The Role of Polymer Chain Stiffness and Guest Nanoparticle Loading in Improving the Glass Transition Temperature of Polymer Nanocomposites

The impact of polymer chain stiffness characterized by the bending modulus (k_θ) on the glass transition temperature (T_g) of pure polymer systems, as well as polymer nanocomposites (PNCs), is investigated using molecular dynamics simulations. At small k_θ values, the pure polymer system and respective PNCs are in an amorphous state, whereas at large k_θ values, both systems are in a semicrystalline state with a glass transition at low temperature. For the pure polymer system, T_g initially increases with k_θ and does not change obviously at large k_θ. However, the T_g of PNCs shows interesting behaviors with the increasing volume fraction of nanoparticles (f_NP) at different k_θ values. T_g tends to increase with f_NP at small k_θ, whereas it becomes suppressed at large k_θ.