Electrical Double Layer Interaction Research Articles

Electrical double-layer interaction between oppositely charged dissimilar oxide surfaces with charge regulation and Stern–Grahame layers

The force of double-layer interaction between dissimilar flat oxide surfaces charged oppositely at infinite separation and with Stern–Grahame layers was calculated as a function of the surface separation under the conditions of charge regulation. The interaction force showed a monotonic attraction with respect to the surface separation, lying between constant surface potential and constant surface charge conditions. The variations of surface potentials and surface charge densities of respective double layers were also presented as functions of the surface separation. When the negative diffuse-layer potential at infinite separation changed its sign to positive as a result of specific adsorption of cations on the negatively changed surface, the double-layer interaction force showed a repulsive force barrier followed by an attraction at some particular separation.

Interaction Forces between BSA Adsorbed Layer on Amino-Thiolated Gold Surfaces

Direct measurement of interaction forces between bovine serum albumin (BSA) adsorbed layers on amino-thiolated gold surfaces has been carried out using colloidal probe atomic force microscopy (AFM). The substrate was prepared via self-assembly of 2-aminoethanethiol on gold in aqueous media. In the absence of BSA, an electric double layer interaction was observed, resulting from protonation of the primary amine groups on the gold surface. Similar electric double layer repulsions were seen in the presence of BSA over a whole range of BSA concentration investigated. These repulsive interactions were found to be dependent on the BSA concentration, that is, the magnitude of the repulsion increases with the BSA concentration. This phenomenon is attributed to the difference in the adsorbed amount of BSA on the amino-thiolated gold surface, which was confirmed using a 27 MHz quartz crystal microbalance (QCM).

Soft matter: from shapes to forces on the nanoscale.

Soft matter deforms in response to imposed external forces. Here we demonstrate how dynamic surface forces are linked to far-field deformations. This offers a new paradigm for determining forces between soft particles in colloidal systems. The particular example we use to illustrate this concept is that of a fluid drop interacting with a solid wall through hydrodynamic drainage flow coupled with repulsive or attractive dissimilar electrical double layer interactions. The force can be deduced from a simple analysis of the drop surface geometry outside the interaction zone.

Dynamic Forces between a Moving Particle and a Deformable Drop

The dynamic interaction forces between a solid silica particle and an immobilized tetradecane droplet have been measured using atomic force microscopy. The dominant colloidal forces are repulsive electrical double layer interactions due to the partitioning of added sodium dodecyl sulfate to the deformable oil/water (O/W) interface. Over a range of drive velocities up to 50 Im/s, these colloidal forces, plus hydrodynamic interactions due to fluid flow in the aqueous film (22 nm thick) between the particle and O/W interface, as well as deformations of the interface, contribute to the overall dynamic force between the silica particle (radius 12 Im) and tetradecane drop (radius of curvature 55 Im). Within the tolerance of experimental parameters, excellent agreement is observed between the measured forces and those predicted by a theory that accounts for the above phenomena. The theory also furnishes details not directly measurable, such as the time-dependent deformations and velocities of the O/W interface and variations of the thickness of the aqueous film between the particle and the drop during the course of the experiment.

Numerical modelling of electro-osmotically driven flow within the microthin liquid layer near an earthworm surface - a biomimetic approach

The electro-osmotic flow near an earthworm body surface is a basic electrokinetic phenomenon that takes place when the earthworm moves in moist soil. The flow within a microthin liquid layer near earthworm's body surface is induced by the electric double layer (EDL) interaction. Such a microscale electro-osmotic flow plays a role of lubrication between the earthworm's body surface and the surrounding medium of moist soil and reduces surface adhesion. In the current paper, the electro-osmotic flow near earthworm surface is numerically simulated to further understand the mechanism of antisoil adhesion. A lattice Poisson method is first employed to solve electric potential and charge distributions in the EDL along an earthworm surface; the external electric field is then obtained by solving the Laplace equation. The motion of electro-osmotic flow controlled by Navier-Stokes equations is simulated by the lattice Boltzmann method. Typically, the simulation of electro-osmotic flow shows that moving vortices, which likely contribute to antisoil adhesion, can be formed near the earthworm body surface by the non-uniform and variational electrical force.

Transient Responses of a Wetting Film to Mechanical and Electrical Perturbations

This article reports real-time observations and detailed modeling of the transient response of thin aqueous films bounded by a deformable surface to external mechanical and electrical perturbations. Such films, tens to hundreds of nanometers thick, are confined between a molecularly smooth mica plate and a deformable mercury/electrolyte interface on a protuberant drop at a sealed capillary tube. When the mercury is negatively charged, the water forms a wetting film on mica, stabilized by electrical double layer forces. Mechanical perturbations are produced by driving the mica plate toward or by retracting the mica plate from the mercury surface. Electrical perturbations are applied to change the electrical double layer interaction between the mica and the mercury by imposing a step change of the bias voltage between the mercury and the bulk electrolyte. A theoretical model has been developed that can account for these observations quantitatively. Comparison between experiments and theory indicates that a no-slip hydrodynamic boundary condition holds at the molecularly smooth mica/electrolyte surface and at the deformable mercury/electrolyte interface. An analysis of the transient response based on the model elucidates the complex interplay between disjoining pressure, hydrodynamic forces, and surface deformations. This study also provides insight into the mechanism and process of droplet coalescence and reveals a novel, counterintuitive mechanism that can lead to film instability and collapse when an attempt is made to thicken the film by pulling the bounding mercury and mica phases apart.

Quantitative Membrane Electrostatics with the Atomic Force Microscope

The atomic force microscope (AFM) is sensitive to electric double layer interactions in electrolyte solutions, but provides only a qualitative view of interfacial electrostatics. We have fully characterized silicon nitride probe tips and other experimental parameters to allow a quantitative electrostatic analysis by AFM, and we have tested the validity of a simple analytical force expression through numerical simulations. As a test sample, we have measured the effective surface charge density of supported zwitterionic dioleoylphosphatidylcholine membranes with a variable fraction of anionic dioleoylphosphatidylserine. The resulting surface charge density and surface potential values are in quantitative agreement with those predicted by the Gouy-Chapman-Stern model of membrane charge regulation, but only when the numerical analysis is employed. In addition, we demonstrate that the AFM can detect double layer forces at a separation of several screening lengths, and that the probe only perturbs the membrane surface potential by <2%. Finally, we demonstrate 50-nm resolution electrostatic mapping on heterogeneous model membranes with the AFM. This novel combination of capabilities demonstrates that the AFM is a unique and powerful probe of membrane electrostatics.

The electro-osmotically driven flow near an earthworm's body surface and the inspired bionic design in engineering

The electro-osmotically driven flow near an earthworm’s body surface is a basic electrokinetic phenomenon that takes place when the earthworm moves in moist soil. The flow in a micro thin layer of water is formed in the vicinity of the earthworm’s body surface as a result of the electric double layer interaction. Such a micro scale electro-osmotically driven flow plays the role of lubrication between the earthworm’s body surface and the surrounding medium of moist soil and reduces the surface adhesion. The examples of bionic design in engineering inspired by such natural phenomena of the earthworm in soil are reported.

Study on the Interaction between Two Identical Parallel Plates with Iteration Method in Functional Theory

By introducing the functional theory into the calculation of electric double layer (EDL) interaction,the interaction energies of two identical parallel plates were calculated at 128,77,and 25 mV potentials,respectively. Compared with the results from the Debye-Huckel (DH),Langrauir,and numerical methods,respectively,the results showed that DH and Langmuir methods were applicable just for the critical potentials,but the functional approach with quite accurate and simple analytic expression held true at any potential.

Dynamics of Interactions Involving Deformable Drops: Hydrodynamic Dimpling under Attractive and Repulsive Electrical Double Layer Interactions

A model developed previously to analyze force measurements between two deformable droplets in the atomic force microscope [Langmuir 2005, 21, 2912-2922] is used to model the drainage of an aqueous film between a mica plate and a deformable mercury drop for both repulsive and attractive electrical double-layer interactions between the mica and the mercury. The predictions of the model are compared with previously published data [Faraday Discuss. 2003, 123, 193-206] on the evolution of the aqueous film whose thickness has been measured with subnanometer precision. Excellent agreement is found between theoretical results and experimental data. This supports the assumptions made in the model which include no-slip boundary conditions at both interfaces. Furthermore, the successful fit attests to the utility of the model as a tool to explore details of the drainage mechanisms of nanometer-thick films in which fluid flow, surface deformations, and colloidal forces are all involved. One interesting result is that the model can predict the time at which the aqueous film collapses when attractive mica-mercury forces are present without the need to invoke capillary waves or other local instabilities of the mercury/electrolyte interface.

On the effect of image charges and ion-wall dispersion forces on electric double layer interactions

Two effects of interactions between polarizable ions and polarizable walls in electric double layers are investigated: ionic image charge forces and ion-wall dispersion forces. The first must be included for a consistent treatment of the wall-wall van der Waals (vdW) interaction, since it contains the effect of screening of the static part of the vdW interaction. The second has been suggested to give rise to ion specificity in double layer interactions. The strength of the ion-wall dispersion forces are estimated from quantum mechanical calculations of ionic polarizability and from experimental data for the dielectric functions of the media. The ion density profiles and the anisotropic ion-ion distribution functions in the double layer are calculated in the highly accurate anisotropic hypernetted chain approximation, which allows the correct treatment of the image charge forces. The double layer interactions are evaluated from these distribution functions. It is found that it is important to include both kinds of ion-wall forces. Quantitative and sometimes even qualitative differences occur in the double layer interactions depending on the ionic species of the electrolyte due to different strengths of the ion-wall dispersion interactions.

NUMERICAL SIMULATION OF ELECTROKINETIC MICROFLUIDICS IN COLLOIDAL SYSTEMS

ABSTRACT A numerical scheme is presented for simulating electrokinetic microfluidics in systems with arbitrary morphology. This scheme is based on a numerical solution of the coupled Poisson, Nernst–Planck, and Navier–Stokes equations. While traditional finite-difference methods were used to resolve the first two problems, the lattice Boltzmann method was applied to the latter. The developed numerical approach was used for the simulation of electroosmotic flow through a simple cubic array of hard (impermeable, nonconducting) micro-sized spheres. Volumetric electroosmotic flow was studied for dependence on electrical field strength, ζ-potential at the solid-liquid interface, electrical double layer interaction, and numerical grid resolution. Colloid stability and electrokinetics in microfluidic devices with particulate or monolithic fixed-bed elements represent two potential applications of this work.

Measurements of the minimum elevation of nano-particles by 3D nanoscale tracking using ratiometric evanescent wave imaging

Effect of saline concentration on the minimum elevation of nanoparticles has been examined under the electric double layer interactions with the substrate glass surface. The use of ratiometric total internal reflection fluorescence microscopy (R-TIRFM) allows three-dimensional tracking of nanoparticles in the near-wall region within less than 1 μm from the surface. The measurements of minimum elevation were made for polystyrene fluorescent nanospheres of 100, 250, and 500 nm in radii (SG = 1.05) for the salinity ranging from 0.1 to 10 mM. Special care was taken to insure cleaned surface conditions by elaborate sonication and rinsing of the glass substrate. The laser illumination intensity and duration also had to be carefully examined to minimize photobleaching of the fluorescence emission from particles. It is reported that the minimum elevation decreases with increasing saline concentration and with increasing particle sizes, for the first time experimentally and quantitatively to the authors’ knowledge.

The similarity of electric double-layer interaction from the general Poisson–Boltzmann theory

We studied electric double-layer (EDL) interactions in electrolytes with different valence combinations. Our results show that the interactions are similar for electrolytes with the same co-ion valences and concentrations and such similarity increases with the co-ion valence and surface potential. A scaled surface potential was defined and found to be useful in characterizing the difference in EDL interaction. These results show that co-ions play a more important role than counterions in determining EDL potential and interaction in an electrolyte solution, especially for systems with high co-ion valence and/or high surface potentials.

Interaction forces between poly(amidoamine) (PAMAM) dendrimers adsorbed on gold surfaces

Interaction forces between two gold surfaces with adsorbed poly(amidoamine) (PAMAM) dendrimers (generations G3.0 and G5.0) have been investigated using colloidal probe atomic force microscopy (AFM). In the absence of dendrimers or at their low concentrations, an attractive force derived from the van der Waals interaction was observed. On the other hand, this attractive interaction changed to repulsion with increasing dendrimer concentration. The origin of the repulsion can be attributed to either an electric double layer interaction or a steric effect of the adsorbed dendrimers, depending on the concentration of dendrimer. The steric hindrance was also influenced by the generation of the dendrimer; the force-detectable distance in the presence of PAMAM G5.0 dendrimer was slightly longer than that in the presence of G3.0 dendrimer. In order to estimate the occupied area of each dendrimer adsorbed on gold, quartz crystal microbalance (QCM) measurement was also carried out.

Arsenic removal from high-arsenic water by enhanced coagulation with ferric ions and coarse calcite

Arsenic removal from high-arsenic water in a mine drainage system has been studied through an enhanced coagulation process with ferric ions and coarse calcite (38–74 μm) in this work. The experimental results have shown that arsenic-borne coagulates produced by coagulation with ferric ions alone were very fine, so micro-filtration (membrane as filter medium) was needed to remove the coagulates from water. In the presence of coarse calcite, small arsenic-borne coagulates coated on coarse calcite surfaces, leading the settling rate of the coagulates to considerably increase. The enhanced coagulation followed by conventional filtration (filter paper as filter medium) achieved a very high arsenic removal (over 99%) from high-arsenic water (5 mg/l arsenic concentration), producing a cleaned water with the residual arsenic concentration of 13 μg/l. It has been found that the mechanism by which coarse calcite enhanced the coagulation of high-arsenic water might be due to attractive electrical double layer interaction between small arsenic-borne coagulates and calcite particles, which leads to non-existence of a potential energy barrier between the heterogeneous particles.

Colloid Probe AFM Investigation of the Influence of Cross-Linking on the Interaction Behavior and Nano-Rheology of Colloidal Droplets

The repulsive forces between a glass sphere and immobilized colloidal droplets of poly(dimethylsiloxane) (PDMS) (with various levels of internal cross-linking) have been determined in aqueous solution using colloid probe atomic force microscopy. On initial surface approach, droplet deformation is negligible and interaction forces resemble those expected for electrical double layer interaction of rigid spheres. Upon further approach, droplet flattening results in forces that deviate below rigid body electrical double layer interaction. The extent of droplet deformation has been determined in terms of the deviation from hard-sphere interaction. Droplet deformability is strongly dependent on the droplet cross-linking level and hence controlled by some combination of the bulk rheological and interfacial properties of the droplets. Droplet nano-rheology has been determined from the extent of force curve hysteresis. For liquidlike droplets, with low levels of cross-linking, no force curve hysteresis is observed and the elastic deformation may be described by a single spring constant, which is controlled by the interfacial properties. For highly cross-linked droplets, the extent of deformation is controlled by the droplet's bulk rheology rather than the interfacial properties. Upon retraction of the surfaces, force curve hysteresis is observed and is due to the viscoelastic response of the PDMS. The extent of hysteresis is dependent on the rate of approach/retraction and the loading force and has been theoretically analyzed to determine nano-rheological parameters that describe droplet relaxation processes. Elastic moduli and relaxation times of the PDMS droplets vary over several orders of magnitude as a function of cross-linking.

Dielectrophoretic Force on a Sphere near a Planar Boundary

The small gap distance separating a spherical colloidal particle in electrophoretic motion from a planar nonconducting surface is a required parameter for calculating its electrophoretic mobility. In the presence of an externally applied electric field, this gap distance is determined by balancing the van der Waals, electrical double layer interaction, and gravitational forces with a dielectrophoretic (DEP) force. Here, the DEP force was determined analytically by integration of the Maxwell stress over the surface of the particle. The account of this force showed that its previous omission from the analysis always resulted in underpredicted gap distances. Furthermore, the DEP force dominated under conditions of low particle density or high electric field strength and led to much higher gap distances on the order of a few microns. In one particular case, a combination of low particle density and small particle size produced two possible equilibrium gap distances for the particle. However, the particle was unstable in the second equilibrium position when subjected to small perturbations. In general, larger particles had smaller gap sizes. The effects of four other parameters on gap distance were studied, and gap distances were found to increase with lower particle density, higher electric field strength, higher particle and wall zeta potentials, and lower Hamaker constants. Retardation effects on van der Waals attraction were considered.

Electrical double layer interactions between dissimilar oxide surfaces with charge regulation and Stern–Grahame layers

Models of surfaces with intrinsic ionisable amphoteric surface sites governed by the dissociation of acid–base potential determining ion species together with the capacity for the adsorption of anion and cations of the supporting electrolyte are required to describe both the results of electrokinetic and titration measurements of inorganic oxides. The Gouy–Chapman–Stern–Grahame (CGSG) model is one such model that has been widely used in the literature. The electrical double layer interaction between two dissimilar CGSG surfaces has been studied by Usui recently [S. Usui, J. Colloid Interface Sci. 280 (2004) 113] where erroneous discontinuities in the slope of the pressure–separation relation were observed. We revisit this calculation and provide a simple general methodology to analyse the electrical double layer interaction between dissimilar ionisable surfaces with ion adsorption.

Effects of Ionic Strength and Surface Charge on Protein Adsorption at PEGylated Surfaces

PEGylated Nb2O5 surfaces were obtained by the adsorption of poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) copolymers, allowing control of the PEG surface density, as well as the surface charge. PEG (MW 2 kDa) surface densities between 0 and 0.5 nm(-2) were obtained by changing the PEG to lysine-mer ratio in the PLL-g-PEG polymer, resulting in net positive, negative and neutral surfaces. Colloid probe atomic force microscopy (AFM) was used to characterize the interfacial forces associated with the different surfaces. The AFM force analysis revealed interplay between electrical double layer and steric interactions, thus providing information on the surface charge and on the PEG layer thickness as a function of copolymer architecture. Adsorption of the model proteins lysozyme, alpha-lactalbumin, and myoglobin onto the various PEGylated surfaces was performed to investigate the effect of protein charge. In addition, adsorption experiments were performed over a range of ionic strengths, to study the role of electrostatic forces between surface charges and proteins acting through the PEG layer. The adsorbed mass of protein, measured by optical waveguide lightmode spectroscopy (OWLS), was shown to depend on a combination of surface charge, protein charge, PEG thickness, and grafting density. At high grafting density and high ionic strength, the steric barrier properties of PEG determine the net interfacial force. At low ionic strength, however, the electrical double layer thickness exceeds the thickness of the PEG layer, and surface charges "shining through" the PEG layer contribute to protein interactions with PLL-g-PEG coated surfaces. The combination of AFM surface force measurements and protein adsorption experiments provides insights into the interfacial forces associated with various PEGylated surfaces and the mechanisms of protein resistance.