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可生物降解的聚琥珀酸乙烯酯(PES)。1. 晶体生长动力学与形态学

Biodegradable poly(ethylene succinate) (PES). 1. Crystal growth kinetics and morphology.

作者信息

Gan Z, Abe H, Doi Y

机构信息

Polymer Chemistry Laboratory, RIKEN Institute, Hirosawa 2-1, Wako-shi, Saitama 351-0198, Japan.

出版信息

Biomacromolecules. 2000 Winter;1(4):704-12. doi: 10.1021/bm0000541.

DOI:10.1021/bm0000541
PMID:11710201
Abstract

Crystal growth rates of melt-crystallized poly(ethylene succinate) (PES) with a number-average molecular weight Mn of 21,100 and polydispersity of 1.86, respectively, were studied in an extensive temperature range. On the basis of secondary nucleation theory, only one transition between regime III and regime II was found at around 71 degrees C, but no transition of regime II-->I was detected by kinetic analysis. The ratio of nucleation constants KgIII in regime III to KgII in regime II was influenced by the value of activation energy U*, and tended to 2 as predicted by the theory when U* was set as 3688 cal/mol. The morphological changes at spherulitic level and lamellar level in regime II and regime III were examined by using an optical microscope (OM) and atomic force microscope (AFM). Although spherulitic morphologies were found in both regime II and regime III by optical microscopy, further investigations made by following the crystallization process using OM and by checking the lamellar morphology using AFM revealed morphological changes during the crystal growth process and different crystal morphologies in regime II and regime III. Meanwhile by using ultrathin film (approximately 100 nm in thickness), the morphology of lamellar crystals of lozenge-shape outline and composed of single crystals has been studied by AFM technique. The results indicate that there is indeed a transition from regime II to regime III at around 71 degrees C for the isothermal crystallization of PES with an increasing degree of undercooling.

摘要

分别研究了数均分子量(Mn)为(21100)且多分散性为(1.86)的熔融结晶聚琥珀酸乙二酯(PES)在广泛温度范围内的晶体生长速率。基于二次成核理论,在约(71^{\circ}C)时仅发现了III区和II区之间的一个转变,但动力学分析未检测到II区到I区的转变。III区的成核常数(KgIII)与II区的成核常数(KgII)之比受活化能(U*)值的影响,当(U*)设定为(3688)卡/摩尔时,该比值趋于理论预测的(2)。使用光学显微镜(OM)和原子力显微镜(AFM)研究了II区和III区球晶水平和片晶水平的形态变化。尽管通过光学显微镜在II区和III区均发现了球晶形态,但通过使用OM跟踪结晶过程以及使用AFM检查片晶形态进行的进一步研究揭示了晶体生长过程中的形态变化以及II区和III区不同的晶体形态。同时,通过使用超薄膜(厚度约为(100)纳米),利用AFM技术研究了由单晶组成的菱形轮廓片晶的形态。结果表明,对于具有增加过冷度的PES等温结晶,在约(71^{\circ}C)时确实存在从II区到III区的转变。

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