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Title: Communication: Thermodynamic analysis of critical conditions of polymer adsorption

Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.
Authors:
;  [1] ;  [2]
  1. Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854 (United States)
  2. DuPont Central Research and Development, Corporate Center for Analytical Sciences, Macromolecular Characterization, Route 141 and Henry Clay, Wilmington, Delaware 19803 (United States)
Publication Date:
OSTI Identifier:
22251335
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 20; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION; FREE ENERGY; INTERACTIONS; POLYMERS; SOLIDS; SOLVATION; SOLVENTS; SURFACES