Lamellae-Parking Garage Structure-Lamellae Transition in Densely Grafted Layers of Amphiphilic Homopolymers: Impact of Polymerization Degree.

By means of computer modeling, the self-organization of densely grafted macromolecules with amphiphilic monomer units as a function of macromolecular polymerization degree and solvent quality was studied and a diagram of state was constructed. The diagram contains fields of disordered distribution of monomer units and of prolonged aggregates, regions of lamellae with small and big domain spacing, and transition region. Within the transition region, the lamellae with different spacing coexist: the lamellae with big domain spacing are on the top of the grafting layer and the lamellae with small domain spacing are close to the grafting surface. The lamellae are connected with each other and form bicontinuous parking garage structure joining all side groups into a single cluster. The domain spacing of lamellae does not depend on the macromolecular length, but the width of the transition region decreases with the decrease of polymerization degree until total vanishing at relatively short macromolecules. The sharp switch between lamellae and bicontinuous structure opens the perspective for practical applications of densely grafted layers with amphiphilic monomer units.