Crystallization of Polymer-Derived Silicon Carbonitride at 1873 K under Nitrogen Overpressure

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 0.57SiC·0.43Si₃N₄·0.49C is studied as a function of nitrogen overpressure at 1873 K. The ceramic suffers a weight loss at p _N2 < 3.5 bar (1 bar = 100 kPa), does not show a weight change from 3.5 to 11 bar, and gains weight above 11 bar. The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar. The weight-loss transition, at 3.5 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si₃N₄ are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition. The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism. A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism. The supersaturation required to nucleate α-Si₃N₄ crystals is calculated to be 30 kJ/mol.     

乙炔黑吸附聚合制导电聚苯胺

用乙炔黑吸附化学聚合新工艺制备导电聚苯胺，可保持电导率不变，但转化率和堆密度提高，并明显改善了聚苯胺的颗粒形态和制膜加工性，使由其制备的聚苯胺复合正极膜和固体聚苯胺锂蓄电池的电化学性能得以改进。     

双环戊二烯聚合反应热力学和动力学研究

研究了ＤＣＰＤ－ＷＯＣｌ４－ＡｌＥｔ３体系前阶段的反应动力学，采用ＧＣ法分析了不同反应条件下的动力学数据，发现ｌｇ（［ＤＣＰＤ］０／［ＤＣＰＤ］）￣ｔ存在线性关系，说明该体系在前段的聚合反应为一链式反应符合二级反应模型。同时还对该体系聚合反应热力学也进行了研究；对聚合反应的ΔＨｐ、ΔＳｐ、ΔＧｐ进行了讨论。     

高分子材料辐射接枝苯乙烯的研究进展

对各高分子材料辐射接枝苯乙烯的动力学，接枝方法及接枝材料的应用进行了综述，讨论限辐射剂量，剂量率，温度，后效应，溶剂，添加剂和高分子材料厚度及结晶性等方面对接枝反应的影响。     

Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

用复合烷基锂引发丁二烯聚合

对以环己烷为溶剂、四氢呋喃为微观结构调节剂、复合烷基锂为引发剂的丁二烯聚合反应过程进行了研究，考察了不同引发温度、不同配比的复合烷基锂对聚合反应的影响，并与以正丁基锂为引发剂的丁二烯聚合反应过程进行了比较。     

Influence of two-step process and of different stoichiometric ratios on morphologies generated in castor oil epoxy resins

Phase separation during polymerization was studied in a model system consisting of a diepoxide based on diglycidyl ether of bisphenol A (DGEBA), variable amounts of ethylenediamine (EDA) and the mass of castor oil (CO) necessary to obtain a mass fraction equal to 0-15 in a final system where the stoichiometric ratio of amine to epoxy equivalents, r, was equal to 1. A two-step polymerization process was performed by curing first a system with r = 0-5, during variable times before phase separation, and then carrying the system to r = 1. Thermodynamic analysis of samples with different r values led to a linear relationship between the Flory-Huggins interaction parameter and r. The concentration (P) and average size (D?) of dispersed-phase particles followed opposite trends, i.e. P increased while D? decreased, when either r was increased or the time of curing in the first step of a two-step process was decreased. This was explained by assuming that the competition between nucleation and growth was determined by the viscosity at the cloud point, η_cp. Low values of η_cp favoured growth over nucleation and led to fewer but larger particles.     

分子结构对增塑聚氯乙烯性能的影响

研究了聚合度、分子量分布和支化结构对增塑聚氯乙烯加工流变性能和物理力学性能的影响。结果表明，增塑ＰＶＣ的加工流变性能随聚合度的增加而恶化；拓宽分子量分布和引入支化结构均有利于加工流变性能的提高；增塑ＰＶＣ的拉伸强度随聚合度的增加而提高，而压缩永久变形却随之减小；分子量分布对物理力学性能的影响不大；支化ＰＶＣ的拉伸强度略有下降。     

乙烯基三甲基硅烷等离子体聚合反应历程

应用色谱—质谱(GC-MS)及裂解色谱-质谱(PGC-MS)测定了乙烯基三甲基硅烷等离子体聚合反应中的气体冷凝物及聚合物,研究推导了等离子体聚合反应历程。单体在气相中被电子撞击,然后扩散到基底,在基底发生链增长和链终止反应。