Localized Ionic Reinforcement of Double Network Granular Hydrogels

Abstract

Nature produces soft materials with fascinating combinations of mechanical properties. For example, the mussel byssus embodies a combination of stiffness and toughness, a feature that is unmatched by synthetic hydrogels. Key to enabling these excellent mechanical properties are the well‐defined structures of natural materials and their compositions controlled on lengths scales down to tens of nanometers. The composition of synthetic materials can be controlled on a micrometer length scale if processed into densely packed microgels. However, these microgels are typically soft. Microgels can be stiffened by enhancing interactions between particles, for example through the formation of covalent bonds between their surfaces or a second interpenetrating hydrogel network. Nonetheless, changes in the composition of these synthetic materials occur on a micrometer length scale. Here, 3D printable load‐bearing granular hydrogels are introduced whose composition changes on the tens of nanometer length scale. The hydrogels are composed of jammed microgels encompassing tens of nm‐sized ionically reinforced domains that increase the stiffness of double network granular hydrogels up to 18‐fold. The printability of the ink and the local reinforcement of the resulting granular hydrogels are leveraged to 3D print a butterfly with composition and structural changes on a tens of nanometer length scale.