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Effect of molecular weight distribution on the shear dependence of viscosity in polymer systems
Author(s) -
Graessley William W.,
Segal Leon
Publication year - 1970
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690160219
Subject(s) - weissenberg number , molar mass distribution , polymer , polystyrene , shearing (physics) , viscosity , shear rate , thermodynamics , chemistry , reduced viscosity , intrinsic viscosity , relative viscosity , solvent , analytical chemistry (journal) , polymer chemistry , materials science , chromatography , organic chemistry , physics
The viscosity of concentrated solutions of polystyrene were measured in steady shearing flow with a Weissenberg rheogoniometer. The polymers ranged in weight average molecular weight M̄ w from 97,000 to 3,370,000 and in distribution breadth M̄ w / M̄ n from 1.05 to 3.1. The solvent was n ‐butylbenzene, and the solutions ranged in concentration from 0.20 to 0.55 g./cc. These data were supplemented by measurements on bulk polystyrenes and polyethylenes with distribution breadths as high as M̄ w / M̄ n = 20. Master curves of reduced viscosity vs. reduced shear rate were calculated theoretically for each molecular weight distribution. The experimental viscosity data superimposed satisfactorily on these curves and furnished the viscosity at zero shear rate τ 0 and an experimental time constant τ 0 for each solution. The time constant paralleled closely the Rouse relaxation time τ R in all systems. Residual variations in the ratio τ 0 /τ R with molecular weight and concentration correlated uniquely with the product c M̄ w . These results indicate that the viscosity behavior of a polymer can be predicted with reasonable accuracy from data on its molecular weight distribution.