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At least 37 records · Page 2

Tree-inspired lignin microrods-based composite heterogeneous nanochannels for ion transport and osmotic energy harvesting

One of the key processes of tree lignification is that lignin penetrates into the cell wall and fills in the cell wall framework, thereby increasing the hardness and hydrophobic of the tree channels, which is beneficial to consolidate and support the tree cell wall and water transport. Inspired by this natural process, we demonstrated a lignin-based nanofluidic heterogeneous membrane that closely mimics the channels in tree, which can realize ion transport function and effectively capture reverse electrodialysis. The membrane was synthesized by heating dealkaline lignin and PVA at 200 °C and this formed fusiform microrods and a closed-packed membrane. Simultaneously, this membrane composited with anodized aluminum (AAO) channels membrane at 200 °C to form asymmetric heterogeneous nanochannels membrane, which can transport counter-ions and harvest osmotic energy. This membrane implements ion current rectification in 0.1 M KCl electrolyte solution at pH 3 due to the confinement of pores and opposite surface charges in lignin-based heterogeneous nanochannel. An output power density of 0.97 W m- 2 is obtained under a 50-fold salinity gradient, which can be further improved to 1.19 W m -2 by increasing the salinity gradient from 50-fold to 500-fold. Accordingly, this nanofluidic membranes were prepared by using lignin, the key component in tree, which not only mimicked a crucial process of the water and ionic transport process of channels in tree, but also had the prospect in the field of osmotic energy harvesting.

09 BIOMASS FUELS↗

Electrostatic Gating of Ionic Conductance through Heterogeneous van der Waals Nanopores

Nanofluidic ionic transistors typically require gate voltages above 1 V and operate only at submillimolar ionic strengths, limiting their biocompatible applications. We demonstrate ionic transistors consisting of single sub-10 nm nanopores drilled in van der Waals (vdW) heterostructures with internal gate electrodes made of few-layer graphene. These devices deliver up to 10-fold current modulation at gate voltages as low as 0.3 V in 10 mM KCl, and ∼2-fold modulation at near-physiological 100 mM KCl. Baseline conductance with no gate shows surface-charge-dominated transport below 100 mM KCl, consistent with negatively charged hBN walls and ∼5 nm opening of the pores. The surface charge and the electrochemical asymmetry introduced by the three-electrode configuration govern the device’s behavior: negative gate voltage (V G ) enriches ionic concentrations and enhances current, whereas positive V G induces a local depletion zone that suppresses transport. The current modulation by V G is dependent on the polarity of the transmembrane potential and leads to ion current rectification. Molecular dynamics simulations of a nanopore in a hBN–graphene–hBN stack reveal confinement and surface charge-dependent suppression of the relative permittivity of interfacial water. Continuum modeling with radially varying interfacial water permittivity reproduces the asymmetric I–V characteristics and explains how the embedded gate sculpts local potential and ion concentrations. By enabling sub-0.5 V control of ionic transport at up to 100 mM salt concentrations, these devices address a key need in nanofluidics to create low-power ionic circuits and biosensing.

Materials science↗

Surfactant for enhanced oil recovery

A Janus graphene nanosheet (JGN) surfactant formed from a two-dimensional graphene oxide sheet and functionalized to produce an amphiphilic graphene nanosheet. The JGN may be a component of a nanofluid utilized in nanofluid flooding for oil recovery. The JGN may also be used as solid surfactants to form emulsions for oil recovery.

Ren, Zhifeng↗

Additive manufacturing

A nanofluid laser entrainment additive manufacturing apparatus, system and method including a substrate, a dilute nanofluid of inert gas suspended nanoparticles on the substrate, a focused energy beam that irradiates the nanoparticles to selectively melt the nanoparticles, and a raster system that raster scans the focused energy beam across the inert gas suspended nanoparticles to create predetermined shapes by additive manufacturing.

Matthews, Manyalibo Joseph↗

Synaptic Functionality and Neuromorphic Information Processing in Membrane Ion Channel Junctions

The human brain performs complex memory and computational tasks with high energy efficiency by regulating ion transport through membrane channels. These signaling mechanisms have been inspiring the development of nanofluidic memristors that emulate synaptic behavior. Here, in this study, we describe a membrane ion channel synapse (MICS), constructed from aqueous droplets linked by gramicidin A channels, that achieves neuromorphic functionality. MICS exhibits memristive ion transport with hysteretic current–voltage behavior arising from voltage-dependent channel formation and ion transport dynamics. MICS emulates a range of synaptic behaviors including associative learning. We further demonstrate its application in reservoir computing by performing handwritten digit classification and tic-tac-toe game and explore the system parameters that improve the computational performance. This droplet-based biomimetic synapse offers a potentially scalable and energy-efficient platform for next-generation neuromorphic computing systems.

Droplet interface bilayer↗

Ion Transport in Carbon Nanotube Porins with a pH-Switchable Entrance Gate

Molecular transport in nanofluidic channels often differs drastically from conventional bulk transport. Strong confinement in those channels amplifies the roles of surface transport, surface defects, and molecular gates. Here, in this study, we introduce a chemical functionality at the nanotube rim that acts as a pH-triggered molecular gate by forming a movable lid that blocks the pore entrance. We use ion and proton transport measurements to show that these sub-1 nm diameter fluorescent ultrashort carbon nanotube porins (FUNPs) modulate ion transport by switching between the “open” and “closed” conformations of this gate. Specifically, at neutral pH the channel lid is open, allowing unimpeded ion transport through the gate, whereas at acidic pH values the lid forms a “closed” conformation that blocks transport through the nanotube. We also report first-principles MD simulations that confirm this gating mechanism and reveal molecular details of the ion and proton transport processes in these functional nanopores.

Carbon nanotubes↗

Transport of polymer-coated metal–organic framework nanoparticles in porous media

Abstract Injecting fluids into deep underground geologic structures is a critical component to development of long-term strategies for managing greenhouse gas emissions and facilitating energy extraction operations. Recently, we reported that metal–organic frameworks are low-frequency, absorptive-acoustic metamaterial that may be injected into the subsurface to enhance geophysical monitoring tools used to track fluids and map complex structures. A key requirement for this nanotechnology deployment is transportability through porous geologic media without being retained by mineral-fluid interfaces. We used flow-through column studies to estimate transport and retention properties of five different polymer-coated MIL-101(Cr) nanoparticles (NP) in siliceous porous media. When negatively charged polystyrene sulfonate coated nanoparticles (NP-PSS-70K) were transported in 1 M NaCl, only about 8.4% of nanoparticles were retained in the column. Nanoparticles coated with polyethylenimine (NP-PD1) exhibited significant retention (> 50%), emphasizing the importance of complex nanoparticle-fluid-rock interactions for successful use of nanofluid technologies in the subsurface. Nanoparticle transport experiments revealed that nanoparticle surface characteristics play a critical role in nanoparticle colloidal stability and as well the transport.

58 GEOSCIENCES↗

Incorporating the molecular-scale into a hydrodynamic description of confined aqueous systems

Hydrodynamics provides a continuum-level description of fluid motion, but its applicability at the nanoscale becomes uncertain due to the emerging importance of molecular-level effects such as spatial heterogeneity. Hydrodynamic boundary conditions that incorporate molecular details allow us to partition the system into a near-wall region and a bulk fluid region. We identify a hydrodynamic wall located inside the fluid that determines where slip begins. By extending the hydrodynamic wall with the slip length, the position of the extrapolated wall is established. This offers a unified description of both slip and stagnant flow behaviors, with wall hydrophobicity characterized by the relative location of the extrapolated wall with respect to the physical wall. Employing this concept in analyses of equilibrium molecular dynamics (MD) and non-equilibrium MD simulations of Couette and Poiseuille flows, our results demonstrate consistency between equilibrium and non-equilibrium approaches across different flow types and confinement levels. This demonstrates the robust nature of linear response theory. We then explore the effects of fluid-wall and bulk fluid interactions on the hydrodynamic properties. These findings enhance the effectiveness of molecular-based simulations for investigating complex confined systems in nanofluidics, biology, and colloidal science, offering a complementary molecular-scale perspective to traditional continuum approaches.

flow simulations↗

Design, Deployment, and Characterization of the World’s First Flexible Large Power Transformer

GE Research and its partner Prolec GE have designed, built and deployed in the field the world’s first flexible power transformer. The flexible power transformer is a transmission class 3-phase autotransformer configurable in impedance and in voltage which allows it to serve as a universal spare for multiple units in a given fleet. However, the key innovation in this new concept is the online adjustable leakage impedance which allows the transformer to change its impedance without interrupting the transmission line operation. The flexible power transformer can be designed with up to three low voltage transmission class ratings and up to 12 impedance values changeable both online and offline. This report provides an overview of the design, manufacturing, testing, and commissioning of the 165kV, 60MVA prototype built including the results of the field performance validation tests. The prototype was specified in collaboration with Cooperative Energy, the utility host. It was designed and tested in the factory according to IEEE standard C57.12.00 and followed all protocols for transportation, installation, and commissioning of a power transformer. In addition to the prototype, a flexible protection system capable of automatically adjusting its settings upon the transformer impedance was also developed and deployed in the for testing and validation. On September 3, 2021 the prototype was energized in Cooperative Energy’s substation in Columbia, Mississippi to become the world’s first flexible power transformer in operation. Its performances and impact on the grid operation were demonstrated through different field tests. Results obtained confirm that the impedance of the flexible transformer can be varied under load through its full range, from 4.3% to 9.3%, without adverse impacts on the line operation, the protection system, the transformer stability and health condition. Results also proved that the flexible transformer is very effective in controlling power transfer through the line or load sharing between units operating in parallel. Indeed, it was proven that higher impedances decrease the thruput power of the transformer while lower impedances increase it. Up to 26MW was controllable on a line loading of 45MVA. It was also possible to demonstrate that the variation of the transformer impedance has no effect on the circulating current between units in parallel, except a minor transient during the impedance change. It was also proven that the flexible protection relay can update its protection settings automatically when the impedance change was detected. The prototype has operated continuously for more than 12 months now with a peak load exceeding 50MVA corresponding to >80% of its ONAN power rating. No alarm, trip or sign of failure has been reported by the utility. In addition to the development and deployment of the flexible transformer prototype, investigations were carried out on new nanodielectric fluids to replace the mineral oil used in power transformers with the goal of reducing their footprint and weight. The key parameters that were targeted for improvement included the breakdown voltage to reduce clearances between windings and tank hence the footprint; viscosity and thermal conductivity to increase the cooling efficiency and therefore to reduce the winding material. Several nanodielectric mixtures with mineral oil including with alumina (Al2O3), titania (TiO2) and Borum Nitrate (BN) with different surfactants have been analyzed and tested. Unfortunately, despite encouraging results no nanofluid candidate has been found viable to replace mineral oil. With the formulations tested, breakdown voltages are generally similar to mineral oil at lower particle contents and worse at higher particle contents. Viscosity appreciably increased at particles concertation over 2 wt% and thermal conductivity increased slightly at 5wt% and appears to be 10-15% higher at 10 wt% particle content. It is recommended to continue investigations to find solutions that can help increase the power density of future flexible power transformers. Flexible power transformers can significantly help the future power grid by providing more flexibility and resiliency. Indeed, by providing voltage and impedance flexibility, flexible power transformers reduce the need for multiple spares, hence inventory costs for utilities. With their online controllable impedance, they can provide support to the grid and help manage short-circuit currents, power flow, line congestion, and grid stability which will become more important with higher penetrations of intermittent renewable resources. During the field validation tests, it was demonstrated that up to 26MW was controllable on a line loading of 45MVA when the transformer impedance was varied from its minimum to its maximum range. Also, with the impedance range, the short-circuit currents could be reduced by up to 38% at the load side of the transformer. With its controllable impedance, flexible transformers can be used in future strategies of grid resilience to help better prepare the grid to face forecasted severe events including storms, heat waves and contingencies. The flexible power transformers can also find role in other applications including high voltage transmission cables such as offshore wind farms where solutions for energizing the cables and managing the reactive power are of critical importance. The designed flexible power transformer is now fully validated and ready for commercialization. Further analysis on the benefits of flexible power transformers for grid stability and short-circuit management including current limiting capability, reclosure and line restoration, control of inrush current, sizing of flexible AC components (FACTS) would help its rapid adoption by the industry.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Catalytic Reduction of Graphene Oxide Membranes and Water Selective Channel Formation in Water–Alcohol Separations

Graphene oxide (GO) is a promising membrane system for chemical separation applications due to its 2-D nanofluidics properties and an ability to control interplanar spacing for selectivity. The permeance of water, methanol (MeOH) and isopropyl alcohol (IPA) through 5 µm thick membranes was found to be 0.38 ± 0.15, 0.33 ± 0.16 and 0.42 ± 0.31 LMH/bar (liter/m2·h·bar), respectively. Interestingly, the permeance of a water–alcohol mixture was found to be dramatically lower (~0.01 LMH/bar) than any of its components. Upon removing the solvent mixture, the transmembrane flux of the pure solvent was recovered to near the original permeance. The interlayer space of a dried GO membrane was found to be 8.52 Å, which increased to 12.19 Å. 13.26 Å and 16.20 Å upon addition of water, MeOH and IPA. A decrease in d-space, about 2 Å, was consistently observed when adding alcohol to water wetted GO membrane and an optical color change and reduction in permeance. A newly proposed mechanism of a partial reduction of GO through a catalytic reaction with the water–alcohol mixture is consistent with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potentiometric Studies on Ion-Transport Selectivity in Charged Gold Nanotubes

Under ideal conditions, nanotubes with a fixed negative tube-wall charge will reject anions and transport-only cations. Because many proposed nanofluidic devices are optimized in this ideally cation-permselective state, it is important to know the experimental conditions that produce ideal responses. A parameter called Ccrit, the highest salt concentration in a contacting solution that still produces ideal cation permselectivity, is of particular importance. Pioneering potentiometric studies on gold nanotubes were interpreted using an electrostatic model that states that Ccrit should occur when the Debye length in the contacting salt solution becomes equivalent to the tube radius. Since this “double-layer overlap model” (DLOM), treats all same-charge ions as identical point charges, it predicts that all same-charged cations should produce the same Ccrit. However, the effect of cation on Ccrit in gold nanotubes was never investigated. This knowledge gap has become important because recent studies with a polymeric cation-permselective nanopore membrane showed that DLOM failed for every cation studied. To resolve this issue, we conducted potentiometric studies on the effect of salt cation on Ccrit for a 10 nm diameter gold nanotube membrane. Ccrit for all cations studied were, within experimental error, the same and identical, with values predicted by DLOM. The reason DLOM prevailed for the gold nanotubes but failed for the polymeric nanopores stems from the chemical difference between the fixed negative charges of these two membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potential-induced wetting and dewetting in hydrophobic nanochannels for mass transport control

Wetting and dewetting transitions play a central role in controlling the hydrophobicity of the lining of biological channels in order to regulate aqueous solution permeation. Understanding of the operational characteristics of biological nanochannels led to experimental efforts to mimic their behavior and to achieve potential-induced, repeatedly-switchable wettability transitions in synthetic nanochannels in the early 2010s. Since then, research has identified conditions needed to produce reversible wettability transitions using a number of different environmental stimuli - such as light, pH, and electrostatic charge - in addition to potential. Furthermore, nascent understanding of the underlying phenomena in synthetic nanochannels was rapidly followed by practical applications, including oil-water separations, drug release, and electroactive flow control based on switchable wettability. Furthermore, more practical applications are being developed continuously, as the physical and chemical principles that govern hydrophobic gating at the nanoscale are further elucidated, making it possible to exploit wettability as a design element in nanofluidic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lattice-scale variations in viscosity are correlated with solution structure at mineral-water interfaces

At solid-liquid interfaces, the viscosity increases markedly from the bulk due to the collective interactions of ions and water molecules, influencing phenomena relevant to nanofluidics, colloidal dynamics, and electrochemistry. Here, in this study, we investigated dissipative forces at the boehmite-water interface using 3D atomic force microscopy. We observed an increase in interfacial solution viscosity, η, by 10-100-fold as the nanoprobe approached the surface in normal direction, with up to four oscillatory features showing average peaks of η/η bulk = 44-71. Moreover, the viscosity showed sub-nanometer variations within 0.5 nm from the interface, templated by the underlying crystal lattice and correlated with the interfacial solution structure. Beyond a near-wall region of approximately 1.2 nm, the dissipative response was comparable to that in bulk solution. Molecular dynamics simulations, along with statistical mechanical analyses, provided details on hydrodynamic structures near the interface. Specifically, the lattice-dependent dissipative responses are correlated with extensive hydrogen bonding by interfacial water molecules, which increased friction, particularly along the [001] direction. These results demonstrate how solution viscosity at mineral-water interfaces is anisotropic and correlated with the local solution structure, providing insights into the dynamics of nanocrystal attachment.

Viscosity↗

Specific Ion and Electric Field Controlled Diverse Ion Distribution and Electroosmotic Transport in a Polyelectrolyte Brush Grafted Nanochannel

Controlling ion distribution inside a charged nanochannel is central to using such channels in diverse applications. Here, we show the possibility of using a charged polyelectrolyte (PE) brush grafted nanochannel for triggering diverse nanoscopic ion distribution and nanofluidic electroosmotic transport by controlling the valence and size of the counterions (that screen the charges of the PE brushes) and the strength of an externally applied axial electric field. We atomistically simulate separate cases of fully charged Polyacrylic acid (PAA) brush functionalized nanochannels with Na + , Cs + , Ca 2+ , Ba 2+ , and Y 3+ counterions screening the PE charges. Four key findings emerge from our simulations. First, we find that the counterions with a greater valence and a smaller size prefer to remain localized inside the brush layer. Second, for the case where there is an added chloride salt with the same cation (as the screening counterions), there are more coions (Cl - ions) in the brush-free bulk than counterions (for counterions Na + , Ca 2+ , Ba 2+ , Y 3+ ): this is a manifestation of the overscreening (OS) of the PE brush layer. Contrastingly, the number of Cs + ions remain higher than the Cl - ions inside the brush-free bulk, ensuring that there is no OS effect for this case. Third, large applied electric field enables a few Na + , Cs + , and Ba 2+ counterions to leave the brush layer and to go to the bulk: this makes the OS of the PE brush layer disappear for the cases of PE brushes being screened by the Na+ and Ba 2+ ions. On the other hand, no such electric-field-mediated disappearance of OS is observed for the cases of Ca 2+ and Y 3+ screening counterions; we attribute this to the firm attachment of these counterions to the negatively charged monomers. Free energy associated to a counterion binding to a PE chain corroborates this diversity in the counterion-specific response to the applied electric field. Lastly, we demonstrate that such diverse ion distributions, along with specific electric-field-strength-dependent ion properties, lead to (1) EOS transport in nanochannels grafted with PAA brushes screened with Cs + ions to be always counterion dominated, (2) EOS transport in nanochannels grafted with PAA brushes screened with Ca 2+ and Y 3+ ions to be always coion dominated, and (3) EOS transport in nanochannels grafted with PAA brushes screened with Na + and Ba 2+ ions to be coion dominated for smaller electric fields and counterion dominated for larger electric fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Transport in Self-Assembled Peptoid Membranes with Carbon Nanotube Porin Channels

Artificial membranes that combine high ionic selectivity with mechanical robustness remain a key challenge for next-generation separation technologies. Here, we report ion transport measurements in biomimetic membranes composed of crystalline peptoid nanosheets co-assembled with carbon nanotube porins (CNTPs). Pure peptoid sheets formed defect-free, ion-impermeable membranes, which were then suspended over small SiN x nanopore apertures for ion transport measurements. Incorporation of CNTPs into the peptoid sheet matrix made these membranes ion permeable, with ion conductance values consistent with ion transport through individual and multiple carbon nanotube channels. In conclusion, the modularity and molecular order of peptoid membranes, combined with the exceptional conductance properties of CNTPs, position this platform as a versatile framework for assembling programmable, selective, and robust nanofluidic membranes that can bridge the performance gap between biological and synthetic membrane materials.

Biotechnology↗

Overscreening, Coion-Dominated Electroosmosis, and Electric Field Strength Mediated Flow Reversal in Polyelectrolyte Brush Functionalized Nanochannels

Controlling the direction and strength of nanofluidic electrohydrodyanmic transport in the presence of an externally applied electric field is extremely important in a number of nanotechnological applications. Here, we employ all-atom molecular dynamics simulations to discover the possibility of changing the direction of electroosmotic (EOS) liquid flows by merely changing the electric field strength in a nanochannel functionalized with polyelectrolyte (PE) brushes. In exploring this, we have uncovered three facets of nanoconfined PE brush behavior and resulting EOS transport. First, we identify the onset of an overscreening effect: such overscreening refers to the presence of more counterions (Na + ) within the brush layer than needed to neutralize the negative brush charges. Accordingly, as a consequence of the overscreening, in the bulk liquid outside the brush layer, there is a greater number of co-ions (Cl – ) than counterions in the presence of an added salt (NaCl). Second, this specific ion distribution ensures that the overall EOS flow is along the direction of motion of the co-ions. Such co-ion-dictated EOS transport directly contradicts the notion that EOS flow is always dictated by the motion of the counterions. Finally, for large-enough electric fields, the brush height reduces significantly, causing some of the excess overscreening-inducing counterions to squeeze out of the PE brush layer into the brush-free bulk. As a result, the overscreening effect disappears and the number of co-ions and counterions outside the PE brush layer become similar. Despite that there is an EOS transport, this EOS transport, unlike the standard EOS transport that occurs due to the imbalance of the co-ions and counterions, occurs since a larger residence time of the water molecules in the first solvation shell of the counterions (Na + ) ensures a water transport in the direction of motion of the counterions. In this work, the net effect is the reversal of the direction of the EOS transport by merely changing the strength of the electric field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous Energy Generation and Flow Enhancement (Electroslippage Effect) in Polyelectrolyte Brush Functionalized Nanochannels

Energy generation through nanofluidics is a topic of great nanotechnological relevance. In this work, we conduct all-atom molecular dynamics (MD) simulations of the transport of water and ions in a pressure-driven flow in nanochannels grafted with charged polyelectrolyte (PE) brushes and discover the possibility of simultaneous electrokinetic energy generation and flow enhancement (henceforth denoted as the electroslippage effect). Such PE-brush-functionalized nanochannels have been recently shown to demonstrate an overscreening (OS) effect (characterized by the presence of a greater number of screening counterions within the PE brush layer than needed to screen the PE brush charges), a consequent presence of excess coions within the PE brush-free bulk, and a coion-driven electroosmotic (EOS) transport in the presence of small to moderate applied axial electric fields. Here, however, we find that the streaming current, which represents the current generated by the flow-driven downstream advection of the charge imbalance present within the electric double layer (EDL) that screen the PE brush charges, is governed by the migration of the counterions. This stems from the fact that the highest contribution to the overall streaming current arises from the region near the PE brush-water interface (where there is an excess of counterions), while the brush-free bulk yields a hitherto unreported, but small, coion-dictated streaming current. This downstream advection of the charge imbalance (and the resultant counterion-driven streaming current) eventually leads to the development of an electric field (streaming electric field) in the direction that is opposite to the direction of the counterion-driven streaming current. The streaming current and the streaming electric field interact to generate the electrokinetic energy. Equally importantly, this streaming electric field induces an EOS transport, which becomes coion-driven, due to the presence of excess coions in the brush-free bulk. For the case of nanochannels grafted with negatively charged PE brushes, the streaming electric field will be in a direction that is opposite to the pressure-driven transport, and hence the coion (or anion) driven EOS flow, will be in the same direction as the pressure-driven transport. On the other hand, for the case of nanochannels grafted with positively charged PE brushes, the streaming electric field will be in the same direction as the pressure-driven flow, and hence the coion (or cation) driven EOS flow, will again be in the same direction as the pressure-driven flow. Therefore, whenever there occurs the presence of the OS and the resulting coion-driven EOS transport in PE brush grafted nanochannels, regardless of the sign of the charges of the PE brushes, this EOS transport will always aid the pressure-driven transport and will cause the most fascinating increase in the net volume flow rate across the nanochannel cross section, which is the electroslippage effect.

overscreening↗