Effects of supercritical fluids, pressure, temperature, and molecular structure on the rheological properties of molten polymers

Since high pressures are involved in most plastics forming processes, reliable high-pressure rheological data are required for the simulation of the processes. The effect of pressure is in some ways the reverse of that of temperature; for example increasing temperature decreases the viscosity, while pressure increases it. Supercritical fluids (SCFs) such as carbon dioxide and nitrogen can act as physical blowing agents in the manufacture of foams and as plasticizers to reduce melt viscosity during processing. The effects of dissolved SCF, pressure, and temperature on the rheological properties of a melt must be known to achieve optimum processing conditions. We used a rotational rheometer and a high-pressure sliding plate rheometer, in which the shear strain, temperature, pressure, and SCF concentration are all uniform. A shear stress transducer senses the stress in the center of the sample to avoid edge effects. It was possible to use shift factors for temperature, pressure and SCF (CO2 or N-2) concentration to obtain a master curve. The effect of temperature could be described by the Arrhenius or WLF models, and the effect of pressure was described by the Barus equation. The effect of SCF concentration could be described by the Fujita-Kishimoto equation. The relative effects of pressure and temperature on the viscosity were quantified. To study the effects of short and long chain branching and a phenyl side group, three polymers were used: polyethylene, polypropylene, and polystyrene. We quantified the effects of short- and long-chain branching, pressure, temperature and dissolved SCF on the rheological properties of these three polymers by use of shift factors.