Donets, S. orcid.org/0000-0003-3342-112X and Sommer, J.-U. orcid.org/0000-0001-8239-3570 (2018) Molecular dynamics simulations of strain-induced phase transition of poly(ethylene oxide) in water. The Journal of Physical Chemistry B, 122 (1). pp. 392-397. ISSN 1520-6106
Abstract
We study the dilute aqueous solutions of poly(ethylene oxide) (PEO) oligomers that are subject to an elongating force dipole acting on both chain ends using atomistic molecular dynamics. By increasing the force, liquid–liquid demixing can be observed at room temperature far below the lower critical solution temperature. For forces above 35 pN, fibrillar nanostructures are spontaneously formed related to a decrease in hydrogen bonding between PEO and water. Most notable is a rapid decrease in the bifurcated hydrogen bonds during stretching, which can also be observed for isolated single chains. The phase-segregated structures display signs of chain ordering, but a clear signature of the crystalline order is not obtained during the simulation time, indicating a liquid–liquid phase transition induced by chain stretching. Our results indicate that the solvent quality of the aqueous solution of PEO depends on the conformational state of the chains, which is most likely related to the specific hydrogen-bond-induced solvation of PEO in water. The strain-induced demixing of PEO opens the possibility to obtain polymer fibers with low energy costs because crystallization starts via the strain-induced demixing in the extended state only.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 American Chemical Society. This is an author produced version of a paper subsequently published in Journal of Physical Chemistry B. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 26 Sep 2018 09:15 |
Last Modified: | 20 Dec 2018 01:39 |
Published Version: | https://doi.org/10.1021/acs.jpcb.7b10793 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpcb.7b10793 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:135669 |