Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings

Experimental validation of the predicted melt phase behavior of A/B mixed brush on planar substrate is presented using poly(methyl methacrylate) (A)/ polystyrene (B) (PMMA/PS) with equal number of A/B chains as an example. Well-defined mixed A/B brushes are synthesized using a single component inimer coating to achieve high grafting density (0.9 chains/nm²), uniformity of grafting sites, and predictable chain length. The inimer coating is a copolymer of nitroxide-mediated polymerization (NMP) inimer, atom transfer radical polymerization (ATRP) inimer, styrene, and glycidyl methacrylate (GMA). Cross-linking of the film provides the required stability to probe the melt morphology. Our studies show that even with equal grafting density of the A and B the morphology can be modulated by varying the length of B chains while keeping that of A fixed. We show the transition of self-assembled structures from disorder to cylinder to ripple phase at sub-30 nm length scale on a planar surface by thermal annealing of mixed brushes. These results are supported by a phase diagram established through Monte Carlo simulation using a coarse-grained particle-based model.