Entanglement Locking in the Unique Elasticity of Polydimethylsiloxane Rubbers

The viscoelasticity behavior of the polydimethylsiloxane (PDMS) rubber blends of high molecular weight polymers modified by low molecular weight agents is studied in compression mode by stress–strain curves, the creep and step‐strain, and dynamic‐mechanical experiments. The strain spectra highlight the dynamics of active chains at high frequencies and of dangling ends in the low frequencies field. At low deformation, the blending agent enhances the elastic properties by increasing the density of the active chains in the rubber network, in agreement with the classical theories of elasticity. At high deformation, in analogy with the rheological studies on similar liquid blends, the Entanglement Locking model is proposed: the short chains of the blending agent are adsorbed on entanglement sites of long dangling chains, giving effective crosslinks via high entropy dynamics. In this way, the long‐term entanglement locking enhances the density of active chains and elastic behavior. At high deformation, the entanglement locking model enriches the rubber elasticity theories according to the tube network model and Mooney–Rivlin equation. The models herein and the possibility they offer for improving rubber viscoelasticity are valuable for the development of polymer physics and technology.