Mesoscale simulation of semiflexible chains. II. Evolution dynamics and stability of fiber bundle networks

TL;DR

This paper uses mesoscale simulations to study the formation, evolution, and stability of fiber bundle networks formed by semiflexible chains, revealing mechanisms of coarsening, phase separation, and the effects of surface energy.

Contribution

It introduces a mesoscale simulation model for fiber network formation, analyzing how surface energy influences network stability and coarsening in semiflexible chains.

Findings

Networks form when surface energy exceeds a critical value.

Coarsening halts at the persistence length of fibers.

Crystallization of particles leads to micro-phase separation.

Abstract

Network formation of associative semiflexible fibers and mixtures of fibers and colloidal particles is simulated for the Johnson-Kendall-Roberts (JKR) model of elastic contacts, and a phase diagram in terms of particle elasticity and surface energy is presented. When fibers self-assemble they form a network for sufficiently large fiber-solvent surface energy. If the surface energy is above the value where single particles crystallize the adhesion forces drive diffusion-limited aggregation. Two mechanisms contribute to coarsening: non-associated chains joining existing bundles, and fiber bundles merging. Coarsening stops when the length of the network connections is roughly the persistence length, independent of surface energy. If the surface energy is below the value where single particles crystallize, a network can still be formed but at a much slower (reaction limited) rate. Loose (liquid-like) assemblies between chains form when they happen to run more-or-less parallel. These assemblies grow by diffusion and aggregation and form a loose network, which sets in micro-phase separation, i.e. syneresis. Only when the clusters crystallize, the coarsening process stops. In this case the length of the network connections is larger than the persistence length of a single chain, and depends on the value of the surface energy. All networks of semiflexible homopolymers in this study show syneresis. Mixtures of fibers and colloid particles also form fiber bundle networks, but by choosing the colloid volume fraction sufficiently low, swelling gels are obtained. Applications of this model are in biological systems where fibers self-assemble into cell walls and bone tissue.