The applications of conventional hydrogels are often limited due to their weak mechanical properties and poor functionality. Tremendous progress has been made in developing tough and flexible hydrogels for a variety of engineering applications. In this work, tough physical hydrogels were developed by copolymerizing oppositely charged monomers, which demonstrated their excellent mechanical properties, viscoelasticity and stimuli-triggered healing ability. In order to improve the processability of tough physical hydrogels to form complicated 3D structures, an extrusion-based 3D printing method through direct sol−gel transition was developed. We systematically investigated the effects of material properties and printing parameters on the printability of pregel and mechanical properties of printed hydrogels. The printed hydrogel structures showed excellent mechanical properties in terms of extensibility, strength, and toughness, where a synthetic spider-web with titin-like folded domains and the heterogeneous printing of tough nonresponsive and responsive hydrogels with programable deformations were carried out as the demonstrations. Moreover, conductive polymer hydrogels with remarkable mechanical properties, high conductivity, and easy processability were developed, which were applied to fabricate strain sensors using advanced manufacturing methods.
The present 3D printing based on direct sol−gel transition of tough physical hydrogels is facile yet powerful to fabricate complicated structures, which should be applicable to other tough physical hydrogels with dynamic noncovalent bonds. The additive manufacturing strategy in this study significantly extents the functionality of tough physical hydrogels in the fields of tissue engineering, artificial organs, drug delivery, and soft actuators, etc.