The birefringence and orientation angle of sodium polystyrene sulfonate in aqueous solvents containing 95% glycerol by volume were measured in steady shear and on the inception and cessation of steady shear using the two‐color flow birefringence technique. Polyelectrolyte concentrations ranged from 1 to 9 mg/ml and NaCl concentrations ranged from 0 to 0.1 M. With increased ionic strength from increased NaCl and polyion concentrations, the steady‐state birefringence decreased, and the average orientation angle with respect to the flow direction increased. The more extended conformations of the no‐salt solutions resulted in larger overshoots on the inception of shear and longer relaxation times on the cessation of shear. Rheological effects of increased Na+ concentration with polyelectrolyte concentration were at least partially offset by entanglements.

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