Highly stretchable ionically crosslinked acrylate elastomers inspired by polyelectrolyte complexes.

Dynamic bonds are a powerful approach to tailor the mechanical properties of elastomers and introduce shape-memory, self-healing, and recyclability. Among the library of dynamic crosslinks, electrostatic interactions among oppositely charged ions have been shown to enable tough and resilient elastomers and hydrogels. In this work, we investigate the mechanical properties of ionically crosslinked ethyl acrylate-based elastomers assembled from oppositely charged copolymers. Using both infrared and Raman spectroscopy, we confirm that ionic interactions are established among polymer chains. We find that the glass transition temperature of the complex is in between the two individual copolymers, while the complex demonstrates higher stiffness and more recovery, indicating that ionic bonds can strengthen and enhance recovery of these elastomers. We compare cycles to increasing strain levels at different strain rates, and hypothesize that at fast strain rates ionic bonds dynamically break and reform while entanglements do not have time to slip, and at slow strain rates ionic interactions are disrupted and these entanglements slip significantly. Further, we show that a higher ionic to neutral monomer ratio can increase the stiffness, but its effect on recovery is minimal. Finally, taking advantage of the versatility of acrylates, ethyl acrylate is replaced with the more hydrophilic 2-hydroxyethyl acrylate, and the latter is shown to exhibit better recovery and self-healing at a cost of stiffness and strength. The design principles uncovered for these easy-to-manufacture polyelectrolyte complex-inspired bulk materials can be broadly applied to tailor elastomer stiffness, strength, inelastic recovery, and self-healing for various applications.

Fracture Toughness and Fatigue Threshold of Tough Hydrogels.

Hydrogels of numerous chemical compositions have achieved high fracture toughness on the basis of one physical principle. As a crack advances in such a hydrogel, a polymer network of strong bonds ruptures at the front of the crack and elicits energy dissipation in the bulk of the hydrogel. The constituent that dissipates energy in the bulk of the hydrogel is called a toughener. A hypothesis has emerged recently that tougheners increase fracture toughness greatly but contribute little to fatigue threshold. Here we ascertain this hypothesis by studying hydrogels of two kinds, identical in all aspects except for tougheners. A Ca-alginate/polyacrylamide hydrogel has ionic bonds, which act as tougheners, resulting in a toughness of 3375 J/m2 and a threshold of 35 J/m2. A Na-alginate/polyacrylamide hydrogel has no ionic bonds, resulting in a toughness of 169 J/m2 and a threshold of 17 J/m2. These results motivate a discussion on the development of fatigue-resistant hydrogels.