Growth kinetics of polymer crystals in bulk

  • G. Strobl
  • T. Y. Cho
Regular Article


Temperature-dependent measurements of spherulite growth rates carried out for i-polystyrene, poly(ε -caprolactone) and linear polyethylene show that the controlling activation barrier diverges at a temperature which is 14K, 22K and 12K, respectively, below the equilibrium melting points. We discuss the existence of such a “zero growth temperature” T zg in the framework of a recently introduced thermodynamic multiphase scheme and identify T zg with the temperature of a (hidden) transition between the melt and a mesomorphic phase which mediates the crystal growth. The rate-determining step in our model of crystal growth is the attachment of chain sequences from the melt onto the lateral face of a mesomorphic layer at the growth front. The necessary straightening of the sequence prior to an attachment is the cause of the activation barrier. A theory based on this view describes correctly the observations. With a knowledge of T zg it is possible to fully establish the nanophase diagram describing the stability ranges of crystalline and mesomorphic layers in a melt. An evaluation of data from small-angle X-ray scattering, calorimetry and optical growth rate measurements yields heats of transition and surface free energies of crystals and mesophase layers, as well as the activation barrier per monomer associated with the chain stretching. According to the theory, the temperature dependence of the crystallization rate is determined by both the activation energy per monomer and the surface free energy of the preceding mesomorphic layer. Data indicate that the easiness of crystallization in polyethylene is first of all due to a particularly low surface free energy of the mesomorphic layer.


87.15.Nn Properties of solutions; aggregation and crystallization of macromolecules 61.41.+e Polymers, elastomers, and plastics 


  1. 1.
    J.D Hoffman, G.T Davis, J.I. Lauritzen, in Treatise on Solid State Chemistry, edited by N.B. Hannay, Vol. 3 (Plenum, 1976) p. 497.Google Scholar
  2. 2.
    P.J. Barham, R.A. Chivers, A. Keller, J. Martinez-Salazar, S.J. Organ, J. Mater. Sci. 20, 1625 (1985).CrossRefADSGoogle Scholar
  3. 3.
    G. Strobl, Prog. Polym. Sci. 31, 398 (2006).CrossRefGoogle Scholar
  4. 4.
    T.Y. Cho, W. Stille, G. Strobl, Colloid Polym. Sci. 285, 931 (2007).CrossRefGoogle Scholar
  5. 5.
    T.Y. Cho, W. Stille, G. Strobl, Macromolecules 40, 2596 (2007).CrossRefADSGoogle Scholar
  6. 6.
    G. Strobl, Eur. Phys. J. E 3, 165 (2000).CrossRefGoogle Scholar
  7. 7.
    G. Strobl, Eur. Phys. J. E 18, 295 (2005).CrossRefGoogle Scholar
  8. 8.
    T.Y. Cho, B. Heck, G. Strobl, Chin. J. Polym. Sci. 25, 83 (2007).CrossRefGoogle Scholar
  9. 9.
    T. Hippler, S. Jiang, G. Strobl, Macromolecules 38, 9396 (2005).CrossRefADSGoogle Scholar
  10. 10.
    B. Heck, S. Siegenführ, G. Strobl, R. Thomann, Polymer 48, 1352 (2007).CrossRefGoogle Scholar
  11. 11.
    B. Heck, T. Hugel, M. Iijima, E. Sadiku, G. Strobl, New J. Phys. 1, 17 (1999).CrossRefADSGoogle Scholar
  12. 12.
    M. Al-Hussein, G. Strobl, Macromolecules 35, 8515 (2002).CrossRefADSGoogle Scholar
  13. 13.
    J.D. Ferry, W.C. Child, R. Zand, D.M. Stern, M.L. Williams, R.F. Landel, J. Colloid Sci. 12, 53 (1957).CrossRefGoogle Scholar
  14. 14.
    C. Friedrich, private communication (2006).Google Scholar
  15. 15.
    S. Acierno, E. Di Maio, S. Iannace, N. Grizzuti, Rheol. Acta 45, 387 (2006).CrossRefGoogle Scholar
  16. 16.
    J.P. Armistead, J.D. Hoffman. Macromolecules 35, 3895 (2002).CrossRefADSGoogle Scholar
  17. 17.
    T.Y. Cho, B. Heck, G. Strobl, Colloid Polym. Sci. 282, 825 (2004).CrossRefGoogle Scholar
  18. 18.
    P.J. Flory, A. Vrij, J. Am. Chem. Soc. 85, 3548 (1963).CrossRefGoogle Scholar
  19. 19.
    B. Wunderlich, Macromolecular Physics, Vol. 3 (Academic Press, 1980) p. 58.Google Scholar
  20. 20.
    G. Strobl, The Physics of Polymers, 3rd edition (Springer, 2007) p. 64.Google Scholar

Copyright information

© EDP Sciences, Società Italiana di Fisica and Springer-Verlag 2007

Authors and Affiliations

  1. 1.Physikalisches InstitutAlbert-Ludwigs-Universität FreiburgFreiburgGermany

Personalised recommendations