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Interfaces and soft confinement promote crystallization in polymer nanodroplets

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Abstract

We employ all-atom molecular dynamics simulations to study polyethylene (PE) crystallization under soft nanoconfinement in water. The hydrophobic PE phase separates from water and forms nanodroplets above the crystal melting temperature. By cooling the PE nanodroplets of different sizes in simulations, we show that the polymer-water interface can induce partial orientational order to polymer segments in the precursor state and enhance crystal nucleation. Curvature imposed by nanoconfinement, however, hinders PE crystallization, resulting in rare occurrences of crystalline atoms at highly curved droplet centers. We observe crystals nucleate at the PE-water interface and grow inward. For large droplets, the growth of multiple nuclei formed at the droplet interfaces leads to polycrystalline droplets after crystallization. Sufficiently small droplets can deform and elongate to accommodate the formation of large single crystallites and high crystallinity.

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Acknowledgments

W. Zhang acknowledges the support of this project by the start-up fund from Dartmouth College. Computational time was provided by the High-Performance Computing (HPC) at Dartmouth College. Elaine L. Jiao thanks the Women in Science Project at Dartmouth College for its support.

Funding

The research leading to these results received funding from Dartmouth College.

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Author notes

  1. Caleb Liu and Anderson D. S. Duraes have contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Dartmouth College, 41 College Street, Hanover, NH, 03755, USA

    Caleb Liu, Anderson D. S. Duraes, Elaine L. Jiao & Wenlin Zhang

Authors
  1. Caleb Liu
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  2. Anderson D. S. Duraes
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  3. Elaine L. Jiao
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Contributions

Conceptualization: Wenlin Zhang; Methodology: Anderson D.S. Duraes and Wenlin Zhang; Formal analysis and investigation: Caleb Liu, Elaine L. Jiao, and Anderson D.S. Duraes; Writing—original draft preparation: Caleb Liu, Elaine L. Jiao, and Anderson D.S. Duraes; Writing—review and editing: Caleb Liu, Anderson D.S. Duraes, and Wenlin Zhang; Funding acquisition: Wenlin Zhang; Resources: Wenlin Zhang; Supervision: Wenlin Zhang.

Corresponding authors

Correspondence to Anderson D. S. Duraes or Wenlin Zhang.

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Liu, C., Duraes, A.D.S., Jiao, E.L. et al. Interfaces and soft confinement promote crystallization in polymer nanodroplets. MRS Advances (2024). https://doi.org/10.1557/s43580-024-00856-7

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