Decoupling Bulk Thermodynamics and Wetting Characteristics of Block Copolymer Thin Films

The consequences on certain physical properties of controlled levels of epoxidation of the poly(isoprene) blocks in poly(styrene- b -isoprene) (PS-PI) diblock copolymers and poly(isoprene) (hPI) homopolymers have been studied, where the products after epoxidation are denoted PS-PIxn and hPIxn, respectively. The effective interaction parameters χ eff between the PS and the PIxn blocks were estimated by applying mean-field theory to the lamellar periodicities identified by small-angle X-ray scattering and to the order-to-disorder transition temperatures determined by dynamic mechanical spectroscopy. These results were fit to a binary segment–segment interaction parameter model indicating a nonlinear change in χ eff with percent epoxidation. In contrast, contact angle measurement on hPIxn and lamellar orientations of thin-film PS-PIxn suggest that the surface energy of PIxn increases linearly with epoxidation. This decoupling of bulk and thin-film thermodynamic behaviors is attributed to the different roles that a random copolymer architecture plays in establishing three-dimensional order versus wetting at a two-dimensional surface.