Electrical Double Layer Interaction Research Articles

Probing the Interfacial Interaction Mechanisms of Nitrogen with Dodecane/Toluene: Implications for Foam Flooding.

Interfacial interactions between deformable bubbles and oil drops have attracted much attention in foam flooding. However, interactions involving nitrogen bubbles have not been reported. In this work, the interaction forces between nitrogen and dodecane/toluene in aqueous solutions were quantified using the atomic force microscopy bubble probe technique. The effects of the solution pH, ionic type, and solution concentration on the interactions were analyzed. The van der Waals (vdW), electric double layer (EDL), and hydrophobic (HB) interactions were involved in the low-concentration solutions. The EDL repulsion in NaCl increased with solution pH, while in CaCl2 and MgCl2, the EDL repulsion in general decreased and then increased with pH, attributed to the adsorption of OH- and divalent cations and their hydration products. The adsorption of divalent cations at the toluene/water interface was pronounced by cation-π interactions. At pH 10, precipitated divalent cation hydroxides at the bubble/water and oil/water interfaces adsorbed more cations, causing the increase of the surface potential. At high salinity, the EDL interaction was suppressed and the vdW repulsion became predominant. The vdW force of nitrogen with toluene was stronger than that with dodecane. Under all of the solution conditions, the attractive interaction could not overcome the total repulsive interaction at the minimum separation, and thus no bubble attachment was observed, which implied that a stable bubble/liquid/oil film was essential for maintaining foam stability. This work provides useful insights into the interfacial interaction mechanisms in nitrogen foam flooding. The findings can be readily extended to other engineering systems such as oil flotation and bubble-oil-water emulsions.

Impact of temperature and salinity on fines detachment: AFM measurements and XDLVO theory

Fine particle detachment and subsequent migration can lead to severe pore plugging and consequent permeability decline. Therefore, it is crucial to quantify the critical condition when fine particle detachment occurs. The frequently observed deviations or even contradictions between experimental results and theoretical predictions of fines detachment arise from an insufficient understanding of adhesion force that can be highly influenced by salinity and temperature. To clarify the intrinsic influence of salinity and temperature on fines detachment, adhesion forces between carboxyl microspheres and hydrophilic silica substrates in an aqueous medium were measured at various salinities and temperatures using atomic force microscopy (AFM). The AFM-measured adhesion force decreases with increasing salinity or temperature. Trends of mean measured adhesion forces with temperature and salinity were compared with the DLVO and XDLVO theories. DLVO theory captured the trend with temperature via the impact of temperature on electric double layer interactions, whereas XDLVO theory captured the observed trend with salinity via the impact of salinity on the repulsive hydration force. Our results highlight the significance of hydration force in accurately predicting the fate of fines in porous media.

Effects of chemical solution components on the contact angle of typical minerals in soil: quartz, orthoclase and plagioclase

Different chemical solutions can significantly change the contact angle (CA) of soil, but few studies have studied the change rule and action mechanism of the CA from the mineral composition of soil essence. In unsaturated soil mechanics, the CA is an important parameter to calculate the wet suction between soil particles in unsaturated soil. When the chemical composition of the soil pore liquid changes, the CA will also change, which will affect the wet suction and other parameters, thus changing the macroscopic mechanical properties of the soil. In this study, the CA of air-solution-mineral phases with different solution components (pH, type and concentration of salt solution) of different minerals (quartz, orthoclase and plagioclase) were measured. The results show that the CAs of quartz, orthoclase and plagioclase all rise first and then drop with the rise of pH. The peak CAs are pH = 5, pH = 4 and pH = 3, respectively. Quartz, orthoclase and plagioclase all have valley values in different concentrations of NaCl and KCl solutions. In CaCl2 solution, only quartz has valley value, while orthoclase and plagioclase increase monotonously. Quartz in soil plays a main role in the influence of soil CA, followed by orthoclase and plagioclase. The CA of different minerals in different chemical solutions is mainly controlled by electric double layer interaction and functional groups interaction. In different salt solution environment, in addition to the above two effects, the mineral CA is also affected by the surface tension.

Enhancing biofilm formation with powder carriers for efficient nitrogen and phosphorus removal

This study assesses the improvement in nitrogen and phosphorus removal from wastewater achieved through the integration of zeolite and attapulgite carrier materials into the activated sludge (AS) process. It was found that the addition of these materials significantly enhanced the processing performance of the reactor. Specifically, the use of zeolite and attapulgite powders increased sludge particle sizes to averages of 231.56 μm and 219.62 μm, respectively. This facilitated micro-granule formation, substantially improving the settling characteristics of the sludge and boosting the activity and proliferation of essential microbes. Illumina MiSeq sequencing demonstrated significant accumulations of DGAOs (Candidatus_Competibacter) and DPAOs (Candidatus_Accumulibacter). Furthermore, these carriers augmented the protein content in extracellular polymers, enhancing the hydrophobicity of the sludge and promoting aggregation. Comparative analysis based on the extended Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory indicated a preferential adhesion affinity of sludge for zeolite compared to attapulgite, attributed primarily to Lewis acid-base and electric double-layer interactions. These findings underscore zeolite's enhanced efficacy in biomass fixation and suggest significant potential for the technological advancement of wastewater treatment plants.

Mechanical and physicochemical characteristics of sub-millimeter and macrobubbles: Insights from AFM analysis, zeta potential measurements and rise velocity

This study presents the change in mechanical and physicochemical behaviour of macrobubbles and sub-millimeter bubbles with respect to pH. While macrobubbles conventionally range from 100 μm to 2 mm in diameter, this study focuses on the comparatively less-explored sub-millimeter bubble range, centered around a median diameter of 500 μm. The difference in sub-millimeter bubbles (500 μm) compared to their larger counterparts (1100 μm) within macrobubble size range were evidenced through atomic force microscopy (AFM) analysis, zeta potential measurements, and rise velocity experiments. The adhesion force and energy between bubbles and the silicon nitride cantilever tip showed a decreasing trend with increasing pH, notably diminishing by about 50% beyond pH 9. Although no significant differences were statistically revealed between the two bubble sizes at lower pH, the adhesion force and energy were consistently smaller for macrobubble compared to sub-millimeter bubble at higher pH beyond pH 9. This finding suggests that the electrical double layer (EDL) interactions are influenced by the specific surface area, particularly in the alkaline region. Zeta potential measurements exhibited a cubic trend, with an isoelectric point at pH 3.5 and a minimum zeta potential at pH 11. The study also depicted a similar trend in the rise velocity of bubbles, suggesting a direct relationship between bubble stiffness and its rise velocity. Therefore, changes in pH affected the bubbles' properties, while on the other hand, certain physicochemical properties are also influenced by bubble sizes.

Rheological Behavior of an Aqueous Suspension of Oxidized Carbon Nanohorn (CNHox).

Oxidized carbon nanohorn (CNHox) a carbon nanomaterial that has attracted attention due to its unique material properties. It is expected to be applied in various areas like cancer treatment, gene-expression technology, fluids with high thermal conductivity, lubricants, and so on. While the rheological measurements of suspensions provide information on the effective size and interactions of suspended particles, the rheological behaviors of aqueous suspensions of CNHox have never been systematically investigated. To clarify the rheological behaviors of aqueous suspensions of CNHox, their viscosity and dynamic viscoelasticity were measured with changing particle concentration and salt concentration. The viscosity of a CNHox suspension showed yield stress at low shear rates and showed shear-thinning behavior with increasing shear rates. The viscosity of 5 weight % CNHox suspensions was comparable to that of 60 weight % silica suspensions. This high viscosity at a low CNHox concentration is probably due to the porous structure and large effective volume of the CNHox particle. The estimated effective volume of CNHox calculated by the Krieger-Dougherty equation was 18.9 times larger than the actual volume calculated by the mass concentration and density. The dependence of rheological behavior of the CNHox suspension on salt concentration was weak compared to that of the colloidal silica suspension. This weak dependence on salt concentration may be due to the roughness of the particle surface, which would weaken the effect of electric double-layer interactions and/or van der Waals interactions between particles. These rheological behaviors of the aqueous suspension of CNHox shown in this research will be useful in efforts to improve the efficiency of its utilization for the various applications.

Ion- and surface-sensitive interactions during oxygen evolution reaction in alkaline media

Abstract Clean and sustainable energy has turned towards electrochemical water splitting as a viable solution in minimizing carbon emissions. Electrolysis of water converts electrical energy to chemical energy, through the production of hydrogen and oxygen gases, which can be harnessed for potential applications without contributing to greenhouse emissions. While this energy storage process shows great potential, its efficiency is hindered by the sluggish kinetics of the oxygen evolution reaction (OER). As a result, its widespread application in green electrolytic technologies is limited hence investigations on improving OER kinetics are of utmost importance. Recent research breakthroughs indicate that alkali metal cations are more than passive observers. They play complex roles in the electric double layer (EDL), which positively influences the OER kinetics. The presence of numerous ions and their combinations presents a challenge of complexity. This study aims to delve into the impact of alkali metal cations on OER activity due to the variance in their hydration energies. Specific investigations focusing on different alkali metal cations in solution, such as Li+, Na+, and K+, was conducted on RuO2 to gain a deeper understanding of how these ions interact with both reactants and intermediate species in the reaction kinetics. Traditional electrochemical tests, including cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and accelerated degradation test (ADT) measurements were employed to elucidate critical aspects such as surface activation, electric double layer interactions, catalytic activity and stability, ohmic resistance, and mass and charge transport.

Exploring the mechanisms of calcium carbonate deposition on various substrates with implications for effective anti-scaling material selection

The unexpected scaling phenomena have resulted in significant damages to the oil and gas industries, leading to issues such as heat exchanger failures and pipeline clogging. It is of practical and fundamental importance to understand the scaling mechanisms and develop efficient anti-scaling strategies. However, the underlying surface interaction mechanisms of scalants (e.g., calcite) with various substrates are still not fully understood. In this work, the colloidal probe atomic force microscopy (AFM) technique has been applied to directly quantify the surface forces between calcite particles and different metallic substrates, including carbon steel (CR1018), low alloy steel (4140), stainless steel (SS304) and tungsten carbide, under different water chemistries (i.e., salinity and pH). Measured force profiles revealed that the attractive van der Waals (VDW) interaction contributed to the attachment of the calcium carbonate particles on substrate surfaces, while the repulsive electric double layer (EDL) interactions could inhibit the attachment behaviors. High salinity and acidic pH conditions of aqueous solutions could weaken the EDL repulsion and promote the attachment behavior. The adhesion of calcite particles with CR1018 and 4140 substrates was much stronger than that with SS304 and tungsten carbide substrates. The bulk scaling tests in aqueous solutions from an industrial oil production process showed that much more severe scaling behaviors of calcite was detected on CR1018 and 4140 than those on SS304 and tungsten carbide, which agreed with surface force measurement results. Besides, high salinity and acidic pH can significantly enhance the scaling phenomena. This work provides fundamental insights into the scaling mechanisms of calcite at the nanoscale with practical implications for the selection of suitable anti-scaling materials in petroleum industries.

Clay micromechanics: Numerical modelling of electrical double-layer interactions to develop particle-based models for clay

Discrete element modelling of clays requires defining the interaction energy between two particles. The Derjaguin, Landau, Verwey and Overbeek (DLVO) theory combining the effect of the van der Waals forces and the Coulombic forces due to the double layer of counterions provides a widely accepted framework to characterise the pair potential energy. Solutions of the Poisson-Boltzmann (PB) equation to quantify the Coulombic forces are only available for the case of infinitely extended and uniformly charged facing plates (1D conditions). However, these assumptions are not representative of a clay particle system. Particles should be represented by platelets of finite size and finite thickness, with different charges between the edge and the basal planes. This paper addresses the problem of deriving the Coulombic interaction forces for plates of finite size and thickness in 3D configuration by solving the Poisson-Boltzmann equation numerically via the Finite Element Method (FEM). It is shown that 2D particles (plates of infinitesimal thickness) provide an adequate representation of Coulombic interaction as long as the particles are uniformly charged. The advantage of 2D particles is to reconcile numerical modelling with analytical solutions available in the literature. The use of 2D particles is questionable when considering different charges between basal planes and edges.

Revisiting DLVO theory to inform particle-scale modelling of clays

Particle-scale modelling of clays requires defining an energy-separation function for a pair of platy particles. The Derjaguin, Landau, Verwey and Overbeek (DLVO) theory provides a convenient framework for developing such a function as it embeds the combined effect of pore-fluid temperature, dielectric permittivity, and electrolyte concentration. Therefore, it can underpin the modelling of clay mechanical behaviour associated with thermal and environmental loading. The DLVO theory assumes particle interactions to be controlled by the van der Waals forces and the Coulombic forces via the Electrical Double-Layer (EDL). This paper first explores the 1D EDL interactions via the thermodynamics-based Grand Potential for the case of parallel sheets (with infinitesimal and infinite thickness). For infinitesimal thickness sheets, it is shown that i) the approximate analytical solutions of the Poisson-Boltzmann equation provide a qualitatively robust representation of EDL interactions, ii) the EDL interaction is qualitatively similar regardless of whether the interaction is modelled assuming constant surface charge or surface potential thus eliminating the uncertainty about the most appropriate electrical boundary condition to model EDL interactions; iii) the mechanical pressure required to ‘aggregate’ two sheets interacting via the EDL is finite and not infinite as often assumed in the literature (i.e. van der Waals forces do not need to be invoked to generate the energy barrier that triggers face-to-face aggregation but it remains fundamental for the quantitative definition of the potential energy barrier responsible for particle aggregation). Finally, the paper compares the 1D solutions for infinitely extended particles with the numerical solutions derived for face-to-face finite cuboidal particles with different aspect ratios to investigate the 1D analytical solutions that can conveniently be used as a benchmark in particle-scale modelling.

Probing the surface forces between air bubbles and bitumen via direct force Measurements: Effects of aqueous chemistry

The surface interactions of air bubbles and other components (e.g., particles, oil droplets) significantly influence the operation efficiency of a variety of engineering processes such as oily water treatment, bitumen extraction and flotation. Herein, the surface interactions of air bubbles with two types of Athabasca bitumen samples in aqueous solutions of varying pH, salinity, type of cations and in the presence of surfactants have been systematically characterized using a bubble probe atomic force microscope (AFM) technique. AFM imaging has revealed that exposure to high concentrations of NaCl and CaCl2 solutions or alkaline environments causes roughening of the bitumen surfaces. The results of surface force measurements demonstrate that the interaction and attachment behaviors between bubbles and bitumen are significantly affected by ionic strength, solution pH, and the presence of surfactants. The experimental force measurement results could be accurately described by a theoretical model that incorporates Reynolds lubrication theory and augmented Young-Laplace equation, with the inclusion of disjoining pressure. In low-salinity conditions, the bubble-bitumen interaction is dominated by electric double layer (EDL) repulsion, which prevents surface attachment. This effect is more pronounced at elevated pH conditions. In high-salinity solutions, however, the EDL interactions are significantly reduced, and the hydrophobic interaction becomes the dominant factor, overcoming the van der Waals repulsion and leading to the attachment of bubbles to bitumen surfaces. Raising aqueous pH weakens the bubble-bitumen hydrophobic interaction, whereas the introduction of calcium ions strengthens this interaction, resulting in enhanced surface attachment. Interestingly, even in high-salinity conditions, the presence of a small number of surfactants can inhibit bubble-bitumen contact, mainly caused by reduced hydrophobic attraction and increased steric repulsion. This work provides valuable nanoscale insights into how bubbles and bitumen interact in intricate aqueous environments, and the results show practical implications for controlling similar interfacial phenomena in various engineering processes.

Algae–water–silica interactions in low and high ionic strength environments

The interaction between algae and solid surfaces is of direct interest for the optimization of biofuel production technologies. Silica is particularly relevant due the use of solgel matrices for enhanced growth and ease of processing, where ionic strength variation is an important consideration. Here, an inverted fluorescence experiment is used to perform measurements of the distance between a silica surface and algae in solution. At low ionic strength, the average algae–silica distance is approximately 90 nm but increases to roughly 130 nm at 1 M NaCl, contradicting the prediction based on simple electrical double layer interaction models. These findings illustrate the role of biochemical and electrostatic interactions at charged aqueous interfaces of relevance to biofuel production.

Connecting Colloidal Forces to the Equilibrium Thickness of Particulate Deposits on a Substrate in Contact with a Suspension Using Classical Density Functional Theory

We study contributions of colloidal forces, i.e., hydrophobic, van der Waals, and electrical double layer interactions, to the thickness of a colloidal deposit in equilibrium with an aqueous suspension by using classical density functional theory, which we expand to obtain a Ginzburg-Landau type energy functional. We regard colloidal particles as clusters of molecular segments-a reminiscent of polymer statistical physics and of the classic Hamaker treatment of van der Waals interactions between particles. This approach appropriately accounts for the integral interaction energy between colloidal particles, which may take magnitudes of many times the characteristic molecular thermal energy kBT (Boltzmann constant times temperature). The analysis highlights the well-known insight that entropy is mostly governed by the solvent molecules and gives physical values to the statistical coefficients in a Ginzburg-Landau type energy functional.

A Coarse-Grained Interaction Model for Sodium Dominant Montmorillonite.

Montmorillonite is the main crystalline mineral present in bentonite. It is an absorbent, swelling material; the physical chemistry underlying its ability to absorb water and swell occurs at the nanoscale, governed by electrical double-layer interactions. In turn, absorption and swelling lead to important changes in the macroscopic transport properties of the clay. Mesoscale models can help us establish a link between these nanoscale processes and macroscale properties, notably by providing a detailed description of its pore network. Models on the scale of hundreds to thousands of nanometers are required, which cannot realistically be handled using traditional all-atom molecular dynamics simulations. This work presents a coarse-grained (CG) mesoscale model of sodium montmorillonite. In our model, montmorillonite platelets are represented by two types of particles: central nonhydrogen-bonded particles and edge hydrogen-bonding particles. The particle interactions are described by two-body potentials, which were optimized based on all-atom molecular dynamics simulations. Specifically, several potential mean force calculations involving dry and hydrated montmorillonite were performed, using the ClayFF potential to calculate interatomic forces. The CG model was validated by testing the scalability of the model, testing its ability to reproduce potentials of mean force reported elsewhere in the literature, and by comparing the calculated elastic properties of a system containing 1000 Na montmorillonite platelets to experimentally measured elastic properties of bentonite. The simulated elastic properties obtained using our mesoscale model agree with these experimental values.

Proposition of a bubble-particle attachment model based on DLVO van der Waals and electric double layer interactions for froth flotation modelling

Proposition of a bubble-particle attachment model based on DLVO van der Waals and electric double layer interactions for froth flotation modelling

Electro‐kinetically enhanced mass transport of charged macro‐solutes through a microchannel with porous walls

AbstractElectrokinetics of the solute transport across the porous walls of micro channel is important from its practical application but less explored. Transport of the charged macro‐solutes across perm‐selective walls in a microchannel is investigated. The extended Nernst–Planck equation describes the charged macro‐solutes distribution in the mass transfer boundary layer over the porous wall. The transverse electromigration of the charged macro‐solute either augments or suppresses the concentration polarization and the permeation rate depending on the wall and solute surface potential (attractive or repelling). The wall potential is screened due to the electrical double layer interaction of the wall and charged solute. It is observed that the charged solute concentration over the channel wall enhances by two times in case of oppositely charged interactions (unlike solute and channel wall) compared to like charges. The findings of this study can facilitate understanding of electrokinetic based drug delivery and separation systems involving charged solutes.

Relationship between soil erodibility by concentrated flow and shear strength of a Haplic Acrisol with a cationic polyelectrolyte

To clarify the relationship between rill erodibility in an excess shear stress model for concentrated flow erosion and soil particle–particle interactions, we examined the rill erodibility and aggregation-dispersion behavior of Shimajiri Maaji soil, classified as a Haplic Acrisol, with different amounts of cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC). The effect of particle–particle interaction on rill erodibility was determined by performing shear strength measurements and rill erosion experiments as a function of the PDADMAC dose without changing other soil conditions. Moreover, the mechanisms of particle–particle interactions were examined by comparing the electrophoretic mobility (EPM) with the transmission of the supernatant of the soil suspension and soil shear strength. The EPM and transmission showed that the Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction governed the aggregation-dispersion behavior. At the same time, the shear strength monotonically increased with increasing PDADMAC dose, even when charge reversal and electric double layer (EDL) repulsion occurred. This result suggests that the shear strength is sensitive not only to the EDL interaction but also to the interactions, the so-called non-DLVO forces, such as bridging interaction. The difference between transmission and shear strength should be due to the difference in the characteristic length because the transmission is attributed to the collision/approaching process between particles, whereas the shear strength is attributed to the broken/retracting process of particle–particle contact. Rill erodibility decreased with increasing shear strength. Furthermore, our quantitative analysis demonstrated that rill erodibility can be represented by a linear function of shear strength. These results clearly show that a high attractive force between soil particles results in low rill erodibility. The strong particle–particle attraction protects soil particles from peeling off by increasing the shear stress of the flowing water. Our study suggests that shear strength measurement can be used to quickly estimate the effect of soil conditioners on rill erodibility in the field.

Simulation study on the flow behaviors of weak electrolyte solutions in nano-sized and micron-sized pores considering electric double layer interactions

ABSTRACT The interactions between the ions in the weak electrolyte solutions and the charged solid wall result in the formation of an electric double layer (EDL) in nano-sized and micron-sized pores. However, in nano-sized pores, EDLs may be overlapping. Herein, a widely applicable Poisson-Nernst-Planck equation combined with the Navier–Stokes equation was adopted for the flow of weak electrolyte solutions under pressure-driven conditions. Meanwhile, the finite element method was utilized to solve the governing equations and investigate the influence of EDL interactions on flow behaviors in different pore radii (25 nm~5 μm). The results showed that as the pore radius increased, the influence of EDL interactions on fluid flow behaviors first increased and then decreased. The influence of EDL interactions on fluid flow behaviors was the most noticeable when the pore radius was close to the EDL thickness. Furthermore, the influence of EDL interactions appeared to be negligible in the pore radius greater than 5 μm. When EDL interactions were ignored, the volume flow in the pores of the circular, square, and equilateral triangle was increased by about 13%. This study provides new insights into the flow behaviors of weak electrolyte solutions in nano-sized and micron-sized pores.

DC-electrokinetic motion of colloidal cylinder(s) in the vicinity of a conducting wall.

The boundary effects on DC-electrokinetic behavior of colloidal cylinder(s) in the vicinity of a conducting wall is investigated through a computational model. The contribution of the hydrodynamic drag, gravity, electrokinetic (i.e., electrophoretic and dielectrophoretic), and colloidal forces (i.e., forces due to the electrical double layer and van der Waals interactions) are incorporated in the model. The contribution of electrokinetic and colloidal forces are included by introducing the resulting forces as an external force acting on the particle(s). The colloidal forces are implemented with the prescribed expressions from the literature, and the electrokinetic force is obtained by integrating the corresponding Maxwell stress tensor over the particles' surfaces. The electrokinetic slip-velocity together with the thin electrical double layer assumption is applied on the surfaces. The position and velocity of the particles and the resulting electric and flow fields are obtained and the physical insight for the behavior of the colloidal cylinders are discussed in conjunction with the experimental observations in theliterature.

Nanofabricated chitosan/graphene oxide electrodes for enhancing electrosorptive removal of U(VI) from aqueous solution

The radioactive pollution caused by uranium-containing effluents brings serious detriments to environmental safety and human health. Herein the chitosan/graphene oxide (CS/GO) electrodes were nano-fabricated for the effective electrosorption of U(VI) from aqueous solution. The cyclic voltammetry measurements were conducted to determine the specific capacitance of the CS/GO materials. The U(VI) electrosorption was performed on capacitive deionization (CDI) system. The results showed that CS/GO-4 presented best electrosorption performance for U(VI) among various CS/GO materials, which is associated with a well-balanced meso-/micro- porous structure for promoting ion transfer and superior conductivity for ion trapping through electrical double-layer (EDL) interaction. The isotherms could be described by Langmuir model, whereas the kinetics could be fitted by Langmuir model. The maximum removal capacity for U(VI) electrosorption by CS/GO-4 reached 271.2 mg/g at 0.9 V, which was almost double that achieved at 0.0 V. The electrosorption mechanism may involve in the formation of electrical double-layer (EDL) and the coordination of U(VI) by the amine and carboxyl groups of CS/GO materials. The electrosorption-desorption cycles further demonstrated that the potential application of CS/GO electrode materials for the electrosorptive removal of U(VI) from radioactive wastewater.