Effect of dilution on a block copolymer in the complex phase window

The phase behavior of a styrene–isoprene (SI) diblock copolymer, with block molecular weights of 1.1 × 10⁴ and 2.1 × 10⁴ g/mol, respectively, is examined in the neutral solvent bis(2-ethylhexyl) phthalate (DOP) and the styrene-selective solvent di-n-butyl phthalate (DBP). DBP is a good solvent for PS, but is near a theta solvent for PI at approximately 90°C. Small-angle X-ray scattering (SAXS), rheology, and static birefringence are used to locate and identify order–order (OOT) and order–disorder transitions (ODT); all three techniques gave consistent results. The neat polymer adopts the gyroid (G) phase at low temperatures, with an OOT to hexagonally-packed cylinders (C) at 185°C, and the ODT at 238°C. Upon dilution with the neutral solvent DOP, the C window is diminished, until for a polymer concentration ϕ = 0.65, a direct G to disorder (D) ODT is observed. These results reflect increased stability of the disordered state, based on the different concentration scalings of the interaction parameter, χ, at the OOT and ODT. The OOT follows the dilution approximation, i.e., χ_OOT ∼ ϕ⁻¹, but the ODT is found to follow a stronger concentration dependence, i.e., χ_ODT ∼ ϕ^−1.4, similar to the scaling of ϕ^−1.6 found previously for lamellar SI diblocks in toluene and DOP. Addition of the selective solvent DBP produces dramatic changes in the phase behavior relative to DOP and the melt state; these include transitions to lamellar (L) and perforated layer (PL) structures. The observed phase sequences can be understood in terms of trajectories across the SI melt phase map (temperature vs. composition): addition of a neutral solvent or increasing temperature corresponds to a “vertical” trajectory, whereas adding a selective solvent amounts to a “horizontal” trajectory. When the solvent selectivity depends on temperature, as it does for the SI/DBP system, increasing temperature results in a diagonal trajectory. For both neutral and selective solvents the domain spacing, d*, scales with ϕ and χ as anticipated by self-consistent mean-field theory. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3101–3113, 1998