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Banded spherulites and twisting lamellae in poly–ε–caprolactone

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Abstract

By crystallization of poly–ε–caprolactone (PCL) at temperatures (55 ∘C ≥ Tc ≥ 50 ∘C) close to the melting point (Tm = 61 ∘C), banded spherulites form. These structures show a periodicity of P = 32 µm as determined by polarized optical microscopy (POM). In weakly-to-non-banded spherulites formed under similar conditions, a less sharp distribution of characteristic length scales is observed, that exhibits the same mean value. Within bright and dark regions of the banded spherulites, the two-dimensional molecular order parameter of different crystal directions of the lamellae is deduced from tightly focused (15 × 50 µm2) polarized infrared-spectroscopy measurements. From the oscillation of the order parameters of the crystalline \(\underline {a}\)-, \(\underline {b}\)-, and \(\underline {c}\)-axes, banding in pure PCL is proven to result from lamellae growing in a helicoidal fashion along the spherulites radius. No deviation of lamellar growth and radius is determined within experimental uncertainty (± 4∘). Furthermore, spatially averaged IR-microscopy results in the same characteristic polarization dependence in banded and weakly-to-non-banded spherulites. In conjunction with the mentioned characteristic length scales, we conclude that the mechanism, which results in banding, is also active in non-banded spherulites of PCL.

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Acknowledgments

The authors thank the German Science Foundation for the financial support in the framework of the colloborative research center “SFB TRR 102: Polymers under multiple constraints: restricted and controlled molecular order and mobility.” Furthermore, we like to thank Martha Schulz and Prof. Thomas Thurn-Albrecht (University Halle-Wittenberg) for fruitful discussions and help with the interpretation of the results.

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  1. Molecular Physics Department, Peter Debye Institut für weiche Materie, University Leipzig, Linestraße 5, 04103, Leipzig, Germany

    Wilhelm Kossack & Friedrich Kremer

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Kossack, W., Kremer, F. Banded spherulites and twisting lamellae in poly–ε–caprolactone. Colloid Polym Sci 297, 771–779 (2019). https://doi.org/10.1007/s00396-019-04503-8

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