No abstract

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid-like mechanical behavior and water-like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non-conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide-alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as -57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m . It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.

Dynamic crosslinking of extremely stretchable hydrogels with rapid self-healing ability is described. Using this new strategy, the obtained hydrogels are able to elongate 100 times compared to their initial length and to completely self-heal within 30 s without external energy input.

The development of hydrogels for cartilage replacement and soft robotics has highlighted a challenge: load-bearing hydrogels need to be both stiff and tough. Several approaches have been reported to improve the toughness of hydrogels, but simultaneously achieving high stiffness and toughness remains difficult. Here we report that alginate-polyacrylamide hydrogels can simultaneously achieve high stiffness and toughness. We combine short-and long-chain alginates to reduce the viscosity of pregel solutions and synthesize homogeneous hydrogels of high ionic cross-link density. The resulting hydrogels can have elastic moduli of ∼1 MPa and fracture energies of ∼4 kJ m −2 . Furthermore, this approach breaks the inverse relation between stiffness and toughness: while maintaining constant elastic moduli, these hydrogels can achieve fracture energies up to ∼16 kJ m −2 . These stiff and tough hydrogels hold promise for further development as load-bearing materials.

Using strong fibers to reinforce a hydrogel is highly desirable but difficult. Such a composite would combine the attributes of a solid that provides strength and a liquid that transports matter. Most hydrogels, however, are brittle, allowing the fibers to cut through the hydrogel when the composite is loaded. Here we circumvent this problem by using a recently developed tough hydrogel. We fabricate a composite using an alginate-polyacrylamide hydrogel reinforced with a random network of stainless steel fibers. Because the hydrogel is tough, the composite does not fail by the fibers cutting the hydrogel; instead, it fails by the fibers pulling out of the hydrogel against friction. Both stiffness and strength can be increased significantly by adding fibers to the hydrogel. Before failure the composite dissipates a significant amount of energy, at a tunable level of stress, attaining large deformation. Potential applications of tough hydrogel composites include energy-absorbing helmets, tendon repair surgery, and stretchable biometric sensors.