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Results for “Shear-induced crosslinking”

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Responsive lignin for shape memory applications

Here, we analyze thermally unstable lignin linkages that generate reactive sites and promote crosslinking reactions during thermal annealing at 180 °C. This results in significantly enhanced glass transition temperature (Tg). We use these characteristics of lignin to enhance interfacial reactivity of a lignin-based multiphase polymer synthesized by a dynamic shear process. An approximately 18 °C increase in Tg and more than 230% increase in storage modulus (E') are achieved by thermally annealing the 50 wt% hardwood lignin-nitrile rubber composite for 5 h at 180 °C. Tunable chemical and physical crosslinks within lignin and rubber resulted in shape programmability demonstrating excellent strain recovery of the synthesized renewable materials. The substantial improvement of the elastic work density of the lignin-based elastomers allows a broader applicable stress window for stress/strain sensing. The renewable materials also exhibit a better strain recovery after thermal annealing.

36 MATERIALS SCIENCE↗

Molecular simulation study of role of polymer–particle interactions in the strain-dependent viscoelasticity of elastomers (Payne effect)

The strain-amplitude dependence of viscoelastic behavior of model crosslinked elastomers containing various concentrations of spherical nanoparticles (NPs) was studied by non-equilibrium molecular dynamics simulation. All the filler NPs were in monodispersed state and the interactions between these particles were purely repulsive. The polymer–particle interactions were attractive and their interaction energies were tuned in a broad range. Through the computational study, many important features of the behavior of particle-reinforced elastomers observed in experiments, including the Payne effect, were successfully reproduced. It was shown that the magnitude of the Payne effect was found to depend on the polymer–particle interaction and the filler loading. By examining the microstructures of the simulation systems and their evolution during oscillatory shear, four different mechanisms for the role of the polymer–particle interactions in the Payne effect were revealed that consist of the debonding of polymer chains from NP surfaces, the breakage of polymer-shell-bridged NP network, the rearrangement of the NPs in the network into different layers and the shear-induced yielding of the rigid polymer shell in-between neighboring NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗