TY - JOUR
T1 - Effect of dilution on a block copolymer in the complex phase window
AU - Hanley, Kenneth J.
AU - Lodge, Timothy P.
PY - 1998/12
Y1 - 1998/12
N2 - 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., χOOT ∼ φ-1, but the ODT is found to follow a stronger concentration dependence, i.e., χODT ∼ 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.
AB - 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., χOOT ∼ φ-1, but the ODT is found to follow a stronger concentration dependence, i.e., χODT ∼ 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.
KW - Block copolymer
KW - Gyroid
KW - Neutral solvent
KW - Order-disorder transition
KW - Order-order transition
KW - Selective solvent
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U2 - 10.1002/(SICI)1099-0488(199812)36:17<3101::AID-POLB10>3.0.CO;2-X
DO - 10.1002/(SICI)1099-0488(199812)36:17<3101::AID-POLB10>3.0.CO;2-X
M3 - Article
AN - SCOPUS:0032300239
SN - 0887-6266
VL - 36
SP - 3101
EP - 3113
JO - Journal of Polymer Science, Part B: Polymer Physics
JF - Journal of Polymer Science, Part B: Polymer Physics
IS - 17
ER -