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On the bridge hypothesis in the glass transition of freestanding polymer films

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A Correction to this article was published on 20 October 2023

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Abstract

Freestanding thin polymer films with high molecular weights exhibit an anomalous decrease in the glass-transition temperature with film thickness. Specifically, in such materials, the measured glass-transition temperature evolves in an affine way with the film thickness, with a slope that weakly depends on the molecular weight. De Gennes proposed a sliding mechanism as the hypothetical dominant relaxation process in these systems, where stress kinks could propagate in a reptation-like fashion through so-called bridges, i.e. from one free interface to the other along the backbones of polymer macromolecules. Here, by considering the exact statistics of finite-sized random walks within a confined box, we investigate in details the bridge hypothesis. We show that the sliding mechanism cannot reproduce the basic features appearing in the experiments, and we exhibit the fundamental reasons behind such a fact.

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Data produced for this article are available upon reasonable request to the authors.

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Acknowledgements

The authors acknowledge financial support from the European Union through the European Research Council under EMetBrown (ERCCoG-101039103) grant. The authors also acknowledge financial support from the Agence Nationale de la Recherche under EMetBrown (ANR-21-ERCC-0010-01), Softer (ANR-21-CE06-0029) and Fricolas (ANR-21-CE06-0039) grants, as well as from the UHJ-France association and the Scopus Foundation. Finally, they thank the Soft Matter Collaborative Research Unit, Frontier Research Center for Advanced Material and Life Science, Faculty of Advanced Life Science at Hokkaido University, Sapporo, Japan, as well as the Natural Sciences and Engineering Research Council of Canada.

Author information

Authors and Affiliations

  1. Gulliver, CNRS UMR 7083, ESPCI Paris, Univ. PSL, 75005, Paris, France

    Haggai Bonneau & Elie Raphaël

  2. School of Chemistry, Center for the Physics and Chemistry of Living Systems, Ratner Institute for Single Molecule Chemistry, and the Sackler Center for Computational Molecular and Materials Science, Tel Aviv University, 6997801, Tel Aviv, Israel

    Maxence Arutkin

  3. Department of Physics and Astronomy, University of Waterloo, Waterloo, ON, N2L 3G1, Canada

    Rainni Chen & James A. Forrest

  4. Univ. Bordeaux, CNRS, LOMA, UMR 5798, F-33400, Talence, France

    Thomas Salez

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  1. Haggai Bonneau
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Contributions

JF, ER and TS conceived the study. HB and MA performed the analytical research. RC performed the numerical simulations. HB wrote the first draft of the manuscript. All the authors discussed the results and contributed to the writing of the manuscript.

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Correspondence to Thomas Salez.

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For Fyl, who has always encouraged the young and not-so-young people around him to be inventive and to have fun in their pursuit of science.

The original online version of this article was revised: “A dedication to the collection: Festschrift in honor of Philip (Fyl) Pincus has been added”.

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Bonneau, H., Arutkin, M., Chen, R. et al. On the bridge hypothesis in the glass transition of freestanding polymer films. Eur. Phys. J. E 46, 8 (2023). https://doi.org/10.1140/epje/s10189-023-00272-z

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