聚甲基乙撑碳酸酯/天然高分子复合材料研究进展

聚甲基乙撑碳酸酯(PPC)是一种新型热塑性脂肪族聚碳酸酯,具有良好的生物降解性、高阻隔性和生物相容性等优点,但其热性能和力学性能较差,通过物理和化学方法改性是提高其性能的重要研究方向之一。本文综述了近年来采用淀粉、纤维素和甲壳素等天然高分子对PPC的改性研究,尤其是天然高分子含量和预处理方法等对复合材料性能的影响,并对PPC/天然高分子复合材料的发展作了总结和展望。     

Continuous Spectroscopy Characterization of Emulsions

In emulsion polymerization, the formation of particles has an important effect on the rate of reaction and on the final properties of the latex. To investigate particle nucleation mechanisms in emulsion polymerization it is necessary to establish the initial conditions of the emulsified system before the reaction takes place. This research reports on a technique to continuously monitor the droplet size distribution of liquid-liquid emulsions using spectroscopy. The on-line particle characterization methodology is based on an integrated sampling and dilution strategy combined with spectroscopy methods. It is shown that the sampling system integrated with a multiwavelength turbidity detector provides reliable estimates of droplet populations as function of the dispersed phase concentration in emulsions of saturated hydrocarbons. The results provide not only the groundwork necessary for the elucidation of particle nucleation during emulsion polymerization process but also suggests the potential of this combined technology to further our understanding of liquid-liquid emulsions.     

A Fully Integrated Continuous‐Flow System for Asymmetric Catalysis: Enantioselective Hydrogenation with Supported Ionic Liquid Phase Catalysts Using Supercritical CO2 as the Mobile Phase

A continuous‐flow process based on a chiral transition‐metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO₂) as the mobile phase is presented for asymmetric catalytic transformations of low‐volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high‐pressure continuous‐flow setup, the product was isolated in analytically pure form without the use of any organic co‐solvent and with no detectable catalyst leaching. Phase‐behaviour studies and high‐pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO₂. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long‐term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L ^?1 h^?1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger‐scale application.     

两大部类持续扩大再生产的优化

基于经典的马克思两大部类社会再生产公式,建立了离散确定型的持续扩大再生产的优化问题的动态规划模型.在生产资料部类的不变资本产出率高于另一部类的条件下,动态规划的指标函数是作为决策变量的生产资料部类积累率的单调函数,因而可以使用逆序解法或者顺序解法,获得唯一的最优策略和最优指标函数.借助《资本论》中的一个举例,计算验证了最优解.     

Comparison of multigrid algorithms for high‐order continuous finite element discretizations

We present a comparison of different multigrid approaches for the solution of systems arising from high‐order continuous finite element discretizations of elliptic partial differential equations on complex geometries. We consider the pointwise Jacobi, the Chebyshev‐accelerated Jacobi, and the symmetric successive over‐relaxation smoothers, as well as elementwise block Jacobi smoothing. Three approaches for the multigrid hierarchy are compared: (1) high‐order h‐multigrid, which uses high‐order interpolation and restriction between geometrically coarsened meshes; (2) p‐multigrid, in which the polynomial order is reduced while the mesh remains unchanged, and the interpolation and restriction incorporate the different‐order basis functions; and (3) a first‐order approximation multigrid preconditioner constructed using the nodes of the high‐order discretization. This latter approach is often combined with algebraic multigrid for the low‐order operator and is attractive for high‐order discretizations on unstructured meshes, where geometric coarsening is difficult. Based on a simple performance model, we compare the computational cost of the different approaches. Using scalar test problems in two and three dimensions with constant and varying coefficients, we compare the performance of the different multigrid approaches for polynomial orders up to 16. Overall, both h‐multigrid and p‐multigrid work well; the first‐order approximation is less efficient. For constant coefficients, all smoothers work well. For variable coefficients, Chebyshev and symmetric successive over‐relaxation smoothing outperform Jacobi smoothing. While all of the tested methods converge in a mesh‐independent number of iterations, none of them behaves completely independent of the polynomial order. When multigrid is used as a preconditioner in a Krylov method, the iteration number decreases significantly compared with using multigrid as a solver. Copyright © 2015 John Wiley & Sons, Ltd.     

多频超声反应槽连续强化酸化油酯交换制备生物柴油研究

以平均酸值高达33.07 mgKOH/g不可食用的廉价酸化油为原料,利用自行设计的多频超声溢流槽连续强化酯交换反应生物柴油生产装置,先后经预酯化、酯交换两步反应,高效、低耗的制备生物柴油。主要考察了室温下物料流量(停留时间)、超声功率、超声频率及组合、KOH用量、醇油物质的量比对酯交换反应的影响及单位产品能耗。结果表明,多频组合超声辐射比单频更有利于生物柴油的制备;预酯化后的油料在流量为25 L/h(物料停留时间为54 min),催化剂(KOH)用量为1.2%(质量分数),醇油物质的量比为6∶1和各反应槽功率为200 W的条件下,甲酯产率达96.83%。50 L废弃酸化油能制得符合国标GB19147—2009的生物柴油48L,整个生物柴油制备过程总耗时和总耗电量仅为8.667 h、5.42 kWh。     

Continuous Porous Aromatic Framework Membranes with Modifiable Sites for Optimized Gas Separation

Continuous microporous membranes are widely studied for gas separation, due to their low energy premium and strong molecular specificity. Porous aromatic frameworks (PAFs) with their exceptional stability and structural flexibility are suited to a wide range of separations. Main-stream PAF-based membranes are usually prepared with polymeric matrices, but their discrete entities and boundary defects weaken their selectivity and permeability. The synthesis of continuous PAF membranes is still a major challenge because PAFs are insoluble. Herein, we successfully synthesized a continuous PAF membrane for gas separation. Both pore size and chemistry of the PAF membrane were modified by ion-exchange, resulting in good selectivity and permeance for the gas mixtures H₂/N₂ and CO₂/N₂. The membrane with Br^? as a counter ion in the framework exhibited a H₂/N₂ selectivity of 72.7 with a H₂ permeance of 51844 gas permeation units (GPU). When the counter ions were replaced by BF₄^?, the membrane showed a CO₂ permeance of 23058 GPU, and an optimized CO₂/N₂ selectivity of 60.0. Our results show that continuous PAF membranes with modifiable pores are promising for various gas separation situations.     

Mild Microfluidic Approaches to Oxide Nanoparticles Synthesis

Oxide nanoparticles (oxide NPs) are advanced materials with a wide variety of applications in different fields. The use of continuous flow methods is particularly appealing for their synthesis due to the high control achieved over the reaction conditions and the easy process scalability. The present review focuses on the preparation of oxide NPs using microfluidic setups at low temperature (≤80 °C), since the employment of mild reaction conditions is crucial for developing sustainable and cost-effective processes. A particular emphasis will be put on the improvement over the final product features (e. g., size, shape, and size distribution) given by flow methods with respect to conventional batch procedures. The main issues that arise by treating NPs suspensions in microfluidic systems are product deposition or channel clogging; mitigation strategies to overcome these drawbacks will also be presented and discussed.     

Reliability of Speaking and Maximum Voice Range Measures in Screening for Dysphonia

Speech range profile (SRP) is a graphical display of frequency-intensity occurring interactions during functional speech activity. Few studies have suggested the potential clinical applications of SRP. However, these studies are limited to qualitative case comparisons and vocally healthy participants. The present study aimed to examine the effects of voice disorders on speaking and maximum voice ranges in a group of vocally untrained women. It also aimed to examine whether voice limit measures derived from SRP were as sensitive as those derived from voice range profile (VRP) in distinguishing dysphonic from healthy voices. Ninety dysphonic women with laryngeal pathologies and 35 women with normal voices, who served as controls, participated in this study. Each subject recorded a VRP for her physiological vocal limits. In addition, each subject read aloud the "North Wind and the Sun" passage to record SRP. All the recordings were captured and analyzed by Soundswell's computerized real-time phonetogram Phog 1.0 (Hitech Development AB, T?by, Sweden). The SRPs and the VRPs were compared between the two groups of subjects. Univariate analysis results demonstrated that individual SRP measures were less sensitive than the corresponding VRP measures in discriminating dysphonic from normal voices. However, stepwise logistic regression analyses revealed that the combination of only two SRP measures was almost as effective as a combination of three VRP measures in predicting the presence of dysphonia (overall prediction accuracy: 93.6% for SRP vs 96.0% for VRP). These results suggest that in a busy clinic where quick voice screening results are desirable, SRP can be an acceptable alternate procedure to VRP.