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This paper studies a polymer network in which crosslinks are degradable but polymer chains are not. We show that entanglements markedly enhance the mechanical properties of the polymer network before degradation and slow down degradation. We synthesize polyacrylamide hydrogels with disulfide crosslinks. In a precursor of a low water-to-monomer molar ratio and low crosslinker-to-monomer molar ratio, the monomers are crowded and the resulting polymer chains are long, so that the entanglements greatly outnumber crosslinks. The as-synthesized hydrogels are submerged in pure water to swell to equilibrium. We show that entanglements enhance the swell resistance of the hydrogel, as well as stiffen and toughen the hydrogel. We further show that entanglements slow down degradation when the hydrogel is submerged in an aqueous solution of cysteine. This work demonstrates that entanglements substantially expand the properties space of degradable polymers. 

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). Wanget 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. Kimet 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 

Degradable polymers are under intense development for sustainability and healthcare. Evidence has accumulated that the chemical reaction that decomposes a polymer an also grow a crack. Even under a small load, the crack speed can be orders of magnitude higher than the overall rate of degradation, leading to premature failure. Here, we demonstrate that a crack slows down markedly in a composite of two degradable materials. In a homogeneous degradable material, the stress concentrates at the crack tip, so that a relatively small applied stretch induces a high stress and a high rate of reaction. The fracture behavior of a composite that consists of two degradable materials, a stiff material for the fibers and a compliant material for the matrix, with strong adhesion between both, is different: The soft matrix blunts the crack and distributes the stresses at the crack tip over a long length of the fibers. The same rate of reaction requires a larger applied stretch. This stress de-concentration retards crack growth in the composite. We demonstrate this concept using a composite made of stiff polydimethylsiloxane (PDMS) fibers in a soft PDMS matrix. In the presence of water molecules in the environment, siloxane bonds in the PDMS hydrolyze, causing hydrolytic crack growth. We show that a hydrolytic crack grows much more slowly in a PDMS composite than in homogeneous PDMS, and may even arrest in the composite. It is hoped that this concept will contribute to the development of degradable materials that resist premature failure. 

Biological tissues, such as heart valves and vocal cords, function through complex shapes and high fatigue resistance. Achieving both attributes with synthetic materials is hitherto an unmet challenge. Here we meet this challenge with hydrogels of heterogeneous structures. We fabricate a three-dimensional hydrogel skeleton by stereolithography and a hydrogel matrix by cast. Both the skeleton and matrix are elastic and stretchable, but the skeleton is much stiffer than the matrix, and their polymer networks entangle topologically. When such a hydrogel is stretched, the compliance of the matrix deconcentrates stress in the skeleton and amplifies fatigue resistance. We fabricate a homogeneous hydrogel and a heterogeneous hydrogel, each in the shape of a human heart valve. Subject to cyclic pressure, the former fractures in  560 cycles but the latter is intact after 50,000 cycles. Soft materials of complex shapes and high fatigue resistance open broad opportunities for applications.