Effects of polydispersity on the order-disorder transition in block copolymer melts

We prepared controlled-polydispersity poly(ethylene-alt-propylene)-b- poly(DL-lactide) (PL) and polystyrene-b-polyisoprene (SI) block copolymers to study the effects of the molecular weight distribution on the order-disorder transition at controlled composition and overall molecular weight. Small-angle X-ray scattering and rheological measurements were carried out to characterize the changes in the order-disorder transition in these self-assembled materials as a function of their composition and polydispersity index. We determined that in both asymmetric PL and SI systems increasing polydispersity in the minority component resulted in a decrease in the segregation strength at the order-disorder transition, whereas increasing polydispersity in the majority component results in an increase in the segregation strength at the order-disorder transition. We speculate that increasing PDI in the majority domain weakens the effective potential holding the phase-separated microdomains ordered on a lattice.