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Title: Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties

Abstract

The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chain stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.

Authors:
 [1]
  1. James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States)
Publication Date:
OSTI Identifier:
22490907
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 2; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY; ENTHALPY; ENTROPY; FLEXIBILITY; GLASS; POLYMERS

Citation Formats

Xu, Wen-Sheng, Freed, Karl F., E-mail: freed@uchicago.edu, and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637. Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties. United States: N. p., 2015. Web. doi:10.1063/1.4926359.
Xu, Wen-Sheng, Freed, Karl F., E-mail: freed@uchicago.edu, & Department of Chemistry, The University of Chicago, Chicago, Illinois 60637. Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties. United States. https://doi.org/10.1063/1.4926359
Xu, Wen-Sheng, Freed, Karl F., E-mail: freed@uchicago.edu, and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637. 2015. "Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties". United States. https://doi.org/10.1063/1.4926359.
@article{osti_22490907,
title = {Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties},
author = {Xu, Wen-Sheng and Freed, Karl F., E-mail: freed@uchicago.edu and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637},
abstractNote = {The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chain stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.},
doi = {10.1063/1.4926359},
url = {https://www.osti.gov/biblio/22490907}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 2,
volume = 143,
place = {United States},
year = {Tue Jul 14 00:00:00 EDT 2015},
month = {Tue Jul 14 00:00:00 EDT 2015}
}