Adaptive structure of gels and microgels with sliding cross-links: enhanced softness, stretchability and permeability

Abstract

We propose an experimentally-inspired model of gels and microgels with sliding cross-links, and use this model to study the mechanical and structural properties with molecular dynamics simulations. In the model, the gels and microgels are made of linear polymer chains with threaded rings, which are capable of sliding along the chains, and bulky end-groups keeping the rings threaded (thus mimicking polyrotaxanes); the chains are covalently linked to each other not through the backbones but through the rings. Both gels and microgels are shown to be much softer in the regime of intermediate and large deformations and also much more stretchable than the topologically equivalent chemical counterparts. The physical reason for that is the mobility of the cross-links which leads to the formation of long, longitudinally oriented “subchains” between cross-linked rings upon uniaxial deformation. The microgels are tested for adsorption on a solid flat surface and for interaction with colloidal particles of different sizes. We demonstrate that the sliding microgel is subjected to stronger flattening on the surface than the chemical one. Enforced penetration of solid particles into the sliding microgel without breaking of covalent bonds is predicted even if the size of the particles is comparable to or larger than the mesh size of the chemical microgel and smaller than the size of polyrotaxane. This penetration is accompanied by the disappearance of the cavity: the microgel is characterized by adaptive porosity tunable to the guest-object.