Surfactant-Induced Patterns in Polymer Brushes.

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The properties of surfaces with grafted macromolecules are determined by a fine structure of the macromolecular layer, whereas the mixtures of macromolecules with surfactants are very rich in structure types. Using the scaling mean-field theory, we consider the self-assembly in polymer brushes into various patterns induced by interactions with low-molecular surfactants. The interaction energies of the parts of a surfactant molecule with the polymer units are assumed to be greatly different. With increasing the grafting density, the formation of lamellae perpendicular to the grafting plane, a continuous layer with oblong or round pores, or a homogeneous brush is predicted. The driving force of the pattern formation is a gain in the interaction energy of surfactant molecules oriented at the lateral surfaces of lamellae or pores. The process of pore formation in a homogeneous brush caused by a temperature change at definite grafting densities is described as the first-order phase transition. It is accompanied by a stepwise extension of the brush and by orientational ordering of surfactant molecules. The transitions between the other patterns are of the second order. The thickness of lamellae and the distance between pores are approximately twice the surfactant molecule size except for the extremely high grafting densities. The diagrams of brush patterns are presented and discussed.