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Cloning polymer single crystals through self-seeding

Abstract

In general, when a crystal is molten, all molecules forget about their mutual correlations and long-range order is lost. Thus, a regrown crystal does not inherit any features from an initially present crystal. Such is true for materials exhibiting a well-defined melting point. However, polymer crystallites have a wide range of melting temperatures, enabling paradoxical phenomena such as the coexistence of melting and crystallization. Here, we report a self-seeding technique that enables the generation of arrays of orientation-correlated polymer crystals of uniform size and shape (‘clones’) with their orientation inherited from an initial single crystal. Moreover, the number density and locations of these cloned crystals can to some extent be predetermined through the thermal history of the starting crystal. We attribute this unique behaviour of polymers to the coexistence of variable fold lengths in metastable crystalline lamellae, typical for ordering of complex chain-like molecules.

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Figure 1: Transforming a large compact dendritic single crystal into a plethora of uniquely oriented small crystals.
Figure 2: Nucleating crystals at the periphery of the seeding crystal following a two-step crystallization procedure.
Figure 3: A control experiment using an organometallic homopolymer.
Figure 4: Average number density N of baby crystals after annealing at different self-seeding temperatures (TSS).
Figure 5: Schematic presentation of essential steps in polymer crystallization enabling cloning.
Figure 6: Distribution of local lamellar thickness (stem length L) within a polymer crystal obtained by dynamic Monte Carlo simulation.

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Acknowledgements

We acknowledge V. Bellas (Technische Universität Darmstadt, Germany) for synthesizing the PFS polymer, and K. Albrecht, A. Mourran and M. Möller (DWI Aachen, Germany) for providing the P2VP-PEO block copolymer. J.X. is grateful to B. Stühn, I. Alig and B.-J. Jungnickel for helpful discussions. Financial support provided through the German Research Foundation (DFG), the European Community’s ‘Marie-Curie Actions’ under contract MRTN-CT-2004-005516 [BioPolySurf] and by the European COST Action P12 is acknowledged. W.H. is grateful for research support from the Chinese Ministry of Education (NCET-04-0448) and the National Natural Science Foundation of China (NNSFC Grants 20474027, 20674036, 20825415).

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The idea for this work arose from a visit by J.X. to ICSI-Mulhouse. J.X. and Y.M. carried out all experiments. Computer simulations were done by Y.M. and W.H. The control and coordination of polymer synthesis at TUD/DKI was assured by M.R. G.R. supervised and coordinated the whole project. All authors have contributed equally in defining the content and writing the present manuscript.

Corresponding authors

Correspondence to Jianjun Xu or Wenbing Hu.

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Xu, J., Ma, Y., Hu, W. et al. Cloning polymer single crystals through self-seeding. Nature Mater 8, 348–353 (2009). https://doi.org/10.1038/nmat2405

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