Abstract
We predict the thermodynamic and structural behavior of solutions of self-assembling chains, cross-links and end-cap molecules. We find that at the mean-field level, the entropy of self-assembled junctions induces an effective attraction that can result in equilibrium between a sol phase and a connected network. A connected network can also be formed in a non-thermodynamic transition upon increase of the monomer or cross-link density, or with decreasing temperature. For rigid rods, at low temperatures, we predict a transition from an isotropic network to anisotropic bundles of rods linked by cross-links, that is triggered by the interplay between the configurational entropy of the cross-link distribution, and the rotational and translational entropy of the rods.
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