Tuning the permeability of regular polymeric networks by the cross-link ratio

S Milster and WK Kim and M Kanduc and J Dzubiella, JOURNAL OF CHEMICAL PHYSICS, 154, 154902 (2021).

DOI: 10.1063/5.0045675

The amount of cross-linking in the design of polymer materials is a key parameter for the modification of numerous physical properties, importantly, the permeability to molecular solutes. We consider networks with a diamond-like architecture and different cross-link ratios, concurring with a wide range of the polymer volume fraction. We particularly focus on the effect and the competition of two independent component-specific solute-polymer interactions, i.e., we distinguish between chain-monomers and cross-linkers, which individually act on the solutes and are altered to cover attractive and repulsive regimes. For this purpose, we employ coarse-grained, Langevin computer simulations to study how the cross-link ratio of polymer networks controls the solute partitioning, diffusion, and permeability. We observe different qualitative behaviors as a function of the cross-link ratio and interaction strengths. The permeability can be tuned ranging over two orders of magnitude relative to the reference bulk permeability. Finally, we provide scaling theories for the partitioning and diffusion that explicitly account for the component-specific interactions as well as the cross-link ratio and the polymer volume fraction. These are in overall good agreement with the simulation results and grant insight into the underlying physics, rationalizing how the cross-link ratio can be exploited to tune the solute permeability of polymeric networks.

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