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Heterogeneity in polymer melts from melting of polymer crystals

Nature Materials volume 4, pages 635–641 (2005)Cite this article

An Erratum to this article was published on 01 June 2006

Abstract

Semi-crystalline polymers containing amorphous and crystalline regions usually have intimately mixed chains. The resulting topological constraints (entanglements) in the amorphous regions limit the drawability in the solid state. By controlled synthesis the number of entanglements can be reduced. Ultimately, crystals composed of single chains are feasible, where the chains are fully separated from each other. If such separation can be maintained in the melt a new melt state can be formed. Here we show that through slow and carefully controlled melting such polymer crystals form a heterogeneous melt with more entangled regions, where the chains are mixed, and less entangled ones, composed of individually separated chains. Chain reptation, required for the homogenization of the entanglement distribution, is found to be considerably hindered. The long-lived heterogeneous melt shows decreased melt viscosity and provides enhanced drawability on crystallization. This novel route to create heterogeneous melt should be applicable to polymers in general.

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Figure 1: A schematic view of crystals differing in the distribution of entanglements.
Figure 2: On annealing at 136 ∘C a different melting behaviour is depicted.
Figure 3: NMR line shapes and T2 relaxation curves of fast-heated (10 K min−1, red) and slow-heated (0.2 K min−1, blue) UHMW-PE melts of commercial and metallocene grade recorded at T=423 K.
Figure 4: The role of melting kinetics in the entanglement process of disentangled metallocene grade.
Figure 5: A possible route to transform the heterogeneous melt into a homogeneous melt.
Figure 6: The stress–strain curves of the crystals formed from heterogeneous and homogeneous melts.

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Acknowledgements

The authors wish to thank H. E. H. Meijer, C. Bailly, J. F. Vega, R. Duchateau and P. Magusin for constructive discussions.

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Authors and Affiliations

  1. Department of Chemical Engineering, Eindhoven University of Technology, 5600 MB, Eindhoven, PO Box 513, The Netherlands

    Sanjay Rastogi & Dirk R. Lippits

  2. Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128, Mainz, Germany

    Sanjay Rastogi, Robert Graf, Yefeng Yao & Hans W. Spiess

  3. Dutch Polymer Institute, PO Box 902, 5600AX, Eindhoven, The Netherlands

    Sanjay Rastogi & Gerrit W. M. Peters

  4. Department of Mechanical Engineering, Eindhoven University of Technology, 5600 MB, Eindhoven, PO Box 513, The Netherlands

    Gerrit W. M. Peters

Authors
  1. Sanjay Rastogi
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  2. Dirk R. Lippits
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  3. Gerrit W. M. Peters
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  4. Robert Graf
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  5. Yefeng Yao
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  6. Hans W. Spiess
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Correspondence to Sanjay Rastogi.

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Supplementary annexures I - IV and supplementary figures (PDF 309 kb)

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Rastogi, S., Lippits, D., Peters, G. et al. Heterogeneity in polymer melts from melting of polymer crystals. Nature Mater 4, 635–641 (2005). https://doi.org/10.1038/nmat1437

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