Numerical Investigation of Diffusioosmotic Flow in a Tapered Nanochannel.

Diffusioosmosis concerns ionic flow driven by a concentration difference in a charged nano-confinement and has significant applications in micro/nano-fluidics because of its nonlinear current-voltage response, thereby acting as an active electric gating. We carry out a comprehensive computation fluid dynamics simulation to investigate diffusioosmotic flow in a charged nanochannel of linearly varying height under an electrolyte concentration gradient. We analyze the effects of cone angle (α), nanochannel length (l) and tip diameter (dt), concentration difference (Δc = 0-1 mM), and external flow on the diffusioosmotic velocity in a tapered nanochannel with a constant surface charge density (σ). External flow velocity (varied over five orders of magnitude) shows a negligible influence on the diffusioosmotic flow inside the tapered nanochannel. We observed that a cone angle causes diffusioosmotic flow to move towards the direction of increasing gap thickness because of stronger local electric field caused by the overlapping of electric double layers near the smaller orifice. Moreover, the magnitude of average nanoflow velocity increases with increasing |α|. Flow velocity at the nanochannel tip increases when dt is smaller or when l is greater. In addition, the magnitude of diffusioosmotic velocity increases with increasing Δc. Our numerical results demonstrate the nonlinear dependence of tapered, diffusioosmotic flow on various crucial control parameters, e.g., concentration difference, cone angle, tip diameter, and nanochannel length, whereas an insignificant relationship on flow rate in the low Peclet number regime is observed.

Renewable Power Generation by Reverse Electrodialysis Using an Ion Exchange Membrane.

Reverse electrodialysis (RED) is a promising technology to extract sustainable salinity gradient energy. However, the RED technology has not reached its full potential due to membrane efficiency and fouling and the complex interplay between ionic flows and fluidic configurations. We investigate renewable power generation by harnessing salinity gradient energy during reverse electrodialysis using a lab-scaled fluidic cell, consisting of two reservoirs separated by a nanoporous ion exchange membrane, under various flow rates (qf) and salt-concentration difference (Δc). The current-voltage (I-V) characteristics of the single RED unit reveals a linear dependence, similar to an electrochemical cell. The experimental results show that the change of inflow velocity has an insignificant impact on the I-V data for a wide range of flow rates explored (0.01-1 mL/min), corresponding to a low-Peclet number regime. Both the maximum RED power density (Pc,m) and open-circuit voltage (ϕ0) increase with increasing Δc. On the one hand, the RED cell's internal resistance (Rc) empirically reveals a power-law dependence of Rc∝Δc-α. On the other hand, the open-circuit voltage shows a logarithmic relationship of ϕ0=BlnΔc+ß. These experimental results are consistent with those by a nonlinear numerical simulation considering a single charged nanochannel, suggesting that parallelization of charged nano-capillaries might be a good upscaling model for a nanoporous membrane for RED applications.

Filling of charged cylindrical capillaries.

We provide an analytical model to describe the filling dynamics of horizontal cylindrical capillaries having charged walls. The presence of surface charge leads to two distinct effects: It leads to a retarding electrical force on the liquid column and also causes a reduced viscous drag force because of decreased velocity gradients at the wall. Both these effects essentially stem from the spontaneous formation of an electric double layer (EDL) and the resulting streaming potential caused by the net capillary-flow-driven advection of ionic species within the EDL. Our results demonstrate that filling of charged capillaries also exhibits the well-known linear and Washburn regimes witnessed for uncharged capillaries, although the filling rate is always lower than that of the uncharged capillary. We attribute this to a competitive success of the lowering of the driving forces (because of electroviscous effects), in comparison to the effect of weaker drag forces. We further reveal that the time at which the transition between the linear and the Washburn regime occurs may become significantly altered with the introduction of surface charges, thereby altering the resultant capillary dynamics in a rather intricate manner.

Streaming potential and electroviscous effects in soft nanochannels: towards designing more efficient nanofluidic electrochemomechanical energy converters.

In this paper we provide analytical solutions for the streaming potential and electroviscous effects in soft nanochannels. The analysis is based on the solution of the linearized Poisson-Boltzmann equation, valid for small electrostatic potentials. We identify the important dimensionless parameters that dictate these two effects. Results are provided for a large range of electric double layer (EDL) thickness values, spanning from the case of very thin to very large overlapped EDL thicknesses. We compare the results with those of a rigid nanochannel, having zeta potential equal to the electrostatic potential at the solid-polyelectrolyte interface of the soft nanochannels. For the soft nanochannel, the streaming potential varies very weakly with the EDL thickness and can be substantially larger than that corresponding to the rigid nanochannel. The electroviscous effects for the soft nanochannel, unlike the rigid nanochannel, virtually always exhibit a monotonic decrease with the EDL thickness, and for certain parameter ranges can be several times larger than that for a rigid nanochannel. Most importantly, for the soft nanochannels the electrochemomechanical energy conversion, associated with the generation of streaming potential, is found to be highly efficient, with the efficiency being several times higher than that of a rigid nanochannel.

Effect of finite ion sizes in an electrostatic potential distribution for a charged soft surface in contact with an electrolyte solution.

We provide a theory to analyze the impact of finite ion sizes (or steric effect) in electrostatic potential distribution for a charged soft surface in contact with an electrolyte solution. The theory is based on a free energy model that appropriately accounts for the contribution of finite ion sizes as well as the structural characteristics of a soft interface, represented by a combination of a rigid surface and a fixed charge layer (FCL), with the FCL being in contact with an electrolyte solution forming an electric double layer (EDL). This FCL contains a particular kind of ion which is impermeable to the electrolyte solution, and this impermeability is quantified in terms of the corresponding Donnan potential of the "membrane" represented by the FCL-electrolyte interface. We find that consideration of the finite ion size increases the magnitude of this Donnan potential, with the extent of increase being dictated by three length scales, namely, the thickness of the FCL, the thickness of the electrolyte EDL, and the thickness of an equivalent EDL within the FCL. Such regulation of the Donnan potential strongly affects the distribution of the permeable electrolyte ions within the FCL, which in turn will have significant implications in several processes involving "soft" biological membranes.