Inspired by the ability of the sea cucumber to (reversibly) increase the stiffness of its dermis upon exposure to a stimulus, we herein report a stimuli-responsive nanocomposite that can reversibly increase its stiffness upon exposure to warm water. Nanocomposites composed of cellulose nanocrystals (CNCs) that are grafted with a lower critical solution temperature (LCST) polymer embedded within a poly(vinyl acetate) (PVAc) matrix show a dramatic increase in modulus, for example, from 1 to 350 MPa upon exposure to warm water, the hypothesis being that grafting the polymers from the CNCs disrupts the interactions between the nanofibers and minimizes the mechanical reinforcement of the film. However, exposure to water above the LCST leads to the collapse of the polymer chains and subsequent stiffening of the nanocomposite as a result of the enhanced CNC interactions. Backing up this hypothesis are energy conserving dissipative particle dynamics (EDPD) simulations which show that the attractive interactions between CNCs are switched on upon the temperature-induced collapse of the grafted polymer chains, resulting in the formation of a percolating reinforcing network.

Core-Modified Dissipative Particle Dynamics (CM-DPD) with a modified depletion potential and full hydrodynamics description is used to study non-equilibrium properties of colloidal gels with short range attraction potentials at an intermediate volume fraction (ϕ = 0.2) under start-up shear deformation. Full structural and rheological analysis using the stress fabric tensor complemented by bond number and bond distribution evolution under flow reveals that similarly to dilute colloidal gels, flow-induced anisotropy and strain-induced stretching of bonds are present during the first yielding transition. Unlike in low volume fraction depletion gels however, a small fraction of bond dissociation is required to facilitate bond rotation at intermediate volume fractions. The strain at which structural stretching and anisotropy in bond distribution emerge coincides with the first maximum in the shear stress (first yielding transition). At higher strains, depending on flow strength, a second peak in stress signal appears which is attributed to the compaction and melting of clusters. In this work, for the first time we provide evidence that multibody hydrodynamic interactions are essential to predict the correct dynamics of depletion gels under flow, namely two-step yielding process.