Fracture, fatigue, and friction of polymers in which entanglements greatly outnumber cross-links

Abstract

Description Longer and stronger; stiff but not brittle Hydrogels are highly water-swollen, cross-linked polymers. Although they can be highly deformed, they tend to be weak, and methods to strengthen or toughen them tend to reduce stretchability. Two papers now report strategies to create tough but deformable hydrogels (see the Perspective by Bosnjak and Silberstein). Wang et al. introduced a toughening mechanism by storing releasable extra chain length in the stiff part of a double-network hydrogel. A high applied force triggered the opening of cycling strands that were only activated at high chain extension. Kim et al. synthesized acrylamide gels in which dense entanglements could be achieved by using unusually low amounts of water, cross-linker, and initiator during the synthesis. This approach improves the mechanical strength in solid form while also improving the wear resistance once swollen as a hydrogel. —MSL Gels and elastomers with sparse cross-links and dense entanglements have improved mechanical properties without embrittlement. In gels and elastomers, the role of entanglements on deformation has been studied, but their effects on fracture, fatigue, and friction are less well understood. In this study, we synthesized polymers in which entanglements greatly outnumber cross-links. The dense entanglements enable transmission of tension in a polymer chain along its length and to many other chains. The sparse cross-links prevent the polymer chains from disentangling. These polymers have high toughness, strength, and fatigue resistance. After submersion in water, the polymers swell to equilibrium, and the resulting hydrogels have low hysteresis, low friction, and high wear resistance.