Double Layer Theory Research Articles

Graphene microelectrode arrays for neural activity detection.

We demonstrate a method to fabricate graphene microelectrode arrays (MEAs) using a simple and inexpensive method to solve the problem of opaque electrode positions in traditional MEAs, while keeping good biocompatibility. To study the interface differences between graphene-electrolyte and gold-electrolyte, graphene and gold electrodes with a large area were fabricated. According to the simulation results of electrochemical impedances, the gold-electrolyte interface can be described as a classical double-layer structure, while the graphene-electrolyte interface can be explained by a modified double-layer theory. Furthermore, using graphene MEAs, we detected the neural activities of neurons dissociated from Wistar rats (embryonic day 18). The signal-to-noise ratio of the detected signal was 10.31 ± 1.2, which is comparable to those of MEAs made with other materials. The long-term stability of the MEAs is demonstrated by comparing differences in Bode diagrams taken before and after cell culturing.

Electronic desalting for controlling the ionic environment in droplet-based biosensing platforms.

The ability to control the ionic environment in saline waters and aqueous electrolytes is useful for desalination as well as electronic biosensing. We demonstrate a method of electronic desalting at micro-scale through on-chip micro electrodes. We show that, while desalting is limited in bulk solutions with unlimited availability of salts, significant desalting of ≥1 mM solutions can be achieved in sub-nanoliter volume droplets with diameters of ∼250 μm. Within these droplets, by using platinum-black microelectrodes and electrochemical surface treatments, we can enhance the electrode surface area to achieve >99% and 41% salt removal in 1 mM and 10 mM salt concentrations, respectively. Through self-consistent simulations and experimental measurements, we demonstrate that conventional double-layer theory over-predicts the desalting capacity and, hence, cannot be used to model systems that are mass limited or undergoing significant salt removal from the bulk. Our results will provide a better understanding of capacitive desalination, as well as a method for salt manipulation in high-throughput droplet-based microfluidic sensing platforms.

Prediction of Compressibility Data for Highly Plastic Clays Using Diffuse Double-Layer Theory

AbstractMontmorillonite-rich clays are important in many engineering applications. The compressibility of such plastic clays at high consolidation pressures is important for predicting routine settlement and for applications in nuclear-waste repositories. Laboratory measurement of compressibility data at high consolidation pressures is not only time consuming but very expensive also. Theoretical predictions can help to determine the compressibility of plastic clays at high consolidation pressures. A linear relationship between e/eNvs. 1/√P (eN is the normalization void ratio at normalization pressure N and P is the consolidation pressure) was derived using diffuse double-layer theory. The compressibility data of several plastic clays in published studies were found to support the derived relationship. A generalized theoretical equation was proposed to predict the compressibility data over a wide range of consolidation pressures using an experimentally measured void ratio at low consolidation pressure. The compressibility data for different plastic clays were predicted accurately up to maximum consolidation pressures that ranged from 0.7 to 30 MPa using an experimentally measured void ratio near the pre-consolidation pressure. The preconsolidation pressures for different clays considered here ranged from 25 to 133 kPa. The proposed predictive model is supported by experimental data, is simple, and does not require knowledge of clay-surface and pore-fluid parameters.

Prediction of protein-DNA complex mobility in gel-free capillary electrophoresis.

Selection of protein binders from highly diverse combinatorial libraries of DNA-encoded small molecules is a highly promising approach for discovery of small-molecule drug leads. Methods of kinetic capillary electrophoresis provide the high efficiency of partitioning required for such selection but require the knowledge of electrophoretic mobility of the protein-ligand complex. Here we present a theoretical approach for an accurate estimate of the electrophoretic mobility of such complexes. The model is based on a theory of the thin double layer and corresponding expressions used for the mobilities of a rod-like short oligonucleotide and a sphere-like globular protein. The model uses empirical values of mobilities of free protein, free ligand, and electroosmotic flow. The model was tested with a streptavidin-dsDNA complex linked through biotin (small molecule). The deviation of the prediction from the experimental mobility did not exceed 4%, thus confirming that not only is the model adequate but it is also accurate. This model will facilitate reliable use of KCE methods for selection of drug leads from libraries of DNA-encoded small molecules.

Experimental evidence for hyperfiltration of saline water through compacted clay aquitard in the Hebei Plain

It becomes an increasing concern that groundwater quality in exploited deep confined aquifer may deteriorate due to brackish water leakage from its overlying saline aquifer in Hebei Plain. However, the monitoring data show that the TDS does not significantly change in the exploited aquifer. Some physics or chemistry processes must have taken place in aquitards during brackish leakage. The semi-permeable membrane function of clay aquitard during the process of hyperfiltration (reverse osmosis) should be one of the most important processes. To confirm and test this hyperfiltration mechanism, a series of experiments were performed in which NaCl solutions were hydraulically forced through different clay sampled from aquitard. The solution 7 g/L in NaCl was forced through at 20 °C by a fluid pressure of 0.5 kN. The results show that hyperfiltration indeed happens in caly aquitard. Semi-permeability is quantified by the reflection coefficient σ. The mean rejection coefficients (σ) for clay samples #1, #2 and #3 were estimated to be 0.063, 0.164 and 0.040, respectively. This behavior of clay was well explained with the theory of the diffuse double layer. The hyperfiltration effect is to the great extent responsible for the chemical process in the aquitard.

Discussing of influence mechanism of Chinese herbal monomer on physical stability of cream

This study left flavonoids and alkaloids Chinese herbal monomer with common parent nucleus as cream base carriages drug respectively, cream base were prepared with stable span 60-tween 80 emulsification system. The near-infrared stability analysis technology was performed to quantitatively characterize the physical stability of cream. Base on the theory of gel network structure, theory of emulsification, theory of solubility parameter and theory of double layer, the influence mechanism of Chinese herbal monomer on physical stability of cream was discussed. The results showed that tetrahydropalmatine, matrine and naringenin had similar solubility parameter value with cream base material, creams prepared with those Chinese herbal monomer have higher Zeta potential value and stronger physical stability, and that those creams had similar microstructure information with cream base. However, a larger solubility parameter difference exists between baicalin, baicalein, berberine, palmatine and cream base material. Creams prepared with those Chinese herbal monomers had lower Zeta potential value and poorer physical stability, and that those creams had great different microstructure information with cream base.

Effect of Tube Geometry and Curvature on Film Condensation in the Presence of a Noncondensable Gas

Based on the double boundary layer theory, a generalized mathematical model was developed to study the distributions of gas film, liquid film, and heat transfer coefficient along the tube surface with different geometries and curvatures for film condensation in the presence of a noncondensable gas. The results show that: (i) for tubes with the same geometry, gas film thickness, and liquid film thickness near the top of the tube decrease with the increasing of curvature and the heat transfer rate increases with it. (ii) For tubes with different geometries, one need to take into account all factors to compare their overall heat transfer rate including gas film thickness, liquid film thickness and the separating area. Besides, the mechanism of the drainage and separation of gas film and liquid film was analyzed in detail. One can make a conclusion that for free convection, gas film never separate since parameter A is always positive, whereas liquid film can separate if parameter B becomes negative. The separating angle of liquid film decreases with the increasing of curvature.

Modification of the surface of activated carbon electrodes for capacitive mixing energy extraction from salinity differences

The “capacitive mixing” (CAPMIX) is one of the techniques aimed at the extraction of energy from the salinity difference between sea and rivers. It is based on the rise of the voltage between two electrodes, taking place when the salt concentration of the solution in which they are dipped is changed. We study the rise of the potential of activated carbon electrodes in NaCl solutions, as a function of their charging state. We evaluate the effect of the modification of the materials obtained by adsorption of charged molecules. We observe a displacement of the potential at which the potential rise vanishes, as predicted by the electric double layer theories. Moreover, we observe a saturation of the potential rise at high charging states, to a value that is nearly independent of the analyzed material. This saturation represents the most relevant element that determines the performances of the CAPMIX cell under study; we attribute it to a kinetic effect.

Colloido-chemical characteristics of porous glasses with different compositions in KNO3 solutions. 1. Structural and electrokinetic characteristics of membranes

The structural (specific surface area, liquid-filtration coefficient, average pore radius, volume porosity, and structural-resistance coefficient) and electrokinetic (counterion transport numbers, specific electrical conductivity, and electrokinetic potential) characteristics of porous glasses with different compositions have been determined in potassium nitrate solutions with concentrations of 10−3–10−1 M. All the membranes under investigation have been shown to exhibit the dependences of efficiency coefficients and counterion transport numbers on electrolyte concentration and pore size that are predicted by the theory of an electrical double layer. It has been established that, at a constant electrolyte concentration, the absolute values of electrokinetic potential increase with the average pore radius because of variations in the slipping-plane position.

Assessing the anion type effect on the hydro-mechanical properties of smectite from macro and micro-structure aspects

The expansivity of clayey soils is a complicated phenomenon which may affect the stability of geotechnical structures and geo-environmental projects. In all common factors for the monitoring of soil expansion, less attention is given to anion type of pore space solutions. Therefore, this paper is concerned with the impact of various concentrations of different inorganic salts including NaCl, <TEX>$Na_2SO_4$</TEX>, and <TEX>$Na_2CO_3$</TEX> on the macro and microstructure behavior of the expandable smectite clay. Comparison of the responses of the smectite/NaCl and smectite/<TEX>$Na_2SO_4$</TEX> mixtures indicates that the effect of anion valance on the soil engineering properties is not very pronounced, regardless of the electrolyte concentration. However, at presence of carbonate as potential determining ions (PDIs) the swelling power increases up to 1.5 times compared to sulfate or chloride ions. The samples with <TEX>$Na_2CO_3$</TEX> are also more deformable and show lower osmotic compressibility than the other mixtures. This demonstrates that the barrier performance of smectite greatly decreases in case of anions with the non-specific adsorption (e.g., <TEX>$Cl^-$</TEX> and <TEX>$SO{_4}^{2-}$</TEX>) as the salinity of solution increases. Based on the results of the X-ray diffraction and sedimentation tests, the high soil volumetric changes upon exposure to carbonate is attributed to an increase in the repulsive forces between smectite basic unit layers due to the PDI effect of <TEX>$CO{_3}^{2-}$</TEX> and increasing the pH level which enhance the buffering capacity of smectite. The study concluded that the nature of anion through its influence on the re-arrangement of soil microstructure and osmotic phenomena governs the hydro-mechanical parameters of expansive clays. It seems not coinciding with the double layer theory of the Gouy-Chapman double layer model.

Developing a general interaction potential for hydrophobic and hydrophilic interactions.

We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.

Research on the critical conditions for clay particle release during saline aquifer freshening process

Water sensitivity phenomenon occurs during saline aquifer freshening process in seawater intrusion area, and clay particles released in the phenomenon can damage the infiltration capacity of the aquifer. In order to find out the factors and mechanisms for clay particle release, laboratory column infiltration experiments simulating saline aquifer freshening process were designed to measure the critical conditions (critical flow velocity, critical salt concentration and critical ionic strength) and force analysis for clay particle according to DLVO electric double layer theory was employed to illustrate the mechanisms for particle release. The research results showed that critical flow velocity for clay particle release is influenced by salt concentration of injecting solution. When salt concentration of injecting solution is very high, clay particles are not released, indicating that there does not exist a critical flow velocity in this situation. As salt concentration of injecting solution decreases, particles start to be released. The critical salt concentration for clay particle release is 0.052 mol L−1 in our work, which was determined by a constant-flux experiment for stepwise displacement of high concentration NaCl solution. The critical ionic strength for clay particle release decreases as Ca2+ molar content percentage of the mixed solution of NaCl and CaCl2 increases following the first-order exponential decay equation y = 0.0391e−0.266x + 0.0015.

Structure of water at charged interfaces: a molecular dynamics study.

The properties of water molecules located close to an interface deviate significantly from those observed in the homogeneous bulk liquid. The length scale over which this structural perturbation persists (the so-called interfacial depth) is the object of extensive investigations. The situation is particularly complicated in the presence of surface charges that can induce long-range orientational ordering of water molecules, which in turn dictate diverse processes, such as mineral dissolution, heterogeneous catalysis, and membrane chemistry. To characterize the fundamental properties of interfacial water, we performed molecular dynamics (MD) simulations on alkali chloride solutions in the presence of two types of idealized charged surfaces: one with the charge density localized at discrete sites and the other with a homogeneously distributed charge density. We find that, in addition to a diffuse region where water orientation shows no layering, the interface region consists of a "compact layer" of solvent next to the surface that is not described in classical electric double layer theories. The depth of the diffuse solvent layer is sensitive to the type of charge distributions on the surface and the ionic strength. Simulations of the aqueous interface of a realistic model of negatively charged amorphous silica show that the water orientation and the distribution of ions strongly depend on the identity of the cations (Na(+) vs Cs(+)) and are not well represented by a simplistic homogeneous charge distribution model. While the compact layer shows different solvent net orientation and depth for Na(+) vs Cs(+), the depth (~1 nm) of the diffuse layer of oriented waters is independent of the identity of the cation screening the charge. The details of interfacial water orientation revealed here go beyond the traditionally used double and triple layer models and provide a microscopic picture of the aqueous/mineral interface that complements recent surface specific experimental studies.

Critical interparticle distance for the remarkably enhanced dielectric constant of BaTiO3-Ag hybrids filled polyvinylidene fluoride composites

Discrete nano Ag-deposited BaTiO3 (BT-Ag) hybrids with varied Ag content were synthesized, and the hybrids filled polyvinylidene fluoride (PVDF) composites were prepared. The effect of Ag content on the dielectric properties of the composites were analyzed based on the diffused electrical double layer theory. Results showed that with a higher Ag content in BT-Ag hybrids, the dielectric constant of BT-Ag/PVDF composites increases fast with the filler loading, while the dielectric loss and conductivity showed a suppressed and moderate increase. The dielectric constant of BT-0.61Ag/PVDF (61 wt. % of Ag in BT-Ag hybrid) composites reached 613, with the dielectric loss of 0.29 at 1 kHz. It was deduced that remarkably enhanced dielectric constant appeared when the interparticle distance decreased to a critical value of about 20 nm.

Model evaluation of geochemically induced swelling/shrinkage in argillaceous formations for nuclear waste disposal

Argillaceous formations are being considered as host rocks for geologic disposal of nuclear waste in a number of countries. One advantage of emplacing nuclear waste in such formations is the potential self-sealing capability of clay due to swelling, which is of particular importance for the sealing and healing of disturbed rock zones (DRZ). It is therefore necessary to understand and be able to predict the changes in swelling properties within clay rock near the waste-emplacement tunnel. In this paper, considering that the clay rock formation is mostly under saturated conditions and the swelling property changes are mostly due to geochemical changes, we propose a modeling method that links a THC simulator with a swelling module that is based on diffuse double layer theory. Simulations were conducted to evaluate the geochemically induced changes in the swelling properties of the clay rock. Our findings are as follows: (1) geochemically induced swelling/shrinkage occurs exclusively in the EBS–clay formation interface, within a few meters from the waste-emplacement tunnels; (2) swelling/shrinkage-induced porosity changes are generally much smaller than those caused by mineral precipitation/dissolution processes; (3) geochemically induced swelling/shrinkage of the host clay rock is affected by variations in the pore water chemistry, exchangeable cations, and smectite abundance. Neglecting any of these three factors might lead to a miscalculation of the geochemically induced swelling pressure.

Integrated sorption and diffusion model for bentonite. Part 2: porewater chemistry, sorption and diffusion modeling in compacted systems

It is important to understand the coupled processes of sorption and diffusion of radionuclides (RNs) in compacted bentonite, and to develop mechanistic models that can aid in the prediction of the long-term performance of geological disposal systems of radioactive waste. The integrated sorption and diffusion (ISD) model was developed based on the consistent combination of clay–water interaction, sorption and diffusion models. The diffusion model based on the electrical double layer theory describing relative ionic concentrations and viscoelectric effects at the negatively charged clay surface was coupled with porewater chemistry and sorption models. This ISD model was successfully tested for various actinides with a complex chemistry (Np(V), Am(III), U(VI) under conditions where variably charged carbonate complexes are formed) considered in Part 1, by using published diffusion and sorption data (Da, De, Kd) as a function of partial montmorillonite density. Quantitative agreements were observed by considering uncertainty in porewater chemistry and dominant aqueous species. It can therefore be concluded that the ISD model developed here is able to adequately explain the sorption and diffusion behavior of various RNs with a complex chemistry in compacted bentonites. The performed modeling indicates that uncertainties are mainly related to porewater chemistry and RN speciation and that these parameters need to be carefully evaluated.

Influence of phosphate sorption on dispersion of a Ferralsol

Soil dispersion induces soil erosion and colloidal leaching. Nutrients are lost at the same time and this causes water contamination. Phosphate is an essential element for living organisms. Because phosphate influences soil dispersion and it is an important limited resource, this influence must be evaluated well in order to diminish negative effects on soil structure. In this paper, we firstly evaluated the influence of phosphate sorption on soil dispersion by calculating repulsive potential energy between soil particles. Ferralsol, which is a typical soil in rainy tropical regions, was used as the material. The dispersion-flocculation phenomena were investigated with absorbance of soil suspension under different pH, phosphate adsorption and electrolyte concentration in an Na-NO3-PO4 system. The repulsive potential energy was calculated based on the diffuse double layer theory and the measured zeta potential. We indicated that the measured absorbance increased with the increase of the repulsive potential energy. The repulsive potential energy increased with increasing phosphate sorption up to about 5 to 20 mmol kg−1 at all pH, and it induced the soil dispersion, because phosphate sorption increased the negative charge of the soil. After its peak, it decreased with increasing phosphate sorption because the electrolyte concentration increased and the electrolyte screened the electric field near the soil surface. The repulsive potential energy also increased with increasing pH because of the increase of the negative charge of the soil. Even at low pH, after a certain amount of phosphate sorption, the soil dispersed due to the increase of repulsive potential energy, although the soil flocculated before phosphate application. Because the soil dispersion causes soil and phosphorus loss, the influence of soil pH and phosphate sorption on the soil dispersion should be considered for good soil management.

Capillary model of electroosmotic transport of the free solvent through ion-exchange membranes

An equation for calculating the transport number of a free solvent transferred through an ion-exchange membrane using the physicochemical and structural characteristics of the latter and the properties of an equilibrium solution was derived on the basis of the Stern theory of the electric double layer and the concept that represents the ion-exchange membrane as a capillary system. The model calculations showed that modification of the ion-exchange membrane, which decreased the effective pore radius to 2.0–3.5 nm, almost completely suppressed the electroosmotic transport of free water in the membrane system. The experimentally determined tendencies of variation of water electrotransport due to changes in the structural type of membrane and solution concentration agree well with the suggested model description.

Asymptotic theory of double layer and shielding of electric field at the edge of illuminated plasma

The method of matched asymptotic expansions is applied to the problem of a collisionless plasma generated by UV illumination localized in a central part of the plasma in the limiting case of small Debye length λD. A second-approximation asymptotic solution is found for the double layer positioned at the boundary of the illuminated region and for the un-illuminated plasma for the plane geometry. Numerical calculations for different values of λD are reported and found to confirm the asymptotic results. The net integral space charge of the double layer is asymptotically small, although in the plane geometry it is just sufficient to shield the ambipolar electric field existing in the illuminated region and thus to prevent it from penetrating into the un-illuminated region. The double layer has the same mathematical nature as the intermediate transition layer separating an active plasma and a collisionless sheath, and the underlying physics is also the same. In essence, the two layers represent the same physical object: a transonic layer.

Experimental Investigations and Ageing Studies on Effects of Insulating Barriers in Transformer Oil during High Frequency High Voltage Transients in Inhomogeneous Field

Insulating barriers utilized in complex high voltage insulation systems has been exploited widely by manufacturers of power apparatus. Barriers have found utility in a variety of power apparatus for protection against direct lightning strokes, as an interface at the boundaries of composite insulation materials etc. Though investigations have been carried out by researchers on the breakdown characteristics, barrier position in the gap, influence of space charge etc these characteristics have been analyzed based on aspects pertinent to classical testing procedures only. Advent of high speed switching devices in power systems provides avenues to investigate the effect of insulation performance due to High Frequency High Voltage (HFHV) also. Further, uncharacteristic failures in oil filled distribution transformers have been reported indicated fast transients as the major cause for failures which was not revealed during classical laboratory testing. This research focuses on the influence and effects of solid insulating barriers placed in transformer oil due to HFHV in inhomogeneous fields. Test cell arrangement has been fabricated for carrying out experimental investigations to adhere international standards. Exhaustive experimentation has been performed to infer the influence of the position of barrier, nature of field and breakdown voltage, erosion characteristics of the barrier at an appropriate range of frequencies. A detailed comparison between HFHV and classical power frequency voltage has been carried out. The nature of ionization at the barrier interface and the subsequent increase in the breakdown voltage as explained by Double Electric Layer (DEL) theory has been cross validated. In addition, a study has also been carried out to assess and characterize the ageing of oil based on Dissolved Gas Analysis (DGA) analysis using Weibull distribution.