Journal
MACROMOLECULES
Volume 44, Issue 15, Pages 6209-6219Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma200966a
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Funding
- EPSRC [EP/E010342/1]
- Engineering and Physical Sciences Research Council [EP/E010342/1] Funding Source: researchfish
- EPSRC [EP/E010342/1] Funding Source: UKRI
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The phase diagram for an AB diblock copolymer melt with polydisperse A blocks and monodisperse B blocks is evaluated using lattice-based Monte Carlo simulations. Experiments on this system have shown that the A-block polydispersity shifts the order order transitions (OOTs) toward higher A-monomer content, while the order disorder transition (ODT) moves toward higher temperatures when the A blocks form the minority domains and lower temperatures when the A blocks form the matrix. Although self-consistent field theory (SCFT) correctly accounts for the change in the OOTs, it incorrectly predicts the ODT to shift toward higher temperatures at all diblock copolymer compositions. In contrast, our simulations predict the correct shifts for both the OOTs and the ODT. This implies that polydispersity amplifies the fluctuation-induced correction to the mean-field ODT, which we attribute to a reduction in packing frustration. Consistent with this explanation, polydispersity is found to enhance the stability of the perforated-lamellar phase.
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