Competing Effects of Molecular Additives and Cross-Link Density on the Segmental Dynamics and Mechanical Properties of Cross-Linked Polymers

The introduction of molecular additives into thermosets often results in changes in their dynamics and mechanical properties that can have significant ramifications for diverse applications of this broad class of materials such as coatings, high-performance composites, etc. Currently, there is limited fundamental understanding of how such additives influence glass formation in these materials, a problem of broader significance in glass-forming materials. To address this fundamental problem, here, we employ a simplified coarse-grained (CG) model of a polymer network as a model of thermoset materials and then introduce a polymer additive having the same inherent rigidity and polymer–polymer interaction strength as the cross-linked polymer matrix. This energetically “neutral” or “self-plasticizing” additive model gives rise to non-trivial changes in the dynamics of glass formation and provides an important theoretical reference point for the technologically more important case of interacting additives. Based on this rather idealized model, we systematically explore the combined effect of varying the additive mass percentage (m) and cross-link density (c) on the segmental relaxation dynamics and mechanical properties of a model thermoset material with additives. We find that increasing the additive mass percentage m progressively decreases both the glass-transition temperature T_g and the fragility of glass formation, a trend opposite to increasing c so that these thermoset variables clearly have a competing effect on glass formation in these model materials. Moreover, basic mechanical properties (i.e., bulk, shear, and tensile moduli) likewise exhibit a competitive variation with the increase of m and c, which are strongly correlated with the Debye–Waller parameter ⟨u²⟩, a measure of material stiffness at a molecular scale. Our findings prove beneficial in the development of structure–property relationships for the cross-linked polymers, which could help guide the design of such network materials with tailored physical properties.