Structural and mechanical properties of advanced polymer gels with rigid side-chains using coarse-grained molecular dynamics

Computational modeling was utilized to design complex polymer networks and gels which display enhanced and tunable mechanical properties. Our approach focuses on overcoming traditional design limitations often encountered in the formulation of simple, single polymer networks. Here, we use a coarse-grained model to study an end-linked flexible polymer network diluted with branched polymer solvent chains, where the latter chains are composed of rigid side-chains or spikes attached to a flexible backbone. In order to reduce the entropy penalty of the flexible polymer chains these rigid spikes will aggregate into clusters, but the extent of aggregation was shown to depend on the size and distribution of the rigid side-chains. When the spikes are short, we observe a lower degree of aggregation, while long spikes will aggregate to form an additional secondary network. As a result, the tensile relaxation modulus of the latter system is considerably greater than the modulus of conventional gels and is approximately constant, forming an equilibrium zone for a broad range of time. In this system, the attached long spikes create a continuous phase that contributes to a simultaneous increase in tensile stress, relaxation modulus and fracture resistance. Elastic properties and deformation mechanisms of these branched polymers were also studied under tensile deformation at various strain rates. Through this study we show that the architecture of this branched polymer can be optimized and thus the elastic properties of these advanced polymer networks can be tuned for specific applications. (C) 2014 Elsevier Ltd. All rights reserved.