Title: Interfacial Response and Structural Adaptation of Structured Polyelectrolyte Thin Films

Abstract

Ionizable block copolymers with distinctive block characteristics display the diversity crucial for the design of macromolecules for targeted applications. In contrast to van der Waals copolymers, their interfaces, which are critical to their function, consist of nanodomains, each of a different nature and thus unique interfacial behavior. Here, the interfacial response of a symmetric block copolymer with a sulfonated polystyrene polyelectrolyte center, tethered to polyethylene-r-propylene and terminated by poly(t-butyl styrene) is probed as polymer films are exposed to three polar solvents, water, propanol, and tetrahydrofuran (THF), using molecular dynamics simulations. Each of the solvents captures a distinctive interaction with the individual blocks. We find that at the film boundary, the interfacial response is initially dominated by that of the hydrophobic blocks to all solvents. At later times, the solvent distribution among the blocks, where water molecules associate predominantly with the sulfonated groups and propanol and THF reside at multiple different sites, determines the chemical composition and the polymer conformation at the interface. Altogether, these simulations provide the first direct molecular insight into the interfacial response of ionizable copolymers.

Authors:

Senanayake, Manjula ^[1]; Aryal, Dipak ^[1]; Grest, Gary S.  ^[2];

• Search DOE PAGES for author "Grest, Gary S."
• Search DOE PAGES for ORCID "0000-0002-5260-9788"

Perahia, Dvora  ^[1]

• Search DOE PAGES for author "Perahia, Dvora"
• Search DOE PAGES for ORCID "0000-0002-8486-8645"

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+ Show Author Affiliations

1. Clemson Univ., SC (United States)
2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Publication Date:

Thu Mar 04 00:00:00 EST 2021

Research Org.:

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

Sponsoring Org.:

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

OSTI Identifier:

1770861

Report Number(s):

SAND-2021-2719J
Journal ID: ISSN 0024-9297; 694615

Grant/Contract Number:  

AC04-94AL85000; DMR-1611136; AC02-05CH11231; NA0003525

Resource Type:

Accepted Manuscript

Journal Name:

Macromolecules

Additional Journal Information:

Journal Volume: 54; Journal Issue: 6; Journal ID: ISSN 0024-9297

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Interfaces; Solvents; Cluster chemistry; Molecules; Polymers