Thermodynamic Model of Solvent Effects in Semiflexible Diblock and Random Copolymer Assembly
Abstract
Here, we present a field-theoretic model to predict the equilibrium thermodynamic behavior of semiflexible diblock copolymers and random copolymers in the presence of solvent. We find that in both systems polymer–solvent contacts dramatically influence the thermodynamic behavior with decreasing the copolymer segment length (i.e., molecular weight). When a copolymer has unequal monomer composition, both polymer length and solvent concentration have a strong influence on the phase transition spinodal and magnitude of the critical wave modes. Diblock copolymers exhibit an expanded region of the lamellar phase in the phase diagram with decreasing chain length and polymer concentration. Such effects suggest a breakdown of the dilute approximation for solutions of short diblock copolymers. Random copolymer solutions also exhibit changes in the phase-transition spinodal and critical wave mode at asymmetric chemical compositions. This effect is highly relevant to most random copolymer materials, since a monomer is typically a low-molecular-weight chemical unit.
- Authors:
-
- Stanford Univ., Stanford, CA (United States)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1470934
- Grant/Contract Number:
- AC02-76SF00515; 1511373
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 11; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mao, Shifan, MacPherson, Quinn, Liu, Chunzi, and Spakowitz, Andrew J. Thermodynamic Model of Solvent Effects in Semiflexible Diblock and Random Copolymer Assembly. United States: N. p., 2018.
Web. doi:10.1021/acs.macromol.8b00172.
Mao, Shifan, MacPherson, Quinn, Liu, Chunzi, & Spakowitz, Andrew J. Thermodynamic Model of Solvent Effects in Semiflexible Diblock and Random Copolymer Assembly. United States. https://doi.org/10.1021/acs.macromol.8b00172
Mao, Shifan, MacPherson, Quinn, Liu, Chunzi, and Spakowitz, Andrew J. 2018.
"Thermodynamic Model of Solvent Effects in Semiflexible Diblock and Random Copolymer Assembly". United States. https://doi.org/10.1021/acs.macromol.8b00172. https://www.osti.gov/servlets/purl/1470934.
@article{osti_1470934,
title = {Thermodynamic Model of Solvent Effects in Semiflexible Diblock and Random Copolymer Assembly},
author = {Mao, Shifan and MacPherson, Quinn and Liu, Chunzi and Spakowitz, Andrew J.},
abstractNote = {Here, we present a field-theoretic model to predict the equilibrium thermodynamic behavior of semiflexible diblock copolymers and random copolymers in the presence of solvent. We find that in both systems polymer–solvent contacts dramatically influence the thermodynamic behavior with decreasing the copolymer segment length (i.e., molecular weight). When a copolymer has unequal monomer composition, both polymer length and solvent concentration have a strong influence on the phase transition spinodal and magnitude of the critical wave modes. Diblock copolymers exhibit an expanded region of the lamellar phase in the phase diagram with decreasing chain length and polymer concentration. Such effects suggest a breakdown of the dilute approximation for solutions of short diblock copolymers. Random copolymer solutions also exhibit changes in the phase-transition spinodal and critical wave mode at asymmetric chemical compositions. This effect is highly relevant to most random copolymer materials, since a monomer is typically a low-molecular-weight chemical unit.},
doi = {10.1021/acs.macromol.8b00172},
url = {https://www.osti.gov/biblio/1470934},
journal = {Macromolecules},
issn = {0024-9297},
number = 11,
volume = 51,
place = {United States},
year = {Wed May 23 00:00:00 EDT 2018},
month = {Wed May 23 00:00:00 EDT 2018}
}
Web of Science
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