Heyi Liang

Mimicking biological stress–strain behaviour with synthetic elastomers

Despite the versatility of synthetic chemistry, certain combinations of mechanical softness, strength, and toughness can be difficult to achieve in a single material. These combinations are, however, commonplace in biological tissues, and are therefore needed for applications such as medical implants, tissue engineering, soft robotics, and wearable electronics. Present materials synthesis strategies are predominantly Edisonian, involving the empirical mixing of assorted monomers, crosslinking schemes, and occluded swelling agents, but this approach yields limited property control. Here we present a general strategy for mimicking the mechanical behaviour of biological materials by precisely encoding their stress–strain curves in solvent-free brush- and comb-like polymer networks (elastomers). The code consists of three independent architectural parameters—network strand length, side-chain length and grafting density. Using prototypical poly(dimethylsiloxane) elastomers, we illustrate how this parametric triplet enables the replication of the strain-stiffening characteristics of jellyfish, lung, and arterial tissues.

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration

Active camouflage from a polymer Human skin is soft and compliant, but it can quickly become stiff when deformed to prevent injury. Chameleon skin can change color when the animal goes from a relaxed to an excited state. Although these properties can be captured individually in synthetic materials, the combination of different dynamic responses can be hard to control. Vatankhah-Varnosfaderani et al. created triblock copolymers of the ABA variety, where the A blocks have a linear structure and the B blocks are like bottlebrushes. When strained, these polymers stiffened like human skin and changed color, thus giving the materials a range of adaptive properties. Science, this issue p. 1509 Triblock copolymers show strain stiffening and color responses in a material that could be used for adaptive camouflage. Active camouflage is widely recognized as a soft-tissue feature, and yet the ability to integrate adaptive coloration and tissuelike mechanical properties into synthetic materials remains elusive. We provide a solution to this problem by uniting these functions in moldable elastomers through the self-assembly of linear-bottlebrush-linear triblock copolymers. Microphase separation of the architecturally distinct blocks results in physically cross-linked networks that display vibrant color, extreme softness, and intense strain stiffening on par with that of skin tissue. Each of these functional properties is regulated by the structure of one macromolecule, without the need for chemical cross-linking or additives. These materials remain stable under conditions characteristic of internal bodily environments and under ambient conditions, neither swelling in bodily fluids nor drying when exposed to air.

Molecular Dynamics Simulations of Surface and Interfacial Tension of Graft Polymer Melts

Understanding the surface properties of polymer melts is crucial for designing new polymeric coatings, adhesives, and composites. Here, we study the effect of molecular architecture on surface and interfacial tension of melts of graft and linear polymers by molecular dynamics simulations. In particular, we elucidate the effect of the degree of polymerization of the side chains nsc and their grafting density 1/ ng on the surface tension of the graft polymer/vacuum interface, γG, and the interfacial tension of the interface between graft and linear polymer melts, γGL. For the case of the graft polymer/vacuum interface, our simulations confirm that the surface tension is a linear function of the fraction of the backbone ends fbe and side chain ends fse, γG = γ∞ - γbe fbe - Δγ fse, where γ∞ is the surface tension of the system of graft polymers with infinite molecular weight and γbe and Δγ are surface tension contributions from backbone ends and difference between contributions coming from the side chain ends and grafting points, respectively. This dependence of the surface tension highlights the entropic origin of the surface tension corrections associated with the redistribution of the grafting points and ends at the interface. However, the interfacial tension of the interface between graft and linear polymer melts does not show any significant dependence on the molecular structure of the graft polymers, thus pointing out the dominance of enthalpic contribution to the interfacial tension.