Structural investigation of radiation grafted and sulfonated poly(vinylidene fluoride), PVDF, membranes

(Note: The full text of this document is currently only available in the PDF Version )

Sami Hietala, Svante Holmberg, Milja Karjalainen, Jan Näsman, Mikael Paronen, Ritva Serimaa, Franciska Sundholm and Sakari Vahvaselkä


Abstract

Radiation grafted and sulfonated poly(vinylidene fluoride), PVDF, membranes have been studied by thermal analysis and X-ray diffraction to determine the changes in membrane crystallinity and structure during preparation. Commercial PVDF films were irradiated with an electron beam, grafted with styrene and finally sulfonated. Both the crystallinity and the size of the crystallites of PVDF decrease in the grafting reaction. A further decrease in crystallinity is observed in the sulfonation reaction. The residual crystallinity of PVDF was considerable (10–20%) even in membranes which had been subjected to severe reaction conditions. These results can be explained by assuming that the grafting takes place mainly in the amorphous region of the PVDF, and close to the surfaces of the crystals, but that grafts do not penetrate into the crystals. The proton conductivity of the grafted and sulfonated PVDF membranes reached values comparable to those of Nafion membranes.


References

  1. L. W. Niedrach, W. T. Grubb, in Fuel Cells, ed. W. Mitchell, Academic Press, New York, 1963, ch. 3 Search PubMed.
  2. Fuel Cell Handbook, ed. A. J. Appleby and R. L. Foulkes, Van Nostrand, New York, 1989, pp. 277–295 Search PubMed.
  3. L. Mandelkern, in The Radiation Chemistry of Macromolecules, ed. M. Dole, Academic Press, New York, 1972, vol. 1, ch. 13 Search PubMed.
  4. D. O. Geymer, in The Radiation Chemistry of Macromolecules, ed. M. Dole, Academic Press, New York, 1973, vol. 1, ch. 1 Search PubMed.
  5. J. L. Garnett, Radiat. Phys. Chem., 1979, 14, 79 CrossRef CAS.
  6. B. Gupta, F. N. Büchi and G. G. Scherer, J. Polym. Sci., Part A: Polym. Chem., 1994, 32, 1931 CrossRef CAS.
  7. B. Gupta and G. G. Scherer, Chimia, 1994, 48, 127 CAS.
  8. F. Vigo, G. Capanelli, C. Uliana and S. Munari, Desalination, 1981, 36, 63 CrossRef CAS.
  9. E.-S. A. Hegazy, I. Ishigaki, A. M. Dessouki, A. Rabie and J. Okamoto, J. Appl. Polym. Sci., 1982, 27, 535 CrossRef CAS.
  10. A. Niemöller and G. Ellinghorst, Makromol. Chem., 1987, 148, 1.
  11. F. Büchi, B. Gupta, M. Rouilly, P. C. Hauser, A. Chapiro and G. G. Scherer, Proc. 27th IECEC Conf., San Diego, August 1992, Society of Automotive Engineers, San Diego, CA, 1992, vol. 3, p. 419 Search PubMed.
  12. N. Betz, A. Le Moël, J. P. Durand, E. Balanzat and C. Darnez, Macromolecules, 1992, 25, 213 CrossRef CAS.
  13. A. Elmidaoui, A. T. Cherif, J. Brunea, F. Duclert, T. Cohen and C. Gavach, J. Membr. Sci., 1992, 67, 263 CrossRef CAS.
  14. S. Holmberg, T. Lehtinen, J. Näsman, D. Ostrovskii, M. Paronen, R. Serimaa, F. Sundholm, G. Sundholm, L. Torell and M. Torkkeli, J. Mater. Chem., 1996, 6, 1309 RSC.
  15. G. G. Scherer, Ber. Bunsen-Ges. Phys. Chem., 1990, 94, 1008 Search PubMed.
  16. G. G. Scherer, E. Killer and D. Grman, Int. J. Hydrog. Energy, 1992, 17, 115 CrossRef CAS.
  17. A. Chapiro and A. M. Jedrychowska-Bonamour, Eur. Polym. J., 1984, 20, 1079 CrossRef CAS.
  18. M. V. Rouilly, R. Kötz, O. Haas, G. G. Scherer and A. Chapiro, J. Membr. Sci., 1993, 81, 89 CrossRef CAS.
  19. T. Lehtinen, F. Sundholm, G. Sundholm, P. Björnbom and M. Bursell, Electrochim. Acta, submitted Search PubMed.
  20. S. Hietala, M. Karjalainen, T. Lehtinen, D. Ostrovskii, M. Paronen, R. Serimaa, F. Sundholm and G. Sundholm, Appl. Macromol. Chem. Phys., submitted Search PubMed.
  21. K. Nagakawa and Y. Ishida, J. Polym. Sci., Phys. Edn., 1973, 11, 2153 Search PubMed.
  22. E. Benedetti, S. Catanorchi, A. D'Alessio, G. Moggi, P. Vergamini, M. Pracella and F. Ciardelli, Polym. Int., 1996, 41, 35 CrossRef CAS.
  23. R. Serimaa and S. Vahvaselkä, unpublished work.
  24. J. Brandrup and E. H. Immergut, Polymer Handbook, Wiley, New York, 3rd edn., 1989, p. VI-226 and VI-258 Search PubMed.
  25. B. Gupta and G. G. Scherer, Makromol. Chem., 1993, 210, 151 CAS.
  26. F. J. Baltá-Calleja and C. G. Vonk, X-Ray Scattering of Synthetic Polymers, Elsevier, Amsterdam, 1989, pp. 175–204 Search PubMed.
  27. R. Hasegawa, Y. Takahashi, Y. Chatani and H. Tadukuro, Polymer J., 1972, 3, 600 Search PubMed.
  28. L. D. Majdanac, D. Poleti and M. J. Teodorovic, Acta Polymerica, 1991, 42, 351 CrossRef CAS.
  29. W. Kraus and G. Nolze, the computer program Powder Cell, version 1.8.
  30. R. Y. M. Huang and P. J. F. Kanitz, J. Appl. Polym. Sci., 1969, 13, 669 CrossRef CAS.
  31. G. Gebel, E. Ottomani, J. J. Allegraud, N. Betz and A. Le Moël, Nucl. Instrum. Meth. Phys. Res. B, 1995, 105, 145 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.