Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

A lower critical ordering transition in a diblock copolymer melt

Abstract

DIBLOCK copolymers, comprised of two distinct homopolymers covalently bonded together at one end, undergo a transition on cooling from a state in which the segments of the blocks are homogeneously mixed to one in which they are segregated locally1,2. This microphase separation is driven by the enthalpy of unfavourable interactions between segments. Here we report the microphase separation of a diblock copolymer melt on heating. Similar in nature to the lower critical solution temperature seen in polymer mixtures, this lower critical ordering transition is driven by entropic factors—specifically, by a negative volume change on mixing of the blocks. The transition to the microphase-separated state alters the rheological and mechanical properties of the copolymer markedly, the material gaining a non-zero equilibrium modulus above the ordering transition. This suggests potential technological applications of these copolymer systems as 'smart' materials.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Similar content being viewed by others

References

  1. Goodman, I. (ed.) Developments in Block Copolymers (Applied Science, New York, 1982).

  2. Meier, D. J. (ed.) Block Copolymers: Science and Technology (MMI Hardwood Academic, Midland, 1983).

  3. Meier, D. J. J. Polym. Sci. C26, 81–98 (1969).

    Google Scholar 

  4. Leary, D.F. & Williams, M. C. J. Polym. Sci. B8, 335–340 (1970).

    Article  Google Scholar 

  5. Helfand, E. & Wasserman, Z. R. Macromolecules 9, 879–887 (1976).

    Article  ADS  CAS  Google Scholar 

  6. Semenov, A. N. Soviet Phys. JETP 61, 733–742 (1985).

    Google Scholar 

  7. Ohta, T. & Kawasaki, K. Macromolecules 19, 2621–2632 (1986).

    Article  ADS  CAS  Google Scholar 

  8. Olvera de la Cruz, M., Mayes, A. M. & Swift, B. W. Macromolecules 25, 944–948 (1992).

    Article  ADS  CAS  Google Scholar 

  9. Hashimoto, T., Nagatoshi, K., Todo, A., Hasegawa, H. & Kawai, H. Macromolecules 7, 364–373 (1974).

    Article  ADS  CAS  Google Scholar 

  10. Hashimoto, T., Todo, A., Itoi, H. & Kawai, H. Macromolecules 10, 377–384 (1977).

    Article  ADS  CAS  Google Scholar 

  11. Hashimoto, T., Shibayama, M. & Kawai, H. Macromolecules 13, 1237–1247 (1980).

    Article  ADS  CAS  Google Scholar 

  12. Thomas, E. L., Alward, D. B., Kinning, D. J., Handlin, D. L. & Fetters, L. J. Macromolecules 19, 2197–2202 (1986).

    Article  ADS  CAS  Google Scholar 

  13. Hasegawa, H., Tanaka, H., Yamasaki, K. & Hashimoto, T. Macromolecules 20, 1651–1662 (1987).

    Article  ADS  CAS  Google Scholar 

  14. Thomas, E.L., Anderson, D.M., Henkee, C. S. & Hoffman, D. Nature 334, 598–601 (1992).

    Article  ADS  Google Scholar 

  15. Almdahl, K., Koppi, K. A., Bates, F. S. & Mortensen, K. Macromolecules 25, 1743–1751 (1992).

    Article  ADS  Google Scholar 

  16. Leibler, L. Macromolecules 13, 1602–1617 (1980).

    Article  ADS  CAS  Google Scholar 

  17. Ramos, A. R. & Cohen, R. E. Polym. Engng Sci. 17, 639–646 (1977).

    Article  CAS  Google Scholar 

  18. Fischer, E. W. & Jung, W. G. Makromol. Chem., Makromol. Symp. 26, 179–189 (1989).

    Article  CAS  Google Scholar 

  19. Bates, F. S., Rosedale, J. H., Bair, H. E. & Russell, T. P. Macromolecules 22, 2557–2564 (1989).

    Article  ADS  CAS  Google Scholar 

  20. Bates, F. S., Rosedale, J. H. & Fredrickson, G. H. J. chem. Phys. 92, 6255–6270 (1990).

    Article  ADS  CAS  Google Scholar 

  21. Rosedale, J. H. & Bates, F. S. Macromolecules 23, 2329–2338 (1990).

    Article  ADS  CAS  Google Scholar 

  22. Fredrickson, G. H. & Helfand J. chem. Phys. 87, 697–705 (1987).

    Article  ADS  CAS  Google Scholar 

  23. Yang, H., Hadziioannou, G. & Stein, R. S. J. Polym. Sci., Polym. Phys. edn 21, 1591–1595 (1983).

    Google Scholar 

  24. Russell, T. P. in Handbook of Synchrotron Radiation vol. 3 (eds Brown, G. S. & Moncton, D. E.) 379–469 (North-Holland, Amsterdam, 1991).

    Google Scholar 

  25. Bank, M., Leffingwell, J. & Thies, C. J. Polym. Sci. Part A-2 10, 1097–1109 (1972).

    Article  CAS  Google Scholar 

  26. McMaster, L. P. Macromolecules 6, 760–773 (1973).

    Article  ADS  CAS  Google Scholar 

  27. Nishi, T., Wang, T. T. & Kwei, T. K. Macromolecules 8, 227–234 (1975).

    Article  ADS  CAS  Google Scholar 

  28. Lacombe, R. H. & Sanchez, I. C. J. phys. Chem. 80, 2568–2580 (1976).

    Article  CAS  Google Scholar 

  29. Paul, D. R. & Newman, S. Polymer Blends (Academic, New York, 1978).

    Book  Google Scholar 

  30. Mortensen, K., Brown, W. & Norden, B. Phys. Rev. Lett. 68, 2340–2343 (1992).

    Article  ADS  CAS  Google Scholar 

  31. Mortensen, K. Europhys. Lett. 19, 599–604 (1992).

    Article  ADS  CAS  Google Scholar 

  32. Yeung, M., Desai, R. C., Shi, A.-C. & Noolandi, J. Phys. Rev. Lett. (in the press).

  33. Mam, S., Malone, M. F. & Winter, H. H. J. Rheol. 36, 1625–1649 (1992).

    Article  ADS  Google Scholar 

  34. Bauer, B., Hammouda, B. & Russell, T. P. Macromolecules (in the press).

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Russell, T., Karis, T., Gallot, Y. et al. A lower critical ordering transition in a diblock copolymer melt. Nature 368, 729–731 (1994). https://doi.org/10.1038/368729a0

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/368729a0

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing