封闭型异氰酸酯固化剂的制备及应用

以甲苯二异氰酸酯、三羟甲基丙烷为原料合成预聚物,分别与甲乙酮肟和多种醇醚类混合物进行封端反应,合成溶剂性和水性封闭异氰酸酯固化剂。采用红外光谱和化学滴定等方法对预聚物和固化剂进行表征和分析。合成的固化剂与树脂按比例混合,制备涂膜,并对漆膜的性能作了初步探讨。     

Mathematical model for the pultrusion of blocked PU–UP matrix composites

The thermokinetic behavior of blocked polyurethane (PU)–unsaturated polyester (UP)–based composites during the pultrusion of glass‐fiber‐reinforced composites was investigated utilizing a mathematical model that accounted for the heat transfer and heat generation during curing. The equations of continuity and energy balance, coupled with a kinetic expression for the curing system, were solved using a finite difference method to calculate the temperature profiles and conversion profiles in the thickness direction in a rectangular pultrusion die. A kinetic model, dP/dt = A exp(?E/RT)P^m(1 ? P)ⁿ, was proposed to describe the curing behavior of a blocked PU–UP resin. Kinetic parameters for the model were obtained from dynamic differential scanning calorimetry scans using a multiple regression technique, which was able to predict the effects of processing parameters on the pultrusion. The effects of processing parameters including pulling speed, die wall temperature, and die thickness on the performance of the pultrusion also were evaluated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1996–2002, 2003     

Characterization of boron-doped diamond electrodes by electrochemical impedance spectroscopy

Charge transfer on boron doped diamond (BDD) electrodes was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The diamond films of 5 μm thickness and boron content between 200 ppm and 3000 ppm were prepared by the hot filament CVD technique on niobium substrate and mounted in a Teflon holder as rotating disk electrodes. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na₂ SO ₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. Significant deviation in the redox behaviour of BDD and active Pt electrodes was indicated by a shift of the peak potentials in the cyclic voltammograms with increasing sweep rate and lower limiting diffusion current densities under rotating disk conditions. In the impedance spectra an additional capacitive element appeared at high frequencies. The potential and rotation dependence of the impedance spectra can be described quantitatively in terms of a model based on diffusion controlled charge transfer on partially blocked electrode surfaces. Direct evidence for the non-homogeneous current distribution on the diamond surface was obtained by SECM measurements.     

Wrinkling of epoxy powder coatings

Differential scanning calorimetry (DSC) and mechanical profilometry were used to study wrinkle formation in curing epoxy powder coatings. Powder coating formulations were studied that contained solid epoxy resins, methylene disalicylic acid (MDSA) crosslinker, and an amine‐blocked Lewis acid catalyst. Both the crosslinker (MDSA) and the amine‐blocked catalyst are required for wrinkle formation. Evaporation of the blocking amine from the free surface of the coating generated a depthwise gradient in the extent of polymerization and crosslinking, and hence in the degree of solidification, as evidenced by the formation of a mechanical skin prior to wrinkling. It is hypothesized that compressive elastic stress develops in the still swellable skin when unreacted low‐molecular‐weight material from beneath diffuses up into the monomer‐ or oligomer‐depleted crosslinking skin and swells it. This compressive stress, if above a critical value, buckles the skin to produce wrinkles. Experimentally observed compositional requirements for wrinkle formation were consistent with the proposed mechanism. The size of the wrinkles can be controlled by varying formulation parameters such as the amount of catalyst or crosslinker. Increasing the amount of catalyst decreased both the wavelength and the amplitude of the wrinkle pattern. Increasing the amount of crosslinker initially increased the amplitude of the wrinkles; after reaching a maximum level, the wrinkle amplitude decreased. DSC was a useful tool to understand the critical reactions responsible for wrinkling in this system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 116–129, 2005     

Reactive Hot Melts on the Basis of Polyester and Polyamide

Hot melts show many advantages over other adhesives, for instance, their lack of solvent and their very short setting time just by cooling. The weak point of hot melts in comparison to thermosetting resins is their limited thermal resistance. There is no doubt that the high performance hot melts on the basis of polyester and polyamide show a better heat performance than the widely-used rubbery hot melts. Nevertheless, it is true that the thermal resistance is limited by the melting point of the hot melt. To improve the heat performance, without losing the favourable hot melt properties, crosslinkable hot melts have been created. For the example, copolyamide/blocked isocyanate blends, it can be shown that crosslinkable hot melts are achievable in a wide range of reactivities. After curing, which takes place during the bonding process, these hot melts withstand temperatures of over 220°C even if the melting point of the initial hot melt was 100°C.     

起节点上并行算法设计策略的研究

本文分析了超节点这一新型体系结构上的算法设计方法,并具体讨论了超节点上的数据分配和任务划分,最后举出一个实例－－高斯消去法的分块算法,提出了如何在现有共享算法和分布算法的基础上,开发超节点上的并行算法。     

R个修理工同步多重休假的温贮备机器维修问题分析

研究了带有多个温贮备部件的机器维修问题,系统中有R个修理工,修理工进行同步多重休假,同时考虑了顾客止步和中途退出的现象。文中利用马尔可夫过程理论建立了系统稳态概率满足的方程组,并采用矩阵分块的方法得到了系统稳态概率的精确表达式,从而得到了系统相关的排队指标,建立了相关费用函数。最后利用数值分析的方法研究了修理工个数对系统费用函数的影响。     

低温阴极电泳漆的制备及性能

随着人们对环境保护以及低能量消耗要求的不断提高,低温固化阴极电泳漆已经成为电泳漆的发展趋势之一。合成了封闭物异氰酸酯固化交联剂,并探讨了反应时间和反应温度对封闭率的影响,最后以氨化改性环氧树脂为基料树脂合成了低温固化阴极电泳漆。实验结果表明：在150℃／20min的固化条件下,漆膜能得到完全固化,经过漆膜综合性能实验,在选择合适的电泳工艺参数下,可以得到硬度较高、耐潮、耐盐、耐酸碱性能好的漆膜。     

一种准确简便地标定氧化锆氧量分析仪的新方法

本文提出仅用一种标准气或不用标准气标定氧化锆氧量分析仪的新方法。它符合我国的相关检定规程,适宜含氧量下限不小于0．1％的氧量分析仪的首次检定、后续检定和使用中的检验,尤其适宜在发电厂使用了较长时间后,对“检测器的多孔陶瓷过滤网已破损或其气孔被堵塞程度不明”的情况下进行检定或标定。     

封端型阳离子水性聚氨酯纸张增强剂的制备与应用

通过预聚体分散法制备出封闭交联型阳离子聚氨酯(CBPU)纸张增强剂。探讨了CBPU封闭率、添加量对纸张力学性能的影响,并采用傅里叶变换红外光谱(FT-IR)、动态激光光散射(DLS)和扫描电子显微镜(SEM)对CBPU的分子结构、乳液粒径及纸张表面形貌进行了表征。结果表明,增加CBPU封闭率和添加量,能明显提高纸张的强度指标,尤其是湿抗张指数与湿强度。较佳CBPU封闭率与乳液添加量分别为10%及5%(占绝干浆量),此时纸张湿强度可达30·32%。产物分子结构中出现了叔胺基、咪唑环和氨基甲酸酯结构。乳液粒径随着封闭率的增加而增大。电子扫描观察可以看出,经聚氨酯处理后纸页纤维间出现较多丝状与薄膜状物质,从而增强了纤维间的连接。