The C36 Laves phase in diblock polymer melts

Benjamin R. Magruder, Kevin D. Dorfman

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The C14 and C15 Laves phases form as micelle packing structures in many types of soft matter, but the related C36 phase, which consists of alternating C14-type and C15-type layers, has not been observed in any such system. To understand this absence in the context of diblock polymers, we used self-consistent field theory to relate the morphology and energetics of C36 to other known mesophases. Two case studies were conducted: blends of AB diblock polymers with A homopolymers (where A forms the micelle core), in which C14 and C15 have stability windows, and neat AB diblock melts, in which Laves phases are metastable. Laves phases exhibit nearly identical micelle morphologies and nearly degenerate free energies, with the free energy of C36 being a near-perfect bisector of the C14 and C15 free energies in all cases, revealing an intrinsic symmetry in free energy that is attributed solely to the structural relationship between the phases in which the packing of C36 is intermediate between C14 and C15. Based on this connection between structure and free energy, C36 is thus not expected to form in flexible diblock polymers, since C14 and C15 can always form insteadviafacile mass transfer.

Original languageEnglish (US)
Pages (from-to)8950-8959
Number of pages10
JournalSoft Matter
Issue number39
StatePublished - Oct 21 2021

Bibliographical note

Funding Information:
We acknowledge Guo Kang Cheong, Logan Case, and Akash Arora, whose scripts and SCFT calculations were very useful as tools to help generate the data herein. This work was supported by the NSF Grant DMR-1725272. Computational resources were provided by the Minnesota Supercomputing Institute.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

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