Rheologica Acta

, Volume 36, Issue 2, pp 187–196 | Cite as

Stability of the T∞FT < T∞α relation between Vogel temperatures of flow and glass transition against determination variants

  • Mario Beiner
  • Sven Reissig
  • Klaus Schröter
  • Ernst-Joachim Donth
Original Contribution
Received:
Accepted:

Abstract

Dynamic shear measurements in the frequency range from 10−4 to 500 rad/s at the flow and main transition of a polydisperse poly(vinyl acetate) and a monodisperse polystyrene sample are presented. For both samples the Vogel temperature of the flow transition T∞FT is smaller than the Vogel temperature of the main transition T∞α, independent of the criteria used for data evaluation. The difference between the two Vogel temperatures corresponds to results for samples with other molecular weight and polydispersity from the literature. The T∞FT<T∞α relation is discussed in terms of short (α) and long (FT) dynamic glass transitions in entangled polymers. The relation is explained by preaveraging of the energy landscape for the long flow transition by the short glass transition.

Key words

Glass transition flow transition polystyrene poly(vinyl acetate) Vogel temperature 
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Andrade EN (1962) The validity of the t1/3 law of flow of metals. Philos Magazine 7:2003–2014Google Scholar
  2. Angell CA (1991) Relaxation in liquids, polymers and plastic crystals — strong/fragile patterns and problems. J Non-Cryst Solids 131–133:13–31Google Scholar
  3. Beiner M (1995) Thesis, Universität HalleGoogle Scholar
  4. Bierbach T (1995) Diploma thesis, Universität HalleGoogle Scholar
  5. Böhmer R, Ngai KL, Angell CA, Plazek DJ (1993) Nonexponential relaxations in strong and fragile glass formers. J Chem Phys 99:4201–4209Google Scholar
  6. Boyer RF (1966) Introductory remarks for symposium on transitions and relaxations in polymers. J Polym Sci C14:3–14Google Scholar
  7. Donth E (1992) Relaxation and thermodynamics in polymers. Glass transition. Akademie-Verlag, BerlinGoogle Scholar
  8. Donth E, Beiner M, Reissig S, Korus J, Garwe F, Vieweg S, Kahle S, Hempel E, Schröter K (1996) Fine structure of the main transition in amorphous polymers: entanglement spacing and characteristic length of the glass transition. Discussion of examples. Macromolecules 29:6589–6600Google Scholar
  9. Ferry JD (1980) Viscoelastic properties of polymers. Wiley, New YorkGoogle Scholar
  10. Goldstein MJ (1969) Viscous liquids and the glass transition: a potential energy barrier picture. Chem Phys 51:3728–3739Google Scholar
  11. Honerkamp J, Weese J (1993) A nonlinear regularization method for the calculation of relaxation spectra. Rheol Acta 32:6573Google Scholar
  12. Lomellini P, Lavagnini L (1992) Molecular weight polydispersity effects on the melt viscoelasticity of styrene-acrylonitrile random copolymers. Rheol Acta 31:175–182Google Scholar
  13. Masuda T, Kitagawa K, Inoue T, Onogi S (1970) Rheological properties of anionic polystyrenes: II. dynamic viscoelasticity of blends of narrow-distribution polystyrenes. Macromolecules 3:116–125Google Scholar
  14. Ngai KL, Plazek DJ (1986) A quantitative explanation of the difference in the temperature dependences of the viscoelastic softening and terminal dispersions of linear amorphous polymers. J Polym Sci, Part B: Polym Phys Ed 24:619–632Google Scholar
  15. Ngai KL, Plazek DJ (1995) Identification of different modes of molecular motion in polymers that cause thermorheological complexity. Rubber Chem Techn 68:376–434Google Scholar
  16. Pfandl W, Link G, Schwarzl FR (1984) Dynamic shear properties of a technical polystyrene melt. Rheol Acta 23:277–290Google Scholar
  17. Plazek DJ (1980) The temperature dependence of the viscoelastic behavior of poly(vinyl acetate). Polym J 12:43–53Google Scholar
  18. Plazek DJ, O'Rourke VM (1971) Viscoelastic behavior of low molecular weight polystyrene. J Polym Sci, Part A 9:209–243Google Scholar
  19. Plazek DL, Plazek DJ (1983) Viscoclastic behavior of atactic polypropylene. Macromolecules 16:1469–1475Google Scholar
  20. Plazek DJ, Zheng XD, Ngai KL (1992) Viscoelastic properties of amorphous polymers: 1. Different temperature dependences of segmental relaxation and terminal dispersion. Macromolecules 25:4920–4924Google Scholar
  21. Reissig S, Beiner M, Korus J, Schröter K, Donth E (1995) Confirmation of Plazek's slight shoulder in the shear retardation spectrum of poly(vinyl acetate) at the dynamic glass transition. Macromolecules 28:5394–5395Google Scholar
  22. Reissig S, Beiner M, Vieweg S, Schröter K, Donth E (1996) Fine structure of the glass transition in amorphous polymers: slight shoulder in the shear H spectrum at the L peak. Macromolecules 29:3996–3999Google Scholar
  23. Schlosser E, Schönhals A (1991) Dielectric relaxation during physical ageing. Polymer 32:2135–2140Google Scholar
  24. Vogel H (1921) Das Temperaturabhängig-keitsgesetz der Viskosität von Flüssigkeiten. Physik Z 22:645–646Google Scholar
  25. Williams ML, Landel RF, Ferry JD (1955) The temperature dependence of relaxation mechanism in amorphous polymers and other glassforming liquids. J Am Chem Soc 77:3701–3707Google Scholar

Copyright information

© Steinkopff Verlag 1997

Authors and Affiliations

  • Mario Beiner
    • 1
  • Sven Reissig
    • 1
  • Klaus Schröter
    • 1
  • Ernst-Joachim Donth
    • 1
  1. 1.Universität Halle Fachbereich PhysikHalle/SaaleGermany

Personalised recommendations