MOLECULAR WEIGHT DEPENDENCE OF CRYSTAL PATTERN TRANSITIONS OF POLY(ETHYLENE OXIDE)

作     者：Guo-liang Zhang Liu-xin Jin Ping Zheng 王维 Xiao-jing Wen 

作者机构：Center for Synthetic Soft MaterialsThe Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer ChemistryCollege of ChemistryNankai University School of Resources and MaterialsNortheastern University at Qinhuangdao 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2013年第31卷第5期

页      面：798-808页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：financially supported by the National Science Foundation of China(No.20874053) 

主　　题：Poly(ethylene oxide) Crystallization Pattern formation Transition Molecular weight dependence. 

摘      要：Crystal patterns in ultrathin films of six poly（ethylene oxide） fractions with molecular weights from 25000 to 932000 g/mol were characterized within crystallization temperature range from 20 ℃to 60℃. Labyrinthine, dendritic and faceted crystal patterns were observed in different temperature ranges, and then labyrinthine-to-dendritic and dendritic-to- faceted transition temperatures T_L-D and T_D-F were quantitatively identified. Their molecular weight dependences are T_L-D（M_w） = T_L-D（∞） -K_L-D/M_w, where T_L-D（∞） = 38.2 ℃ and K_L-D = 253000 ℃.g/mol and T_D-F（M_w） = T_D-F（∞） -K_D-F/M_w, where T_D-F（∞） = 54.7 ℃ and K_D-F= 27000 ℃.g/mol. Quasi two-dimensional blob models were proposed to provide empirical explanations of the molecular weight dependences. The labyrinthine-to-dendritic transition is attributed to a molecular diffusion process change from a local-diffusion to diffusion-limited-aggregation （DLA） and a polymer chain with M_w ≈253000 g/mol within a blob can join crystals independently. The dendritic-to-faceted transition is attributed to a turnover of the pattern formation mechanism from DLA to crystallization control, and a polymer chain with a M_w ≈27000 g/tool as an independent blob crosses to a depletion zone to join crystals. These molecular weight dependences reveal a macromolecular effect on the crystal pattern formation and selection of crystalline polymers.