Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers
Andreas Mueller, Aaron P. Lindsay, Ashish Jayaraman, Steven Weigand, Timothy P. Lodge, Mahesh K. Mahanthappa, Frank S. Bates
Abstract
We report the sensitivity of diblock copolymer particle packing symmetry to the ratio α = Nhomo/Ncore, where Nhomo and Ncore are the respective homopolymer and core-block degrees of polymerization. Three poly(ethylene oxide)-b-poly(2-ethylhexyl acrylate) (OA) diblock copolymers with O volume fractions fO = 0.15, 0.16, and 0.20 were blended with O homopolymers characterized by α = 0.23, 0.42, 0.80, and 1.00. Small-angle X-ray scattering revealed rich phase behavior as a function of α, the overall particle core volume fraction (fcore), and temperature. BCC, HCP, and Frank–Kasper σ, C14, C15, and dodecagonal quasicrystal phases, were all identified. “Dry-brush” homopolymer distribution (α = 0.80 and 1.00) favor C14 and C15 phases with macrophase separation at high homopolymer loadings. “Wet-brush” homopolymer distributions in the particle cores (α = 0.42) lead to narrow σ or C15 windows and cylinders at greater O concentrations. Solvent-like swelling (α = 0.23) favors widespread σ phase formation.