Yuan Kangrui, Xu Zhanwen, Huang Xianbo, Li Weihua
State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China.
National-certified Enterprise Technology Center, Kingfa Science and Technology Co., Ltd., Science City, Guangzhou, 510663, China.
Chemistry. 2023 Jul 26;29(42):e202301043. doi: 10.1002/chem.202301043. Epub 2023 Jun 19.
Recently, a few AB-type multiblock copolymers have been successfully designed to form stable square cylinder phase based on self-consistent field theory (SCFT) calculations. The previous works only identify the stability region of the square phase but not analyzing its stability, which is closely related to the free-energy landscape. In this work, we have reexamined the stability of the square phase in linear pentablock and star triblock copolymers by drawing the free-energy landscape with respect to the two dimensions of a rectangular unit cell. Our results demonstrate that the square phase continuously transfers to the rectangular phase as the degree of packing frustration is gradually released. Moreover, the prolate contour lines of the free-energy landscape indicate the weak stability of the square phase in the copolymer. In contrast, the stability of the square phase is notably improved in the copolymer due to its enhanced concentration of bridging configurations. Our work sheds light on the understanding of the stability of the square cylinder phase in block copolymers. Accordingly, we propose some possible strategies for further designing new AB-type block copolymer systems to obtain more stable square phase.
