Phase behavior of neat triblock copolymers and copolymer/homopolymer blends near network phase windows

The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well as the identification of double gyroid (Q²³⁰), alternating gyroid (Q²¹⁴), and orthorhombic (O⁷⁰) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.