Phase Behavior of Gradient Copolymers

A multiblock model is developed for the study of the phase behavior of gradient copolymers. The model is able to describe gradient copolymer chains with arbitrary composition profiles. The validity of the multiblock model of gradient copolymers is established by good agreement between RPA (random phase approximation) results for a continuous composition distribution and a multiblock model. The phase behavior of gradient copolymers is examined using self-consistent mean-field theory (SCMFT) for multiblock copolymers. Phase diagrams of gradient copolymer melts with different gradient profiles are constructed by solving the SCMFT equations. It is discovered that the phase behavior depends sensitively on the gradient profiles. In particular, new triple points are observed, and the stability region of phases with curved interfaces shrinks as the gradient profile becomes smooth. For linear gradient copolymers, the lamellar phase is predicted to be the only stable ordered phase.