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Well-Ordered Nanoporous ABA Copolymer Thin Films via Solvent Vapor Annealing, Homopolymer Blending, and Selective Etching of ABAC Tetrablock Terpolymers

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Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States
Cite this: ACS Appl. Mater. Interfaces 2015, 7, 49, 27331–27339
Publication Date (Web):December 7, 2015
Copyright © 2015 American Chemical Society

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    Solvent vapor annealing treatments are used to control the orientation of nanostructures produced in thin films of a poly(styrene)-block-poly(isoprene)-block-poly(styrene)-block-poly((±)-lactide) (PS–PI–PS–PLA) and its blends with PLA homopolymer. The PS–PI–PS–PLA tetrablock terpolymer, previously determined to adopt a core(PLA)–shell(PS) cylindrical morphology in the bulk, gave perpendicular alignment of PLA cylinders over a limited range of thicknesses using a mixed solvent environment of tetrahydrofuran and acetone. On the other hand, perpendicular alignment was achieved regardless of film thickness by inclusion of 5 wt % homopolymer PLA in the PS–PI–PS–PLA tetrablock. Tapping mode atomic force microscopy (AFM) was used to visualize film surface morphologies. Subsequent reactive ion etching (RIE) and basic hydrolysis of PLA produced 15 nm pores in a PS–PI–PS triblock thin film matrix. Nanoporosity was confirmed by scanning electron microscopy (SEM) images and the vertical continuity of pores was confirmed by cross-sectional SEM analysis.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b08856.

    • Diagram of solvent annealing chamber and additional AFM and SEM images of PS–PI–PS–PLA polymer and PS–PI–PS–PLA/PLA polymer blend thin films (PDF)

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    Cited By

    This article is cited by 11 publications.

    1. Cameron K. Shelton, Ronald L. Jones, Joseph A. Dura, and Thomas H. Epps, III . Tracking Solvent Distribution in Block Polymer Thin Films during Solvent Vapor Annealing with in Situ Neutron Scattering. Macromolecules 2016, 49 (19) , 7525-7534.
    2. Melania Bednarek, Mateusz Grabowski. Polylactide/poly(vinyl monomer) block copolymers for specific applications. Polymer Reviews 2024, , 1-41.
    3. Xianger Xia, Xiaoshuang Li, Kunkai Ma, Yezhen Chen, Zhenchao Luan, Hongyue Chu, Bing Geng, Mei Yan. A rapid fabrication of flexible fluoropolymer with porous structure based on a high internal phase emulsion template. Polymer International 2024, 73 (2) , 94-107.
    4. Yi Zhai, Chao Li, Longcheng Gao. Degradable block copolymer-derived nanoporous membranes and their applications. Giant 2023, 16 , 100183.
    5. Karim Aissou, Muhammad Mumtaz, Daniel Hermida‐Merino, Eduardo Solano, Didier Cot, Belkacem Tarek Benkhaled, Damien Quémener, Stéphanie Roualdes, Guillaume Fleury, Georges Hadziioannou. Square arrays of vertically aligned nanoporous cylinders from a linear ABC triblock terpolymer. Journal of Polymer Science 2023, 61 (13) , 1259-1269.
    6. Nikola Toshikj, Jason Richard, Michel Ramonda, Jean-Jacques Robin, Sebastien Blanquer. Self-assembled biodegradable block copolymer precursors for the generation of nanoporous poly(trimethylene carbonate) thin films. Polymer 2023, 274 , 125880.
    7. Dinglei Zhong, Jiemei Zhou, Yong Wang. Hollow-fiber membranes of block copolymers by melt spinning and selective swelling. Journal of Membrane Science 2021, 632 , 119374.
    8. Yang Cong, Wei Zhai, Changsong Wu. Morphology Evolution of Block Copolymer Blend Thin Films Induced by Solvent Vapor Annealing. Soft Materials 2021, 19 (1) , 117-128.
    9. Yizhou Zhang, Noelia E. Almodovar-Arbelo, Jacob L. Weidman, David S. Corti, Bryan W. Boudouris, William A. Phillip. Fit-for-purpose block polymer membranes molecularly engineered for water treatment. npj Clean Water 2018, 1 (1)
    10. Dennis Ndaya, Reuben Bosire, Lalit Mahajan, Scarlet Huh, Rajeswari Kasi. Synthesis of ordered, functional, robust nanoporous membranes from liquid crystalline brush-like triblock copolymers. Polymer Chemistry 2018, 9 (12) , 1404-1411.
    11. Huanhuan Zhang, Lin Xu, Yuqing Lai, Tongfei Shi. Influence of film structure on the dewetting kinetics of thin polymer films in the solvent annealing process. Physical Chemistry Chemical Physics 2016, 18 (24) , 16310-16316.

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