Role of additive size in the segmental dynamics and mechanical properties of cross-linked polymers

Thermoset materials often involve the addition of molecular and nanoparticle additives to alter various chemo-physical properties of importance in their ultimate applications. The resulting compositional heterogeneities can lead to either enhancement or degradation of thermoset properties, depending on the additive chemical structure and concentration. We tentatively explore this complex physical phenomenon through the consideration of a model polymeric additive to our coarse-grained (CG) thermoset investigated in previous works by simply varying the size of additive segments compared to those of polymer melt. We find that the additive modified thermoset material becomes chemically heterogeneous from additive aggregation when the additive segments become much smaller than those of the thermoset molecules, and a clear evidence is observed in the spatial distribution of local molecular stiffness estimated from Debye-Waller factor 〈u²〉. Despite the non-monotonic variation trends observed in dynamical and mechanical properties with decreasing additive segmental size, both the structural relaxation time and moduli (i.e., shear modulus and bulk modulus) exhibit scaling laws with 〈u²〉. The present work highlights the complex role of additive size played in the dynamical and mechanical properties of thermoset polymers, which should provide a better understanding for the glass formation process of cross-linked polymer composites.