Skip to main content
Log in

Thermal contraction and volume relaxation of amorphous polymers

  • Original Contributions
  • Published:
Rheologica Acta Aims and scope Submit manuscript

Abstract

Two experimental techniques are described for the determination of the change of specific volume of polymers with temperature and aging time, which allow measurements between − 160 °C and + 200 °C. Four technical amorphous polymers, PS, PVC, PMMA and PC have been investigated. Volume-temperature curves under constant rate of cooling are presented and interpreted with respect to relaxation processes known from other physical investigations. The rate dependence of dilatometric glass transition temperatures is compared with the time dependence of rheometric glass transition temperatures from shear creep data. Volume relaxation data at constant aging temperature are presented. Aging is found to proceed until very low temperatures in the glassy state for e.g. PMMA.

For polystyrene, a comparison is made between the predictions of a very simple theory of volume relaxation due to Kovacs with experimental data, using additional information from volume temperature curves and the time temperature shift of the shear creep transition. The theory predicts a rate of volume relaxation which is much lower than that found by experiment.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Struik LCE (1978) Physical aging in amorphous polymers and other materials. Elsevier Scientific Publishing Company, Amsterdam

    Google Scholar 

  2. Kovacs AJ (1963) Transition vitreuse dans les polymères amorphes. Fortschr Hochpolym-Forsch 3:394

    Google Scholar 

  3. Kovacs AJ (1958) J Polym Sci 30:131

    Google Scholar 

  4. Doolittle AK (1951) J Appl Phys 22:1471

    Google Scholar 

  5. Kovacs AJ, Hutchinson JM, Aklonis JJ (1977) Isobaric volume and enthalpy recovery of glasses. (I) A critical survey of recent phenomenological approaches, in: Gaskell PH (ed) The Structure of Non-Crystalline Materials, Taylor and Francis, pp 153

    Google Scholar 

  6. Williams ML, Landel RF, Ferry JD (1955) J Amer Chem Soc 77:4701

    Google Scholar 

  7. Schwarzl FR, Zahradnik F (1980) Rheol Acta 19:137

    Google Scholar 

  8. Schwarzl FR (1980) The glass transition of amorphous polymers and the free volume, in: Astarita, Marrucci and Nicolais (eds) Rheology, Vol 1, pp 243, Plenum Publishing Corp, New York

    Google Scholar 

  9. Kovacs AJ (1955) Industrie des plastiques modernes, Paris 7, Nr 1, 34

  10. Hellwege K-H, Hennig J, Knappe W (1962) Kolloid-Z u Z f Polym 186:29

    Google Scholar 

  11. Brather A, Link G, Luchscheider R (1980) Kolloid-Z u Z f Polym 258:130

    Google Scholar 

  12. Hartwig G, KFZ Karlsruhe, private communication

  13. Boyer RF, Turley SG (1978) Molecular Motion in Polystyrene, in: Meier DJ (ed), Molecular basis of transitions and relaxations, Gordon and Breach, London, pp 333

    Google Scholar 

  14. Sinnott KM (1962) SPE Trans 2:65

    Google Scholar 

  15. Yano O, Wada Y (1971) J Polym Sci A-2, 9:669

    Google Scholar 

  16. Mc Cammon RD, Saba RG, Work RN (1969) J Polym Sci A-2, 7:1721

    Google Scholar 

  17. Irvine JD, Work RN (1973) J Polym Sci Polym Phys Ed 11:175

    Google Scholar 

  18. Illers K-H, Jenckel E (1958) Rheol Acta 1:322

    Google Scholar 

  19. Illers K-H, Jenckel E (1959) J Polym Sci 41:528

    Google Scholar 

  20. Roe JM, Simha R (1974) Intern J Polym Mater 3:193

    Google Scholar 

  21. Goldbach G, Rehage G (1967) Kolloid-Z u Z f Polym 216/17:56

    Google Scholar 

  22. Boyer RF (1966) J Polym Sci C-14:267

    Google Scholar 

  23. Höcker H, Blake GJ, Flory PJ (1971) Trans Faraday Soc 67:2251

    Google Scholar 

  24. Plazek DJ (1975) Am Chem Soc Coat and Plast Prepr 35:389

    Google Scholar 

  25. Pfandl W, Link G, Schwarzl FR (1984) Rheol Acta 23:277

    Google Scholar 

  26. Heydemann P, Quicking HD (1963) Kolloid-Z 193:16

    Google Scholar 

  27. Wittmann JC, Kovacs AJ (1969) J Polym Sci C-16:4443

    Google Scholar 

  28. Gall WG, McCrum NG (1961) J Polym Sci 50:489

    Google Scholar 

  29. Wada Y, Yamamoto K (1956) J Phys Soc Japan 11:887

    Google Scholar 

  30. Heijboer J, Dekking P, Staverman AJ (1953/54) Proc 2nd Int Congr Rheology, Oxford, pp 123, Butterworth Scientific Publ, London

    Google Scholar 

  31. Heijboer J (1978) Secondary loss peaks in glassy amorphous polymers, in: Meier DJ (ed) Molecular basis of transitions and relaxations, Gordon and Breach, London, pp 75

    Google Scholar 

  32. Bree HW, Heijboer J, Struik LCE, Tak AGM (1974) J Polym Sci, Ed Polym Phys 12:1857

    Google Scholar 

  33. Ishida Y (1960) Kolloid-Z u Z f Polym 168:29

    Google Scholar 

  34. Heijboer J (1982) Dynamic mechanical properties of amorphous polymers in: Static and Dynamic Properties of the Polymeric Solid State, D. Reidel Publ Comp, Dordrecht

    Google Scholar 

  35. Petri SEB, Morre RS, Flick JR (1972) J Appl Phys 43:4318

    Google Scholar 

  36. Heijboer J (1969) Br Polym 1:3

    Google Scholar 

  37. Ishida Y, Matsuoka S (1965) Am Chem Soc, Polym Preprints 6, Nr 2, 795

  38. Illers KH, Breuer H (1963) J Colloid Sci 18:1

    Google Scholar 

  39. Hellwege K-H, Hennig J, Knappe W (1962) Kolloid-Z u Z f Polym 186:29

    Google Scholar 

  40. Kovacs AJ (1958) J Polym Sci 30:131

    Google Scholar 

  41. Doolittle AK (1951) J Appl Phys 22:1471

    Google Scholar 

  42. Cohen MH, Turnbull D (1959) J Chem Phys 31:1164

    Google Scholar 

  43. Gibbs JH, DiMarzio EA (1958) J Chem Phys 28:373

    Google Scholar 

  44. Williams ML, Landel RF, Ferry JD (1955) J Am Chem Soc 77:4701

    Google Scholar 

  45. Zahradnik F, Schwarzl FR, Rheol Acta (to be published)

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Greiner, R., Schwarzl, F.R. Thermal contraction and volume relaxation of amorphous polymers. Rheol Acta 23, 378–395 (1984). https://doi.org/10.1007/BF01329190

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01329190

Key words

Navigation