Effect of Cross-Link Homogeneity on the High-Strain Behavior of Elastic Polymer Networks

Cross-link heterogeneity and topological defects have been shown to affect the moduli of polymer networks in the low-strain regime. Probing their role in the high-strain regime, however, has been difficult because of premature network fracture. Here, we address this problem by using a double-network approach to investigate the high-strain behavior of both randomly and regularly cross-linked networks with the same backbone chemistry. Randomly cross-linked poly(n-butyl acrylate) networks with target molecular weights between cross-links of 5-30 kg/mol were synthesized via free-radical polymerization, while regularly cross-linked poly(n-butyl acrylate) networks with molecular weights between cross-links of 7-38 kg/mol were synthesized via cross-linking of tetrafunctional star polymers. Both types of networks were then swollen in a monomer/cross-linker mixture, polymerized to form double networks, and characterized via uniaxial tensile testing. The onset of strain stiffening was found to occur later in regular networks than in random networks with the same modulus but was well-predicted by the target molecular weight between cross-links of each sample. These results indicate that the low- and high-strain behavior of polymer networks result from different molecular-scale features of the material and suggest that controlling network architecture offers new opportunities to both further fundamental understanding of architecture-property relationships and design materials with independently controlled moduli and strain stiffening responses.