Modeling swelling behavior of thermoresponsive polymer brush with lattice density functional theory.

ABSTRACT

A key problem in designing thermoresponsive polymer brushes on a solid surface is to find a relation between the targeted thermoresponsive properties and controllable conditions. Usually, a temperature-thickness curve showing the heating-induced swelling behavior of polymer brushes is chosen as the relation by either experimental or theoretical investigation. In this work, a lattice density functional theory (LDFT) developed previously is employed to investigate the temperature-thickness curves for five different types of polymer brushes, where the density profiles of polymer brushes calculated by LDFT are compared directly with simulation. It is found that the thermoresponsive behavior of a polymer brush can be characterized by the bulk phase behaviors of its corresponding polymer solution, including UCST, LCST, both UCST and LCST, closed LOOP and hourglass-shaped, which implies that the bulk phase diagram of polymer solutions can help us to find an appropriate polymer brush for a targeted thermoresponsive behavior. As an example, we show that the swelling behavior of a thermoresponsive polymer brush found in the experiment could be predicted by our LDFT results with the bulk phase diagram of real polymer solution only.