Relaxation of shear and normal stresses in step‐shear deformation of a polystyrene solution. Comparison with the predictions of the Doi–Edwards theory

The shear stress σ, two components of birefringence, and extinction angle were measured for a concentrated polystyrene solution in step‐shear deformation of magnitude of shear 0.3 ≤ γ ≤ 4.0. The stress‐optical coefficient did not depend on either γ or time. The first and the second normal‐stress differences v1 and v2 were evaluated with the use of the stress‐optical law. Over a certain range of long times, σ could be factored as σ = γh(γ)G(t) and the quantity h(γ) agreed with the prediction of the Doi–Edwards theory based on the de Gennes tube model of entangled polymer chains. At short times the effect of γ on σ/γ was smaller than at long times. The relaxation spectrum became approximately independent of γ at the short‐time end of the rubbery plateau region. The ratios v1/σ and v2/v1 were independent of time and were in quantitative agreement with those predicted by the Doi–Edwards theory: v1/σ was equal to γ, v2/v1 was negative, and |v2/v1| decreased with increasing γ.