Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

Mah, Adeline Huizhen; Laws, Travis; Li, Wei; Mei, Hao; Brown, Chance C.; Ievlev, Anton; Kumar, Rajeev; Verduzco, Rafael; Stein, Gila E.

doi:10.1021/acs.macromol.8b02242

Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

Journal Article · Tue Feb 05 23:00:00 EST 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.8b02242· OSTI ID:1494878

Mah, Adeline Huizhen ^[1]; Laws, Travis ^[2]; ^[3]; Mei, Hao ^[4]; Brown, Chance C. ^[3]; ^[3]; ^[5]; ^[6]; ^[2]

Univ. of Houston, Houston, TX (United States). Materials Science and Engineering Program and Dept. of Chemical and Biomolecular Engineering
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS), and Computational Chemical and Materials Sciences
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering, Dept. of Materials Science and NanoEngineering

We present a combined experimental and computational study of surface segregation in thin films of nearly athermal blends of linear and bottlebrush polymers. The lengths of bottlebrush backbone (N_b), bottlebrush side chain (N_sc), and linear polystyrene host (N_m) are systematically varied to examine the effects of polymer architecture on phase behavior. From the experiments, combinations of architectural parameters are identified that produce enrichment and depletion of bottlebrush at the polymer–air interface. These surface segregation behaviors are consistent with entropy-dominated thermodynamics. In addition, the experiments reveal conditions where bottlebrush and linear polymers are equally preferred at the surface. Simulations based on the self-consistent field theory (SCFT) qualitatively capture the three types of surface segregation behaviors and highlight the delicate interplay of entropic and enthalpic effects. Finally, our investigations demonstrate that controlling both entropic and enthalpic driving forces is critical for the design of surface-active bottlebrush polymer additives.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1494878

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 4 Vol. 52; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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