Abstract
A molecular theory for the rheological properties of moderately concentrated polymer solutions is developed on the basis of a model of interacting dumbbells. The interaction is treated in a mean field approximation, leading to an effective one-particle potential and a Gaussian stationary distribution function. Various rheological functions such as birefringence, shear viscosity and first normal-stress coefficient for simple shear flow and the Trouton viscosity for simple extensional flow are calculated. Good qualitative agreement with experimental observations is found, especially at intermediate flow rates. It is predicted, for example, that the birefringence increases approximately linearly with shear rate at intermediate shear rates and that the concentration dependence of the gradient varies asc 1/2. The typical non-Newtonian behaviour is obtained for the shear viscosity. For small concentrations the onset of shear rate dependence decreases asc −1/2. At intermediate shear rates an apparent power law is obtained with an exponent between − 0.5 and − 1.0, decreasing with concentration.
Similar content being viewed by others
References
Gennes PG de (1971) J Chem Phys 55:572
Gennes PG de (1979) Scaling Concepts in Polymer Physics. Cornell University Press, Ithaka
Doi M, Edwards SF (1978) J Chem Soc Faraday Trans II 74:1789, 1802, 1819; (1979) 75:38
Curtiss CF, Bird RB (1981) J Chem Phys 74:2016, ... Bird RB, Saab HH, Curtiss CF (1982) J Phys Chem 86:1102; (1982) J Chem Phys 77:4747; Saab HH, Bird RB, Curtiss CF (1982) J Chem Phys 77:4758
Giesekus H (1982) J Non-Newtonian Fluid Mech 11:69; (1982) Rheol Acta 21:366
Kuhn W (1934) Kolloid-Z. 68:2
Bird RB, Hassager O, Armstrong RC, Curtiss CF (1977) Dynamics of Polymeric Liquids, Vol 2: Kinetic Theory, Wiley, New York
Hess W, to be published in J Polym Sci
Cerf R, Scheraga HA (1952) Chem Rev 51:185
Peterlin A, Munk P (1972) Streaming Birefringence. In: Weissberger A (ed) Physical Methods of Chemistry IIIc
Janeschitz-Kriegl H (1983) Polymer Melt Rheology, Springer, Berlin
Kuhn W, Grün F (1942) Kolloid-Z. 101:248
Tsvetkov VN, Frisman E (1945) Acta Physicochim USSR 20:61
Jordan DO, Mathieson AR, Porter MR (1956) J Polym Sci 21:463
Graessley WW (1974) Adv Polym Sci 16:1
Endo H, Fujimoto T, Nagasawa M (1971) J Polym Sci Pt A-2 9:345
Sakei M, Fujimoto T, Nagasawa M (1972) Macromolecules 5:786
Kulicke WM, Kniewske R, Klein J (1982) Prog Polym Sci 8:373
Markowitz H, Williamson B (1957) Trans Soc Rheol 1:25
Williams MC (1965) AIChE 11:467
Münstedt H, Laun HM (1981) Rheol Acta 20:679
Philippoff W (1960) Trans Soc Rheol 4:159
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Heß, W. Molecular theory for moderately concentrated polymer solutions in shear flow. Rheol Acta 23, 477–488 (1984). https://doi.org/10.1007/BF01329280
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01329280