Order–Order Transition between Equilibrium Ordered Bicontinuous Nanostructures of Double Diamond and Double Gyroid in Stereoregular Block Copolymer

Order–Order Transition between Equilibrium Ordered Bicontinuous Nanostructures of Double Diamond and Double Gyroid in Stereoregular Block Copolymer
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DOI:
10.1021/ma202057g
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发表时间:
2012-03
期刊:
影响因子:
5.5
通讯作者:
C. Chu;Wen-Fu Lin;J. Tsai;Chia-Sheng Lai;S. Lo;Hsin‐Lung Chen;T. Hashimoto
C. Chu;Wen-Fu Lin;J. Tsai;Chia-Sheng Lai;S. Lo;Hsin‐Lung Chen;T. Hashimoto
中科院分区:
化学1区
文献类型:
--
作者:
C. Chu;Wen-Fu Lin;J. Tsai;Chia-Sheng Lai;S. Lo;Hsin‐Lung Chen;T. Hashimoto

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While ordered bicontinuous double diamond (OBDD) in block copolymers has always been considered as an unstable structure relative to ordered bicontinuous double gyroid (OBDG), here we report the existence of a thermodynamically stable OBDD structure in a diblock copolymer composed of a stereoregular block. A slightly asymmetric syndiotactic polypropylene-block-polystyrene (sPP-b-PS) as cast from xylene was found to display the OBDD morphology. When the OBDD-forming diblock was heated, this structure transformed to the OBDG phase at ca. 155 °C. Interestingly, OBDD was recovered upon cooling even in the temperature range above melting point of sPP, indicating that OBDD was a thermodynamically stable structure for sPP-b-PS melt, which was in contradiction to the conventional view. We propose that the larger free energy cost encountered in OBDD due to the larger packing frustration may be compensated sufficiently by the release of free energy due to local packing of the conformationally ordered segments of sP...