Phase diagram of polymer blends containing block copolymers

The phase transition and phase separation behavior occurring in mixtures containing an A–B block copolymer and an A homopolymer is discussed. With a pure block copolymer an order‐disorder transition can be induced by raising the temperature, whereby the ordered lattice of segregated microdomains becomes unstable and gives way to a homogeneous liquid structure. Small amounts of a homopolymer added to a block copolymer can be accommodated in the microdomains consisting of the same type of monomeric units, up to a solubility limit that depends on the relative lengths of the homopolymer and the copolymer block and on the temperature. The order‐disorder transition temperature of the block copolymer is also affected by the added homopolymer. At the other extreme of concentration, spherical micelles of block copolymer are formed when a small amount of the copolymer is added in the bulk homopolymer, and the critical micelle concentration again depends on the relative lengths of the molecules and blocks involved and on the temperature. Measurements were made with light scattering and small‐angle X‐ray scattering techniques to determine the phase behavior of mixtures containing a styrene‐butadiene block copolymer and either a polystyrene or a polybutadiene. The resulting phase diagram exhibits a fascinating complexity. Comparison with recent theories treating these phenomena shows that a good agreement is generally obtained on a qualitative or semi‐quantitative level, but a quantitative agreement is often not attained.