Thermodynamic Insights into Variation in Thermomechanical and Physical Properties of Isotactic Polypropylene: Effect of Shear and Cooling Rates.

In order to elucidate the effect of shear and cooling process on structural, thermomechanical, and physical properties of polymer melt, excess entropy, a thermodynamic quantity is calculated from radial distribution function generated from equilibrated parts of the molecular simulation trajectories. The structural properties are calculated, which includes the density of polypropylene melt, end to end distance, radius of gyration of the polypropylene polymer chain, and monomer-monomer radial distribution function. Non-equilibrium molecular dynamics simulation was employed to investigate the role of the applied shear rate on the properties of polypropylene. Furthermore, a range of cooling rates were employed to cool the melt. Thermomechanical properties, such as Young's modulus, and physical properties, such as glass transition temperature, were determined for different cases. Results showed that slow cooling and high shear substantially improved the Young's modulus and glass transition temperature of the i-PP. Furthermore, a two-body contribution to the excess entropy was used to elucidate the structure-property relationships in the polymer melt as well as the glassy state and the dependence of shear and cooling rate on these properties. We have used the Rosenfeld excess entropy-viscosity relationship to calculate the viscous behavior of the polymer under a steady shear condition.