Accelerated Aging of PS Blocks in PS- b-PMMA Diblock Copolymer under Hard Confinement.

This letter presents an accelerated physical aging of polystyrene (PS) blocks in polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) diblock copolymers under hard confinement. The three-dimensional hard nanoconfinement was provided by the PMMA component owing to its high elasticity and was formed via self-assembled microphase separation. Aging was observed by measuring enthalpy recovery of the PS blocks in the copolymers for which the degree of polymerization ( N) of PS blocks is fixed, whereas the N of PMMA blocks varies. Our results demonstrate that the aging speed of the PS blocks can increase by a factor of three to that of the neat PS as the N of PMMA blocks increases. Therefore, the hard confinement accelerates physical aging of the PS blocks, i.e., the relatively soft component in the copolymer.