Abstract
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.
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Notes
In the original article, the expression is given for the longest stress relaxation time of the Rouse model whose value is half the value of \( \tau _R \)
References
Bach A, Almdal K, Rasmussen HK, Hassager O (2003) Elongational viscosity of narrow molar mass distribution polystyrene. Macromolecules 36:5174–5179
Bhattacharjee PK, Oberhauser JP, McKinley GH, Leal LG, Sridhar T (2002) Extensional rheometry of entangled solutions. Macromolecules 35:10131–10148
Doi M, Edwards SF (1986) The theory of polymer dynamics. Oxford Science, New York
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 44:1293–1317
Ferry JD (1980) Viscoelastic properties of polymers, 3rd ed. Wiley, New York
Graessley WW (1974) The entanglement concept in polymer rheology. Adv Polym Sci 16:1–179
Janeschitz-Kriegl H (1983) Polymer melt rheology and flow birefringence. Springer, Berlin Heidelberg New York
Jasse B, Koenig JL (1979) Fourier transform infrared study of uniaxially oriented atactic polystyrene. J Polym Sci Polym Phys Ed 17:799–810
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 36:646–656
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 47:809–818
Li L, Masuda T, Takahashi M, Ohno H (1988) Elongational viscosity measurements on polymer melts by a Meissner-type rheometer. J Soc Rheol Jpn 16:117–124
Majeste JC, Montford JP, Allal A, Marin G (1998) Viscoelasticity of low molecular weight polymers and the transition to the entangled regime. Rheol Acta 37:486–499
Marrucci G, Grizzuti N (1988) Fast flows of concentrated polymers: Predictions of the tube model on chain stretching. Gazz Chim Italiana 118:179–185
Marrucci G, Ianniruberto G (2004) Interchain pressure effect in extensional flows of entangled polymer melts. Macromolecules 37:3934–3942
Matsumoto T, Bogue DC (1977) Stress birefringence in amorphous polymer under nonisothermal conditions. J Polym Sci Polym Phys Ed 15:1663–1674
Mead DW, Leal LG (1995) The reptation model with segmental stretch. I) Basic equations and general properties. Rheol Acta 34:339–359
van Meerveld J (2004a) Modified constraint release in molecular based reptation models for fast flows. J non-Newtonian Fluid Mech 122: 263–272
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: 259–267
Meissner J, Hostettler J (1994) A new elongational rheometer for polymer melts and other highly viscoelastic liquids. Rheol Acta 33:1–21
Menezes EV, Graessley WW (1982) Nonlinear rheological behavior of polymer systems for several shear-flow histories. J Polym Sci Polym Phys Ed 20:1817–1833
Muller R, Froelich D (1985) New extensional rheometer for elongational viscosity and flow birefringence measurements: some results on polystyrene melts. Polymer 26:1477–1482
Muller R, Pesce JJ (1994) Stress-optical behavior near the Tg and melt flow-induced anisotropy in amorphous polymers. Polymer 35:734–739
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 263:392–395
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 39:1704–1712
Öttinger HC (1999) A thermodynamically admissible reptation model for fast flows of entangled polymers. J Rheol 43:1461–1493
Schweizer T (2000) The uniaxial elongational rheometer RME—six years of experience. Rheol Acta 39:428–443
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 37:827–846
Venerus DC, Zhu S-H, Öttinger HC (1999) Stress and birefringence measurements during the uniaxial elongation of polystyrene melts. J Rheol 43:795–813
Ward IM (1975) Structure and properties of oriented polymers. Applied Science Publishers, London
Ye X, Larson RG, Pattamaprom C, Sridhar T (2003) Extensional properties of monodisperse and bidisperse polystyrene solutions. J Rheol 47:443–468
Acknowledgements
The authors are grateful to Martin Colussi for performing the GPC measurements, to Marina Karlina, Werner Schmidheiny, and Fredy Mettler for their assistance in conducting the experiments. Clarisse Luap thanks Martin Kröger and Jan van Meerveld for helpful discussions.
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Luap, C., Müller, C., Schweizer, T. et al. Simultaneous stress and birefringence measurements during uniaxial elongation of polystyrene melts with narrow molecular weight distribution. Rheol Acta 45, 83–91 (2005). https://doi.org/10.1007/s00397-005-0452-5
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DOI: https://doi.org/10.1007/s00397-005-0452-5