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Blending of a block copolymer with a large amount of homopolymer can result in the formation of a micellar phase consisting of spherical domains of the aggregating copolymer block. We show that transitions in micelle shape and mesophase type($ can occur by increasing the molecular weight of the homopolymer matrix, by increasing the aggregating block molecular weight, or by increasing the volume fraction of the copolymer. The new morphologies include cylindrical micelles, vesicles, and lamellar type structures. These transitions can be understood in terms of the general rule of domain morphology as a function of relative microphase volume fractions put forth by Molaul for neat block copolymers and later extended by Sadron and Gallot2 to the case of block copolymers in preferential solvents.

We report the observation of the ordered bicontinuous double diamond (OBDD) structure in binary blends of poly(styrene-isoprene) diblock copolymer and homopolystyrene. The overall polystyrene volume fraction range is 64 - 67 PSvol% for the OBDD structure in binary blends of a lamellar diblock (SI 27/22) and a homopolymer (14.0 hPS). This composition range is approximately within the polystyrene volume fraction range established for pure diblock copolymers in the strong segregation regime having the OBDD structure. Ordered lamellae are observed at approximately 65 PSvol% when the homopolystyrene molecular weight is greater than the molecular weight of the polystyrene block of the copolymer. This observation is discussed in terms of the decreased degree of mixing between the homopolymer and the corresponding block and the resultant effect on the interfacial curvature.

A wide range of morphologies and thereby physical properties can be achieved in block copolymer/homopolymer blends by varying the copolymer composition, copolymer concentration and molecular weights. Recently we investigated micelle shape transitions in diblock copolymer with homopolymer blends at low copolymer concentration. In this paper we study the microstructure over a wider concentration range for a polystyrene-polybutadiene (PS/PB) diblock copolymer of molecular weight 20.5 × 103/20.5 × 103 blended with 17.2 × 103 molecular weight homopolystyrene (hPS).Figure 1 shows schematically a possible spectrum of microdomain structures dependent on the copolymer concentration of a lamellar PS/PB and hPS. Below the critical micelle concentration (CMC) the block copolymer is molecularly dispersed in the homopolymer exhibiting a homogeneous phase. As diblock concentration increases the minority (i.e. PB) forms spherical and/or cylindrical micelles randomly dispersed in the hPS. Further increases in diblock concentration induces long range ordering of various microdomains. In addition three biphasic regions are proposed in which two phases coexist: isotropic cylinders with ordered cylinders, ordered cylinders with ordered bicontinuous double diamond (OBDD), and OBDD with swollen lamellae.