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Title: Vertical Phase Segregation Induced by Dipolar Interactions in Planar Polymer Brushes

In this paper, we present a generalized theory for studying structural properties of a planar dipolar polymer brush immersed in a polar solvent. We show that an explicit treatment of the dipolar interactions yields a macroscopic concentration dependent effective “chi” (the Flory–Huggins-like interaction) parameter. Furthermore, it is shown that the concentration dependent chi parameter promotes phase segregation in polymer solutions and brushes so that the polymer-poor phase consists of a finite/nonzero polymer concentration. Such a destabilization of the homogeneous phase by the dipolar interactions appears as vertical phase segregation in a planar polymer brush. In a vertically phase segregated polymer brush, the polymer-rich phase near the grafting surface coexists with the polymer-poor phase at the other end. Predictions of the theory are directly compared with prior reported experimental results for dipolar polymers in polar solvents. Excellent agreements with the experimental results are found, hinting that the dipolar interactions play a significant role in vertical phase segregation of planar polymer brushes. We also compare our field theoretical approach with the two-state and other models invoking ad hoc concentration dependence of the chi parameter. Interplay between the short-ranged excluded volume interactions and long-ranged dipolar interactions is shown to play an important rolemore » in affecting the vertical phase separation. Finally, effects of mismatch between the dipole moments of the polymer segments and the solvent molecules are investigated in detail.« less
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  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division. Center for Nanophase Materials Sciences
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Grant/Contract Number:
Accepted Manuscript
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Additional Journal Information:
Journal Volume: 49; Journal Issue: 18; Journal ID: ISSN 0024-9297
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
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