Industrial & Engineering Chemistry Research, Vol.48, No.11, 5460-5471, 2009
Shear Viscosity of CO2-Plasticized Polystyrene Under High Static Pressures
High-pressure shear viscosity measurements of polymer/supercritical fluid systems are numerous, but most involve pressure-gradient equipment such as a capillary or slit die with pressure drops exceeding 10%. Pressure change across the measurement region introduces some errors when quantifying the effect of blowing agents and other diluents on viscosity. This source of errors was removed by using a static-pressure, Couette rheometer. The viscosity of polystyrene (PS)/carbon dioxide (CO2) was measured from 140 to 180 degrees C and from 3 to 6 wt % CO2. The effect of pressure on diluent-free PS viscosity was required to calculate the CO2 concentration shift factor. Thus, viscosities at both atmospheric and elevated pressure (via helium, an insoluble gas) were measured using the same equipment and method. The Fillers-Moonan-Tschoegl (FMT) model was overdefined for obtaining free volume parameters, but it was a helpful correlation tool to obtain the pressure effect on viscosity. Pressure and concentration shift factors obtained from the experiments were compared with empirical free-volume plasticization models, one based on glass transition temperature, the other on P-V-T behavior. Unfortunately, neither model demonstrated quantitative agreement with the experimental data within the 3-6 wt % CO2 range examined. The WLF-Chow model, based on T-g data, fared better than the P-V-T-based model.