Original article Biomath 2 (2013), 1312302, 1–5 B f Volume ░, Number ░, 20░░ BIOMATH ISSN 1314-684X Editor–in–Chief: Roumen Anguelov B f BIOMATH h t t p : / / w w w . b i o m a t h f o r u m . o r g / b i o m a t h / i n d e x . p h p / b i o m a t h / Biomath Forum Multiscale Analysis of Ionic Transport in Periodic Charged Media Claudia Timofte Faculty of Physics, University of Bucharest Bucharest, Romania claudiatimofte@yahoo.com Received: 23 September 2013, accepted: 30 December 2013, published: 23 January 2014 Abstract—A macroscopic model for describing the ion transport in periodic charged porous media is rigorously derived. Our results can serve as a tool for biophysicists to analyze the ion transport through protein channels. Also, such a model is useful for describing the flow of electrons and holes in a semiconductor device. Keywords-homogenization; ion transport; the periodic unfolding method. I. INTRODUCTION AND SETTING OF THE PROBLEM The goal of this paper is to obtain the effective beha- vior of a system of coupled partial differential equations appearing in the modeling of transport phenomena in periodic charged porous media or in the modeling of the flow of holes and electrons in semiconductors. Such a system is known in the literature as the Poisson- Nernst-Planck system, for the case of ion flow through membrane channels, or as the van Roosbroeck model, for the case of the transport of holes and electrons in semiconductors. For the physical aspects behind these models and for a review of the recent literature, we refer to [8], [13], [14], [15], [16] and [19]. Let us briefly describe the geometry of the problem. We assume, as it is customary in the literature, that the porous medium has a periodic microstructure. More precisely, for n ≥ 2, we consider a smooth bounded connected open set Ω in Rn, with | ∂Ω |= 0. In what follows, we shall only consider the natural cases n = 2 or n = 3. We assume that the unit cell Y = (0, 1)n consists of two smooth parts, the fluid part Yf and, respectively, the solid part Ys, which are supposed to be open, nonempty and disjoint sets such that Y = Yf ∪Ys and Yf ∩Ys = Γ. We suppose that the solid part has a Lipschitz boundary and does not intersect the boundary of the basic cell Y . Therefore, the fluid zone is connected. Let ε < 1 be a real parameter taking values in a sequence of positive numbers converging to zero. For each k ∈ Zn, let Y ks = k + Ys and Kε = {k ∈ Zn | εY ks ⊆ Ω}. We denote by Ωsε = ⋃ k∈Kε εY ks the solid part, by Ωε = Ω \ Ωsε the fluid part and we set θ = ∣∣Y \Ys∣∣ . It is easy to see that if the solid part is not allowed to reach the fixed exterior boundary of the domain Ω, the intersection between the outer boundary ∂Ω and the Citation: Claudia Timofte, Multiscale Analysis of Ionic Transport in Periodic Charged Media, Biomath 2 (2013), 1312302, http://dx.doi.org/10.11145/j.biomath.2013.12.302 Page 1 of 5 http://www.biomathforum.org/biomath/index.php/biomath http://dx.doi.org/10.11145/j.biomath.2013.12.302 C Timofte, Multiscale Analysis of Ionic Transport in Periodic Charged Media interior boundary Γε of the porous medium is empty, i.e.: Γε ∩∂Ω = ∅. In such a periodic porous medium, we shall consider, at the microscale, the Poisson-Nernst-Planck system, with suitable boundary and initial conditions. The Nernst- Planck equations, describing the diffusion in the fluid phase, are coupled with the Poisson equation cha- racterizing the electrical field which can influence the ionic transfer. More precisely, if we denote by [0,T], with T > 0, the time interval of interest, we shall be interested in analyzing the asymptotic behavior, as ε → 0, of the solution of the following system: −∆ Φε = c+ε − c−ε + D in (0,T) × Ωε, −∇Φε ·ν = εσεG(Φε) on (0,T) × Γε, ∇Φε ·ν = 0 on (0,T) ×∂Ω, ∂tc ± ε −∇· (∇c±ε ± c±ε ∇Φε) = F±(c+ε ,c−ε ) in (0,T) × Ωε, (∇c±ε ± c±ε ∇Φε) ·ν = 0 on (0,T) × Γε, (∇c±ε ± c±ε ∇Φε) ·ν = 0 on (0,T) ×∂Ω, c±ε (0,x) = c ± 0 (x) in Ωε. (1) Here, ν is the unit outward normal to Ωε, Φε represents the electrostatic potential, c±ε are the concentrations of the ions (or the density of electrons and holes in the particular case of van Roosbroeck model), D ∈ L∞(Ω) is the given doping profile, F± is a reaction term and G is a nonlinear function which takes into account the effect of the electrical double layer phenomenon arising at the interface Γε. We assume that σε = σ (x ε ) , with σ(y) being a Y -periodic, bounded, smooth real function such that σ(y) ≥ δ > 0, and G is a conti- nuously differentiable function, monotonously increasing and such that G(0) = 0. Also, we shall suppose that there exist C ≥ 0 and r, with 0 ≤ r ≤ n/(n− 2) for n = 3 and 0 ≤ r < ∞ for n = 2, such that | G′(s) |≤ C(1+ | s |r−1), ∀s ∈ R. Let us notice that this hypothesis concerning the smoothness of the nonlinearity G can be relaxed by using a regularization technique, such as Yosida approximation (see [18]). Also, the results of this paper can be obtained, under our assumptions, without imposing any growth condition (see [17]). In practical applications, based on the Gouy-Chapman theory, one can use the Grahame equation (see [2], [8] and [9]) in which G(s) = K1 sinh(K2s), K1,K2 > 0. For the case of lower potentials, sinh(x) can be expanded in a power series of the form sinh(x) = x + x3 3! + ... and one can use the approximations sinh x ≈ x or sinh x ≈ x + x3/3!. Concerning the reaction terms, we deal, as in [13], with the linear case in which F±(c+ε ,c − ε ) = ∓(c + ε − c − ε ), but we can also address by our techniques the more general case in which F±(c+ε ,c − ε ) = ∓(a εc+ε − b εc−ε ), with aε(x) = a (x ε ) , bε(x) = b (x ε ) , where a(y) and b(y) are Y -periodic, bounded, smooth real functions such that a(y) ≥ a0 > 0, b(y) ≥ b0 > 0. For the case of other nonlinear reaction rates F± and more general functions G, see [6], [10], [11] and [18]. We assume that the initial data are non-negative and bounded independently of ε and∫ Ωε (c+0 − c − 0 + D)dx = ε ∫ Γε σεG(Φε)ds. (2) We also assume that the potential Φε has zero mean value in Ωε. Let us mention that, for simplifying the notation, we have suppressed in system (1) some constant physical relevant parameters. We consider here only two oppositely charged species, i.e. positively and negatively charged particles, with concentrations c±ε , but all the results can be generalized for the case of N species. For the case in which we consider different scalings in (1), see [13] and [18]. Also, let us remark that we can treat the case in which the electrostatic potential is defined all over the domain Ω, with suitable transmission conditions at the interface Γε (see, for instance, [8] or [16]). Biomath 2 (2013), 1312302, http://dx.doi.org/10.11145/j.biomath.2013.12.302 Page 2 of 5 http://dx.doi.org/10.11145/j.biomath.2013.12.302 C Timofte, Multiscale Analysis of Ionic Transport in Periodic Charged Media From the Nernst-Planck equation, it is easy to see that the total mass M = ∫ Ωε (c+ε + c − ε )dx is conserved and suitable physical equilibrium conditions hold true, at the microscale and, also, at the macroscale (see, for details, [8] and [18]). Using similar arguments as in [8] or [13], we can prove the well posedness of problem (1) in suitable func- tion spaces and we can obtain proper energy estimates. The high complexity of the geometry and of the go- verning equations implies that an asymptotic procedure becomes necessary for describing the solution of such a problem. Using the periodic unfolding method recently intro- duced by D. Cioranescu, A. Damlamian, G. Griso, P. Donato and R. Zaki (see [3], [5] and [4]), we can prove that the asymptotic behavior of the solution of our problem is governed by a new coupled system of equations (see (3)-(5)). In particular, the evolution of the macroscopic electrostatic potential is governed by a new law, similar to Grahame’s law (see [8] and [9]). An advantage of this approach is that we can avoid the use of extension operators and, therefore, we can deal in a rigorous manner with media which are less regular than those usually considered in the literature (composite materials and biological tissues are highly heterogeneous media with not very smooth interfaces, in general). Similar problems have been considered, using diffe- rent techniques, in [8], [13] or [15]. As already men- tioned, our approach is based on a new method, i.e. the periodic unfolding method, which allows us to consider very general heterogeneous media. Another novelty brought by our paper consists in dealing with a general nonlinear boundary condition for the electrostatic potential and with more general reaction terms. The rest of the paper is organized as follows: in Section 2, we formulate our main convergence result, while Section 3 is devoted to the proof of this result. The paper ends with some conclusions and a few references. II. THE MAIN RESULT Using the periodic unfolding method, we are allowed to pass to the limit in the weak formulation of problem (1) and to obtain the effective behavior of the solution of our microscopic model. Theorem 1. The solution (Φε, c+ε ,c − ε ) of system (1) converges, as ε → 0, to the unique solution (Φ, c+,c−) of the following macroscopic problem in (0,T) × Ω: −div (D0 ∇Φ) + 1 | Yf | σ0G = c + − c− + D, ∂ c± ∂ t − div(D0 ∇c± ±D0 c±∇Φ) = F±0 , (3) with the boundary conditions on (0,T) ×∂Ω:{ D0 ∇Φ ·ν = 0, (D0 ∇c± ±D0 c±∇Φ) ·ν = 0 (4) and the initial conditions c±(0,x) = c±0 (x), ∀x ∈ Ω. (5) Here, σ0 = ∫ Γ σ(y)ds, F±0 (c +,c−) = ∓(c+ − c−) and D0 = (d0ij) is the homogenized matrix, defined as follows: d0ij = 1 |Yf| ∫ Yf ( δij + ∂χj ∂yi (y) ) dy , in terms of the functions χj, j = 1, ...,n, solutions of the cell problems χj ∈ H1per(Yf ) , ∫ Yf χj = 0, −∆ χj = 0 in Yf, (∇χj + ej) ·ν = 0 on Γ, (6) where ei, 1 ≤ i ≤ n, are the vectors of the canonical basis in Rn. III. PROOF OF THE MAIN RESULT We shall only sketch the proof of our main conver- gence result. For details, we refer to [18]. Let us consider now the equivalent variational formu- lation of problem (1): Find (Φε, c+ε , c − ε ), with Φε ∈ L∞(0,T; H1(Ωε)), c±ε ∈ L∞(0,T; L2(Ωε)) ∩L2(0,T; H1(Ωε)), ∂tc ± ε ∈ L2(0,T; (H1(Ωε)) ′ ) (7) such that, for any t > 0 and for any ϕ1, ϕ2 ∈ H1(Ωε), (Φε, c + ε , c − ε ) satisfy:∫ Ωε ∇Φε ·∇ϕ1 dx− ∫ Γε ∇Φε ·νϕ1 dσ = Biomath 2 (2013), 1312302, http://dx.doi.org/10.11145/j.biomath.2013.12.302 Page 3 of 5 http://dx.doi.org/10.11145/j.biomath.2013.12.302 C Timofte, Multiscale Analysis of Ionic Transport in Periodic Charged Media ∫ Ωε (c+ε − c − ε + D) ϕ1 dx, (8) 〈∂tc±ε , ϕ2〉(H1)′ ,H1 + ∫ Ωε (∇c±ε ± c ± ε ∇Φε) ·∇ϕ2dx = ∫ Ωε F±(c+ε ,c − ε )ϕ2 dx (9) and c±ε (0,x) = c ± 0 (x) in Ωε. (10) There exists a unique weak solution (Φε, c+ε , c − ε ) of problem (8)-(10) (see [8], [13] or [18]). Moreover, exactly like in [13], we can prove that the concentration fields are non-negative, i.e. are bounded from below uniformly in ε. Also, the concentration fields are bounded from above uniformly in ε. Under the above hypotheses, by standard techniques, we can show that there exists a constant C ∈ R+, inde- pendent of ε, such that the following a priori estimates hold true: ‖Φε‖L2((0,T )×Ωε) + ‖∇Φε‖L2((0,T )×Ωε) ≤ C max 0≤t≤T ‖c−ε ‖L2(Ωε) + max 0≤t≤T ‖c+ε ‖L2(Ωε)+ ‖∇c−ε ‖L2((0,T )×Ωε) + ‖∇c + ε ‖L2((0,T )×Ωε)+ ‖∂tc−ε ‖L2(0,T ;(H1(Ωε))′ ) + ‖∂tc + ε ‖L2(0,T ;(H1(Ωε))′ ) ≤ C. As already mentioned, we are interested in obtaining the limit behavior, as ε → 0, of the solution (Φε, c+ε , c−ε ) of problem (8)-(10). Our approach is based on the periodic unfolding method introduced by D. Cioranescu, A. Damlamian, G. Griso, P. Donato and R. Zaki (see [3] and [5]). This approach has the advantage that we do not need to use extension operators like in [8] or [13]. Using the properties of the unfolding operator Tε intro- duced in [3] and [5] and the above a priori estimates, we can easily prove that there exist Φ ∈ L2(0,T; H1(Ω)), Φ̂ ∈ L2((0,T) × Ω; H1per(Yf )), c± ∈ L2(0,T; H1(Ω)), ĉ± ∈ L2((0,T) × Ω; H1per(Yf )), such that, up to a subsequence, Tε(Φε) ⇀ Φ weakly in L2((0,T) × Ω; H1(Yf )), Tε(∇Φε) ⇀ ∇Φ +∇yΦ̂ weakly in L2((0,T)×Ω×Yf ), Tε(c±ε ) → c ± strongly in L2((0,T) × Ω; H1(Yf )), Tε(∇c±ε ) ⇀ ∇c ±+∇yĉ± weakly in L2((0,T)×Ω×Yf ). For proving Theorem 1, let us take, first, in the Poisson equation (8), the test function ϕ1(t,x) = ψ0(t,x) + εψ1(t,x, x ε ), with ψ0 ∈D((0,T); C∞(Ω)) and ψ1 ∈D((0,T) × Ω; H1per(Yf )). Unfolding each term by using the operator Tε and passing to the limit with ε → 0, we obtain (see, for details, [18]): T∫ 0 ∫ Ω×Yf (∇Φ(t,x)+ ∇yΦ̂(t,x,y)) (∇ψ0(t,x) + ∇yψ1(t,x,y)) dxdy dt+ σ0 T∫ 0 ∫ Ω Gψ0(t,x) dxdt = T∫ 0 ∫ Ω×Yf (c+(t,x) − c−(t,x)+ D(x))ψ0(t,x)dxdy dt. (11) Then, by density, it follows that (11) holds true for any ψ0 ∈ L2(0,T; H1(Ω)) and ψ1 ∈ L2((0,T) × Ω; H1per(Yf )). Taking ψ0(t,x) = 0, we obtain −∆y Φ̂(t,x,y) = 0 in (0,T) × Ω ×Yf, ∇y Φ̂ ·ν = −∇x Φ(t,x) ·ν on (0,T) × Ω × Γ, Φ̂(t,x,y) periodic in y. By linearity, we get Φ̂(t, x, y) = n∑ j=1 χj(y) ∂Φ ∂xj (t, x), (12) where χj, j = 1, n, are the solutions of the cell problems (6). Taking ψ1(t,x,y) = 0, integrating with respect to x and using (12), we easily get the macroscopic problem for the electrostatic potential Φ. Now, taking in the Nernst-Planck equation (9) the test function ϕ2(t,x) = ψ0(t,x) + εψ1(t,x, x ε ), Biomath 2 (2013), 1312302, http://dx.doi.org/10.11145/j.biomath.2013.12.302 Page 4 of 5 http://dx.doi.org/10.11145/j.biomath.2013.12.302 C Timofte, Multiscale Analysis of Ionic Transport in Periodic Charged Media with ψ0 ∈D((0,T); C∞(Ω)) and ψ1 ∈D((0,T) × Ω; H1per(Yf )), unfolding each term by using the operator Tε and passing to the limit with ε → 0, we get (see [18]) − T∫ 0 ∫ Ω×Yf (c±(t,x)) ∂tψ0(t,x) dxdy dt+ T∫ 0 ∫ Ω×Yf (∇c±(t,x) + ∇yĉ±(t,x,y))(∇xψ0(t,x)+ ∇yψ1(t,x,y)) dxdy dt = T∫ 0 ∫ Ω×Yf F±0 (c +,c−)ψ0(t,x) dxdy dt. (13) By standard density arguments, we see that (13) holds true for any ψ0 ∈ L2(0,T; H1(Ω)) and ψ1 ∈ L2((0,T)× Ω; H1per(Yf )). Taking, first, ψ0(t,x) = 0, and, then, ψ1(t,x,y) = 0, we obtain exactly the macroscopic problem for the concentrations c±. 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Van Roosbroeck, ”Theory of flow of electrons and holes in germanium and other semiconductors”, Bell System Technical J., vol. 29, pp. 560-607, 1950. http://dx.doi.org/10.1002/j.1538-7305.1950.tb03653.x Biomath 2 (2013), 1312302, http://dx.doi.org/10.11145/j.biomath.2013.12.302 Page 5 of 5 http://dx.doi.org/10.1137/080713148 http://dx.doi.org/10.1137/100817942 http://dx.doi.org/10.1007/s10958-011-0443-2 http://dx.doi.org/10.1007/s10659-013-9427-4 http://dx.doi.org/10.1021/cr60130a002 http://dx.doi.org/10.1016/j.jmaa.2012.01.052 http://dx.doi.org/10.4310/CMS.2011.v9.n3.a3 http://dx.doi.org/10.1007/s11565-007-0018-9 http://dx.doi.org/10.1002/j.1538-7305.1950.tb03653.x http://dx.doi.org/10.11145/j.biomath.2013.12.302 Introduction and setting of the problem The main result Proof of the main result Conclusion References