Wall slip is one of the most important characteristics of polymer melts’ elasticity behaviours as well as the most significant factor which affects the flow of polymer melts. Based on the traditional Mooney method, through a double-barrel capillary rheometer, the relationship between velocities of wall slip, shear stress, shear rate, diameters of dies, and temperature of polypropylene (PP), high-density polyethylene (HDPE), polystyrene (PS), and polymethylmethacrylate (PMMA) is explored. The results indicate that the velocities of the wall slip of PP and HDPE increase apparently with shear stress and slightly with temperature. Meanwhile, the rise of temperature results in the decrease of critical shear stress. The wall-slip velocities of PS and PMMA are negative which means that the Mooney method based on the adsorption–desorption mechanism has determinate limitation to calculate the wall-slip velocity. Based on the entanglement–disentanglement mechanism, a new wall-slip model is built. With the new model, the calculation values of velocity of PP and HDPE correspond to the experimental values very well and the velocities of PS and PMMA are positive. The velocities of PS and PMMA increase obviously with the rise of shear stress. The rise of temperature results in the increase of velocity and decrease of critical shear stress. Then, the molecular dynamics simulation is used to investigate the combining energy between four polymer melts and the inside wall. The results show that at the given temperature and pressure, the molecules of PS and PMMA combine with atoms of the wall more tightly than those of PP and HDPE which means when wall slip occurs, the molecules of PS and PMMA near the wall will adsorb to the surface of the wall. However, those of PP and HDPE will be easy to slip. Therefore, the wall-slip mechanism of PP and HDPE is the adsorption–desorption mechanism, and that of PS and PMMA is the entanglement–disentanglement mechanism. According to the different wall-slip mechanisms of four polymers, an all-sided calculation method of wall-slip velocity is raised which consummates the theory of wall slip of polymer melts.
Segregated structures of ring polymer melts near the surface: a molecular dynamics simulation study
