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Mechanistic Study on the Shape Transition of Block Copolymer Particles Driven by Length-Controlled Nanorod Surfactants
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    Mechanistic Study on the Shape Transition of Block Copolymer Particles Driven by Length-Controlled Nanorod Surfactants
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    • Kang Hee Ku
      Kang Hee Ku
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
      More by Kang Hee Ku
    • Ji Ho Ryu
      Ji Ho Ryu
      School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of Korea
      More by Ji Ho Ryu
    • Jinwoo Kim
      Jinwoo Kim
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
      More by Jinwoo Kim
    • Hongseok Yun
      Hongseok Yun
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
      More by Hongseok Yun
    • Chongyong Nam
      Chongyong Nam
      School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of Korea
    • Jae Man Shin
      Jae Man Shin
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
      More by Jae Man Shin
    • Youngkwon Kim
      Youngkwon Kim
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
    • Se Gyu Jang
      Se Gyu Jang
      Functional Composite Materials Research Center, Korea Institute of Science and Technology (KIST), Jeonbuk 55324, Republic of Korea
      More by Se Gyu Jang
    • Won Bo Lee*
      Won Bo Lee
      School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of Korea
      *E-mail: [email protected] (W.B.L.).
      More by Won Bo Lee
    • Bumjoon J. Kim*
      Bumjoon J. Kim
      Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea
      *E-mail: [email protected] (B.J.K.).
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    Chemistry of Materials

    Cite this: Chem. Mater. 2018, 30, 23, 8669–8678
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    https://doi.org/10.1021/acs.chemmater.8b04020
    Published October 30, 2018
    Copyright © 2018 American Chemical Society

    Abstract

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    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.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b04020.

    • Additional TEM and SEM images of NR-containing PS-b-P4VP(PDP) particles; synthetic procedures for CuPt NR surfactants; and detailed free energy calculation and DPD simulation method to demonstrate the coassembly of NRs and BCPs within emulsion droplet (PDF)

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    This article is cited by 40 publications.

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    Chemistry of Materials

    Cite this: Chem. Mater. 2018, 30, 23, 8669–8678
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.8b04020
    Published October 30, 2018
    Copyright © 2018 American Chemical Society

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