Relaxation characteristics and intrinsic birefringence and viscosity of polystyrene solutions for a wide range of molecular weights

A comparison is made between measurements on polystyrene solutions and the relaxation characteristics and intrinsic birefringence and viscosity given by the theory for the flexible Gaussian chain of variable number of segments and with internal viscosity and internal hydrodynamic interaction. This is done in order to determine the applicability of the theory to polymers over a wide range of molecular weights, including the low molecular weight range in which there may be conflict with the theoretical assumption of chains having a large number of segments. The longest, terminal relaxation time and the number of chain segments are determined from measurements of the frequency dependence of oscillatory flow birefringence while the intrinsic birefringence and viscosity are determined from steady flow measurements. The range of molecular weights studied is from approximately 900 at 106. It is found that the segment weight is approximately 1000 and the number of segments is in direct proportion to the molecular weight for the range from 1 to 1000 segments. The terminal relaxation time has a molecular weight dependence of the type given by the theory but with better agreement for higher molecular weights. While the measured dependences of the intrinsic viscosity and birefringence are in agreement with theory for molecular weights greater than 5 × 104, they deviate significantly for molecular weights below 1 × 104. The ratio of the intrinsic birefringence to intrinsic viscosity, which in theory is a constant independent of molecular weight, is found to change at the lower molecular weights.