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The debate regarding the possible molecular origins of the Mullins effect has been ongoing since its discovery. Molecular dynamics (MD) simulations were carried out to elucidate the underlying mechanism of the Mullins effect. For the first time, the key characteristics associated with the Mullins effect, including (a) the majority of stress softening occurring in the first stretch, (b) continuous softening with stress increase, (c) a permanent set, and (d) recovery with heat treatment, are captured by molecular modeling. It is discovered that the irreversible disentanglement of polymer chains is physically sufficient to interpret these key characteristics, providing molecular evidence for this long-controversial issue. Our results also reveal that filled polymers exhibit three distinct regimes, i.e., the polymer matrix, the interface, and the filler. When subjected to external strain, the polymer matrix suffers from excess deformation, indicating strong heterogeneity within the filled polymer, which offers molecular insight for the formulation of physics-based constitutive relations for filled polymers.

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In polymer composites, organosilanes are often used to modify the surface property of silica nanoparticles and improve the interfacial properties. Surface properties of the modified silica, such as grafting density and consequent surface energy, largely depend on the molecular structure of the silane. Achieving maximum interfacial bonding between the filler and polymer requires precise control of silica surface property. In this work, four silanes with similar molecular structure but different alkyl chain lengths, trimethoxy(propyl)silane, trimethoxy(octyl)silane, hexadecyltrimethoxysilane and trimethoxy(octadecyl)silane, are selected as model agents to study their roles in influencing silica surface property. The grafting density of silane on the silica is well controlled by regulating the reaction conditions. Three main surface characters, silane grafting density, surface energy and surface potential, are measured. More importantly, a linear relationship has been correlated when plotting grafting density vs. surface energy and grafting density vs. surface potential. Utilizing these relationships, a linear model has been developed to predict grafting density and surface energy by simply measuring surface potential. This model has been validated by both commercial silica and synthesized silica particles of different sizes.