Theoretical analysis of the elastic free energy contributions to polymer brushes in poor solvent: A refined mean-field theory

CW Li and D Romeis and M Koch and H Merlitz and JU Sommer, JOURNAL OF CHEMICAL PHYSICS, 157, 104902 (2022).

DOI: 10.1063/5.0103351

We consider polymer brushes in poor solvent that are grafted onto planar substrates and onto the internal and external surfaces of a cylinder using molecular dynamics simulation, self-consistent field (SCF), and mean-field theory. We derive a unified expression for the mean field free energy for the three geometrical classes. While for low grafting densities, the effect of chain elasticity can be neglected in poor solvent conditions, it becomes relevant at higher grafting densities and, in particular, for concave geometries. Based on the analysis of the end monomer distribution, we introduce an analytical term that describes the elasticity as a function of grafting density. The accuracy of the model is validated with molecular dynamics simulations as well as SCF computations and shown to yield precise values for the layer thickness over a wide range of system parameters. We further apply this model to analyze the gating behavior of switchable brushes inside nanochannels. Published under an exclusive license by AIP Publishing.

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