Physical networks from entropy-driven non-covalent interactions

Physical networks typically employ enthalpy-dominated crosslinking interactions that become more dynamic at elevated temperatures, leading to network softening. Moreover, standard mathematical frameworks such as time-temperature superposition assume network softening and faster dynamics at elevated temperatures. Yet, deriving a mathematical framework connecting the crosslinking thermodynamics to the temperature-dependent viscoelasticity of physical networks suggests the possibility for entropy-driven crosslinking interactions to provide alternative temperature dependencies. This framework illustrates that temperature negligibly affects crosslink density in reported systems, but drastically influences crosslink dynamics. While the dissociation rate of enthalpy-driven crosslinks is accelerated at elevated temperatures, the dissociation rate of entropy-driven crosslinks is negligibly affected or even slowed under these conditions. Here we report an entropy-driven physical network based on polymer-nanoparticle interactions that exhibits mechanical properties that are invariant with temperature. These studies provide a foundation for designing and characterizing entropy-driven physical crosslinking motifs and demonstrate how these physical networks access thermal properties that are not observed in current physical networks.