An effectivecharge model for the trapping of impurities of fluids in channels with nanostructured walls.  
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PMID: 23302600 Owner: NLM Status: PubMednotMEDLINE 
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: We present model equations for the trapping and accumulation of particles in a cylindrical channel with nanostructured inner walls when a fluid passes through, carrying a moderate load of impurities. The basic ingredient of the model is the introduction of a phenomenological 'effectivecharge density' of the walls, related to the electrical charges exposed in the nanotexture. The effective charge is gradually reduced as the flow runs through the channel and the trapped impurities cover the internal walls. Based on the proposed equations, the position and time dependence of the areal density of trapped impurities, and the filtration performance, may be calculated. It is proposed that experimentally testing these results may help to understand the enhanced trapping capability observed in many diverse nanotextured channel structures. 
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Manuel V Ramallo 
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Type: Journal Article Date: 20130110 
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Title: Nanoscale research letters Volume: 8 ISSN: 19317573 ISO Abbreviation: Nanoscale Res Lett Publication Date: 2013 
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Created Date: 20130318 Completed Date: 20130319 Revised Date: 20130418 
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Nlm Unique ID: 101279750 Medline TA: Nanoscale Res Lett Country: United States 
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Languages: eng Pagination: 19 Citation Subset:  
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Departamento de Física da Materia Condensada, Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain. ramallo@condmat.eu. 
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Journal Information Journal ID (nlmta): Nanoscale Res Lett Journal ID (isoabbrev): Nanoscale Res Lett ISSN: 19317573 ISSN: 1556276X Publisher: Springer 
Article Information Download PDF Copyright ©2013 Ramallo; licensee Springer. openaccess: Received Day: 18 Month: 9 Year: 2012 Accepted Day: 27 Month: 12 Year: 2012 collection publication date: Year: 2013 Electronic publication date: Day: 10 Month: 1 Year: 2013 Volume: 8 Issue: 1 First Page: 19 Last Page: 19 PubMed Id: 23302600 ID: 3600046 Publisher Id: 1556276X819 DOI: 10.1186/1556276X819 
An effectivecharge model for the trapping of impurities of fluids in channels with nanostructured walls  
Manuel V Ramallo1  Email: ramallo@condmat.eu 
1Departamento de Física da Materia Condensada, Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain 
Recently, [^{1}^{}^{8}] researchers from both academia and industry have experimentally demonstrated that a variety of nanostructures and nanotextured media (see some examples later in this introduction) can efficaciously trap nanoimpurities carried by fluids when a flow is induced by external hydrostatic pressure. These findings are not only scientifically interesting, but also promising for the socially and economically important application of purification of drinking water and other liquids [^{4},^{7}^{}^{9}]. When compared to conventional porous filters, the new media have the important advantages of retaining impurities of sizes typically in the tens of nanometers and, at the same time, presenting a resistance to hydrodynamic flow orders of magnitude smaller than what conventional models would predict for channels of diameters as small as the particles being trapped.
Roughly, we can divide the structures presenting such enhanced impurity trapping capability into two groups: (a) The first group corresponds to those formed by nanometricdiameter channels through which the fluid flows [^{1}^{}^{4}]. A wellknown example is the nanotube arrays grown and experimentally tested by Srivastava and coworkers [^{1}]. Other specially interesting examples are graphene membranes although, by now, they have been probed only through molecular dynamics simulations [^{2}]. In any nanometricdiameter channel, simple size exclusion will play a major role in the retention of nanoimpurities. However, in addition, these structures also exhibit remarkable capability to trap some ions significantly smaller than the channels’ diameter [^{1},^{2}]. The resistance to flow is observed to be well lower than what conventional models predict for these diameters, a phenomena often attributed to waternanostructure interactions (see, e.g., [^{1}]) though not yet fully understood at the quantitative calculation level. (b) The second group corresponds to nanostructures embedded in larger structures, resulting in filters composed by channels with micrometric diameters and inner walls coated with nanoparticles. Examples are conventional microfilters coated with Y_{2}O_{3}[^{5}], ZrO_{2}[^{6}], or Al_{2}O_{3}[^{7},^{8}] nanopowders (further examples can be found in the reviews [^{3},^{4},^{9}]). These structures have been observed by their growers to have a surprisingly good filtration performance for nanometric impurities, as small as approximately 10 nm, in spite of the relatively large diameter of the channels (note that in a channel with a diameter of 1 μm only about 0.04% of the fluid will transit closer than 10 nm from the walls) [^{3}^{}^{9}]. Their hydrodynamic resistance is quite low, similar to the one of conventional micrometric filters. Their trapping capability is observed to depend on pH and zeta potential [^{5}^{}^{8}] and, thus, electrostatic and polar attraction may be suspected to play a significant role in the filtration mechanism and dynamics. However, attempts to modelize them have been scarce. The authors of [^{7},^{8}] empirically characterized their filters using generalpurpose plugflow adsorption models, like those used for column chromatography, and fitting the Langmuir and BET isotherms. While these models may be very useful for the design of improved filters, further theoretical work modelling the trapping capability and time evolution explicitly in terms of the charge of the walls, and also more detailed measurements, seems to be needed to further understand the impurity trapping mechanism and dynamics of this type of channels with nanostructured walls.
The purpose of this ‘Nano Idea Letter’ is to propose a specific model for the nanoimpurity trapping capability of cylindricallike channels with nanostructured inner walls of the type composing filters of category ‘b’ in the previous paragraph. We explore theoretically a simplified but realistic view in which the improved filtration capability is primarily due to the fact that the nanotexturing exposes electrical charges in the walls which induce both electrostatic and van der Waals attractions over the impurities in the fluid. This nanostructuring also provides chemical anchors for the binding of those impurities once they collide with the channel walls. Correspondingly, our basic ingredients will be the introduction of an effectivecharge density, z_{e}, of the inner walls of the channels and writing down as a function of z_{e} the impurity trapping probability. As it could be expected, z_{e }will depend on the areal density n of impurities already trapped in the inner walls of the channel. We obtain within the model the evolution of n and z_{e }with position x and with time t when the liquid is flowing through the channel.
The model produces agreement with the initial trapping performances quantitatively reported by experimentalists in various systems. Also, we propose that further detailed measurements as a function of time may be crucial to test these ideas more thoroughly. We believe that some aspects of the model could also be useful to partly explain the trapping of the smaller ions in the nanodiameter channels of category ‘a’. However, its full applicability to that case is limited by our use of classical dynamics for the carrying fluid. Hence, we do not focus here on that category (also, for these nanodiameter channels, in which the number of fluid atoms is manageably small, molecular dynamics simulations as those in [^{2}] could be a more reliable, albeit not general, approach).
Our starting point, and most of our basic notations, is illustrated in Figure 1. We consider a channel with nanostructured inner walls, its nominal shape being cylindricallike with average radius r_{0}and length L. We divide it into slices along the axial coordinate x, each with differential thickness dx. A fluid flows through the channel due to externally applied hydrostatic pressure, carrying a load of impurities. Some of those impurities will become trapped by the inner wall of the channel, then reducing its effective radius to a value r_{e}(x,t) = r_{0}−r_{1}n(x,t), where t is the time, n is the number areal density of trapped impurities in the inner wall, and r_{1}is a constant proportional to the average volume of impurities. Throughout this letter, by ‘areal density’ we refer to quantities normalized using the nominal area of the inner wall (2Πr_{0}dx for a differential slice) and not the cross section of the channel. Also, for simplicity, we consider all impurities equal among them (subsequent generalization to multiple chemical species should be easy). The average radius of the impurities is noted ρ_{0}. The impurity concentration in the fluid is considered to be moderate enough as to not significantly affect its viscosity and as for the impurities in the fluid to be noninteracting with each other (specially when colliding with the channel wall).
We now introduce the important concept of a phenomenological ‘effective charge’ of the inner wall of the channel. We quantify this effective charge via its areal density z_{e}, and as already commented on in the introduction, it reflects the fact that the nanostructured walls expose charges that induce both electrostatic and van der Waals attractions over the components of the impurities in the fluid. Indeed, z_{e} will depend on the areal density of already trapped impurities n (which will screen out the wall) and also on the chemistry specifics of the wall and impurities. Let us focus on the mutual interplays between n and z_{e} and in obtaining an equation for their evolution with time as flow passes through the channel. In particular, the interdependence z_{e}(n) may be naturally expected to be continuously decreasing when n increases, to take a finite value z_{0} at n = 0 (clean filter), and to saturate to zero when n reaches some critical value n^{sat} at which all active centers of the wall become well covered by impurities. We thus postulate the simplest z_{e}(n) dependence fulfilling such conditions:
(1)
ze=z01−nnsat,ifn<nsat0,ifn≥nsat=z01−nnsat, 
where the notation ∥…∥ stands for min{1,…}. Obviously, other sensible choices for z_{e}(n) are possible such as, e.g., z_{e}(n) = z_{0}(1−∥n/n^{sat}∥)z_{1}, with z_{1} as a positive coefficient that probably covers at a good approximation most actual possibilities depending on its value, as it corresponds to a z_{e}(n) functionality with downwards curvature if 0 < z_{1 }< 1, to no curvature for z_{1 }= 1 (i.e., Equation 1), and to upwards curvature for z_{1 } >1. For simplicity, we shall consider in this letter only the case z_{1 }= 1. Note also that z_{e} may depend on position and time via the n(x,t) dependence.
The role played by z_{e }in our model will be in fact twofold. First, it affects how large the distance is within which if the impurity approximates the inner wall then the latter attracts the former so much as to consider it as a collision. This attraction distance may be seen as an effective radius, ρ_{e}, of the impurity (see Figure 1), so if the distance from the center of the impurity to the center of the channel is larger than r_{e}−ρ_{e}, the impurity will actually touch the wall (dressed with already trapped impurities). Let us discuss the ρ_{e}(z_{e}) dependence. We consider first the simplest case of an unscreened electrostatic interaction, in which the potential energy of an impurity at a distance ρ_{e} from the wall is ∝ze/ρe. Its kinetic energy associated to the thermal agitation is ∝kBT. By equating both and also taking into account the finite bare size of impurities, we obtain ρe=ρ0+ρ1′ze as a reasonable approximation, where ρ1′ is a constant inversely proportional to temperature. More interesting is the case in which ions in the carrying fluid partly screen out the electrostatic interaction. The precise algebraic distance dependence of the screened electrostatic energy may be different for each specific channel, fluid, and impurity, but we adopt here the common DebyeHückel approximation in which this energy at a distance ρ_{e} from the surface is taken as ∝(ze/ρe)exp(−ρe/λD) where λ_{D} is the socalled Debye length. In aqueous liquids, λ_{D }is a function of the ionic strength, and for concreteness, we will consider it to be dominated by the background electrolytes in the fluid rather than by the impurities to be filtered out (this seems to be the case at least of the measurements in [^{5},^{6}]), so λ_{D} is essentially independent on the concentration of the impurities to be trapped by the channel walls. By equating now the screened potential energy at ρ_{e} to the thermal kinetic energy, we get
(2)
zeρe−ρ0exp−ρe−ρ0λD=ρ1z0ρ0. 
In the righthand side of this equation, for convenience, we have expressed the thermal kinetic energy in units of the unscreened potential in the clean channel at a distance ρ_{0} from the surface, so ρ_{1} is an nondimensional coefficient proportional to T. We have also taken into account the finite bare size of the impurities by using ρ_{e}−ρ_{0} instead of ρ_{e} in the potential energy term. From the above equation, ρ_{e }can be obtained with the help of the principal Lambert W function as follows:
(3)
ρe=ρ0+λDWρ0zeλDρ1z0. 
Although W(x) can be easily evaluated by modern computers, it is worthwhile to mention its asymptotes W(x)≃x for x ≪ 1 and W(x)≃lnx−lnlnx for x≳3. In particular, the first limit means that for small values of z_{e}, it is recovered in the linearity of ρ_{e }with z_{e} found for the unscreened interaction, with ρ1′=ρ0/(ρ1z0). In the remaining part of this letter, we shall use the full Equation 3 for the ρ_{e}(z_{e}) functionality.
We may now obtain the fraction f_{e }of impurities that flow, at given t and x values, near a collision distance from the impuritydressed wall. For that, we assume that the fluid velocity profile is given by the Poiseuille law, [^{10}]u(r)∝re2−r2, where u is the fluid velocity and r the distance to the channel’s axis (see [^{11}] for an explicit discussion supporting that at least for channels of radius ≳10 nm, the flows of waterlike liquids driven by hydrostatic pressure are in fact in the Poiseuille regime). Then, f_{e }is given by the fraction of the fluid mass that passes through the outer ring r_{e }−ρ_{e }≤ r ≤ r_{e}, i.e., fe=∫re−ρereu(r)rdr/∫0reu(r)rdr. The result of those integrations is
(4)
fe=ρere−12−12. 
In the considerations leading to Equation 4, we have implicitly taken the concentration of impurities as constant along the radial coordinate r. However, in principle, it could be expected that near the walls the electric potential will influence the distance between impurities. To test whether this effect may be of relevance, a Debyelike concentration profile Cimp(r)=Cbulk(1+zeC′e−(r−re)/λD) was also considered. The corresponding f_{e }is then given by ∫re−ρereCimp(r)u(r)rdr/∫0reCimp(r)u(r)rdr, the explicit algebraic result being too cumbersome to be reproduced here. As it will be commented on in detail later in this letter, we have observed that both Equation 4 and the more complicated alternative are able to predict essentially the same filtering performances and time evolutions, and so in the following, we will employ the simpler Equation 4 unless stated otherwise.
The second influence played by z_{e }in our model concerns the probability that an impurity gets actually bound to the inner wall of the channel once it actually is within a collision distance from that wall. We express the probability that a given impurity entering a differential slice of the channel with thickness dx gets trapped in that slice as Ωtrap=feΩtrap′dx, where Ωtrap′ is then a trapping probability per unit length for the impurities flowing near a collision distance from the surface. This Ωtrap′ will obviously depend on the chemistry of impurities and active centers of the nanostructure and also on the number density of active centers not yet saturated by existing bindings. The latter indicates that Ωtrap′ will grow with z_{e}, and in particular, we may adopt the natural firstorder approximation Ωtrap′=Ω0+Ω1ze (Ω_{0}corresponds then to the value in a conventional nonnanostructured filter and Ω_{0 }≪ Ω_{1}z_{0}).
Let us now build, on the basis of the above relationships, equations for the evolution of the areal density of trapped impurities, n, as a function of time t and position x when an impure fluid flows through the channel due to hydrostatic pressure. We start by considering the differential channel slice going from x up to x + dx, and we write down the expression for ∂n/∂t evaluated at that slice, which may evidently be expressed as Φ_{imp}Ω_{trap}/(2Πr_{0}dx), where Φ_{imp} is the flow of impurities brought by the incoming fluid (in units of s^{−1}; the factor (2Πr_{0}dx)^{−1 }is due to the areal density normalization in the definition of n). In its turn, Φ_{imp} can be written as Φ_{imp }= C_{imp}Φ where Φ is the fluid flow and C_{imp }the incoming number concentration of impurities. Gathering together the previous results in this letter, we get
(5)
∂n(x,t)∂t=Cimp(x,t)Φ(t)2Πr0Ω0+Ω1ze(n(x,t))×ρe(ze(n(x,t)))r0−r1n(x,t)−12−12, 
with the z_{e}(n) and ρ_{e}(z_{e}) dependences given by Equations 1 and 3.
In order to solve the filtration dynamics (i.e., to obtain n(xt) and C_{imp}(xt)), it is necessary to supplement Equation 5 with formulas for Φ(t) and C_{imp}(xt). Regarding the fluid flow, we apply the Poiseuille law for incompressible fluids of viscosity η in a cylindrical channel of length L and radius r_{e}(xt): [^{10}]
(6)
Φ(t)=ΠP8η∫0Lr0−r1n(x,t)−4dx. 
In this equation, P is the pressure difference between both ends of the finitelength channel, which we take constant with time. Note that Φ becomes zero when at some x, the n value becomes n^{clog }≡ r_{0}/r_{1}, i.e., r_{e} becomes zero at that location and the channel becomes fully closed by impurities. Note also that Equation 6 reduces in the particular case r_{0 }≫ r_{1}n(x,t) (which is common in experiments) to Φ=ΠPr04/(8ηL).
We construct now the supplementary equation for C_{imp}(x,t). For that, we again consider the differential channel slice going from x up to x + dx. The number of impurities that become trapped in its walls during an interval dt is (2Πr_{0}dx)(∂n/∂t)dt (the factor 2Πr_{0}dx is again due to the areal normalization in the definition of n). The numbers of impurities entering and exiting the slice in the liquid flow are Φ(t)C_{imp}(x,t)dt and Φ(t)C_{imp}(x + dx,t)dt respectively. Mass conservation balance therefore gives
(7)
∂Cimp(x,t)∂x=−2Πr0Φ(t)∂n(x,t)∂t. 
Notice that Equations 5 to 7 are coupled to each other. In fact, they form now a closed set that can be numerically integrated by providing the specific values for the characteristics of the filter, for any given pressure difference P and incoming impurity concentration C_{imp}(0,t). In what follows, for simplicity, we will always consider for the latter a constant value C_{0}. The computation to numerically integrate Equations 5 to 7 is relatively lightweight (e.g., calculating our Figure 2 took about 15 min in a current personal computer that considered 2 × 10^{4 }finiteelement xslices).
We show in Figure 2 an example of the results obtained by numerically integrating Equations 5 to 7 using some representative values for the parameters involved (and always in the case of constant P and C_{imp}, and starting from a clean initial state n(xt = 0)=0). In particular, we have chosen parameter values that reproduce the case of channels coated with Y_{2}O_{3} nanopowders as measured in [^{5}] (they are essentially valid also for the quite similar case of channels with ZrO_{2} nanocoating reported by the same group in [^{6}]). In these filters, the channels have a typical value of the nominal radius r_{0 }= 500 nm and length L = 7.25 mm. They were shown [^{5}] to efficaciously retain MS2 viruses (of radius ρ_{0 }= 13 nm) carried by water with NaCl as background electrolyte and a conductivity of 400μS/cm (corresponding then to λ_{D}≃5.1 nm) feed at a pressure P = 3 bar. The incoming impurity number concentration was Cimp(x=0,t)=1010/m3. For the saturation areal density n^{sat}, we will estimate, based on figure nine of [^{5}], a quite conservative value n^{sat }= 1.5 × 10^{15}/m^{2}, corresponding to 0.25/ρ02. For the parameter r_{1}, we will use the value 4ρ03, also consequent in the order of magnitude with figure nine of [^{5}]. These numbers imply that at saturation (n = n^{sat}), the effective radius of the channel is resat=487 nm. Note that this value is rather close to the cleanstate value of 500 nm, and then it would correspond to an increase of the hydrodynamic resistance of only about 10% (unfortunately, the nanocoatings in [^{5},^{6}] seem to be washed out before they can be fully saturated; however, other nanocoated filters [^{4},^{7},^{8}] have been shown to have hydrodynamic resistance only moderately increased at saturation, what is indeed an advantage of paramount importance for applications). We will also assume a null Ωtrap′ value at the saturated state, i.e., Ω_{0 }= 0 (so that we neglect conventional filtration mechanisms and focus on the effects of nanostructuring alone). In order to proceed with the numerical calculation of Equations 5 to 7, only two parameters remain to be given estimated values: Ω_{1}z_{0}(Ω_{1} and z_{0} do not appear separately in Equations 5 to 7) and ρ_{1}(or equivalently, via Equation 3, the effective impurity radius in the clean state of the channel, ρeclean). We have found that the values Ω_{1}z_{0 }= 1.2 × 10^{5}/m and ρ_{1 }= 0.11 produce results in reasonable agreement with the available experimental information, as we discuss below. The value ρ_{1 }= 0.11 corresponds to ρeclean=33 nm, or ρ_{0} + 4λ_{D}.
Figure 2a presents the results corresponding to integrating Equations 5 to 7 using these parameter values, for the areal density of trapped impurities at the entrance of the channel n(x = 0,t) and at its exit point n(x = Lt) and also for the global average areal density of trapped impurities n¯(t)=L−1∫0Ln(x,t)dx. Figure 2b presents the corresponding logarithmic removal value (LRV), calculated as −log10[Cimp(x=L,t)/Cimp(x=0,t)]. Note that in Figure 2a,b, the time axis is logarithmic and that for convenience, it was normalized by the time t_{1/2} defined by the condition n¯(t1/2)=nsat/2 (halfsaturation time). The agreement of these numerical results with the measured filtration performance reported in [^{5},^{6}] is fairly good. In particular, we obtain an initial LRV of 6.5 log, equal to the LRV measured in [^{5},^{6}] when the actual filters (composed by a macroscopic array of microchannels) were challenged with only about 1 L of water (the authors of [^{5},^{6}] estimate that such volume carries a total amount of impurities that is orders of magnitude smaller than the total available binding centers in their filter, so the measurement is expected to correspond to almost clean channels, as in fact seems to be confirmed by microscopy images [^{5}]). The calculated LRV is of 4 log at t/t_{1/2}≃0.7, which is also in fair agreement with the observation of a 4 log filtration in [^{5},^{6}] after passing through the macroscopic filter approximately from 200 to 1,000 L, depending on the measurement. However, obviously, a more stringent determination of the parameter values, and in general of the degree of validity of our equations, would need more precise and detailed data. Unfortunately, to our knowledge, no measurements exist for the time evolution of the filtering efficiency of channels with nanostructured walls with a tdensity and precision sufficient for a fully unambiguous quantitative comparison with the corresponding results of our equations; in fact, one of the main motivations of the present Nano Idea Letter is to propose (see our conclusions) that such measurements should be made, in order to further clarify the mechanism behind the enhanced impurity trapping capability of the channels with nanostructured inner walls.
As a further test, we have repeated the same numerical integration as in Figure 2a,b but considering a radial impurity concentration profile Cimp(r)∝1+zeC′e−(r−re)/λD, instead of a constant one as in Equation 4. We have obtained very similar results, provided that the parameter Ω_{1}z_{0} is conveniently varied: In particular, we observed that the filtration dynamics results obtained using Equation 4 and any given value γ for Ω_{1}z_{0 }can be reproduced using the above Debyelike profile if employing for Ω_{1}z_{0} a new value (specifically, the new value can be estimated, by comparing the initial filtration performance, as γIr0−ρeclean1I0Cimp(r)/I01Ir0−ρecleanCimp(r), where Ixy(x)=∫xrey(x)u(x)dx ; for instance, taking z0C′=200, which probably is a fair first approximation for the measurements in [^{5}^{}^{8}], the parameter values used in Figure 2 correspond to 3.2 × 10^{4}/m as equivalent Ω_{1}z_{0 }value when using the Debye approach). These results indicate then that, as it could be expected, the wall charge effect on the radial gradient of the concentration may be safely summarized, for our present purposes, as one of the factors influencing the value of the trapping probability coefficient Ω_{1}z_{0} to be used when applying Equation 4.
In Figure 2a, it is possible to identify in our results for the areal density of trapped impurities some tranges in which the tdependence is relatively simple: (1) The initial time behavior is an approximately linear n(t) growth; (2) in the intermediate regime, the growth of n(t) becomes approximately logarithmic; and (3) at sufficiently large t values, the saturation limit is reached, in which n approaches a value n^{sat} at a slow pace. These regimes are easily seen in Figure 2a for n(x = 0,t), n(x = L,t), and n¯(t), albeit in each case they are located at different t/t_{1/2 }ranges. The figure also evidences that it is possible for the linear and logarithmic tranges to overlap each other (the case of n¯(t) with the parameter values used in Figure 2).
In the case of a very short cylindrical channel (so that all xderivatives may be neglected), it is possible to find analytical expressions for the n(t) evolution in the linear and logarithmic regions: For the linear regime, by just introducing in Equation 5 the condition t ≃ 0, we find:
(8)
n(t)≃Alint 
with
(9)
Alin=(Ω0+Ω1z0)CimpP16ηLr0×ρ0−r0+λDWρ0λDρ12−r022. 
The logarithmic regime can be found by using the condition n ≃ n^{sat}/2:
(10)
n(t)≃nsat2+Aloglntt1/2 
with
(11)
Alog=(2Ω0+Ω1z0)t1/2CimpP512ηLr0×2ρ0−2r0+λDWρ0λDρ1+r1nsat2−2r0−r1nsat22. 
In obtaining the above Equations 8 to 11, we have assumed that n(0) = 0 and that ρ_{e }< r_{e} at t = 0 or t_{1/2}.
This letter has proposed a model for the main generic features of the channels with nanostructured inner walls with respect to trapping and accumulation of impurities carried by fluids. This includes, e.g., their capability to clean the fluid from impurities of a size much smaller than the channels’ nominal radius, with comparatively small resistance to flow (much smaller than in conventional channels with a radius as small as the impurities). The model attributes the enhanced filtration capability to the longrange attraction exerted by the exposed charges in the nanostructured walls and also to their binding capability once the impurities actually collide with them. Both features were quantitatively accounted for by means of a phenomenological ‘effectivecharge density’ of the nanostructured wall. The model also predicts the time evolution of the trapped impurity concentration and of the filtering capability, including three successive regimes: a linear regime, a logarithmic regime, and the saturated limit.
We believe that our equations could make possible some valuable future work, of which two specific matters seem to us more compelling: First, it would be interesting to check at the quantitative level the agreement with experiments of the time evolutions predicted above. For that, we propose to perform timedependent measurements made in controlled flow setups. We have chosen in our equations flow constraints which seem appropriate for this purpose; however, the model can be tested with different setups by just numerically integrating Equation 5 under the corresponding experimental constraints. One of the prime purposes of this letter is in fact to suggest such measurements.
A second interesting future work (already in progress in our research group) is the design of optimal geometries for the combinations of channels forming filters. Our model opens this possibility because of the explicit use of the Poiseuille relations that allow the calculation of the resistance to flow of complex associations of those channels, in series and/or parallel. The effective diffusivity and tortuosity of the pathways’ network are also accounted for by these equivalentcircuit analyses.
The author declares that he has no competing interests.
This work has been supported by the MICINN project FIS201019807 and by the Xunta de Galicia 2010/XA043 and 10TMT206012PR projects. All projects are cofunded by ERDF from the European Union.
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Figures
[Figure ID: F1] 
Figure 1
Representation of a nanostructured channel filter as modelled in the present letter. The nominal shape of the channel is supposed to be cylindrical with length L, and the figure shows only the differential slice with axial coordinate from x to x + dx. The radiuses r_{0 }and ρ_{0 }correspond to the average dimensions of the bare channel and impurities. The effective radiuses r_{e }and ρ_{e }vary as trapped impurities cover the inner wall, via their dependences on, respectively, the areal density n of trapped impurities and on the areal density z_{e }of effective charge of the inner wall. This z_{e }reflects that exposed charges in a nanostructured surface attract the impurities in the fluid and also constitute binding anchors for those impurities. It is expected to diminish as impurities cover the surface, for which we assume the simple z_{e}(n) dependence given by Equation 1 of the main text. 
[Figure ID: F2] 
Figure 2
Time dependence. (a) Results, obtained by integrating Equations 5 to 7, for the time dependence of the areal density of trapped impurities (continuous lines) at the entrance of the channel n(x = 0,t) and at its exit point n(x = L,t), and also the global average areal density of trapped impurities n¯(t)=L−1∫0Ln(x,t)dx. The areal density axis is normalized by the saturation value n^{sat}. The time axis is normalized by the halfsaturation time, defined by n¯(t1/2)=nsat/2. The parameter values used are as follows (see main text for details): ρ_{0 }= 13 nm, ρ_{1 }= 0.11, λ_{D }= 5.1 nm, nsat=1.5×1015/m2=0.25/ρ02, r_{0 }= 500 nm, r1=8.8×10−24,m3=4ρ03, Ω_{0 }= 0, Ω_{1}z_{0 }= 1.2 × 10^{5}/m, L = 7.25 mm, P = 3×10^{5} Pa, η = 10^{−3 }Pa·s, and Cimp(x=0,t)=1010/m3. We also show the linear, logarithmic, and saturated behaviors (as dashed, dotted, and dotdashed lines respectively). (b) Time dependence of the logarithmic removal value (LRV), calculated using the same parameter values as in Figure 2a. 
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Keywords: Nanostructures embedded in larger systems, Fluid impurity trapping in nanostructures, Effectivecharge density. 
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