Journal of Chemical Physics, Vol.109, No.10, 4108-4118, 1998
Liquid-crystalline behavior of rod-coil diblock copolymers
The exact mean-field phase behavior of the Semenov-Vasilenko model for rod-coil diblock copolymers is studied by applying self-consistent field techniques. The behavior depends on three quantities : the rod/coil immiscibility chi N, the coil volume fraction f, and the ratio nu of the characteristic coil to rod dimensions. When chi N less than or similar to 5, the rods and coils mix producing a nematic phase, and at larger chi N, they microphase separate forming a lamellar phase. The nonlamellar phases expected at f greater than or similar to 0.7 are not treated here. The lamellar phase is typically a smectic-C structure with monolayers of tilted rods. A thorough understanding of the model is achieved by closely examining segment distributions and various contributions to the free energy. The tilt angle theta is generally controlled by a competition between rod/coil interfacial tension and stretching of the coils. Lowering f reduces the latter contribution, causing theta --> 0 and producing a continuous transition to a smectic-A structure. Beyond that, there is a tendency to form structures with the rods arranged in bilayers, but this is strongly suppressed by a large steric penalty. We suggest that small amounts of solvent can greatly alleviate this penalty, and therefore could significantly affect some aspects of the phase behavior.