Citation: Guo-liang Zhang, Liu-xin Jin, Ping Zheng, Wei Wang, Xiao-jing Wen. MOLECULAR WEIGHT DEPENDENCE OF CRYSTAL PATTERN TRANSITIONS OF POLY(ETHYLENE OXIDE)[J]. Chinese Journal of Polymer Science, ;2013, 31(5): 798-808. doi: 10.1007/s10118-013-1273-0 shu

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

Received Date: 20 December 2012
Revised Date: 28 January 2013

Fund Project: This work was financially supported by the National Science Foundation of China (No. 20874053).

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 TL-D and TD-F were quantitatively identified. Their molecular weight dependences are TL-D(Mw) = TL-D() - KL-D/Mw, where TL-D() = 38.2℃ and KL-D = 253000℃g/mol and TD-F(Mw) = TD-F()-KD-F/Mw, where TD-F() = 54.7℃ and KD-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 Mw253000 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 Mw27000 g/mol 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.
- Poly(ethylene oxide),
- Crystallization,
- Pattern formation,
- Transition,
- Molecular weight dependence
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