Molecular Theories of Polymer Viscosity

  • G. Marrucci
  • G. Ianniruberto
Part of the Modeling and Simulation in Science, Engineering and Technology book series (MSSET)


The viscosity of polymeric liquids crucially depends on polymer concentration c and molar mass M. These dependencies can generally be predicted from relatively simple theories, because what really matters is the chain-like structure of the polymer molecule rather than its detailed chemistry. In this chapter we summarize the main concepts leading to these predictions throughout the concentration range, i.e., from dilute solutions up to polymer melts. However, only the so-called zero-shear viscosity will be considered because the nonlinear effects arising from the coupling between flow and molecular “structure” are more complex and fall outside the scope of this chapter. In dilute solutions the important concept is that of “intrinsic” viscosity which, through dependence on M, reveals structural features of the polymer (flexible chain vs. rigid rodlike, for example) as well as the solvent quality. In semidilute solutions of long polymers, the overall structure of the system becomes that of an impermanent network of entangled chains. The viscosity is then related to the elasticity of the network and to the kinetics of chain disengagement. Typically, the viscosity scaling takes the form of power laws in both M and c. The M dependencies remain the same in the particularly relevant case of polymer melts. The chapter ends with a brief description of systems with localized interactions (or sticky points) in which the viscosity is particularly sensitive to the strength of such interactions.


Friction Coefficient Intrinsic Viscosity Complex Flow Chain Segment Molecular Theory 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Annable, T., Buscall, R., Ettelaie, R., and Whittlestone, D., The rheology of solutions of associating polymers: Comparison of experimental behavior with transient network theory, J. Rheol., 37, 695 (1993).CrossRefGoogle Scholar
  2. 2.
    de Gennes, P.G., Reptation of a polymer chain in the presence of fixed obstacles, J. Chem. Phys., 55, 572 (1971).CrossRefGoogle Scholar
  3. 3.
    de Gennes, P.G., Scaling Concepts in Polymer Physics, Cornell University Press, Ithaca, New York (1979).Google Scholar
  4. 4.
    Doi, M., Explanation for the 3.4-power law for viscosity of polymeric liquids on the basis of the tube model, J. Polym. Sci.: Polym. Phys. Ed., 21, 667 (1983).CrossRefGoogle Scholar
  5. 5.
    Doi, M., and Edwards, S.F., The Theory of Polymer Dynamics, Clarendon Press, Oxford (1986).Google Scholar
  6. 6.
    Edwards, S.F., The statistical mechanics of polymerised materials, Proc. Phys. Soc. (London), 92, 9 (1967).CrossRefGoogle Scholar
  7. 7.
    Ferry, J.D., Viscoelastic Properties of Polymers, Wiley, New York (1980).Google Scholar
  8. 8.
    Fetters, L.J., Lohse, D.J., Richter, D., Witten, T.A., and Zirkel, A., Connection between polymer molecular weight, density, chain dimensions, and melt viscoelastic properties, Macromolecules,27, 4639 (1994).CrossRefGoogle Scholar
  9. 9.
    Flory, P.J., Principles of Polymer Chemistry, Cornell University Press, Ithaca, New York (1953).Google Scholar
  10. 10.
    Happel, J., and Brenner, H., Low Reynolds Number Hydrodynamics, Prentice Hall, Englewood Cliffs, New Jersey (1965).Google Scholar
  11. 11.
    Kulicke, W.M., and Kniewske, R., The shear viscosity dependence on concentration, molecular weight, and shear rate of polystyrene, Rheol. Acta,23,75 (1984).CrossRefGoogle Scholar
  12. 12.
    Larson, R., Perkins, T., Smith, D.,and Chu, S., Hydrodynamics of a DNA molecule in a flow field, Phys. Rev. E, 55,1794 (1997).CrossRefGoogle Scholar
  13. 13.
    Pearson, D.S., Recent advances in the molecular aspects of polymer viscoelasticity, Rubber Chem. Technol., 60,439 (1987).CrossRefGoogle Scholar
  14. 14.
    Rouse, P.E., A theory of the linear viscoelastic properties of dilute solutions of coiling polymers, J. Chem. Phys., 21,1272 (1953).CrossRefGoogle Scholar
  15. 15.
    Treloar, L.R.G., The Physics of Rubber Elasticity, Clarendon Press, Oxford (1975).Google Scholar

Copyright information

© Springer Science+Business Media New York 2000

Authors and Affiliations

  • G. Marrucci
    • 1
  • G. Ianniruberto
    • 1
  1. 1.Dipartimento di Ingegneria ChimicaUniversità Federico IINapoliItaly

Personalised recommendations