Mechanistic Study on the Shape Transition of Block Copolymer Particles Driven by Length-Controlled Nanorod SurfactantsClick to copy article linkArticle link copied!
- Kang Hee KuKang Hee KuDepartment of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Kang Hee Ku
- Ji Ho RyuJi Ho RyuSchool of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of KoreaMore by Ji Ho Ryu
- Jinwoo KimJinwoo KimDepartment of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Jinwoo Kim
- Hongseok YunHongseok YunDepartment of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Hongseok Yun
- Chongyong NamChongyong NamSchool of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of KoreaMore by Chongyong Nam
- Jae Man ShinJae Man ShinDepartment of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Jae Man Shin
- Youngkwon KimYoungkwon KimDepartment of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Youngkwon Kim
- Se Gyu JangSe Gyu JangFunctional Composite Materials Research Center, Korea Institute of Science and Technology (KIST), Jeonbuk 55324, Republic of KoreaMore by Se Gyu Jang
- Won Bo Lee*Won Bo Lee*E-mail: [email protected] (W.B.L.).School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of KoreaMore by Won Bo Lee
- Bumjoon J. Kim*Bumjoon J. Kim*E-mail: [email protected] (B.J.K.).Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of KoreaMore by Bumjoon J. Kim
Abstract

Interface engineering of evaporative emulsion droplets containing block copolymers (BCPs) provides an effective route to generate nonspherical particles. Here, we demonstrate the impact of length-controlled nanorods (NRs) on the interfacial properties of BCP emulsions to produce anisotropic BCP particles. A series of lamellae- and cylinder-forming polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and a series of NRs with different lengths (l) are coassembled, and selective arrangement of the NRs on the P4VP domain at the particle surface enables the production of striped football (prolate) and convex lens-shaped (oblate) particles. In particular, the ratio of the NR length to the size of the NR-hosting domain (l/L), which is varied from 0.07 to 3.60, is the key parameter in determining the location of the NRs in the BCP particles as well as the final particle shape. The oblate particles are generated only in the range of 0.36 ≤ l/L ≤ 0.96, whereas the prolate particles are produced for much wider range of l/L ≥ 0.83 without upper limit. This difference is attributed to larger entropic penalty for the NRs confined within the P4VP cylinders than the entropic penalty for those within the lamellae. To better understand and support our experimental observations, we performed dissipative particle dynamics simulation and calculated the free energy for the NR/BCP assembly within the emulsion droplets.
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