Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Kosgallana, Chathurika; Senanayake, Manjula; Mohottalalage, Supun S.; Wijesinghe, Sidath; He, Lilin; Grest, Gary S.; Perahia, Dvora

doi:10.1021/acs.macromol.3c01646

Title: Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Journal Article · 13 February 2024 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.3c01646 · OSTI ID:2301685

Kosgallana, Chathurika ^[1];

^[2]; Mohottalalage, Supun S. ^[3];

^[4]; He, Lilin ^[5];

^[6];

^[1]

Clemson Univ., SC (United States)
Clemson Univ., SC (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Clemson Univ., SC (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Clemson Univ., SC (United States); Appalachian State University, Boone, NC (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Ionic assemblies, or clusters, determine the structure and dynamics of ionizable polymers and enable their many applications. Fundamental to attaining well-defined materials is controlling the balance between van der Waals interactions that govern the backbone behavior and the forces that drive the formation of ionic clusters. Here, using small angle neutron scattering and fully atomistic molecular dynamics simulations, the structure of a model ionomer, sulfonated polystyrene in toluene solutions, was investigated as the cluster cohesion was tweaked by the addition of ethanol. The static structure factor was measured by both techniques and correlated with the size of the ionic clusters as the polymer concentration was varied. The conjunction of SANS results and molecular insight from MD simulations enabled the determination of the structure in these inhomogeneous networks on multiple length scales. Additionally, we find that across the entire concentration range studied, a network driven by the formation of ionic clusters was formed, where the size of the clusters drives the inhomogeneity of these systems. Tweaking the ionic clusters through the addition of ethanol impacts the packing of the sulfonated groups, their shape, and their size distribution, which in turn, affects the structure of these networks.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)

Grant/Contract Number:: SC0019284; AC02-05CH11231; NA0003525; DMR-0520547; MRI-1725573

OSTI ID:: 2301685

Alternate ID(s):: OSTI ID: 2333731

Report Number(s):: SAND-2024-03976J

Journal Information:: Macromolecules, Vol. 57, Issue 4; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

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