Direct Characterization of In-Plane Phase Separation in Polystyrene Brush/Cyclohexane System

The phase behavior of polystyrene (PS) brushes in cyclohexane (CHX) was investigated, for the first time, by environmental atomic force microscopy as a function of the graft density and temperature. The polystyrene brushes of three different graft densities exhibited island-, bicontinuous-, and hole-shape microdomains in the direction parallel to the substrate. The size of such "in-plane" microdomains is close to the end-to-end distance of PS brush chain due to the anchoring of one of the chain ends of PS brushes to the substrate. The microdomain structure disappeared as the temperature increased, and new structure with same morphological features reappeared by lowering temperature. This reversible temperature response corresponds to the in-plane phase separation of the PS brush/CHX system. The UCST type binodal line shifted toward slightly lower temperature in the PS brush/CHX system compared to that of the corresponding nongrafted polymer solution, i.e., PS/CHX system, in excellent agreement with our previous Monte Carlo simulation study.