Wettabilities and Adhesive/Autohesive Properties of Poly(Tetrafluoroethylene) Surfaces Photografted with Hydrophilic Monomers

  • Kazunori Yamada
  • Joji Isoda
  • Toyokichi Ebihara
  • Mitsuo Hirata


Poly(tetrafluoroethylene) (PTFE) plates grafted with methacrylic acid (MAA), acrylic acid (AA), and 2-(dimethylamino)ethyl methacrylate (DMA) were prepared by the combined use of the plasma treatment and photografting. The relation between the wettabilities and chemical compositions of grafted PTFE plates was followed up and their adhesive and autohesive properties were examined from tensile shear strength measurements. In addition, the location of failure was determiened from the analysis by ESCA of the failed surfaces. The wattabilities for all three kinds of grafted PTFE surfaces steeply increased with the grafted amount in the range below 0.5 μmol/cm2, followed by attaining to the individual constant values. The changes in the cos θ and the intensity ratios obtained by an ESCA analysis resembled closely each other in common with all grafted PTFE surfaces. The adheive strength for grafted PTFE plates using epoxy type adhesives was improved at a low grafted amount. The initial increase in the adhesive strength can be ascribed to more enhanced hydrophilic properties of PTFE surfaces by the phohograftings. On the other hand, the autohesive strength increased sharply around 1.0 μmol/cm2 for grafted PTFE plates heat-pressed in the presence of water. The autohesive strength for PTFE-g-PMAA plates reached the value equivalent to the adhesive strength at higher grafted amounts and the grafted amount at which the autohesive strength increased sharply could be decreased to 0.5 μmol/cm2 by immersing them in an aqueous solution of HC1 of pH 3. These results indicate that an increase in the autohesive strength can be caused not only by the entanglements of grafted PMAA chains but also by the formation of hydrogen bonding between carboxyl groups affixed to the grafted PMAA chains. The analysis of the failed surfaces of PTFE-g-PMAA plates by ESCA revealed that for adhesive strength measurements the location of failure was shifted from the inside of the grafted layer consisting of grafted PMAA chains and PTFE chains to the inside of the substrate as the grafted amount increased and the grafted samples whose failure occurred in the inside of the substrate showed a high adhesive strength. It was found that the failure occurred in the inside of the grafted layer regardless of the grafted amount.


Acrylic Acid Plasma Treatment Adhesive Strength Strength Measurement Tensile Shear 
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  1. 1.
    C. Fonseca, J. M. Ferena, J. G. Fatou, and A. Bello, Sulphuric acid etching of polyethylene surfaces, J. Mater. Sci. 20: 3283 (1985).CrossRefGoogle Scholar
  2. 2.
    S. Tasker, R. D. Chambers, and J. P. S. Badyal, Surface defluorination of PTFE by sodium atoms, J. Phys. Chem. 98: 12442 (1994).CrossRefGoogle Scholar
  3. 3.
    D. Briggs, V. J. I. Zichy, D. M. Brewis, J. Comyn, R. H. Dahm, M. A. Green, and M. B. Konieczko, X-ray photoelectron spectroscopy studies of polymer surfaces part 1 chromic acid etching of polyolefins, Surf. Interface Anal. 2: 107 (1980).CrossRefGoogle Scholar
  4. 4.
    M. Morra, E. Occhiello, L. Gila, and F. Garbassi, Surface dynamics vs. adhesion in oxygen plasma treated polyolefins, J. Adhesion 33: 77 (1990).CrossRefGoogle Scholar
  5. 5.
    J. P. Badey, E. Espuche, Y. Jugnet, B. Chabert, and Duc, Tran Minh, Influence of chemical and plasma treatments on the adhesive peoperties of PTFE with an epoxy resin, Int. J. Adhesion Adhesives. 16: 173 (1996).CrossRefGoogle Scholar
  6. 6.
    M. Chtaib, E. M. Roberfroid, Y. Novis, J. J. Pireaux, R. Caudono, P. Lutgen, and G. Feyder, Polymer surface reactivity enhancement by ultraviolet ArF laser irradiation: An x-ray photoelectron spectroscopy study of polytetrtafluoroethylene and polyethyleneterepthalate ultraviolet treated surfaces, J. Vac. Sci. Technol. A7: 3233 (1989).CrossRefGoogle Scholar
  7. 7.
    L. Mascia and G. E. Carr, Plasma treatment of PTFE: Effects of processing parameters on bonding prpperties, Plast. Rub. Process. Appl. 9: 133 (1988).Google Scholar
  8. 8.
    L. J. Gerenser, An x-ray photoemission spectroscopy study of chemical interactions at silver/plasma modified polyethylene interfaces: Correlations with adhesion, J. Vac. Sci. Technol. A6: 2897 (1988).CrossRefGoogle Scholar
  9. 9.
    N. Inagaki, S. Tasaka, and H. Kawai, Improved adhesion of poly(tetrafluoroethylene) by NH3-plasma treatment, J. Adhesion Sci. Technol. 3: 637 (1989).CrossRefGoogle Scholar
  10. 10.
    S. Corn, K. P. Vora, M. Strobel, and C. S. Lyons, Enrichment of adhesion to polyethylene films by CF3C1 plasma treatment, J. Adhesion Sci. Technol. 5: 239 (1991).CrossRefGoogle Scholar
  11. 11.
    M. Morra, E. Occhiello, and F. Garbassi, Surface characterization of plasma-treated PTFE, Surf. Interface Anal. 16: 412 (1990).CrossRefGoogle Scholar
  12. 12.
    M. Morra, E. Occhiello, and F. Garbassi, Hydrophobic recovery and misting behavior of plasma treated PS and PC surfaces, Angew. Makromol. Chem. 189: 125 (1991).CrossRefGoogle Scholar
  13. 13.
    H. Yasuda, A. K. Sahnna, and T. Yasuda, Effect of orientation and mobility of polymer molecules at surfaces on contact angle and its hysteresis, J. Polym. Sci. Polym. Phys. Ed. 19: 1285 (1981).CrossRefGoogle Scholar
  14. 14.
    T. Yasuda, K. Yoshida, and T. Okuda, A study of surface dynamics of polymers. III. Surface dynamics stabilization by plasma polymerization, J. Polym. Sci. Polym. Phys. Ed. 26: 2061 (1988).CrossRefGoogle Scholar
  15. 15.
    N. Inagaki and Y. Yasukawa, Wettable films plasma-polymerized from nitroethane, J. Appl. Polym. Sci. 33: 1641 (1987).CrossRefGoogle Scholar
  16. 16.
    K. Yamada, T. Kimura, H. Tsutaya, and M. Hirata, Hydrophilic and adhesive properties of methacrylic acid-grafted polyethylene plates, J. Appl. Polym. Sci. 44: 993 (1992).CrossRefGoogle Scholar
  17. 17.
    K. Yamada, H. Tsutaya, S. Tatekawa, and M. Hirata, Hydrophilic and adhesive properties of polyethylene plates grafted with hydrophilic monomers, J. Appl. Polym. Sci. 46: 1065 (1992).CrossRefGoogle Scholar
  18. 18.
    K. Yamada, S. Tatekawa, and M. Hiram, Polyethylene film gels prepared by photograftings of hydrophilic monomers, J. Colloid Interface Sci. 162: 144 (1994).CrossRefGoogle Scholar
  19. 19.
    M. Suzuki, A. Kishida, H. Iwata, and Y. Ikada, Graft copolymerization of acrylamide onto a polyethylene surface pretreated with a grow discharge, Macromolecules 19: 1804 (1986).CrossRefGoogle Scholar
  20. 20.
    H. Kubota, N. Koide, Y. Ogiwara, and Y. Hata, Location of methacrylic acid-grafted chains introduced into polyolefm films by means of photografting, J. Polym.Sci. Polym. Lett. 25: 273 (1987).CrossRefGoogle Scholar
  21. 21.
    T. Masuda, M. Kotoura, K. Tsuchihara, and T. Higashimura, Glow-dischargeinduced graft polymerization of acrylic acid onto poly[1-trimethylsily19–1-propyne] film, J. Appl. Polym. Sci. 43: 423 (1991).CrossRefGoogle Scholar
  22. 22.
    K. Yamada, K. Hayashi, K Sakasegawa, H. Onodera, and M. Hirata, Photografting of hydrophilic monomers onto poly(terrafluoroethylene) films treated with oxygen plasmas, Nippon Kagaku Kaishi [J. Chem. Soc. Jpan., Chem. Ind. Chem. 1994: 427 (1994) [in Japanese].Google Scholar
  23. 23.
    M. Hiram, J. Isoda, K. Yamada, and T. Ebihara, Adhesive and autohesive properties of plasma-treated poly(tertafluoroethylene) surfaces photografted by hydrophilic monomers, Polyelectrolytes Potsudam ‘85, First Int. Symp. Polyelectrolytes Int. Bunsen-Discussion-Mtg. Polyelectrolytes Solution Interface at Interfaces, Max-PlanckInstitute for Colloid and Interface Research, p. 128 (1995).Google Scholar
  24. 24.
    K. Yamada, T. Ebihara, T. Gondo, K. Sakasegawa, and M. Hirata, Membrane properties of porous and expanded poly(tetrafluoroethylene) films grafted with hydrophilic monomers and their permeation behavior, J. Appl. Polym. Sci. 61: 1899 (1996).CrossRefGoogle Scholar
  25. 25.
    S. S. Voyutskii and V. M. Zamazii, Self-adhesion (autohesion) of polyisobutylene H, Rub. Chem. Technol. 30, 544 (1957).CrossRefGoogle Scholar
  26. 26.
    S. S. Voyutskii and B. V. Shtarkh, Effect of molecular weight, shape of the molecular and presence of polar groups on the autohesion of high polymers III, Rub. Chem. Technol. 30, 548 (1957).CrossRefGoogle Scholar
  27. 27.
    K. Siegbahn, C. Nordling, A. Fahlman, R. Nordberg, K. Hamrin, J. Hedman, G. Johansson, T. Bergmark, S. E. Karlsson, I. Lingberg, and B. lindberg, ESCA; Atomic, molecular and solid state structure studied by means of electron spectroscopy, Almquist and Wiksells, Uppsala (1967).Google Scholar
  28. 28.
    D. T. Clark, W. J. Feast, D. Kilcast, and W. K. R. Musgrave, Application of ESCA to polymer chemistry. III. Structure and Bonding in Homopolymers of ethylene and the fluoroethylenes and determination of the compositions of fluoro copolymers, J. Polym. Sci. Polym. Chem. Ed. 11: 389 (1973).CrossRefGoogle Scholar
  29. 29.
    D. T. Clark and H. R. Thomas, Application of ESCA to polymer chemistry. XVII. Systematic investigation of the core levels of simple homopolymers, J. Polym.Sci. Polym. Chem. Ed. 16: 791 (1978).CrossRefGoogle Scholar
  30. 30.
    P. Cadman, G. Gossedge, and J. D. Scott, The determination of the photoelectron escape depths in polymers and other materials, J. Electron Spectrosc. Relat. Phenom. 13: 1 (1978).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1997

Authors and Affiliations

  • Kazunori Yamada
    • 1
  • Joji Isoda
    • 1
  • Toyokichi Ebihara
    • 1
  • Mitsuo Hirata
    • 1
  1. 1.Department of Industrial Chemistry College of Industrial TechnologyNihon UniversityChiba 275Japan

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