Influence of untreated and novel electron‐beam‐modified surface‐coated silica filler on the thermorheological properties of ethylene–octene copolymer

We developed surface‐modified silica fillers by coating these with an acrylate monomer, trimethylolpropane triacrylate, or a silane coupling agent, triethoxyvinyl silane, followed by electron‐beam irradiation at room temperature. These were incorporated in an ethylene–octene copolymer rubber. Thermorheological studies of the unvulcanized ethylene–octene copolymer and its untreated and modified silica‐filled composites were done with a shear dynamic oscillating rheometer. Modification of the silica filler, especially via the silanization process followed by electron beam treatment, significantly reduced filler–filler networking as revealed from the log–log plots of storage modulus and complex shear viscosity, and its real component. The rheological complexity of the compositions was analyzed from a double logarithmic plot of the storage modulus and loss modulus. The results obtained from the master curves constructed on the basis of the time–temperature superposition principle and the activation energy calculated from the Arrhenius equation for the flow of above these compounds further supported these findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2453–2459, 2003     

聚醚型聚氨酯的氢键、微相分离及性能

用本体一步法合成了5种不同硬段含量(11.0％～46.9％)的二苯甲烷-4,4′-二异氰酸酯/环氧乙烷封端型聚环氧丙烷聚醚/乙二醇的聚醚型聚氨酯,并借助于IR,DSC,DMS和材料试验机等手段对该聚氨酯的氢键、微相分离及力学性能进行了表征。结果表明:随着硬段含量的增加,其>NH与微区中的>C=O的氢键化程度逐渐提高,软段微区中—O—的氢键化程度逐渐降低;微相分离程度逐渐提高;拉伸强度及硬度随之增加,扯断伸长率在硬段含量40％左右出现极大值。     

Structure of resorcinol,phenol, and furan resins by MALDI‐TOF mass spectrometry and 13C NMR

The structure of traditional, linear phenol–resorcinol–formaldehyde (PRF) resins, urea‐branched PRF resins, and phenol–resorcinol–furfural (PRFuran) resins has been investigated in depth by both matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy and ¹³C NMR. The structure of a variety of oligomers has been obtained, and the structures present in each of the three types of resins related to the very different percentages of resorcinol needed for their equal performance as adhesives. The oligomers type and species distribution appeared very different for each case. PRF resins performance is improved by maximizing either the proportion of resorcinol‐containing oligomers or methylol‐groups containing oligomers, even without any resorcinol, or both. It is equally obtained by the minimization of the relative proportion of the low reactivity Phenol (CH₂ Phenol) species in which resorcinol is not present, this being the most important parameter. This can be obtained by more effective use of the resorcinol by just modifying the resin manufacturing procedure. This parameter instead does not appear to be determinant in PRFuran resins. In these, it is the higher molecular weight of furfural in relation to formaldehyde that engenders for the same manufacturing procedure a correspondingly lower proportion of resorcinol in the resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2665–2674, 2004     

聚合转化率对硫调型氯丁胶结构与性能的影响

研究了硫调型氯丁橡胶乳液聚合中转化率对产晶结构与性能的影响.结果表明,随单体转化率的提高,聚合物的凝胶量及其交联密度增大,致使断链速度减慢,所得断链胶的门尼粘度上升,残存凝胶量增加,分子支化程度增大,分子量分布变宽,焦烧时间缩短。而相应硫化胶的拉伸强度、撕裂强度、冲击弹性和硬度等提高,扯断伸长率和永久变形下降。这些变化一般在转化率为80——85％时有明显转折.综合考虑产量与质量,聚合转化率控制在82±2％较为适宜。     

Pore structure of bulk tungsten carbide powder catalysts

Bulk tungsten carbide catalysts are prepared by direct carburization/reduction of tungsten trioxide in methane-hydrogen mixtures. The catalytic properties of such catalysts have been studied by several authors. The porous structure of these catalysts is studied by adsorption of N₂, Kr, CF₄ and neohexane. Adsorption isotherms and hysteresis loops for the catalysts suggest the presence of a microporous structure made of parallel plates distant approximately by 20 Å. These results are compared to those obtained using such catalysts for hydrogen oxidation and where condensation in the porous structure was observed.     

大型常压锥顶贮罐的设计

以工程实例为依据，论述国内以往较少采用的大型梁柱式支承锥顶贮罐的结构，介绍了国内外相关设计标准，给出了贮罐的典型结构－斜椽，横梁和立柱的计算公式，并用Excel电子表格编制了计算书。     

Molecular motions of non-crystalline poly(aryl ether-ether-ketone) PEEK and influence of elecron beam irradiation

The dynamic mechanical relaxation of non-crystalline poly(aryl ether-ether-ketone) PEEK and the one irradiated with electron beam were studied. The three distinct γ, β, α′ relaxation maxima were observed in unirradiated PEEK from low to high temperature. It was revealed from the study on the irradiation effects that three different molecular processes are overlapped in γ relaxation peak, i.e., molecular motion of water bound to main chain (peak temperature; at ?100°C), local motion of main chain (at ?80°C), and local mode of the aligned and/or oriented moiety (at ?40°C). The β relaxation connected with the glass transition occurred at 150°C and it shifted to higher temperature by irradiation. The α′ relaxation which can be attributed to rearrangement of molecular chain due to crystallization was observed in unirradiated PEEK ～ 180°C and its magnitude decreased with the increase in irradiation dose. This effect indicates the formation of structures inhibiting crystallization such as crosslinking and/or short branching during irradiation. A new relaxation, β′, appeared in the temperature range of 40° to 100°C by irradiation and its magnitude increased with dose. This relaxation was attributed to rearrangement of molecular chain from loosened packing around chain ends, which were introduced into the non-crystalline region by chain scission under irradiation, to more rigid molecular packing, From these observations, we proposed that deterioration in mechanical properties of non-crystalline PEEK by high energy electron beam was brought about not only by chain scission but structural changes such as crosslinking and/or branching in the main chain.     

Ruthenium tetroxide catalysed oxidation of Illinois No. 6 coal: The formation of volatile monocarboxylic acids

Ruthenium tetroxide selectively oxidizes activated aromatic compounds under mild conditions and has been used for the catalytic oxidation of several different coals. The quantities of the volatile monocarboxylic acids with 2–6 carbon atoms have been determined by an isotope dilution technique. The amount of ethanoic acid ranges from 1 to 3mol/100C and the quantities of propanoic acid, and butanoic acid exceed 0.1 mol/100C. Methylpropanoic, pentanoic, 2-methylbutanoic, 3-methylbutanoicand hexanoic acid are formed in lesser amounts. The outcome of the experiment depends upon whether or not the coal has been extracted prior to oxidation. The results for Illinois No. 6 coal expressed in moles of ethanoic acid produced/l00C illustrate this feature: raw whole coal, 1.9; coal extracted by the method of Hayatsu and co-workers, 1.0. Dehydrogenation with benzoquinone prior to oxidation increases the yield of ethanoic acid to $\text{sol1.5mol}\text{100C.}$ The amounts of ethanoic acid obtained from the other extracted coals are 1.0 for Texas lignite, 1.2 for Rawhide subbituminous, 3.4 for Pittsburgh No. 8, 3.3 for a higher ranking bituminous coal (PSOC 726) and 0.7 for an anthracite (PSOC872). The results obtained in this study are compared with related information concerning the distribution of alkyl groups within coal by other methods.     

层次约束结构的虚拟装配建模技术

为了解决虚拟环境下装配建模在信息完备性和模型复杂性等方面的问题,提出了一种基于层次约束结构的虚拟装配模型.该模型分为产品层、部件层、零件层、特征层、几何面层和面片层来表达,不同层元素之间存在层次映射关系,同一层元素之间存在约束关系.通过CAD系统和虚拟装配系统之间的数据转换,实现了虚拟装配模型的生成算法,并给出了根据虚拟装配模型生成的虚拟装配场景图的结构.基于层次约束结构的虚拟装配模型具有信息表达完备,信息集成度高,满足实时性要求等优点,同时还能与CAD系统和虚拟装配场景图实现集成.实例验证了虚拟装配建模的有效性.