Citation: Yu-han Wei, Cai-yuan Pan, Bin-yao Li, Xin-hong Yu, Yan-chun Han. EFFECT OF MOLECULAR WEIGHT AND FILM THICKNESS ON THE CRYSTALLIZATION AND MICROPHASE SEPARATION IN POLYSTYRENE-BLOCK-POLY(L-LACTIC ACID) THIN FILMS AT THE EARLY STAGE[J]. Chinese Journal of Polymer Science, ;2011, 29(3): 325-335. doi: 10.1007/s10118-011-1040-z
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We investigated the effects of molecular weight and film thickness on the crystallization and microphase separation in semicrystalline block copolymer polystyrene-block-poly(L-lactic acid) (PS-b-PLLA) thin films, at the early stage of film evolution (when Tg T TODT) by in situ hot stage atomic force microscopy. For PS-b-PLLA 1 copolymer which had lower molecular weight and higher PLLA fraction, diffusion-controlled break-out crystallization started easily. For PS-b-PLLA 2 with higher molecular weight, crystallization in nanometer scales occurs in local area. After melting of the two copolymer films, islands were observed at the film surface: PS-b-PLLA 1 film was in a disordered phase mixed state while PS-b-PLLA 2 film formed phase-separated lamellar structure paralleling to the substrate. Crystallization-melting and van der Waals forces drove the island formation in PS-b-PLLA 1 film. Film thickness affected the crystallization rate. Crystals grew very slowly in much thinner film of PS-b-PLLA 1 and remained almost unchanged at long time annealing. The incompatibility between PS and PLLA blocks drove the film fluctuation which subsequently evolved into spinodal-like morphology.
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