Solvent friction in polymer solutions and its relation to the high frequency limiting viscosity

The rotational relaxation of the solvent Aroclor 1248 (A1248) has been examined in solutions containing either polystyrene (PS), 0≤c≤0.269 g/cc, or polybutadiene (PB), 0≤c≤0.264 g/cc, by oscillatory electric birefringence. Measurements were performed at eight temperatures from −17.31 to 25.00 °C. In all cases the normalized solvent relaxation time τ/τ0, where τ0 was the value in neat solvent, was an exponential function of concentration. For PS/A1248, ∂ ln(τ/τ0)/∂c was independent of temperature and equal to 13±1 cc/g, whereas for PB/A1248, ∂ ln(τ/τ0)/∂c increased steadily with temperature and was negative for measurement temperatures of 2.81 °C and below. These observations were qualitatively consistent with a picture of solvent clustering or ordering, which was enhanced by the addition of PS but disrupted by PB. Although some features of the data were also consistent with changes in solution free volume, as indicated by measurements of the composition‐dependent glass transition temperature, such conside...