Rheologica Acta

, Volume 45, Issue 1, pp 83–91 | Cite as

Simultaneous stress and birefringence measurements during uniaxial elongation of polystyrene melts with narrow molecular weight distribution

  • Clarisse Luap
  • Christian Müller
  • Thomas Schweizer
  • David C. Venerus
Original Contribution


Tensile stress and flow-induced birefringence have been measured during uniaxial elongation at a constant strain rate of two polystyrene melts with narrow molecular weight distribution. For both melts, the stress- optical rule (SOR) is found to be fulfilled upto a critical stress of 2.7 MPa, independent of strain rate and temperature. Estimation of the Rouse times of the melts, from both the zero-shear viscosity and the dynamic-shear moduli at high frequency, shows that the violation of the SOR occurs when the strain rate multiplied by the Rouse time of the melt exceeds by approximately 3. The presented results indicate that in contrast to current predictions of molecular theories, the regime of extensional thinning observed by Bach et al. (2003) extends well beyond the onset of failure of the SOR, and therefore the onset of chain stretch in the non-Gaussian regime.


Polymer melt Birefringence Elongational flow Polystyrene Rheo-optics Nonlinear viscoelasticity 


  1. Bach A, Almdal K, Rasmussen HK, Hassager O (2003) Elongational viscosity of narrow molar mass distribution polystyrene. Macromolecules 36:5174–5179Google Scholar
  2. Bhattacharjee PK, Oberhauser JP, McKinley GH, Leal LG, Sridhar T (2002) Extensional rheometry of entangled solutions. Macromolecules 35:10131–10148Google Scholar
  3. Doi M, Edwards SF (1986) The theory of polymer dynamics. Oxford Science, New YorkGoogle Scholar
  4. Fang J, Kröger M, Öttinger HC (2000) A thermodynamically admissible reptation model for fast flows of entangled polymers. II. Model predictions for shear and extensional flows. J Rheol 44:1293–1317Google Scholar
  5. Ferry JD (1980) Viscoelastic properties of polymers, 3rd ed. Wiley, New YorkGoogle Scholar
  6. Graessley WW (1974) The entanglement concept in polymer rheology. Adv Polym Sci 16:1–179Google Scholar
  7. Janeschitz-Kriegl H (1983) Polymer melt rheology and flow birefringence. Springer, Berlin Heidelberg New YorkGoogle Scholar
  8. Jasse B, Koenig JL (1979) Fourier transform infrared study of uniaxially oriented atactic polystyrene. J Polym Sci Polym Phys Ed 17:799–810Google Scholar
  9. Kotaka T, Kojima A, Okamoto M (1997) Elongational flow opto-rheometry for polymer melts. 1. Construction of an elongational flow opto-rheometer and some preliminary results. Rheol Acta 36:646–656Google Scholar
  10. Larson RG, Sridhar T, Leal LG, McKinley GH, Likhtman AE, McLeish TCB (2003) Definitions of entanglement spacing and time constants in the tube model. J Rheol 47:809–818Google Scholar
  11. Li L, Masuda T, Takahashi M, Ohno H (1988) Elongational viscosity measurements on polymer melts by a Meissner-type rheometer. J Soc Rheol Jpn 16:117–124Google Scholar
  12. Majeste JC, Montford JP, Allal A, Marin G (1998) Viscoelasticity of low molecular weight polymers and the transition to the entangled regime. Rheol Acta 37:486–499Google Scholar
  13. Marrucci G, Grizzuti N (1988) Fast flows of concentrated polymers: Predictions of the tube model on chain stretching. Gazz Chim Italiana 118:179–185Google Scholar
  14. Marrucci G, Ianniruberto G (2004) Interchain pressure effect in extensional flows of entangled polymer melts. Macromolecules 37:3934–3942Google Scholar
  15. Matsumoto T, Bogue DC (1977) Stress birefringence in amorphous polymer under nonisothermal conditions. J Polym Sci Polym Phys Ed 15:1663–1674Google Scholar
  16. Mead DW, Leal LG (1995) The reptation model with segmental stretch. I) Basic equations and general properties. Rheol Acta 34:339–359Google Scholar
  17. van Meerveld J (2004a) Modified constraint release in molecular based reptation models for fast flows. J non-Newtonian Fluid Mech 122: 263–272CrossRefGoogle Scholar
  18. van Meerveld J (2004b) Validity of the linear stress optical rule in mono-, bi- and polydisperse systems of entangled linear chains. J non-Newtonian Fluid Mech 123: 259–267CrossRefGoogle Scholar
  19. Meissner J, Hostettler J (1994) A new elongational rheometer for polymer melts and other highly viscoelastic liquids. Rheol Acta 33:1–21Google Scholar
  20. Menezes EV, Graessley WW (1982) Nonlinear rheological behavior of polymer systems for several shear-flow histories. J Polym Sci Polym Phys Ed 20:1817–1833Google Scholar
  21. Muller R, Froelich D (1985) New extensional rheometer for elongational viscosity and flow birefringence measurements: some results on polystyrene melts. Polymer 26:1477–1482Google Scholar
  22. Muller R, Pesce JJ (1994) Stress-optical behavior near the Tg and melt flow-induced anisotropy in amorphous polymers. Polymer 35:734–739Google Scholar
  23. Neuert R, Springer H, Hinrichsen G (1985) Orientation analysis of uniaxially drawn polystyrene films doped with fluorescent molecules by fluorescence polarization, UV- and IR-dichroism and birefringence. Colloid Polym Sci 263:392–395Google Scholar
  24. Osaki K, Inoue T, Eumatsu T, Yamashita Y (2001) Evaluation methods of the longuest rouse relaxation time of an entangled polymer in a semidilute solution. J Polym Sci Part B Polym Phys 39:1704–1712Google Scholar
  25. Öttinger HC (1999) A thermodynamically admissible reptation model for fast flows of entangled polymers. J Rheol 43:1461–1493CrossRefGoogle Scholar
  26. Schweizer T (2000) The uniaxial elongational rheometer RME—six years of experience. Rheol Acta 39:428–443Google Scholar
  27. Takahashi M, Isaki T, Takigawa T, Masuda T (1993) Measurement of biaxial and uniaxial extensional flow behavior of polymer melts at constant strain rates. J Rheol 37:827–846Google Scholar
  28. Venerus DC, Zhu S-H, Öttinger HC (1999) Stress and birefringence measurements during the uniaxial elongation of polystyrene melts. J Rheol 43:795–813Google Scholar
  29. Ward IM (1975) Structure and properties of oriented polymers. Applied Science Publishers, LondonGoogle Scholar
  30. Ye X, Larson RG, Pattamaprom C, Sridhar T (2003) Extensional properties of monodisperse and bidisperse polystyrene solutions. J Rheol 47:443–468Google Scholar

Copyright information

© Springer-Verlag 2005

Authors and Affiliations

  • Clarisse Luap
    • 1
  • Christian Müller
    • 1
  • Thomas Schweizer
    • 1
  • David C. Venerus
    • 1
    • 2
  1. 1.Department of MaterialsETH ZürichZürichSwitzerland
  2. 2.Department of Chemical and Environmental Engineering and Center of Excellence in Polymer Science and EngineeringIllinois Institute of TechnologyChicagoUSA

Personalised recommendations