Microphase segregation in bridging polymeric brushes: Regular and singular phase diagrams

A mean‐field theory of deformation‐induced microphase segregation in bridging polymeric brushes anchored to two parallel surfaces is presented. Models with isotropic and orientation‐dependent liquid‐crystalline interactions between segments are considered. For the first model, the problem is similar to that of classical liquid‐vapor phase separation, and the phase diagram in the P ‐ T plane has a line of first‐order transitions terminating at the critical point. We show that the critical pressure is negative implying that a free brush tethered only to one surface always exists at supercritical conditions and hence cannot undergo the collapse phase transition. In the second model, the free energy density depends on two coupled order parameters, one related to segment density and the other to the orientational order, which strongly modifies the phase behavior. Depending on the grafting density the system is described by a phase diagram of a regular or a singular type. In the regular phase diagram the first‐order transition line terminates at the critical point. In a singular diagram, the first‐order transition line extends to infinity; the critical point corresponds to infinite pressure so that the system undergoes the phase transition at arbitrary external pressures. Regular phase diagrams correspond to dense grafting, and singular ones to sparse grafting. The change from a regular phase behavior to another occurs at a certain marginal value of the grafting density. On approaching this value the critical point on the regular diagram moves to infinity, logarithmically with the deviation from the critical grafting density. We relate the analytical properties of the free energy density as a function of the segment concentration to the type of the phase diagram and the shape of the coexistence curve in the temperature‐ concentration plane.