Tough, Stretchable, and Thermoresponsive Smart Hydrogels.

Self-healing, thermoresponsive hydrogels with a triple network (TN) were obtained by copolymerizing N-isopropyl acryl amide (NiPAAm) with polyvinyl alkohol (PVA) functionalized with methacrylic acid and N,N'-methylene bis(acryl amide) crosslinker in the presence of low amounts (<1 wt.%) of tannic acid (TA). The final gels were obtained by crystalizing the PVA in a freeze-thaw procedure. XRD, DCS, and SEM imaging indicate that the crystallinity is lower and the size of the PVA crystals is smaller at higher TA concentrations. A gel with 0.5 wt.% TA has an elongation at a break of 880% at a tension of 1.39 MPa. It has the best self-healing efficiency of 81% after cutting and losing the chemical network. Step-sweep strain experiments show that the gel has thixotropic properties, which are related to the TA/PVA part of the triple network. The low amount of TA leaves the gel with good thermal responsiveness (equilibrium swelling ratio of 13.3). Swelling-deswelling loop tests show enhanced dimensional robustness of the hydrogel, with a substantial constancy after two cycles.