Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model. II. Number-average molecular weight and apparent initiator efficiency

The equations for predicting the number-average molecular weight are derived on the basis of the three stage polymerization model (TSPM) in this paper. By applying the equations, a plotting approach is proposed to determine the apparent initiator efficiency defined as f[(α_td+1)/2] and the constant of chain transfer to monomer, where f is the initiator efficiency and α_td denotes the fraction of the termination rate constants by disproportionation. Using the approach to plot the experimental data in the literature, it is found that the chain transfer to monomer can be neglected for both methylmethacrylate (MMA) and styrene (St) polymerizations, but it can exert a significant effect on ethylmethacrylate (EMA) polymerization. In addition, the apparent initiator efficiency is found to be independent of reaction temperature and initiator concentration at each stage. The values of f[(α_td+1)/2] at gel effect stage are slightly reduced as compared with that at low conversion stage for MMA and EMA polymerizations. However, it decreases significantly at gel effect stage for St polymerization. Using the equations derived and the apparent initiator efficiencies obtained from TSPM plots, the number-average molecular weights at different conversions can be predicted. Comparisons show that the agreement between predictions and experimental data is satisfactory.     

Structure and properties of injection‐molded polypropylenes with different molecular weight distribution and tacticity characteristics

Two series of polypropylenes with different molecular weight distribution and tacticity characteristics were injection molded into flexural test specimens by varying cylinder temperature and the effects of the molecular weight distribution and tacticity on the structure and properties of the moldings were studied. Measured propertied were flexural modulus, flexural strength, heat distortion temperature, Izod impact strength, and mold shrinkage and structures studied were crystallinity, the thickness of skin layer, a*‐axis‐oriented component fraction and crystalline orientation functions. The relations between the structures and properties were also studied. It was found that the molecular weight distribution and tacticity characteristics affect the properties mainly through the molecular orientation and crystallinity, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2142–2156, 2002     

Thermally induced microstructural changes in cotton fibers: A free‐volume study

I measured positron lifetime in natural polymer–cotton fibers as a function of isochronal annealing temperature in the range 27–290°C. The variations in the positron results indicated structural changes occurring in the cotton fibers and determined the glass‐transition temperature as 80°C. Activation energies were measured separately for the crystalline and amorphous regions, indicating the versatility of the technique. These values were close to the O? H bond dissociation energy, suggesting O? H bond dissociation, the most probable process occurring under thermal treatment. As an extension of the positron results, the molecular weight of the cotton fibers was determined to be 1,200,000 based on free volume, which was within the range suggested for cotton. There seemed to be an indication that crosslinking changed the spiral structure of cotton fibers to the network type. However, this needs to be validated by other measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3336–3345, 2002     

Baseline assessment of metals and hydrocarbons in the sediments of Lake Mulwala, Australia

An assessment of hydrocarbon and metal/metalloids (arsenic, cadmium, copper, lead, mercury, selenium, zinc) contamination in sediments from Lake Mulwala, Australia, was undertaken. The objectives of the study were: (i) to determine the extent of contamination in the lake sediments, compared to Australian and international sediment quality guidelines, and (ii) to attempt to identify the contaminant sources to the lake. With the exception of a few samples containing elevated levels of arsenic and/or mercury, the levels of all contaminants in the sediment samples taken from the lake were below the ‘lower trigger’ of the Australian Sediment Quality Guidelines that would warrant further investigation. High molecular weight hydrocarbons (up to 700 mg kg⁻¹) were found in most sediment samples. Non‐metric statistical analysis indicated that the contaminant distribution was different in different parts of the lake, with the lowest concentrations generally found at the influent to the lake. No definitive source(s) of contamination could be identified for either metalloids or hydrocarbons.     

三次谐波系统混沌光场的光子统计特性

本文数值分析了三次谐波系统混沌光场的光子统计特性，从混沌态的遍历性出发计算了基波和谐波光场的Haken因子，得出混沌光场是一种大涨落的光场，其光子统计服从Super-Poisson分布，光场涨落随系统奇怪吸引子分维数增大而变化。     

Effects of high molecular weight component on crystallization of polyethylene under shear flow

Crystallization of polyethylene (PE) blends of low and high molecular weight components under shear flow was studied using time-resolved depolarized light scattering (DPLS), focusing on effects of the high molecular weight component on the shish-kebab structure formation. Anisotropic two-dimensional scattering pattern due to shish-like structure formation was observed above a certain concentration of the high molecular weight PE. The threshold was about 2.5-3 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. On the basis of these results a gel-spinning-like mechanism for the shish-like structure formation has been proposed. The DPLS results also implied that the shish-like structure was mainly formed from the high molecular weight PE. This was confirmed by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) measurements on an elongated PE blend of low molecular weight deuterated PE and high molecular weight hydrogenated PE (3 wt%).     

基于主元分析的多变量统计过程的故障辨识技术

为了更好的进行故障检测与诊断，介绍了主元分析理论，给出了基于主元分析的过程故障辨识机理及策略。仿真实例表明，利用此方法建立的故障诊断模型，能够在不依赖过程机理的前提下高效抽取原始数据空间的主要变化信息，对过程的非正常变化做出反应，同时还能较正确地找出发生故障的原因以及相应环节。     

悬索缆道(带铅鱼)在义棠水文站的应用

文中以山西省首家悬索自动化测流缆道在义棠水文站淤泥质河床的应用为例，叙述了该站缆道的设计、安装、试验研究的基本情况、设计指标、缆道总体布设、信号传输线路的设计及工作原理等。“失重”开关与河底开关的双重保险功能是解决我国北方地区淤泥质河床信号的产生与传输的关键。文中对此做了具体叙述，旨在为类似的缆道工程设计采用时参考。     

Effects of mastication on the distribution of molecular weights and on the mechanical properties of native and commercial dental gutta percha (trans-polyisoprene)

Mastication of gutta percha (trans-polyisoprene) resulted in the selective scission of molecules, producing a narrower distribution of lower molecular weights. The mechanical properties of the samples also underwent a significant change due to mastication. The greater the content of incompatible substances (salts and oxides) in commercial gutta percha. the more substantial were these effects. The atmosphere (air, N₂, O₂) in which the experiments were conducted yielded significantly different results. The decrease in molecular weight was far greater in an O₂ atmosphere than under a current of nitrogen or air, owing to the combination of double bonds with O₂.