Molecular Thermodynamics for Swelling of a Mesoscopic Ionomer Gelin 1:1 Salt Solutions

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For a microphase-separated diblock copolymer ionic gel swollen in salt solution, a molecular-thermodynamic model is based on the self-consistent field theory in the limit of strongly segregated copolymer subchains. The geometry of microdomains is described using the Milner generic wedge construction neglecting the packing frustration. Thermodynamic functions are expressed analytically for gels of lamellar, bicontinuous, cylindrical and spherical morphologies. Molecules are characterized by chain composition, length, rigidity, degree of ionization, and by effective polymer-polymer and polymer-solvent interaction parameters. The model predicts equilibrium solvent uptakes and the equilibrium microdomain spacing for gels swollen in salt solutions. Results are given for details ... continued below

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Victorov, Alexey; Radke, Clayton & Prausnitz,John June 15, 2005.

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For a microphase-separated diblock copolymer ionic gel swollen in salt solution, a molecular-thermodynamic model is based on the self-consistent field theory in the limit of strongly segregated copolymer subchains. The geometry of microdomains is described using the Milner generic wedge construction neglecting the packing frustration. Thermodynamic functions are expressed analytically for gels of lamellar, bicontinuous, cylindrical and spherical morphologies. Molecules are characterized by chain composition, length, rigidity, degree of ionization, and by effective polymer-polymer and polymer-solvent interaction parameters. The model predicts equilibrium solvent uptakes and the equilibrium microdomain spacing for gels swollen in salt solutions. Results are given for details of the gel structure: distribution of mobile ions and polymer segments, and the electric potential across microdomains. Apart from effects obtained by coupling classical Flory-Rehner theory with Donnan equilibria, viz., increased swelling with polyelectrolyte charge and shrinking of gel upon addition of salt, the model predicts the effects of microphase morphology on swelling.

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  • Journal Name: Physical Chemistry Chemical Physics; Journal Volume: 8; Journal Issue: 2; Related Information: Journal Publication Date: 01/14/2006

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  • Report No.: LBNL--57927
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 891621
  • Archival Resource Key: ark:/67531/metadc884325

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  • June 15, 2005

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  • Sept. 21, 2016, 2:29 a.m.

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  • Dec. 16, 2016, 1:14 p.m.

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Victorov, Alexey; Radke, Clayton & Prausnitz,John. Molecular Thermodynamics for Swelling of a Mesoscopic Ionomer Gelin 1:1 Salt Solutions, article, June 15, 2005; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc884325/: accessed September 24, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.