Liquid Crystal-Isotropic Phase Equilibria in Stiff Chain Polymers

  • Wilmer G. Miller
  • Juey H. Rai
  • Elizabeth L. Wee


Most polymers when in solution exist as polymer random coils irrespective of the extent of intramolecular order in the solid state. Certain classes of macromolecules, however, do retain their intramolecular order when molecularly dispersed and behave as stiff chain or rodlike particles. Among these are synthetic polymers such as polyisocyanates1 and polypeptides2 and biological macromolecules such as DNA, tropocollagen3 and tobacco mosaic virus.4 In solution the concentration dependence of stiff and flexible chain polymers can be qualitatively different. In a good solvent flexible chain polymers mix in all proportions with little change in intramolecular or intermolecular order. As the polymer concentration is increased stiff chain polymers may undergo a phase transition from an isotropic to an anisotropic or liquid crystalline solution.4–8 This phenomenon was predicted on the basis of molecular asymmetry alone by Onsager9 and Isihara,10 and later by Flory.11,l2 The Flory lattice model is applicable over the entire composition range and is particularly convenient for comparison with experimental studies.


Shear Rate Phase Boundary Axial Ratio Isotropic Phase Liquid Crystalline 
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  1. 1.
    H. Yu, A. J. Bur and L. J. Fetters, J. Chem. Phys. 44, 2568 (1966).CrossRefGoogle Scholar
  2. 2.
    P. Doty, J. H. Bradbury and A. M. Holtzer, J. Amer. Chem. Soc. 78, 947 (1956).CrossRefGoogle Scholar
  3. 3.
    P. Doty and T. Nishihara in “Recent Advances in Gelatin and Glue Research”, G. Stainsby, Ed., Pergamon Press, London, 1958.Google Scholar
  4. 4.
    G. Oster, J. Gen. Physiol. 33, 445 (1950).CrossRefGoogle Scholar
  5. 5.
    F. C. Bawden and N. W. Price, Proc. Royal Sci. 123B, 274 (1937).CrossRefGoogle Scholar
  6. 6.
    J. D. Bernai and I. Fankuchen, J. Gen. Physiol. 25, 111 (1941).CrossRefGoogle Scholar
  7. 7.
    A. E. Elliott and E. J. Ambrose, Disc. Faraday Soc. 9, 246 (1950).CrossRefGoogle Scholar
  8. 8.
    C. Robinson, Trans. Faraday Soc. 52, 571 (1956).CrossRefGoogle Scholar
  9. 9.
    L. Onsager, Ann. N. Y. Acad. Sci. 51, 627 (1949).CrossRefGoogle Scholar
  10. 10.
    A. Isihara, J. Chem. Phys. 19, 1142 (1951).CrossRefGoogle Scholar
  11. 11.
    P. J. Flory, Proc. Roy, Soc. (London) A234, 60 (1956).Google Scholar
  12. 12.
    P. J. Flory, Proc. Roy. Soc. (London) A234, 73 (1956).Google Scholar
  13. 13.
    E. L. Wee and W. G. Miller, J. Phys. Chem. 75, 1446 (1971).CrossRefGoogle Scholar
  14. 14.
    J. Hermans, Jr., J. Colloid Sci., 17, 638 (1962).CrossRefGoogle Scholar
  15. 15.
    J. H. Rai and W. G. Miller, Macromolecules, 5, 45 (1972).CrossRefGoogle Scholar
  16. 16.
    J. H. Rai, W. G. Miller and R. G. Bryant, Macromolecules, 6, 262 (1973).CrossRefGoogle Scholar
  17. 17.
    G. L. Santee and W. G. Miller, to be submitted to Macromolecules.Google Scholar
  18. 18.
    W. G. Miller, C. C. Wu, E. L. Wee, G. L. Santee, J. H. Rai, and K. G. Goebel, 12th Prague Microsymposium on Macromolecules, August 20–23, 1973.Google Scholar
  19. 19.
    H. Fujita, A. Teramoto, K. Okita, T. Yamashita and S. Ikida, Biopolymers 4, 769, 781 (1966).CrossRefGoogle Scholar
  20. 20.
    R. D. Orwoll and R. L. Vold, J. Amer. Chem. Soc. 93, 5335 (1971).CrossRefGoogle Scholar
  21. 21.
    E. L. Wee and W. G. Miller, J. Phys. Chem. 77, 182 (1973).CrossRefGoogle Scholar
  22. 22.
    K. D. Goebel and W. G. Miller, Macromolecules, 3, 64 (1970).CrossRefGoogle Scholar
  23. 23.
    J. H. Rai and W. G. Miller, J. Phys. Chem. 76, 1081 (1972).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1974

Authors and Affiliations

  • Wilmer G. Miller
    • 1
  • Juey H. Rai
    • 1
  • Elizabeth L. Wee
    • 1
  1. 1.Department of ChemistryUniversity of MinnesotaMinneapolisUSA

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