Recent progresses in developing tough hydrogels promise the great potential of this class of soft and wet materials as biomaterials, soft robotics, smart actuators and sensors. [1][2][3][4][5][6][7][8][9][10] Any practical application of these hydrogels as smart materials, however, requires a combination of mechanical properties including stiffness, strength, toughness, and self-healing. For instance, along with the high strength and toughness, a cartilage substitute material requires a high stiffness to bear the load, while a blood vessel substitute material requires flexibility.Self-healing not only merits the long term durability of the load-bearing materials, but also gives possibility to reconstruct the material with desired shape from its microgels. While many hydrogels possess some of these requirements, it is a challenge to develop hydrogels satisfying all of these criteria. [2,[11][12][13] In this work, we report a new class of physical hydrogels that possess these multiple functions. These hydrogels are obtained from concentrated solution of oppositely charged polyelectrolytes. After dialysis of their small counter ions, the oppositely charged polyelectrolytes form polyion complexes of a wide strength distribution, which give dynamic crosslinking of an extremely wide life time scale. The strong, long life time bonds serve as permanent cross-linking, imparting elasticity, whereas the weak, short life

Double-network hydrogels (DN gels), despite their high water content, are the strongest and toughest soft and wet materials available. However, in conventional DN gels, which show extraordinarily high mechanical performance comparable to that of industrial rubbers, the fi rst network must be a strong polyelectrolyte and this requirement greatly hinders the widespread application of these gels. A general method involving the use of a "molecular stent" for the synthesis of tough DN gels using any hydrophilic polymer as the fi rst network is reported. This is the fi rst reported method for the synthesis of tough DN gels using various neutral or weak polyelectrolyte hydrogels as the fi rst network. This method helps extend the DN gel concept to various functional polymers and may increase the number of applications of hydrogels in various fi elds.

Based on the molecular stent concept, a series of tough double-network hydrogels (St-DN gels) made from the components of proteoglycan aggregates - chondroitin sulfate proteoglycans (1), chondroitin sulfate (2), and sodium hyaluronate (3) - are successfully developed in combination with a neutral biocompatible polymer. This work demonstrates a promising method to create biopolymer-based tough hydrogels for biomedical applications.

Recently, we have reported that polyampholytes, synthesized from free radical copolymerization of anionic monomer and cationic monomer, form physical hydrogels of high toughness and self-healing. The random distribution of the opposite charges forms ionic bonds of a wide distribution of strength. The strong bonds serve as permanent cross-links, imparting elasticity, whereas the weak bonds serves as reversible sacrificial bonds by breaking and reforming to dissipate energy. In this work, we focus on the rupture behaviors of the polyampholyte physical hydrogel, P(NaSS-co-MPTC), copolymerized from sodium p-styrenesulfonate (NaSS) and 3-(methacryloylamino)propyltrimethylammonium chloride (MPTC). Tensile test and pure shear test were performed at various stretch rates in the viscoelastic responses region of the material. Tensile test showed yielding, strain softening, and strain hardening, revealing the dually cross-linked feature of the gel. Pure shear test showed crack blunting at the notched tip and a large yielding zone with butterfly shaped birefringence pattern ahead of the crack tip. After blunting, crack advanced at steady-state velocity with a constant angle. The conditions for the occurrence of crack blunting and variables governing the crack advancing angle are discussed. We found that even for these highly stretchable samples, significant blunting only occurs when the tensile fracture stress σf is larger than modulus E by a factor of about 2, in consistent with Hui’s theoretical prediction for elastic materials. The crack advancing angle θ was found to be proportional to σy/E over a wide stretch rate range, where σy is the yielding stress. In addition, the fracture energy was correlated to small strain modulus by a power law in the viscoelastic response region. This systematic study will merit revealing the fracture mechanism of tough viscoelastic materials including biological tissues and recently developed tough and highly stretchable hydrogels

Oppositely charged homopolyelectrolytes were found to form strong, tough, and self-healing polyion-complex (PIC) hydrogels, similar to polyampholytes (PA) which have opposite charges randomly distributed on the same polymer chains. The excellent mechanical performances of these two novel hydrogels are the results of dynamic ionic bonds formation between entangled polymer chains. For the PIC system, only interchain bonding occurs, while for the PA system both inter- and intrachain bonding exist. In addition, the ion pairs are expected to form stronger bonding in the PIC system than those in the PA system. In this work, we performed a comparative study of PIC hydrogels with the PA hydrogels. The PIC hydrogels are synthesized by sequential homopolymerization of cationic and anionic monomers at varied formulation, and their swelling and mechanical properties are systematically studied in comparison to the PA hydrogels that were synthesized from random copolymerization of anionic monomers and cationic monomers of the similar formulation. Different from the PA system which only forms tough hydrogels around zero net charge composition without chemical cross-linking, the PIC system forms tough physical hydrogels even at weakly offbalanced charge composition. At the charge-balanced composition, the low entanglement concentration of homocharged polyelectrolyte chains leads to tough PIC hydrogels formation at much lower concentrations than that of PA hydrogels. As a result, the PIC hydrogels are much tougher than the PA hydrogels prepared at the same monomer composition. In similar to PA hydrogels, the PIC hydrogels also exhibit broad dynamic mechanical spectra, indicating the formation of ion complexes with widely ranged bond strength. The PIC hydrogels have strong viscoelasticity in comparison with PA hydrogels. However, the two systems show the similar activation energies of the dynamic mechanical spectra. The SEM microstructural observation shows that the PIC hydrogels have segregated structure while PA hydrogels are more homogeneous