P(VDF-TrFE) Copolymer Dynamics as a Function of Temperature and Pressure in the Vicinity of the Curie Transition

Achilleas Pipertzis, Kamal Asadi, George Floudas

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We report on the phase behavior and the respective dynamics in random P(VDF-TrFE) copolymers using standard and temperature-modulated differential scanning calorimetry, X-ray diffraction, and a combination of temperature- and pressure-dependent dielectric spectroscopy measurements. Depending on the copolymer composition, the coexistence of three/four weakly ordered phases was identified in the vicinity of the Curie transition (Tc). With respect to the dynamics, we demonstrate that the segmental dynamics associated with the relaxation of constrained amorphous VDF segments at the crystal/amorphous "phase"can be used as a marker of the Curie transition. The corresponding segmental relaxation freezes at about 50 K above the lower liquid-to-glass temperature associated with the freezing of amorphous segments away from the interface. Pressure-dependent dielectric measurements provided quantitative insight into (i) the molecular origin of the segmental processes (by employing the pressure sensitivity of relaxation times and the pressure coefficient of the respective Tg's), (ii) the nature of the phase transition at Tc, and (iii) information about the stability of phases under the variation of temperature and pressure (through the T-P phase diagram). We show that Tc increases linearly with pressure and is accompanied by small volume changes, implying a weakly first-order thermodynamic transition. Furthermore, pressure stabilizes the ferroelectric phase over a broader temperature range. This could extend the operating temperature range of ferroelectric devices based on P(VDF-TrFE) copolymers.

Original languageEnglish
Pages (from-to)2746-2757
Number of pages12
Issue number7
Early online date31 Mar 2022
Publication statusPublished - 12 Apr 2022

Bibliographical note

Funding Information:
We are grateful to Saleem Anwar (MPI-P) for the film preparation used in the dielectric studies. A.P. was financially supported by the program “PERIFEREIAKI ARISTEIA” (Regional Excellence) cofinanced by the European Union and the Hellenic Republic Ministry of development and investments under NSRF 2014-2020 (Region of Epirus, call 111). This research was supported by the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the “First Call for H.F.R.I. Research Projects to support Faculty members and Researchers and the procurement of high-cost research equipment grant” (Project No. 183). K.A. acknowledges the financial support from the Max Planck Institute for Polymer Research and from the University of Bath.

Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society and Division of Chemical Education, Inc.

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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