Skip to main content

Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy

Abstract

The aim of this study is to analyze the mobility of polymer chains in semicrystalline poly(vinylidene fluoride) (PVDF). PVDF crystallizes from the melt in the α crystalline phase. The transformation from the α phase to the electroactive β phase can be induced by stretching at temperatures in the range between 80 and 140 °C. The spherulitic structure of the crystalline phase is deformed during stretching to form fibrils oriented in the direction of the strain. The amorphous phase confined among the crystalline lamellae is distorted as well and some degree of orientation of the polymer chains is expected. Dynamic-mechanical and dielectric spectroscopy measurements were performed in PVDF films stretched to strain ratios up to 5 at temperatures between 80 and 140 °C. Dynamic-mechanical measurements were conducted between −60 °C and melting and in this temperature range the relaxation spectra show the main relaxation of the amorphous phase (called β-relaxation) and at higher temperatures a relaxation related to crystallites motions (α c-relaxation). Although the mean relaxation times of the β-relaxation are nearly equal in PVDF before and after crystal phase transformation, a significant change of shape of the relaxation spectrum proves the effect of chain distortion due to crystal reorganization. In stretched PVDF the elastic modulus of the polymer in the direction of deformation is significantly higher than in the transversal one, as expected by chain and crystals fibril orientation. The recovery of the deformation when the sample is heated is related with the appearance of the α c-relaxation. Dielectric spectroscopy spectrum shows the main relaxation of the amorphous phase and a secondary process (γ-relaxation) at lower temperatures. Stretching produces significant changes in the relaxation processes, mainly in the strength and shape of the main relaxation β. The Havriliak-Negami function has been applied to analyze the dielectric response.

This is a preview of subscription content, access via your institution.

References

  1. A.J. Lovinger, Developments in semicrystalline polymers (Elsevier, London, 1982).

  2. H.S. Nalwa, Ferroelectric Polymers: Chemistry, Physics, and Applications (Marcel Dekker, New York, 1995).

  3. V. Sencadas, V.M. Moreira, S. Lanceros-Mendez, A.S. Pouzada, R. Gregorio, Mater. Sci. Forum 514-516, 872 (2006).

    Article  Google Scholar 

  4. M.C. Branciforti, V. Sencadas, S. Lanceros-Mendez, R. Gregorio, J. Polym. Sci. Polym. Phys. 45, 2793 (2007).

    ADS  Article  Google Scholar 

  5. V. Sencadas, R. Gregorio, S. Lanceros-Méndez, J. Macromol. Sci. B 48, 514 (2009).

    Article  Google Scholar 

  6. V. Sencadas, R. Gregorio, S. Lanceros-Mendez, J. Non-Cryst. Solids 352, 2226 (2006).

    ADS  Article  Google Scholar 

  7. R. Gregorio, E.M. Ueno, J. Mater. Sci. 34, 4489 (1999).

    Article  Google Scholar 

  8. R.H. Boyd, Polymer 26, 323 (1985).

    Article  Google Scholar 

  9. R.H. Boyd, Polymer 26, 1123 (1985).

    Article  Google Scholar 

  10. L.Y. Tian, X.B. Huang, X.Z. Tang, J. Appl. Polym. Sci. 92, 3839 (2004).

    Article  Google Scholar 

  11. A. Bello, E. Laredo, M. Grimau, Phys. Rev. B 60, 12764 (1999).

    ADS  Article  Google Scholar 

  12. R. Gregorio, E.M. Ueno, J. Mater. Sci. 34, 4489 (1999).

    Article  Google Scholar 

  13. Rashmi, G.K. Narula, P.K.C. Pillai, J. Mater. Sci. 22, 2006 (1987).

    ADS  Article  Google Scholar 

  14. E. Tuncer, M. Wegener, R. Gerhard-Multhaupt, J. Non-Cryst. Solids 351, 2917 (2005).

    ADS  Article  Google Scholar 

  15. V. Sencadas, S. Lanceros-Méndez, J.F. Mano, Thermochim. Acta 424, 201 (2004).

    Article  Google Scholar 

  16. J.F. Mano, V. Sencadas, A.M. Costa, S. Lanceros-Méndez, Mater. Sci. Eng. A 370, 336 (2004).

    Article  Google Scholar 

  17. S. Lanceros-Mendez, M.V. Moreira, J.F. Mano, V.H. Schmidt, G. Bohannan, Ferroelectrics 273, 15 (2002).

    Article  Google Scholar 

  18. H. Vogel, Phys. Z. 22, 645 (1921).

    Google Scholar 

  19. G.S. Fulcher, J. Am. Ceram. Soc. 8, 339 (1925).

    Article  Google Scholar 

  20. G. Tamman, W. Hesse, Z. Anorg, Allg. Chem. 156, 245 (1926).

    Article  Google Scholar 

  21. Z. Liu, P. Maréchal, R. Jérome, Polymer 38, 4925 (1997).

    Article  Google Scholar 

  22. A.M. Vinogradov, V. Hugo Schmidt, G.F. Tuthill, G.W. Bohannan, Mech. Mater. 36, 1007 (2004).

    Article  Google Scholar 

  23. P. Lee-Sullivan, Mater. Res. Innov. 10, 428 (2006).

    Google Scholar 

  24. I. Dmitriev, S. Gladchenko, N. Afanas’eva, V. Lavrent’ev, B. Bukošek, J. Baldrian, G. Elyashevich, Polym. Sci. Ser. A 50, 265 (2008).

    Article  Google Scholar 

  25. V. Sencadas, V.M. Moreira, S. Lanceros-Mendez, A.S. Pouzada, R. Gregorio, Mater. Sci. Forum 514-516, 872 (2006).

    Article  Google Scholar 

  26. M.C. Branciforti, V. Sencadas, S. Lanceros-Mendez, R. Gregorio, J. Polym. Sci. Part. B-Polym. Phys. 45, 2793 (2007).

    ADS  Article  Google Scholar 

  27. A. Linares, J.L. Acosta, Eur. Polym. J. 33, 467 (1997).

    Article  Google Scholar 

  28. J.W. Sy, J. Mijovic, Macromolecules 33, 933 (2000).

    ADS  Article  Google Scholar 

  29. M. Takayanagui, Viscoelastic properties of crystalline polymers, Memoires of the Faculty of Engineering (Kyushu University) XXIII: 41-96.

  30. W.G. Hu, C. Boeffel, K. Schmidt-Rohr, Macromolecules 32, 1611 (1999).

    ADS  Article  Google Scholar 

  31. J.F. Mano, Macromolecules 34, 8825 (2001).

    ADS  Article  Google Scholar 

  32. S. Lanceros-Mendez, J.F. Mano, J.A. Mendes, Ferroelectrics 270, 271 (2002).

    Article  Google Scholar 

  33. V. Sencadas, C.M. Costa, V. Moreira, J. Monteiro, S.K. Mendiratta, J.F. Mano, S. Lanceros-Méndez, e-Polymers 2, 1 (2005).

    Google Scholar 

  34. R. Barbosa, J.A. Mendes, V. Sencadas, J.F. Mano, S. Lanceros-Méndez, Ferroelectrics 294, 73 (2003).

    Google Scholar 

  35. V. Sencadas, R. Barbosa, J.F. Mano, S. Lanceros-Méndez, Ferroelectrics 294, 61 (2003).

    Article  Google Scholar 

  36. M.L. Williams, R.F. Landel, J.D. Ferry, J. Am. Chem. Soc. 77, 3701 (1995).

    Article  Google Scholar 

  37. S. Havriliak, S. Negami, Polymer 8, 161 (1967).

    Article  Google Scholar 

  38. N.M. Alves, J.F. Mano, E. Balaguer, J.M. Meseguer Dueñas, J.L. Gómez Ribelles, Polymer 43, 4111 (2002).

    Article  Google Scholar 

  39. Y. Wang, J.L. Gómez Ribelles, M. Salmerón Sánchez, J.F. Mano, Macromolecules 38, 4712 (2005).

    ADS  Article  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to R. Sabater i Serra.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Sencadas, V., Lanceros-Méndez, S., Sabater i Serra, R. et al. Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy. Eur. Phys. J. E 35, 41 (2012). https://doi.org/10.1140/epje/i2012-12041-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1140/epje/i2012-12041-x

Keywords

  • Soft Matter: Polymers and Polyelectrolytes