网调度方法

提出了一种高风电渗透率下考虑需求侧管理策略的智能微电网调度方法。首先,考虑经济、环境成本指标、清洁能源就地消纳量以及可中断负荷和可转移负荷策略,建立了多目标优化调度模型。然后,引入ε约束法生成Pareto前沿解集,利用归一化方法求出最优折衷解。最后,基于24节点配电系统对所提方法进行分析验证。算例结果表明:建立的多目标优化模型能够有效提升清洁能源的消纳率,提高调度方案经济性,同时有效降低发电污染排放。采用的需求侧管理策略能够有效平抑负荷波动,达到削峰填谷的目的。     

A Facile Approach toward Thermoplastic Triple-Shape Memory Polymers

In this work, a ternary blend of polyolefin elastomer (POE), lauric acid (LA), and poly(ε-caprolactone) (PCL) with triple-shape memory effect (triple-SME) is reported. LA and PCL exhibit distinct thermal transitions and construct two reversible switching networks capable of fixing and releasing different temporary shapes under a mild condition. The ternary blend shows excellent triple-shape memory properties and good toughness. Besides, the permanent shape can be reconfigured by a simple thermal treatment. These particular features make the novel blend a competitive candidate for diverse applications. And the creative combination of crystalline small molecule and semicrystalline polymer expands the freedom for producing triple-shape memory polymers (triple-SMPs).     

Numerical simulation of microstructure formation ofAZ91 using mCA method

A stochastic model for simulating the microstructure formation of Mg alloy AZ91 during solidification was developed based on the finite element method（FEM） for macroscopic model of heat transfer calculation and a modified Cellular Automaton （mCA） for microscopic modeling of nucleation, growth of crystal. In this model, the effect of solute redistribution, interface curvature and preferred orientation was considered. A numerical simulation was developed with C＋＋ program language. The computation was carded out to understand the effect of varying processing parameters, such as nucleation parameters and heat transfer coefficient, on the microstructure formation of AZ91. The result of simulation was displayed on screen.     

自动协议逆向工程研究综述

全面梳理了该领域国内外相关文献,归纳分析了自动协议逆向工程的研究现状和发展趋势。为了更清晰地刻画不同方法的特点和比较异同,提出一种基于协议逆向工程输出结果的分类方法,将协议逆向方法分为侧重于协议格式提取、侧重于协议状态机推断、侧重于完整协议规范描述、侧重于其他输出结果四类,并据此进行分析和比较。基于目前的进展情况和进一步的问题剖析发现,复杂交互场景分析、链路层协议逆向、加密协议分析以及协议状态机优化等应作为自动协议逆向工程领域下一步的重点研究方向。     

纤维素醋酸酯接枝己内酯的聚合研究

以冰醋酸为溶剂,浓硫酸为催化剂,将取代度为2 4的二醋酸纤维素水解为取代度为1 4的醋酸纤维素(CA)。以此醋酸纤维素为接枝骨架,ε 己内酯(ε CL)为接枝单体,在辛酸亚锡的引发下,合成了醋酸纤维素/聚己内酯接枝共聚物(CA g PCL)。研究了反应物纯度、原料配比、引发剂与单体摩尔比、反应时间、反应温度对单体转化率(C%)、接枝率(G%)、接枝效率(GE%)的影响。结果表明,当反应温度为140℃,单体ε 己内酯与醋酸纤维素的质量比为4∶1,引发剂辛酸亚锡与单体ε 己内酯的摩尔比为0 005,反应时间为16h,C%,GE%和G%分别为46 8%,65 2%和122 1%。     

基于CAFE法的单晶铜杆热型连铸过程晶体生长模拟

基于元胞自动机(CA)和有限元(FE)耦合法对单晶铜杆热型连铸过程中晶粒生长及演化过程进行了模拟,获得了稳定状态下铸棒内温度分布及液固相界面的位置和形态,模拟了连铸初期沿热流方向细小等轴晶快速合并形成柱状晶的过程,采用截面形态和极图法分析了定向凝固条件下各个生长时刻的晶粒形貌和晶粒生长取向以及晶粒竞争生长过程中的快速淘汰和慢速淘汰阶段,为热型连铸工艺优化提供了依据。