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Relaxation processes and structural transitions in stretched films of polyvinylidene fluoride and its copolymer with hexafluoropropylene

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Abstract

Relaxation processes and structural transitions in nonstretched and uniaxially stretched films of poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) and its homopolymer polyvinylidene fluoride (PVDF) for comparison were investigated with the aim of understanding the electromechanical properties of this lower-modulus ferroelectric copolymer. The mechanical and the dielectric response at the glass transition (α a relaxation) exhibit similar temperature dependence of the relaxation time, whereas mechanical and dielectric processes above the glass transition are not related. They represent a continuous softening process within the amorphous phase and the dielectric α c relaxation, respectively. The latter is attributed to conformational changes of VDF segments in lamellae of spherulites constituting the nonpolar crystalline α phase. Furthermore, there is a contribution from melting of secondary crystallites formed in the amorphous phase during annealing or storage. Mechanically, this transition appears in nonstretched and stretched films as an accelerated decrease of the elastic modulus that terminates the rubber plateau. Dielectrically, this transition becomes visible as a frequency-independent loss peak only in stretched films, because stretching removes the α c relaxation, which superimposes the transition in nonstretched films. Melting of secondary crystallites is shown to appear in the homopolymer, too, though less pronounced because of more complete primary crystallisation.

Stretching increases the modulus above the glass transition only slightly, and it does not significantly influence the softening process. On the other hand, stretching causes a spontaneous polarisation and introduces order within the amorphous phase, rendering it more polar. Melting of secondary crystallites provides an additional contribution to the polarisation. These findings may explain the relatively high electromechanical activity of P(VDF-HFP) but also its relatively low thermal stability. Moreover, they may be important for correct procedure and analysis of temperature-dependent dielectric measurements on partially crystalline polymers, in particular on those with less favourable sterical conditions for primary crystallisation.

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Acknowledgements

The authors are indebted to Matthias Jaunich and Wolfgang Stark (Federal Institute for Materials Research and Testing, Berlin, Germany) for performing the DMA measurements and to Monika Ehlert and Selina Müller for lab assistance. F. Wang thanks the Deutsche Forschungsgemeinschaft for providing a research fellowship (Ref. Nr. WA 2688/1-1). The authors thank the European Union for partial financial support of equipment within the European Fund for Regional Development (EFRD).

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  1. Applied Condensed-Matter Physics, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476, Potsdam, Germany

    Peter Frübing & Feipeng Wang

  2. Functional Materials and Devices, Fraunhofer Institute for Applied Polymer Research, Geiselbergstraße 69, 14476, Potsdam, Germany

    Michael Wegener

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Correspondence to Peter Frübing.

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Frübing, P., Wang, F. & Wegener, M. Relaxation processes and structural transitions in stretched films of polyvinylidene fluoride and its copolymer with hexafluoropropylene. Appl. Phys. A 107, 603–611 (2012). https://doi.org/10.1007/s00339-012-6838-1

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