The Effect of Shear Rate on the Inherent and Intrinsic Viscosity of Dilute Polystyrene Solutions

Abstract

A study of the effect of shear rate on the inherent and intrinsic viscosities of polystyrene fractions, in dilute solution was carried out. Inherent viscosities were determined for five fractions (of molecular weights ranging from 2.9 x 10 to 4.8 x 106); in three solvents (Benzene, Toluene and Methyl Ethyl Ketone); at five temperatures (from 15°C to 85°C); and shear rates ranging from 1.0 x 103 to 2.8 x 104 sec.-1. Inherent viscosities thus determined were extrapolated to zero rate of shear and the extrapolated values plotted against concentration to determine intrinsic viscosities at zero rate of shear, [N] D=0 The inherent viscosity decreased with increasing shear rate. The slope of the curve of inherent viscosity vs shear rate was found to increase (ie become more negative) with increasing concentration, temperature and molecular weight and to be less in a poor solvent than in a good solvent. At very high molecular weights the value of inherent viscosity was found to decrease non-linearly with shear rate. The intrinsic viscosity was found to decrease with increasing shear rate. The slope of the [N] vs D curve was found to increase with increasing molecular weight and decreasing temperature; the slopes were smaller the poorer the solvent. For the three lower fractions the intrinsic viscosity was found to decrease with increasing temperature, very slightly in Methyl Ethyl Ketone and appreciably in Benzene and Toluene, the relative being greater at higher molecular weights. With the two highest fractions this trend was reversed. The slope of the [N] D=0 vs T curve becoming less negative (and actually positive for Benzene end Toluene). The [N] vs T curves ( [N] at free fall) for the three lower fractions were parallel to those at zero rate of shears but of lower intrinsic viscosity values. With the two highest fractions, the slope of the [N] vs T curve became less negative but not to as great a degree as was found with [N] D=0 vs curves. Intrinsic viscosities obtained at zero rate of shear were applied to the Flory-Fox theory. Calculated intrinsic viscosities for polystyrene fractions in Benzene and Toluene were found to agree to within+-4% of the experimental results. For Methyl Ethyl Ketone a wide variation in values was obtained.