An integrated simulation and statistical technique for investigating the effect of interpenetration polymer brushes in a good solvent

This study presents a novel approach for analyzing the interaction between two parallel surfaces grafted with polymer brushes in a good solvent. In the proposed approach, MD simulations are performed to establish the mean brush height and the standard deviation of the brush height distribution for a given value of the surface separation. The corresponding probability density function (PDF) of the brush height is then determined both with and without the assumption of a brush interpenetration effect, respectively, and a statistical technique is applied to compute the corresponding interaction free energy per unit area of the grafted substrates. Finally, the Derjaguin approximation is employed to determine the corresponding value of the interaction force between the two surfaces. The results obtained for the interaction free energy and interaction force are compared with those derived using the Alexander and de Gennes (AdG) model and the Milner, Witten and Cates (MWC) model, respectively. The value of the normalized interaction free energy computed using the present method is higher than that obtained from the AdG and MWC models at larger surface separations when the brush interpenetration effect is ignored. However, the results obtained by the current method for the interaction force are found to be in better agreement with the experimental data than those obtained using the AdG or MWC models. The enhanced performance of the proposed method is attributed primarily to the use of an adaptive non-Gaussian PDF of the brush height to model the effects of brush interpenetration and fluctuations in the brush conformation at different distances from the grafting plane.