Depletion attraction of sheet-like ion aggregates in low-dielectric ionomer melts

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Abstract

Ionomers are polymers in which an ionic group is covalently bonded to the polymer backbone. Ion aggregates in ionomers have morphologies that allow for the packing of the attached polymer backbone. Using ion-only coarse-grained molecular dynamics, we observe that string-like ion aggregates become flat and sheet-like at lower dielectric constants. A consequence of the changing morphology is that the sheet-like aggregates self-assemble to form ordered, lamellar structures. We use a simple thermodynamic model to demonstrate that depletion attraction mediated by small aggregates can explain the observed order. Our results suggest that depletion attraction can drive ions to form structures that have the size scale suggested by direct visualization, produce the commonly observed experimental correlation peak from X-ray and neutron scattering, and satisfy chain-packing constraints that have been demonstrated to be important in simulations.

Original languageEnglish (US)
Article number064901
JournalJournal of Chemical Physics
Volume146
Issue number6
DOIs
StatePublished - Feb 14 2017

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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