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Polymers 2016, 8(6), 241; doi:10.3390/polym8060241

Predicting the Flory-Huggins χ Parameter for Polymers with Stiffness Mismatch from Molecular Dynamics Simulations

Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802, USA
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Academic Editor: Martin Kröger
Received: 4 May 2016 / Revised: 13 June 2016 / Accepted: 16 June 2016 / Published: 22 June 2016
(This article belongs to the Special Issue Semiflexible Polymers)
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Abstract

The Flory–Huggins χ parameter describes the excess free energy of mixing and governs phase behavior for polymer blends and block copolymers. For chemically-distinct nonpolar polymers, the value of χ is dominated by the mismatch in cohesive energy densities of the monomers. For blends of chemically-similar polymers, the entropic portion of χ, arising from non-ideal local packing, becomes more significant. Using polymer field theory, Fredrickson et al. predicted that a difference in backbone stiffness can result in a positive χ for chains consisting of chemically-identical monomers. To quantitatively investigate this phenomenon, we perform molecular dynamic (MD) simulations for bead-spring chains, which differ only in stiffness. From the simulations, we apply a novel thermodynamic integration to extract χ as low as 10 - 4 per monomer for blends with stiffness mismatch. To compare with experiments, we introduce a standardized effective monomer to map real polymers onto our bead-spring chains. The predicted χ agrees well with experimental values for a wide variety of pairs of chemically-similar polymers. View Full-Text
Keywords: polymers; Flory–Huggins theory; bead-spring chain; molecular dynamics; coarse grain; chain stiffness polymers; Flory–Huggins theory; bead-spring chain; molecular dynamics; coarse grain; chain stiffness
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Kozuch, D.J.; Zhang, W.; Milner, S.T. Predicting the Flory-Huggins χ Parameter for Polymers with Stiffness Mismatch from Molecular Dynamics Simulations. Polymers 2016, 8, 241.

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