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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Andrade EN (1962) The validity of the t1/3 law of flow of metals. Philos Magazine 7:2003–2014
Angell CA (1991) Relaxation in liquids, polymers and plastic crystals — strong/fragile patterns and problems. J Non-Cryst Solids 131–133:13–31
Beiner M (1995) Thesis, Universität Halle
Bierbach T (1995) Diploma thesis, Universität Halle
Böhmer R, Ngai KL, Angell CA, Plazek DJ (1993) Nonexponential relaxations in strong and fragile glass formers. J Chem Phys 99:4201–4209
Boyer RF (1966) Introductory remarks for symposium on transitions and relaxations in polymers. J Polym Sci C14:3–14
Donth E (1992) Relaxation and thermodynamics in polymers. Glass transition. Akademie-Verlag, Berlin
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 29:6589–6600
Ferry JD (1980) Viscoelastic properties of polymers. Wiley, New York
Goldstein MJ (1969) Viscous liquids and the glass transition: a potential energy barrier picture. Chem Phys 51:3728–3739
Honerkamp J, Weese J (1993) A nonlinear regularization method for the calculation of relaxation spectra. Rheol Acta 32:6573
Lomellini P, Lavagnini L (1992) Molecular weight polydispersity effects on the melt viscoelasticity of styrene-acrylonitrile random copolymers. Rheol Acta 31:175–182
Masuda T, Kitagawa K, Inoue T, Onogi S (1970) Rheological properties of anionic polystyrenes: II. dynamic viscoelasticity of blends of narrow-distribution polystyrenes. Macromolecules 3:116–125
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 24:619–632
Ngai KL, Plazek DJ (1995) Identification of different modes of molecular motion in polymers that cause thermorheological complexity. Rubber Chem Techn 68:376–434
Pfandl W, Link G, Schwarzl FR (1984) Dynamic shear properties of a technical polystyrene melt. Rheol Acta 23:277–290
Plazek DJ (1980) The temperature dependence of the viscoelastic behavior of poly(vinyl acetate). Polym J 12:43–53
Plazek DJ, O'Rourke VM (1971) Viscoelastic behavior of low molecular weight polystyrene. J Polym Sci, Part A 9:209–243
Plazek DL, Plazek DJ (1983) Viscoclastic behavior of atactic polypropylene. Macromolecules 16:1469–1475
Plazek DJ, Zheng XD, Ngai KL (1992) Viscoelastic properties of amorphous polymers: 1. Different temperature dependences of segmental relaxation and terminal dispersion. Macromolecules 25:4920–4924
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 28:5394–5395
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 29:3996–3999
Schlosser E, Schönhals A (1991) Dielectric relaxation during physical ageing. Polymer 32:2135–2140
Vogel H (1921) Das Temperaturabhängig-keitsgesetz der Viskosität von Flüssigkeiten. Physik Z 22:645–646
Williams ML, Landel RF, Ferry JD (1955) The temperature dependence of relaxation mechanism in amorphous polymers and other glassforming liquids. J Am Chem Soc 77:3701–3707
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Beiner, M., Reissig, S., Schröter, K. et al. Stability of the T ∞FT < T ∞α relation between Vogel temperatures of flow and glass transition against determination variants. Rheola Acta 36, 187–196 (1997). https://doi.org/10.1007/BF00366824
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00366824