ABSTRACT
Nonequilibrium molecular dynamics simulations were performed for a family of hyperbranched polymers of the same molecular weight but with different chain lengths between branches. Microscopic structural properties including mean squared radius of gyration, distribution of beads from the center of mass and from the core and the interpenetration function of these systems were characterized. A relationship between the zero shear rate mean squared radius of gyration and the Wiener index was established. The molecular and bond alignment tensors were analyzed to characterize the flow birefringence of these hyperbranched polymers. The melt rheology was also studied and the crossover from the Newtonian to non-Newtonian behavior was captured for all polymer fluids in the considered range of strain rates. Rheological properties including the shear viscosity and normal stress coefficients obtained from constant pressure simulations were found to be the same as those from constant volume simulations except at high strain rates due to shear dilatancy. A linear dependence of zero shear rate viscosities on the number of spacer units was found. The stress optical rule was shown to be valid at low strain rates with the stress optical coefficient of approximately 3.2 independent of the topologies of polymers.
ABSTRACT
The melt rheology of four hyperbranched polymer structures with different molecular weights has been studied using nonequilibrium molecular dynamics (NEMD). Systems were simulated over a wide range of strain rates to capture the crossover behavior from Newtonian to non-Newtonian regimes. Rheological properties including shear viscosity and first and second normal stress coefficients were computed and the transition to shear thinning was observed at different strain rates for hyperbranched polymers of different sizes. The results were consistent with previous findings from NEMD simulation of linear and dendritic polymers. Flow birefringence was characterized by taking into account both form and intrinsic birefringences, which result from molecular and bond alignment, respectively. The stress optical rule was tested and shown to be valid only in the Newtonian regime and violated in the strong flow regime where the rule does not take into account flow-induced changes of the microstructure.
ABSTRACT
Hyperbranched polymer melts have been simulated using a coarse-grained model and nonequilibrium molecular dynamics (NEMD) techniques. In order to determine the shear-induced changes in the structural properties of hyperbranched polymers, various parameters were calculated at different strain rates. The radii of gyration which characterize the size of the polymer were evaluated. The tensor of gyration was analyzed and results indicate that hyperbranched polymer molecules have a prolate ellipsoid shape under shear. As hyperbranched polymers have compact, highly branched architecture and layers of beads have increasing densities which might lead to an unusual distribution of mass, the distribution of beads was also studied. The distribution of terminal beads was investigated to understand the spatial arrangement of these groups which is very important for hyperbranched polymer applications, especially in drug delivery.
