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In the field of actuator materials, hydrogels that undergo large volume changes in response to external stimuli have been developed for a variety of promising applications. However, most conventional hydrogels are brittle and therefore rupture when they are stretched to moderate strains (~50%). Thus, gels to be used for actuators still require improved mechanical properties and actuation performance. In this study, we synthesized a tough and thermo-sensitive hydrogel with a large actuation force by forming interpenetrating networks between covalently crosslinked poly(N-isopropylacrylamide) and ionically crosslinked alginate. Poly(N-isopropylacrylamide) was used as a thermo-sensitive actuation material, and alginate was found to enhance the mechanical properties of the hydrogels. Due to the enhanced elastic modulus and energy dissipation in the hybrid gel, the toughness was increased by a factor of 60 over that of pure PNIPAAm gel. Further, based on the results showing that the hybrid gel exhibits an actuation force that is seven times higher than that of pure PNIPAAm gel, the hybrid gel is more applicable to real actuators.

Artificial shape-morphing hydrogels are emerging toward various applications, spanning from electronic skins to healthcare. However, the low freezing and drying tolerance of hydrogels hinder their practical applications in challenging environments, such as subzero temperatures and arid conditions. Herein, we report on a shape-morphing system of tough organohydrogels enabled by the spatially encoded rigid structures and its applications in conformal packaging of “island–bridge” stretchable electronics. To validate this method, programmable shape morphing of Fe (III) ion-stiffened Ca-alginate/polyacrylamide (PAAm) tough organohydrogels down to −50 °C, with long-term preservation of their 3D shapes at arid or even vacuum conditions, was successfully demonstrated, respectively. To further illustrate the potency of this approach, the as-made organohydrogels were employed as a material for the conformal packaging of non-stretchable rigid electronic components and highly stretchable liquid metal (galinstan) conductors, forming a so-called “island–bridge” stretchable circuit. The conformal packaging well addresses the mechanical mismatch between components with different elastic moduli. As such, the as-made stretchable shape-morphing device exhibits a remarkably high mechanical durability that can withstand strains as high as 1000% and possesses long-term stability required for applications under challenging conditions.

We investigated the mechanical and structural properties of composite hydrogels composed of chitosan nanofiber (ChsNF), positively charged alumina-coated silica (ac-SiO2) nanoparticles, carboxylated poly (vinyl alcohol) (cPVA), and borax. ChsNF/cPVA/borax hydrogels without ac-SiO2 exhibited high Young’s modulus but poor elongation, whereas cPVA/ac-SiO2/borax hydrogels without ChsNF had moderate Young’s modulus but high elongation. ChsNF/ac-SiO2/cPVA/borax hydrogels using both ChsNF and ac-SiO2 as reinforcement agents exhibited high extensibility (930%) and high Young′s modulus beyond 1 MPa at a high ac-SiO2 concentration. The network was formed by multiple crosslinking such as the complexation between borate and cPVA, the ionic complexation between ac-SiO2 and cPVA, and the hydrogen bond between ChsNF and cPVA. Structural analysis by synchrotron small-angle X-ray scattering revealed that the nanostructural inhomogeneity in ChsNF/ac-SiO2/cPVA/borax hydrogel was suppressed compared to those of the ChsNF/cPVA/borax and cPVA/ac-SiO2/borax hydrogels.

Hydrogels present a great number of advantages, such as their swelling capacity or their capability to mimic tissues, which make them very interesting biomaterials. However, one of their main disadvantages is their lack of good mechanical properties, which could limit some of their applications. Several strategies have been carried out to develop hydrogels with enhanced mechanical properties, but many of the suggested synthetic pathways to improve this property are expensive and time consuming. In this work, we studied an easy synthetic path to produce tough hydrogels based on different maleic anhydride copolymers crosslinked with polyethylenglycol. The effect of the comonomers in the mechanical properties has been studied, their excellent mechanical properties, good swelling behavior and thermal stability being remarkable. In addition, in order to evaluate their possible applications as scaffolds or in wound healing applications, microsized fibers have been fabricated by electrospinning.

Novel tough hydrogel materials are required for 3D-printing applications. Here, a series of thermoplastic polyurethanes (TPUs) based on poly(ɛ-caprolactone)-b-poly(ethylene glycol)-b-poly(ɛ-caprolactone) (PCL-b-PEG-b-PCL) triblock copolymers and hexamethylene diisocyanate (HDI) were developed with PEG contents varying between 30 and 70 mol%. These showed excellent mechanical properties not only when dry, but also when hydrated: TPUs prepared from PCL-b-PEG-b-PCL with PEG of Mn 6 kg/mol (PCL7-PEG6-PCL7) took up 122 wt.% upon hydration and had an E-modulus of 52 ± 10 MPa, a tensile strength of 17 ± 2 MPa, and a strain at break of 1553 ± 155% in the hydrated state. They had a fracture energy of 17976 ± 3011 N/mm2 and a high tearing energy of 72 kJ/m2. TPUs prepared using PEG with Mn of 10 kg/mol (PCL5-PEG10-PCL5) took up 534% water and were more flexible. When wet, they had an E-modulus of 7 ± 2 MPa, a tensile strength of 4 ± 1 MPa, and a strain at break of 147 ± 41%. These hydrogels had a fracture energy of 513 ± 267 N/mm2 and a tearing energy of 16 kJ/m2. The latter TPU was first extruded into filaments and then processed into designed porous hydrogel structures by 3D-printing. These hydrogels can be used in 3D printing of tissue engineering scaffolds with high fracture toughness.

Artificial shape-morphing hydrogels are emerging toward various applications, spanning from electronic skins to healthcare. However, the low freezing and drying tolerance of hydrogels hinder their practical applications in challenging environments, such as subzero temperatures and arid conditions. Herein, we report on a shape-morphing system of tough organohydrogels enabled by the spatially encoded rigid structures and its applications in conformal packaging of "island-bridge" stretchable electronics. To validate this method, programmable shape morphing of Fe (III) ion-stiffened Ca-alginate/polyacrylamide (PAAm) tough organohydrogels down to -50 °C, with long-term preservation of their 3D shapes at arid or even vacuum conditions, was successfully demonstrated, respectively. To further illustrate the potency of this approach, the as-made organohydrogels were employed as a material for the conformal packaging of non-stretchable rigid electronic components and highly stretchable liquid metal (galinstan) conductors, forming a so-called "island-bridge" stretchable circuit. The conformal packaging well addresses the mechanical mismatch between components with different elastic moduli. As such, the as-made stretchable shape-morphing device exhibits a remarkably high mechanical durability that can withstand strains as high as 1000% and possesses long-term stability required for applications under challenging conditions.

In the field of actuator materials, hydrogels that undergo large volume changes in response to external stimuli have been developed for a variety of promising applications. However, most conventional hydrogels are brittle and therefore rupture when they are stretched to moderate strains (~50%). Thus, gels to be used for actuators still require improved mechanical properties and actuation performance. In this study, we synthesized a tough and thermo-sensitive hydrogel with a large actuation force by forming interpenetrating networks between covalently crosslinked poly(N-isopropylacrylamide) and ionically crosslinked alginate. Poly(N-isopropylacrylamide) was used as a thermo-sensitive actuation material, and alginate was found to enhance the mechanical properties of the hydrogels. Due to the enhanced elastic modulus and energy dissipation in the hybrid gel, the toughness was increased by a factor of 60 over that of pure PNIPAAm gel. Further, based on the results showing that the hybrid gel exhibits an actuation force that is seven times higher than that of pure PNIPAAm gel, the hybrid gel is more applicable to real actuators.

We investigated the mechanical and structural properties of composite hydrogels composed of chitosan nanofiber (ChsNF), positively charged alumina-coated silica (ac-SiO 2 ) nanoparticles, carboxylated poly (vinyl alcohol) (cPVA), and borax. ChsNF/cPVA/borax hydrogels without ac-SiO 2 exhibited high Young's modulus but poor elongation, whereas cPVA/ac-SiO 2 /borax hydrogels without ChsNF had moderate Young's modulus but high elongation. ChsNF/ac-SiO 2 /cPVA/borax hydrogels using both ChsNF and ac-SiO 2 as reinforcement agents exhibited high extensibility (930%) and high Young's modulus beyond 1 MPa at a high ac-SiO 2 concentration. The network was formed by multiple crosslinking such as the complexation between borate and cPVA, the ionic complexation between ac-SiO 2 and cPVA, and the hydrogen bond between ChsNF and cPVA. Structural analysis by synchrotron small-angle X-ray scattering revealed that the nanostructural inhomogeneity in ChsNF/ac-SiO 2 /cPVA/borax hydrogel was suppressed compared to those of the ChsNF/cPVA/borax and cPVA/ac-SiO 2 /borax hydrogels.

Novel tough hydrogel materials are required for 3D-printing applications. Here, a series of thermoplastic polyurethanes (TPUs) based on poly(ɛ-caprolactone)- b -poly(ethylene glycol)- b -poly(ɛ-caprolactone) (PCL- b -PEG- b -PCL) triblock copolymers and hexamethylene diisocyanate (HDI) were developed with PEG contents varying between 30 and 70 mol%. These showed excellent mechanical properties not only when dry, but also when hydrated: TPUs prepared from PCL- b -PEG- b -PCL with PEG of Mn 6 kg/mol (PCL₇-PEG₆-PCL₇) took up 122 wt.% upon hydration and had an E-modulus of 52 ± 10 MPa, a tensile strength of 17 ± 2 MPa, and a strain at break of 1553 ± 155% in the hydrated state. They had a fracture energy of 17976 ± 3011 N/mm² and a high tearing energy of 72 kJ/m². TPUs prepared using PEG with Mn of 10 kg/mol (PCL₅-PEG 10 -PCL₅) took up 534% water and were more flexible. When wet, they had an E-modulus of 7 ± 2 MPa, a tensile strength of 4 ± 1 MPa, and a strain at break of 147 ± 41%. These hydrogels had a fracture energy of 513 ± 267 N/mm² and a tearing energy of 16 kJ/m². The latter TPU was first extruded into filaments and then processed into designed porous hydrogel structures by 3D-printing. These hydrogels can be used in 3D printing of tissue engineering scaffolds with high fracture toughness.

A hydrogel is a three-dimensional polymer network with high water content and has been attractive for many biomedical applications due to its excellent biocompatibility. However, classic hydrogels are mechanically weak and unsuitable for most physiological load-bearing situations. Thus, the development of tough hydrogels used in the biomedical field becomes critical. This work reviews various strategies to fabricate tough hydrogels with the introduction of non-covalent bonds and the construction of stretchable polymer networks and interpenetrated networks, such as the so-called double-network hydrogel. Additionally, the design of tough hydrogels for tissue adhesive, tissue engineering, and soft actuators is reviewed.