Skip to main content
SpringerLink
Log in

Molecular dynamics of solid polymers as revealed by deuteron NMR

  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Pulsed deuteron NMR spectroscopy is described, which has recently been developed to become a powerful tool for studying molecular dynamics in solid polymers. It is shown that by analyzing the line shapes of2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. By applying these techniques to selectively deuterated polymers, motional mechanisms involving different segments of the monomer unit can be monitored. In addition, motional heterogeneities in glassy polymers can be detected.

The information about polymer dynamics available now is illustrated by a number of experimental examples. The chain motion in the amorphous regions of linearpolyethylene is discussed in detail and it is shown that it can clearly be distinguished from the chain motion of an amorphous polymer above the glass transition, wherepolystyrene is used as an example. Localized motions in the glassy state are illustrated through the jump motion phenyl groups exhibit both in the main chain (polycarbonate) and as a side group (polystyrene). The latter polymers also serve as examples for detecting motional heterogeneity. Finally, the mobility in novel classes of systems,liquid crystalline polymers andpolymer model membranes as revealed by2H NMR are described.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ferry, J. D., Viscoelastic Properties of Polymers, 3rd Ed., Wiley, New York (1980).

    Google Scholar 

  2. McCrum, N. G., B. E. Read, G. Williams, Anelastic and Dielectric Effects in Polymeric Solids, Wiley, New York (1967).

    Google Scholar 

  3. Ward, I. M., Mechanical Properties of Solid Polymers, Wiley, New York (1971).

    Google Scholar 

  4. Sillescu, H. in: IUPAC Macromolecules, Edited by H. Benoit, P. Rempp, Pergamon Press, Oxford-New York (1982).

    Google Scholar 

  5. McBrierty, V. J., D. C. Douglass, Macromol. Revs.16, 295 (1981).

    Google Scholar 

  6. Jones, A. A., J. F. O'Gara, P. T. Inglefield, J. T. Bendler, A. F. Yee, K. L. Ngai, Macromolecules, in press (1982).

  7. Waugh, J. S., L. M. Huber, U. Haeberlen, Phys. Rev. Letters20, 180 (1968).

    Google Scholar 

  8. Pines, A., M. G. Gibby, J. S. Waugh, J. Chem. Phys.56, 1776 (1972).

    Google Scholar 

  9. Schaefer, J., E. O. Stejskal, R. Buchdahl, Macromolecules10, 384 (1977).

    Google Scholar 

  10. Haeberlen, U., High Resolution NMR in Solids, Suppl. 1 to Advances in Magnetic Resonance, Academic Press, New York (1976).

    Google Scholar 

  11. Mehring, M., NMR, Basic Principles and Progress, Vol. 11, Springer-Verlag, Berlin-Heidelberg-New York (1976).

    Google Scholar 

  12. Spiess, H. W., NMR, Basic Principles and Progress, Vol. 15, p. 55. Springer-Verlag, Berlin-Heidelberg-New York (1978).

    Google Scholar 

  13. Opella, S. J., J. S. Waugh, J. Chem. Phys.66, 4919 (1977).

    Google Scholar 

  14. Hentschel, R., H. W. Spiess, J. Magn. Resonance35, 157 (1979).

    Google Scholar 

  15. Spiess, H. W., H. Sillescu, J. Magn. Resonance42, 381 (1980).

    Google Scholar 

  16. Spiess, H. W., J. Chem. Phys.72, 6755 (1980).

    Google Scholar 

  17. Hentschel, D., H. Sillescu, H. W. Spiess, Macromolecules14, 1605 (1981).

    Google Scholar 

  18. Abragam, A., The Principles of Nuclear Magnetism, Oxford University Press, Oxford (1961).

    Google Scholar 

  19. Rosenke, K., H. Sillescu, H. W. Spiess, Polymer21, 757 (1980).

    Google Scholar 

  20. Jeener, J., P. Broekaert, Phys. Rev.157, 232 (1967).

    Google Scholar 

  21. Alla, M., R. Eckman, A. Pines, Chem. Phys. Letters71, 148 (1980).

    Google Scholar 

  22. Schajor, W., N. Pislewski, H. Zimmermann, U. Haeberlen, Chem. Phys. Letters76, 409 (1980). U. Haeberlen et al. to be published.

    Google Scholar 

  23. Hentschel, R., J. Schlitter, H. Sillescu, H. W. Spiess, J. Chem. Phys.68, 56 (1978).

    Google Scholar 

  24. Hentschel, R., H. Sillescu, H. W. Spiess, Polymer22, 1516 (1981).

    Google Scholar 

  25. Spiess, H. W., in Developments in Oriented Polymers — 1, edited by I. M. Ward, Appl. Science Publ. London (1982).

    Google Scholar 

  26. Finkelmann, H., H. Ringsdorf, J. H. Wendorff, Makrom. Chem.179, 273 (1978).

    Google Scholar 

  27. Akimoto, A., K. Dorn, L. Gros, H. Ringsdorf, H. Schupp, Angew. Chem.93, 108 (1981).

    Google Scholar 

  28. Hentschel, D., H. Sillescu, H. W. Spiess, R. Voelkel, B. Willenberg, Magn. Reson. Relat. Phenom., Proc. Congr. AMPERE, 19th, p. 381 (1976).

  29. Barnes, R. G., Advances in Nuclear Quadrupole Resonance1, 335 (1972).

    Google Scholar 

  30. Pake, G. E., J. Chem. Phys.16, 327 (1948).

    Google Scholar 

  31. Pechhold, W., S. Blasenbrey, S. Woerner, Kolloid Z. u. Z. Polym.189, 14 (1963).

    Google Scholar 

  32. Monnerie, L., F. Gény, J. Chim., Phys. Physiochim. Biol.66, 1691 (1969).

    Google Scholar 

  33. Schatzki, T. F., Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem.6, 646 (1965).

    Google Scholar 

  34. Anderson, P. W., P. R. Weiss, Rev. Mod. Phys.25, 269 (1953).

    Google Scholar 

  35. Hentschel, D., H. Sillescu, H. W. Spiess, Makromol. Chem.180, 241 (1979).

    Google Scholar 

  36. Pschorn, U., H. W. Spiess, J. Magn. Resonance39, 217 (1980).

    Google Scholar 

  37. Ernst, R. R., W. A. Anderson, Rev. Sci. Instrum.37, 93 (1966).

    Google Scholar 

  38. Powles, J. G., J. H. Strange, Proc. Phys. Soc.82, 6 (1963).

    Google Scholar 

  39. Davis, J. H., K. R. Jeffrey, M. Bloom, M. I. Valic, T. P. Higgs, Chem. Phys. Letters42, 390 (1976).

    Google Scholar 

  40. Blinc, R., V. Rutar, J. Seliger, J. Slak, V. Smolej, Chem. Phys. Letters48, 576 (1977).

    Google Scholar 

  41. Jenner, J., Proc. AMPERE International Summer School II, Basko Polje, Yugoslavia, 1971.

  42. Aue, W. P., E. Bartholdi, R. R. Ernst, J. Chem. Phys.64, 2229 (1976).

    Google Scholar 

  43. Jeener, J., B. H. Meier, P. Bachmann, R. R. Ernst, J. Chem. Phys.71, 4546 (1979).

    Google Scholar 

  44. Bax, A., Two-Dimensional Nuclear Magnetic Resonance in Liquids, D. Reidel Publ. Co., Dordrecht (1982).

    Google Scholar 

  45. Lausch, M., H. W. Spiess, to be published.

  46. Lausch, M., H. W. Spiess, Chem. Phys. Letters71, 182 (1980).

    Google Scholar 

  47. Hentschel, D., Diss. Univ. Mainz, 1982. D. Hentschel, H. Sillescu, H. W. Spiess, to be published in Polymer.

  48. Olf, H. G., A. Peterlin, J. Polym. Sci., Part A-28, 771 (1970).

    Google Scholar 

  49. Ewen, B., E. W. Fischer, W. Piesczek, G. Strobl, J. Chem. Phys.61, 5265 (1975); B. Ewen, D. Richter, ibid.69, 2954 (1978).

    Google Scholar 

  50. Mansfield, M., R. H. Boyd, J. Polym. Sci., Polym. Phys. Ed.16, 1227 (1978).

    Google Scholar 

  51. Meyer, H., H. G. Kilian, Progress Colloid & Polym Sci.64, 154, 166 (1978).

    Google Scholar 

  52. Bergmann, K., J. Polym Sci., Polym. Phys. Ed.16, 1611 (1978).

    Google Scholar 

  53. Fischer, E. W., G. R. Strobl, Y. Tanabe, Jahresbericht 1978/79 des Sonderforschungsbereiches 41, p. 146, Mainz 1980.

  54. Strobl, G. R., M. J. Schneider, I. G. Voigt-Martin, J. Polym. Sci., Polym. Phys. Ed.18, 1361 (1980).

    Google Scholar 

  55. Gaur, U., B. Wunderlich, Macromolecules13, 445 (1980).

    Google Scholar 

  56. Beatty, C. L., F. E. Karasz, J. Macromol. Sci., Rev. Macromol. Chem.17, 37 (1979).

    Google Scholar 

  57. Gény, F., L. Monnerie, J. Polym. Sci., Polym Phys. Ed.17, 131, 147 (1979).

    Google Scholar 

  58. Rosenke, K., H. G. Zachmann, Progr. Colloid Polym. Sci.64, 245 (1978).

    Google Scholar 

  59. Torchia, D. A., A. Szabo, J. Magn. Resonance49, 107 (1982).

    Google Scholar 

  60. Cohen-Addad, J. P., R. Vogin, Phys. Rev. Letters33, 940 (1974); J. P. Cohen-Addad, J. Chem. Phys.63, 4880 (1975).

    Google Scholar 

  61. Cohen-Addad, J. P., M. Domard, S. Boileau, J. Chem. Phys.75, 4107 (1981).

    Google Scholar 

  62. Collignon, J., H. Sillescu, H. W. Spiess, Colloid & Polym. Sci.259, 220 (1981).

    Google Scholar 

  63. Georgiou, A., H. Sillescu, H. W. Spiess, to be published.

  64. Lindner, P., E. Rössler, H. Sillescu, Makromol. Chem.182, 3653 (1981).

    Google Scholar 

  65. Pschorn, U., H. Sillescu, H. W. Spiess, M. Wehrle, to be published.

  66. Rössler, E., H. Sillescu, H. W. Spiess, to be published.

  67. Rössler, E., H. Sillescu, H. W. Spiess, M. Wehrle, to be published.

  68. Gall, C. M., A. DiVerdi, S. J. Opella, J. Amer. Chem. Soc.103, 5039 (1981).

    Google Scholar 

  69. Rice, D. M., R. J. Wittebort, R. G. Griffin, E. Meirovitch, E. R. Stimson, Y. C. Meinwald, J. H. Freed, H. A. Scheraga, J. Amer. Chem. Soc.103, 7707 (1981).

    Google Scholar 

  70. Kinsey, R. A., K. Augustin, E. Oldfield, J. Biol. Chem.256, 9028 (1981).

    PubMed  Google Scholar 

  71. Tonelli, A., Macromolecules6, 682 (1973).

    Google Scholar 

  72. Wendorff, J. H., E. W. Fischer, Kolloid Z. Z. Polym.251, 884 (1973).

    Google Scholar 

  73. Wendorff, J. H., E. W. Fischer, Kolloid Z. Z. Polym.251, 876 (1973).

    Google Scholar 

  74. Locati, G., A. V. Tobolsky, Advan. Mol. Relax. Proc.1, 375 (1970).

    Google Scholar 

  75. Heijboer, J., Intern. J. Polym. Mat.6, 11 (1977).

    Google Scholar 

  76. Schaefer, J., E. O. Stejskal, T. R. Steger, M. D. Sefcik, R. A. McKay, Macromolecules13, 1121 (1980).

    Google Scholar 

  77. Schaefer, J., M. D. Sefcik, E. O. Stejskal, R. A. McKay, W. T. Dixon, Proceedings IUPAC Macro Amherst, 1982, p. 25.

  78. Yee, A. F., S. A. Smith, Macromolecules14, 54 (1981).

    Google Scholar 

  79. Hellmann, G., W. Kuhn, H. W. Spiess, M. Wehrle, to be published.

  80. Finkelmann, H., H. Ringsdorf, J. H. Wendorff, Makromol. Chem.179, 273 (1978).

    Google Scholar 

  81. Shibaev, V. P., N. A. Platé, Y. S. Freidzon, J. Polym. Sci., Poly. Chem. Ed.17, 1655 (1979).

    Google Scholar 

  82. Finkelmann, H., M. Happ, M. Portugall, H. Ringsdorf, Makromol. Chem.179, 2541 (1978).

    Google Scholar 

  83. Ringsdorf, H., A. Schneller, Brit. Polym. J.13, 43 (1981).

    Google Scholar 

  84. Ringsdorf, H., R. Zentel, Makromol. Chem.183, 1245 (1982).

    Google Scholar 

  85. Finkelmann, H., D. Day, Makromol. Chem.180, 2269 (1979).

    Google Scholar 

  86. Wassmer, K. H., E. Ohmes, G. Kothe, M. Portugall, H. Ringsdorf, Makromol. Chem. Rapid Commun.3, 281 (1982).

    Google Scholar 

  87. Geib, H., B. Hisgen, U. Pschorn, H. Ringsdorf, H. W. Spiess, J. Amer. Chem. Soc.104, 917 (1982).

    Google Scholar 

  88. Luz, Z., R. C. Hewitt, S. Meiboom, J. Chem. Phys.61, 1758 (1974).

    Google Scholar 

  89. Hub, H. H., B. Hupfer, H. Koch, H. Ringsdorf, Angew. Chem.92, 962 (1980).

    Google Scholar 

  90. Gros, L., H. Ringsdorf, H. Schupp, Angew. Chem.93, 311 (1981).

    Google Scholar 

  91. Ebelhäuser, R., K. Dorn, H. Ringsdorf, H. W. Spiess, to be published.

  92. Sackmann, E., Ber. Bunsenges. Phys. Chem.82, 891 (1978).

    Google Scholar 

Download references

Author information

Author notes

  1. H. W. Spiess

    Present address: Institut für Physikalische Chemie, Johannes Gutenberg-Universität, Mainz, Germany

Authors and Affiliations

    Authors
    1. H. W. Spiess
      View author publications

      You can also search for this author in PubMed Google Scholar

    Rights and permissions

    Reprints and permissions

    About this article

    Cite this article

    Spiess, H.W. Molecular dynamics of solid polymers as revealed by deuteron NMR. Colloid & Polymer Sci 261, 193–209 (1983). https://doi.org/10.1007/BF01469664

    Download citation

    • Received:

    • Accepted:

    • Issue Date:

    • DOI: https://doi.org/10.1007/BF01469664

    Key words

    Search

    Navigation