Computer simulation study on the swelling of a model polymer network by a chainlike solvent

A molecular-dynamics-particle-transfer method was used to study the swelling of a model polymer network by a short chain solvent. The solvent chains were transferred depending on the difference between the solvent chemical potentials in the coupled simulation boxes, containing pure solvent and gel, respectively. The chemical potentials were computed via the Rosenbluth sampling method. The simulated swelling ratio of the network under subcritical and supercritical conditions is compared with the prediction of a modified Flory-Huggins theory. In addition, the chains exhibit markedly different structural and dynamic properties in the corresponding phases due to the constraint imposed by the network, which are discussed in detail.