The evolution of acidic and ionic aggregates in ionomers during microsecond simulations

Frischknecht, Amalie L.; Winey, Karen I.

doi:10.1063/1.5085069

The evolution of acidic and ionic aggregates in ionomers during microsecond simulations

Journal Article · Mon Feb 11 00:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5085069· OSTI ID:1497630

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Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)

We performed microsecond-long, atomistic molecular dynamics (MD) simulations on a series of precise poly(ethylene-co-acrylic acid) ionomers neutralized with lithium, with three different spacer lengths between acid groups on the ionomers and at two temperatures. Ionic aggregates form in these systems with a variety of shapes ranging from isolated aggregates to percolated aggregates. At the lower temperature of 423 K, the ionic aggregate morphologies to do not reach a steady-state distribution over the course of the simulations. At the higher temperature of 600 K, the aggregates are sufficiently mobile that they rearrange and reach steady state after hundreds of nanoseconds. For systems that are 100% neutralized with lithium, the ions form percolated aggregates that span the simulation box in three directions, for all three spacer lengths (9, 15, 21). In the partially neutralized systems, the morphology includes lithium ion aggregates that may also include some unneutralized acid groups, along with a coexisting population of acid group aggregates that form through hydrogen bonding. In the lithium ion aggregates, unneutralized acid groups tend to be found on the ends or sides of the aggregates.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1497630

Report Number(s):: SAND2019--1700J; 672625

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 150; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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