Permeability of Polymer Membranes beyond Linear Response

نویسندگان

چکیده

The permeability of a membrane to solute penetrants is well defined on the linear response level simply as ratio penetrants’ flux and concentration gradient at boundary layers. However, nonlinearities emerge in flux–force relation j(f) for large driving forces f, which definition becomes ambiguous. Here, we study nonequilibrium permeation orchestrated by generic force using penetrant- monomer-resolved computer simulations transport polymer network, supported exact solutions Smoluchowski (drift–diffusion) equation stationary state. In simulations, consider across finite immersed reservoir penetrants, addressing one- two-component penetrant systems. We calculate f-dependent inhomogeneous steady-state density profiles, layer concentrations, fluxes penetrants. approach, solely coarse-grained equilibrium partitioning diffusion profiles input, exhibits remarkable qualitative agreement with our serves rationalization observations. discuss possible definitions nonequilibrium, permeability, distinguishing between “system” “membrane” permeabilities. particular, introduce concept differential f. latter turns out be highly nonmonotonic function f low-permeable systems, demonstrating how permselectivity substantially tunable beyond response.

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ژورنال

عنوان ژورنال: Macromolecules

سال: 2022

ISSN: ['0024-9297', '1520-5835']

DOI: https://doi.org/10.1021/acs.macromol.2c00605