Engineering the Mechanical Behavior of Polymer Networks with Flexible Self-Assembled V-Shaped Monomers

Recent works demonstrated that the structure of self-assembled monomers can be engineered. Subsequently, performance in polymer-network assemblages of such monomers can be enhanced through microstructural design. This work presents a multiscale analysis of polymers comprising flexible V-shaped monomers. We show that two mechanisms enable the deformation of a chain: conformational entropy and elastic energy stemming from the monomers deformation. The mechanical behavior of a polymer network is obtained through an integration from the chain to the network level. We demonstrate that the shear modulus, the extensibility limit of the network, and the force-elongation response can be tuned by manipulation of the V-shaped monomer structure. As an example, the range of properties that can be achieved in an elastomer comprising 4-arm nanostar monomers subjected to uniaxial extension is examined. We find that appropriate manipulation of the monomer structure can lead to anywhere between an ∼100% decrease to an ∼40% increase in the shear modulus and the extensibility limit.