Role of Defects in Achieving Highly Asymmetric Lamellar Self-Assembly in Block Copolymer/Homopolymer Blends

Shi, WC (Shi, Weichao)^{[ 1,2 ]}

JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2020, 11(7): 2724-2730

DOI: 10.1021/acs.jpclett.0c00459

摘要

Lamellar structure is a prominent state in soft condensed matter. Swelling lamellar layers to highly asymmetric structures by a second component is a facile, cost-effective strategy to impart materials with adaptive size and tunable properties. One key question that remains unsolved is how defects form and affect the asymmetric lamellar order. This study unravels the role of defects by swelling a miktoarm block copolymer with a homopolymer. Ordered lamellae first lose translational order by a significant increase in the number of dislocations and then lose orientational order by the generation of disclinations. The homopolymers are not uniformly distributed in defective lamellae and primarily segregate in the vicinity of disclination cores. The free energy of defects is mainly contributed by molecular splay and significantly alleviated by an increased radius of local curvature. This study provides direct evidence to reveal the role of defects and lamellar order in block copolymer/homopolymer blends and also sheds light on understanding analogous structural transitions in other soft systems, including lyotropic liquid crystals, phospholipid membranes, and polymer nanocomposites.