Self‐assembled structures in polystyrene‐block‐polyisoprene‐blend‐polystyrene and polystyrene‐block‐poly(methyl methacrylate)‐blend‐polystyrene or ‐blend‐poly(methyl methacrylate) in the strong segregation regime

AbstractThis study deals with the investigation of microphase‐separated morphology and phase behaviour in blends of polystyrene‐block‐polyisoprene with homopolystyrene and blends of polystyrene‐block‐poly(methyl methacrylate) with homopoly(methyl methacrylate) or homopolystyrene in the strong segregation regime using small‐angle X‐ray scattering and transmission electron microscopy as a function of composition, molecular weight of homopolymers, rM and temperature. Parameter rM = MH/MC (where MH is the molecular weight of homopolymer and MC that of the corresponding block copolymer) was selected to encompass behaviour of the chains denoted as a ‘wet brush’ (i.e. rM < 1). The relative domain spacing D/Do increases in the regime 0 < rM⩽1 with increasing concentration of homopolymer wP and increasing rM but depends on the specific implemented morphology. We tested a new approximate D/Do versus wP relation in the strong segregation regime using block copolymers of high molecular weights. It is shown that the parameters rM and χ3/2N determine the slope of the D/Do versus wP relation in the strong segregation regime and the new approximation generally matches the experimental data better than the approximations used so far. Copyright © 2010 Society of Chemical Industry