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Structural Evolution Mechanism of Crystalline Polymers in the Isothermal Melt-Crystallization Process: A Proposition Based on Simultaneous WAXD/SAXS/FTIR Measurements

机译:等温熔融结晶过程中结晶聚合物的结构演化机理:基于同时WAXD / SAXS / FTIR测量的命题

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摘要

Time-resolved simultaneous measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) (and FTIR spectra) were performed for various kinds of crystalline polymers in isothermal melt-crystallization processes, from which the common features of the structural evolution process as well as the different behaviors intrinsic to the individual polymer species were extracted. The polymers targeted here were polyethylene, isotactic polypropylene, polyoxymethylene, aliphatic nylon, vinylidene fluoride copolymer, trans-polyisoprene, and poly(alkylene terephthalate). A universal concept of the microscopically viewed structural evolution process in isothermal crystallization may be described as follows: (i) the small domains composed of locally regular but more or less disordered helical chain segments are created in the melt (this important information was obtained by the IR spectral data analysis); (ii) these domains grow larger as the length and number of more regular helical segments increase with time; (iii) the correlation among the domains becomes stronger and they approach each other; and (iv) they merge into the stacked lamellar structure consisting of the regularly arranged crystalline lattices. The inner structure of the domains is different depending on the polymer species, as known from the IR spectral data.
机译:在等温熔融结晶过程中,对各种结晶聚合物进行了广角X射线衍射(WAXD)和小角X射线散射(SAXS)(和FTIR光谱)的时间分辨同时测量。提取了结构演化过程的共同特征以及各个聚合物种类固有的不同行为。这里的目标聚合物是聚乙烯,全同立构聚丙烯,聚甲醛,脂肪族尼龙,偏二氟乙烯共聚物,反式聚异戊二烯和聚对苯二甲酸亚烷基酯。等温结晶中微观观察到的结构演化过程的普遍概念可以描述如下:(i)在熔体中形成由局部规则但或多或少无序的螺旋链段组成的小区域(此重要信息是通过红外光谱数据分析); (ii)随着更多规则螺旋段的长度和数量随时间增加,这些域会越来越大; (iii)各个领域之间的关联性越来越强,并且彼此接近; (iv)它们合并成由规则排列的晶格组成的堆叠的层状结构。如从IR光谱数据已知的,畴的内部结构取决于聚合物种类而不同。

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