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Membrane Swelling

Membrane Swelling

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09/26/2010

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Mathematical Modelling of Membrane Swelling

Tobias Sch¨fer a
tobiass@math.csi.cuny.edu

Department of Mathematics City University of New York New York

Banff, Winter 2005 – p.1/7

2/7 . Many factors play a role: • Flux of ions • Intermembrane electric field • Stress on the membrane ◦ Goal: Develop a model that takes all effects into account in an appropriate way and is still of practical use. Banff.Overview ◦ Question: How can we understand the water content in fuel cell membranes? ◦ Answer: Very complicated. Winter 2005 – p.

Features of the model ◦ Assumptions: • One-dimensional continuum model • Homogenized (averages over microstructures) ◦ Predictions: • Swelling/Deswelling as a response to changes of the pH of the bath • Swelling is slower than deswelling (nonlinear effect) • Swelling in response to changes of an exterior electric field Banff.3/7 . Winter 2005 – p.

Nernst-Planck equation ◦ Nernst-Planck equation c ¯ H ∂¯H + µH zH cH E ¯ ¯ ΓH = φ −D ∂x |zH | + cH U ¯ (1) ◦ Coefficients depend on hydration H (ratio of fluid to solid volume) in a nonlinear way. Winter 2005 – p. 1+H ¯ DH = DH H 2+H 2 Banff.4/7 . ¯ ◦ Examples: Membrane porosity φ and diffusivity DH : H φ= .

5/7 . ∂t ∂ψ ◦ Chemical reaction cs ¯mo cs ¯mo b − cH = ¯ cm = ¯ H H K K + cH ¯ .Continuity condition and chemical reaction ◦ Continuity condition for the ionic flux ∂ (αΓH ) ∂ b H¯H + H¯H = − c c . ¯ Banff. (3) (2) ◦ cb → H + ions bound to the PMAA carboxyl groups. Winter 2005 – p. ¯H cm → ionized PMAA carboxyl groups.

continuity.6/7 . we have dx = (1 + H)dψ Banff. Winter 2005 – p.Equation for H concentration ◦ Combination of the three equations (Nernst-Planck. accounting for swelling. In the one-dimensional case. and chemical reaction) leads to (for the convection-free case U = 0) ∂ cs ¯mo cH H + ¯ ∂t K + cH ¯ ∂ c ¯ H ∂¯H − µH cH E αψ D = ¯ ¯ ∂ψ ∂x + ◦ ψ is the Lagrangian coordinate.

We can eliminate ¯ one of them and are left with a highly nonlinear diffusion equation. Banff.7/7 . H and cH are functions of (ψ. Winter 2005 – p. t).The simple case ◦ Let’s assume • electrical migration is irrelevant (E = 0) • instantaneous mechanical equilibrium c H = Heq = Heq (¯H ) ◦ Both. describing the time evolution of both the H + -concentration and the hydration.

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