Applied Magnetic Resonance

, 27:401 | Cite as

Chain order in filled SBR elastomers: a proton multiple-quantum NMR study

  • K. SaalwächterEmail author
  • M. Klüppel
  • H. Luo
  • H. Schneider


A series of cross-linked styrene-butadiene rubbers (SBR) filled with different amounts of carbon black and silica are investigated by proton multiple-quantum nuclear magnetic resonance (NMR). The method yields reliable information on residual dipolar couplings and their distribution, which in turn are related to local chain order and the effective cross-link density in these systems. Fundamental differences between the response of a linear precursor, which undergoes reptational motion, and vulcanized SBR are discussed. For the latter, it is found that the average chain order parameter as well as its distribution does not change significantly with the amount and the type of filler. This is in surprising contrast to recent results from Hahn-echo relaxometry applied to the same samples, which indicated a significant filler effect on the cross-link density.


Nuclear Magnetic Resonance Carbon Black Residual Dipolar Coupling Topological Constraint Molecular Order 
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  1. 1.
    Kimmich R.: NMR Tomography, Diffusometry, Relaxometry. Berlin: Springer 1997.Google Scholar
  2. 2.
    Fischer E., Grinberg F., Kimmich R., Hafner S.: J. Chem. Phys.109, 846–854 (1998)CrossRefADSGoogle Scholar
  3. 3.
    Kariyo S., Stapf S.: Macromolecules35, 9253–9255 (2002)CrossRefADSGoogle Scholar
  4. 4.
    Cohen-Addad J.P.: J. Chem. Phys.60, 2440–2453 (1973)CrossRefADSGoogle Scholar
  5. 5.
    Cohen-Addad J.P.: Prog. NMR Spectrosc.25, 1–316 (1993)CrossRefADSGoogle Scholar
  6. 6.
    Kuhn W., Grün F.: Kolloid-Z.101, 248–271 (1942)CrossRefGoogle Scholar
  7. 7.
    Cohen-Addad J.P.: J. Chem. Phys.63, 4880–4885 (1975)CrossRefADSGoogle Scholar
  8. 8.
    Gotlib Yu.Ya., Lifshitz M.I., Shevelev V.A., Lishanskij I.S., Balanina I.V.: Vysokomol. Soedin.10, 2299 (1976)Google Scholar
  9. 9.
    Collignon J., Sillescu H., Spiess H.W.: Colloid Polym. Sci.259, 220–226 (1981)CrossRefGoogle Scholar
  10. 10.
    Callaghan P.T., Samulski E.T.: Macromolecules30, 113–122 (1997)CrossRefADSGoogle Scholar
  11. 11.
    Fechete R., Demco D.E., Blümich B.: J. Chem. Phys.118, 2411–2421 (2003)CrossRefADSGoogle Scholar
  12. 12.
    Charlesby A., Folland R., Steven J.H.: Proc. R. Soc. Lond. A355, 189–207 (1977)CrossRefADSGoogle Scholar
  13. 13.
    Fry Ch.G., Lind A.C.: Macromolecules21, 1292–1297 (1988)CrossRefADSGoogle Scholar
  14. 14.
    Ries M.E., Brereton M.G., Klein P.G., Ward I.M., Ekanayake P., Menge H., Schneider H.: Macromolecules32, 4961–4968 (1999)CrossRefADSGoogle Scholar
  15. 15.
    Menge H., Hotopf S., Pönitzsch S., Richter S., Arndt K.-F., Schneider H., Heuert U.: Polymer40, 5303–5313 (1999)CrossRefGoogle Scholar
  16. 16.
    Knörgen M., Menge H., Hempel G., Schneider H., Ries M.E.: Polymer43, 4091–4096 (2002)CrossRefGoogle Scholar
  17. 17.
    Litvinov V.M., De P.P. (eds.): Spectroscopy of Rubbers and Rubbery Materials. Shawbury: Rapra Technology Ltd. 2002.Google Scholar
  18. 18.
    Graf R., Heuer A., Spiess H.W.: Phys. Rev. Lett.80, 5738–5741 (1998)CrossRefADSGoogle Scholar
  19. 19.
    Schneider M., Gasper L., Demco D.E., Blümich B.: J. Chem. Phys.111, 402–415 (1999)CrossRefADSGoogle Scholar
  20. 20.
    Dollase T., Graf R., Heuer A., Spiess H.W.: Macromolecules34, 298–309 (2001)CrossRefADSGoogle Scholar
  21. 21.
    Saalwächter K.: Macromol. Rapid. Commun.23, 286–291 (2002)CrossRefGoogle Scholar
  22. 22.
    Saalwächter K.: Chem. Phys. Lett.362, 331–340 (2002)CrossRefADSGoogle Scholar
  23. 23.
    Saalwächter K., Ziegler P., Spyckerelle O., Haidar B., Vidal A., Sommer J.-U.: J. Chem. Phys.119, 3468–3482 (2003)CrossRefADSGoogle Scholar
  24. 24.
    Saalwächter K.: J. Chem. Phys.120, 454–664 (2004)CrossRefADSGoogle Scholar
  25. 25.
    Saalwächter K.: J. Am. Chem. Soc.125, 14684–14685 (2003)CrossRefGoogle Scholar
  26. 26.
    Luo H., Klüppel M., Schneider H.: Macromolecules37, 8000–8009 (2004)CrossRefADSGoogle Scholar
  27. 27.
    Baum J., Pines A.: J. Am. Chem. Soc.108, 7447–7454 (1986)CrossRefGoogle Scholar
  28. 28.
    Roy A.K., Gleason K.K.: J. Magn. Reson. A120, 139–147 (1996)CrossRefGoogle Scholar
  29. 29.
    Andersen P.W., Weiss P.R.: Rev. Mod. Phys.25, 269–276 (1953)CrossRefADSGoogle Scholar
  30. 30.
    Ball R.C., Callaghan P.T., Samulski E.T.: J. Chem. Phys.106, 7352 (1997)CrossRefADSGoogle Scholar
  31. 31.
    Abragam A.: The Principles of Nuclear Magnetism. Oxford: Oxford University Press 1961.Google Scholar
  32. 32.
    Doi M., Edwards S.F.: The Theory of Polymer Dynamics. New York: Oxford University Press 1988.Google Scholar
  33. 33.
    Litvinov V.M. in: Spectroscopy of Rubbers and Rubbery Materials (Litvinov V.M., De P.P., eds.), pp. 353–400. Shawbury: Rapra Technology Ltd. 2002.Google Scholar
  34. 34.
    Sotta P., Fülber C., Demco D.E., Blümich B., Spiess H.W.: Macromolecules29, 6222–6230 (1996)CrossRefADSGoogle Scholar
  35. 35.
    Kenny J.C., McBrierty V.J., Rigbi Z., Douglass D.C.: Macromolecules24, 436–443 (1991)CrossRefADSGoogle Scholar
  36. 36.
    Saalwächter K., Krause M., Gronski W.: Chem. Mater.16, 4071–4079 (2004)CrossRefGoogle Scholar
  37. 37.
    Hess W.M., Herd C.R., Sebok E.B.: Kautsch. Gummi Kunstst.47, 328–341 (1994)Google Scholar
  38. 38.
    Baumann K., Gronski W.: Prog. Colloid Polym. Sci.90, 97–103 (1992)CrossRefGoogle Scholar
  39. 39.
    Kariyo S., Stapf S.: Solid State Nucl. Magn. Reson.25, 64–71 (2004)CrossRefGoogle Scholar
  40. 40.
    Sachleben J.R., Frydman V., Frydman L.: J. Am. Chem. Soc.118, 9786–9787 (1996)CrossRefGoogle Scholar
  41. 41.
    Saalwächter K., Schmidt-Rohr K.: J. Magn. Reson.145, 161–172 (2000)CrossRefADSGoogle Scholar

Copyright information

© Springer 2004

Authors and Affiliations

  • K. Saalwächter
    • 1
    Email author
  • M. Klüppel
    • 2
  • H. Luo
    • 3
  • H. Schneider
    • 3
  1. 1.Institut für Makromolekulare ChemieUniversität FreiburgFreiburgGermany
  2. 2.Deutsches Institut für Kautschuktechnologie e. V.HannoverGermany
  3. 3.Fachbereich PhysikMartin-Luther-Universität Halle-WittenbergHalleGermany

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