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Surface orientation of amphiphilic block copolymers via thermal annealing

Polymer Journal volume 57, pages 335–339 (2025)Cite this article

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Controlling the surface structure of polymer films is pivotal in various fields because it is closely related to surface properties such as wettability, adhesion, and bioinertness. The surface structure of a multicomponent polymer system is generally governed by thermodynamics, which minimizes the surface free energy (γ) of the system [1,2,3,4]. In diblock copolymer films, a wetting layer incorporating a component with a smaller γ is generally formed at the surface, independent of the bulk microphase structure [1, 5]. In the case of amphiphilic block copolymers, a hydrophobic surface is often obtained because hydrophobic components tend to exhibit smaller γ values than do hydrophilic components [6].

However, spontaneous surface segregation of hydrophilic components in block copolymer films has been observed in certain systems [7,8,9]. A highly effective method for decreasing the γ value of hydrophilic components is the utilization of a large entropic contribution to γ. Oda and Tanaka et al. reported that a rubbery hydrophilic component presented a smaller γ value and segregated to form a hydrophilic surface on an amphiphilic diblock copolymer film owing to enhanced molecular motion [9]. This study demonstrated that utilizing the entropic contribution to γ resulting from significant differences in chain mobility is a powerful tool for controlling the surface chemical composition of polymer films.

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Acknowledgements

This research was partly supported by the JSJP KAKENHI Grant-in-Aid for Scientific Research (C), Grant Number JP24K08541, Japan, and the Sumitomo Foundation, Grant for Basic Science Research Project, Japan (YO).

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  1. Department of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, Hamamatsu, Shizuoka, Japan

    Hayate Narumi & Yukari Oda

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  1. Hayate Narumi
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Correspondence to Yukari Oda.

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Narumi, H., Oda, Y. Surface orientation of amphiphilic block copolymers via thermal annealing. Polym J 57, 335–339 (2025). https://doi.org/10.1038/s41428-024-00999-2

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