Double Layer Interaction Research Articles

Yolk/Shell Colloidal Crystals Incorporating Movable Cores with Their Motion Controlled by an External Electric Field.

Yolk/shell particles composed of a submicrometer-sized movable core and a silica shell are promising building blocks for novel optical colloidal crystals, because the locations of cores in the shell compartment can be reversibly changed by using external stimuli. Two dimensional arrays of yolk/shell particles incorporating movable cores were prepared by a self-assembly method. The movable cores of colloidal crystals in water could be observed with an optical microscope under application of external electric field. The motions of inner silica cores depended on the electric field strength and frequency and were categorized into three cases: (1) Random Brownian motion, (2) anisotropic motion of cores moving in a direction orthogonal to a field, and (3) suppressed motion fixed in the center of shell compartment. Random Brownian motion of cores was scarcely affected by field strength when a high frequency (in the MHz range) electric field was applied. On the other hand, an increase in field strength at low-frequency fields (kHz) transiently changed the core motion from (1) to (2) and a further increase in field strength changed it from (2) to (3). When the silica core was incorporated in a large void a stronger electric field was needed to suppress its motion than when it was in a small void. The high responsivity to electric fields in a low-frequency range indicated the importance of electric double layer (EDL) interaction between core and inner shell in controlling the core location in yolk/shell colloidal crystals. It was also shown that movable titania cores in yolk/shell particles required a low-frequency field with a high strength to change from the random to anisotropic motion. The result suggested that the electrostatic interaction between EDLs of the silica core and the inner silica wall could be stronger than that between EDLs of the titania core and the silica shell.

Mean distance of two Brownian particles trapped in a suspended droplet and its dependence on the Debye length

Abstract The Brownian motion of two particles confined near the bottom of a suspended droplet was considered in order to examine the electrical double-layer interaction between them. The mean distance between the particles was expressed as a function of the Debye screening length. We report the application of Brownian particle trajectories for the experimental determination of the Debye screening length between gold particles trapped within a water droplet. This was computed through a comparison of the mean distance measured by observing the Brownian motion with its theoretical value.

Variation of Local Surface Properties of an Air Bubble in Water Caused by Its Interaction with Another Surface.

Surface and hydrodynamic forces acting between an air bubble and a flat mica surface in surfactant-free water and in 1 mM KCl solution have been investigated by observing film drainage using a modified surface force apparatus (SFA). The bubble shapes observed with the SFA are compared to theoretical profiles computed from a model that considers hydrodynamic interactions, surface curvature, and disjoining pressure arising from electrical double layer and van der Waals interactions. It is shown that the bubble experiences double-layer forces, and a final equilibrium wetting film between the bubble and mica surfaces is formed by van der Waals repulsion. However, comparison with the theoretical model reveals that the double-layer forces are not simply a function of surface separation. Rather, they appear to be changed by one of more of the following: the bubble's dynamic deformation, its proximity to another surface, and/or hydrodynamic flow in the aqueous film that separate them. The same comments apply to the hydrodynamic mobility or immobility of the air-water interface. Together the results show that the bubble's surface is "soft" in two senses: in addition to its well-known deformability, its local properties are affected by weak external forces, in this case the electrical double-layer interactions with a nearby surface and hydrodynamic flow in the neighboring aqueous phase.

Observation of adsorption behavior of biomolecules on ferroelectric crystal surfaces with polarization domain patterns

Lithium tantalate (LiTaO3) is one of the ferroelectric crystals that exhibit spontaneous polarization domain patterns on its surface. We observed the polarization-dependent adsorption of avidin molecules, which are positively charged in a buffer solution at pH 7.0, on LiTaO3 surfaces caused by electrostatic interaction at an electrostatic double layer using atomic force microscopy (AFM). Avidin adsorption in the buffer solution was confirmed by scratching the substrate surfaces using the AFM cantilever, and the adsorption patterns were found to depend on the avidin concentration. When KCl was added to the buffer solution to weaken the electrostatic double layer interaction between avidin molecules and LiTaO3 surfaces, adsorption domain patterns disappeared. From the comparison between the adsorption and chemically etched domain patterns, it was found that avidin molecule adsorption is enhanced on negatively polarized domains, indicating that surface polarization should be taken into account in observing biomolecule behaviors on ferroelectric crystals.

Addressing Colloidal Stability for Unambiguous Electroanalysis of Single Nanoparticle Impacts.

Herein the problem of colloidal instability on electrochemically detected nanoparticle (NP) collisions with a Hg ultramicroelectrode (UME) by electrocatalytic amplification is addressed. NP tracking analysis (NTA) shows that rapid aggregation occurs in solution after diluting citrate-stabilized Pt NPs with hydrazine/phosphate buffers of net ionic strength greater than 70 mM. Colloidal stability improves by lowering the ionic strength, indicating that aggregation processes were strongly affected by charge screening of the NP double layer interactions at high cation concentrations. For the system of lowest ionic strength, the overwhelming majority of observed electrocatalytic current signals represent single NP/electrode impacts, as confirmed by NTA kinetic monitoring. NP diffusion coefficients determined by NTA and NP impact electroanalysis are in excellent agreement for the stable colloids, which signifies that the sticking probability of Pt NPs interacting with Hg is unity and that the observed NP impact rate agrees with the expected steady-state diffusive flux expression for the spherical cap Hg UME.

Interactions between elemental selenium and hydrophilic/hydrophobic surfaces: Direct force measurements using AFM

Understanding the surface interactions between elemental selenium (Se0) and solid substrates is of both fundamental and practical importance in biological systems, water treatment processes, and microelectromechanical/nanoelectromechanical systems where Se0 is present. In this work, for the first time, surface interactions between a Se0 sphere and substrates of varying hydrophobicity, including silica, octadecyltrichlorosilane (OTS) modified silica, and electrodeposited Se0 film, were directly measured in aqueous solutions at different pH and salinity conditions using an atomic force microscope (AFM). In 1mM NaCl, electrical double layer forces and van der Waals forces dominated the interactions between Se0 sphere and hydrophilic silica, and the force-distance profiles could be well fitted by classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Additional hydrophobic attraction was found to play a role in the interactions between Se0 sphere and hydrophobic surfaces (i.e., OTS modified silica, and electrodeposited Se0 film), with Se0-OTS showing relatively larger hydrophobic decay length (D0∼1.3nm) than Se0-Se0 (D0∼1nm). In 0.5M NaCl, the electrical double layer interaction was significantly compressed. The change of zeta potentials of Se0, OTS and silica surfaces with pH showed good agreement and same trend as that of the fitted surface potentials based on the force measurements. This work provides useful information regarding the interaction mechanism of Se0 and surfaces of varying hydrophobicity in aqueous solutions.

Numerical simulations of sonochemical production and oriented aggregation of BaTiO3 nanocrystals

Numerical simulations of sonochemical production and oriented attachment of BaTiO3 nanocrystals are performed in aqueous solution with pH 14. It is suggested that most significant effect of ultrasound is the dissolution of Ti-based gel in aqueous solution. It results in the dissolution-precipitation mechanism in the production of BaTiO3 nanoparticles, while with mechanical stirring without ultrasound it is the in situ mechanism that BaTiO3 is gradually formed on Ti-based gel. The oriented attachment of spherical BaTiO3 nanocrystals occurs by van der Waals torque (Casimir torque). Large aggregates of nanocrystals do not attach with each other as the repulsive double layer interaction is stronger for larger aggregates. For smaller spherical nanocrystals, the alignment of the crystal axes is less accurate due to more significant rotational Brownian motion of the nanocrystals.

DLVO Approximation Methods for Predicting the Attachment of Silver Nanoparticles to Ceramic Membranes.

This article examines the influence of three common stabilizing agents (citrate, poly(vinylpyrrolidone) (PVP), and branched poly(ethylenimine) (BPEI)) on the attachment affinity of silver nanoparticles to ceramic water filters. Citrate-stabilized silver nanoparticles were found to have the highest attachment affinity (under conditions in which the surface potential was of opposite sign to the filter). This work demonstrates that the interaction between the electrical double layers plays a critical role in the attachment of nanoparticles to flat surfaces and, in particular, that predictions of double-layer interactions are sensitive to boundary condition assumptions (constant charge vs constant potential). The experimental deposition results can be explained when using different boundary condition assumptions for different stabilizing molecules but not when the same assumption was assumed for all three types of particles. The integration of steric interactions can also explain the experimental deposition results. Particle size was demonstrated to have an effect on the predicted deposition for BPEI-stabilized particles but not for PVP.

Effects of van der Waals forces and salt ions on the growth of water films on ice and the detachment of CO2 bubbles

We study the effect of salts on the thickness of wetting films on melting ice and interactions acting on CO2 bubble near ice-water and vapor-water interfaces. Governing mechanisms are the Lifshitz and the double-layer interactions in the respective three-layer geometries. We demonstrate that the latter depend on the Casimir-Polder interaction of the salt ions dissolved in water with the respective ice, vapor and CO2 interfaces, as calculated using different models for their effective polarizability in water. Significant variation in the predicted thickness of the equilibrium water film is observed for different salt ions and when using different models for the ions' polarizabilities. We find that CO2 bubbles are attracted towards the ice-water interface and repelled from the vapor-water interface.

Evaporation, viscous flow, and electrostatic interaction of charged interfaces in the apparent contact line region

We consider evaporation of an aqueous solution near an apparent contact line separating a macroscopically dry area of a heated solid substrate and a constant-curvature meniscus far away from the substrate. Viscous flow, described by a lubrication-type model, is coupled to the interaction of electrical double layers formed near the solid-liquid and liquid-vapor interfaces. The electrostatic interaction is described using the nonlinear Poisson-Boltzmann equation and is shown to affect both normal and shear stress balances at the deformable interface. For steady configurations, we find that the apparent contact line region becomes wider and the total evaporation rate there increases as the substrate potential is increased. Motion of the apparent contact line in response to changes in the substrate temperature is also investigated. The contact line speed is found to increase when the electrostatic effects are incorporated into the model.

Electric Double-Layer Interaction between Dissimilar Charge-Conserved Conducting Plates.

Small metallic particles used in forming nanostructured to impart novel optical, catalytic, or tribo-rheological can be modeled as conducting particles with equipotential surfaces that carry a net surface charge. The value of the surface potential will vary with the separation between interacting particles, and in the absence of charge-transfer or electrochemical reactions across the particle surface, the total charge of each particle must also remain constant. These two physical conditions require the electrostatic boundary condition for metallic nanoparticles to satisfy an equipotential whole-of-particle charge conservation constraint that has not been studied previously. This constraint gives rise to a global charge conserved constant potential boundary condition that results in multibody effects in the electric double-layer interaction that are either absent or are very small in the familiar constant potential or constant charge or surface electrochemical equilibrium condition.

Hydrophobic nano-asperities in control of energy barrier during particle–surface interactions

To explain differences in colloidal interactions for spherical hydrophobic particles, a theoretical analysis of the interaction potential was carried out for a model rough particle interacting with a smooth and flat surface in an electrolyte solution. The attractive hydrophobic interaction potential was added to repulsive retarded van der Waals and repulsive electrical double layer interaction potentials. The rough microscopic particles were modeled as spheres decorated with nano-sized hemispherical asperities. Parameters that reflect common flotation separation systems were selected for testing this theoretical model and computation of the energy barrier applicable to particle–surface interactions. It was found that hydrophobic asperities with the radius of only a few nanometers reduced the energy required for particle attachment to a hydrophobic surface by several times. The value of this energy barrier was reduced by as much as two orders of magnitude when the radius of nano-sized asperities increased to a few tens of nanometers. Theoretical analysis also revealed that surface coverage of microscopic particles by nano-sized asperities was not as important as the size of the asperities.

Particle Deposition and Removal of Relevance to Wet Processing in Semiconductor Manufacturing

Removal of particulate contaminants from surfaces is a critical area in the processing of wafers to build integrated circuits and is typically done using wet chemical formulations. Strategies for particle removal require an understanding of particle deposition mechanisms. In the first part of this review paper, colloid chemical principles underlying particle deposition on surfaces is discussed. Specifically, the importance of van der Waals and electrical double layer interaction energy on particle–surface interaction is reviewed. This is followed by a description of commonly used particle removal methods in wafer processing, viz., megasonic cleaning, brush cleaning, and nanospray cleaning. The importance of particle deposition conditions used in research on particle removal efficiency is highlighted through a study on the effect of aging.

Heterocoagulation in Bidisperse Magnetorheological Fluids Containing Like-Charged Nanosized and Micron Particles Without a Magnetic Field

Based on extended Derjaguin–Landau–Verwey–Overbeek theory, a heterocoagulation model is proposed for magnetorheological (MR) fluids containing like-charged nanosized and micron particles without a magnetic field. This model considers three major interactions, namely van der Waals attraction, electrical double layer (EDL) interaction, and steric repulsion. The EDL interaction has been identified as the most important factor. The surface potential ratio β (ψ2/ψ1) between two dissimilar particles with like charge plays an important role in controlling the change of EDL interaction. At higher β ratios, the EDL interaction becomes attractive when the surface separation falls within a certain range. Two groups of MR fluid samples have been used in experimental studies based on electroacoustic measurements. In the first group, the ratio and the sum of the zeta potentials between carbonyl iron particles and ceria were 4 and −734.57 mV, respectively. In the second group, these parameters were 1.38 and −108.17 mV, respectively. The experimental results suggested that the second group did not undergo heterocoagulation, whereas the first group showed extensive heterocoagulation. The difference in surface potentials between particles of two different phases has been found to be critical for determining the state of dispersion or heterocoagulation in concentrated MR fluid systems.

Streaming potential method for characterizing the overlapping of diffuse layers of the electrical double layers between oppositely charged particles

Interaction of the electrical double layers (EDLs) between negatively charged quartz grains and positively charged iron (Fe)/aluminum (Al) oxide colloids was investigated in this work by comparing the difference in zeta potentials between the single quartz in electrolyte and quartz with Fe/Al oxide suspensions. The Fe/Al oxides used were α-Fe2O3, amorphous Fe hydroxide, gibbsite and amorphous Al hydroxide. The zeta potential of quartz was measured using a self-made streaming potential apparatus. Our results indicated that the overlapping degree of diffuse layers of the EDLs between quartz and Fe/Al oxides increased with increased concentration of Fe/Al oxides and decreased with the decrease in negative surface charge on quartz due to ferric coating. The overlapping degree of diffuse layers of the EDLs between quartz and Fe/Al oxides decreased with increased ionic strength due to the decreased thickness of the diffuse layers. The results should provide a useful reference for using the streaming potential method to investigate the effect of the colloidal transport process on the properties of bulk soil in situ.

Ray-theory approach to electrical-double-layer interactions.

A novel approach is presented for analyzing the double-layer interaction force between charged particles in electrolyte solution, in the limit where the Debye length is small compared with both interparticle separation and particle size. The method, developed here for two planar convex particles of otherwise arbitrary geometry, yields a simple asymptotic approximation limited to neither small zeta potentials nor the "close-proximity" assumption underlying Derjaguin's approximation. Starting from the nonlinear Poisson-Boltzmann formulation, boundary-layer solutions describing the thin diffuse-charge layers are asymptotically matched to a WKBJ expansion valid in the bulk, where the potential is exponentially small. The latter expansion describes the bulk potential as superposed contributions conveyed by "rays" emanating normally from the boundary layers. On a special curve generated by the centers of all circles maximally inscribed between the two particles, the bulk stress-associated with the ray contributions interacting nonlinearly-decays exponentially with distance from the center of the smallest of these circles. The force is then obtained by integrating the traction along this curve using Laplace's method. We illustrate the usefulness of our theory by comparing it, alongside Derjaguin's approximation, with numerical simulations in the case of two parallel cylinders at low potentials. By combining our result and Derjaguin's approximation, the interaction force is provided at arbitrary interparticle separations. Our theory can be generalized to arbitrary three-dimensional geometries, nonideal electrolyte models, and other physical scenarios where exponentially decaying fields give rise to forces.

Effect of Rough Nanoparticle Orientation on DLVO Energy Interaction

This study investigated the effect of the orientation of rough nanoparticles on Derjaguin and Landau, Verwey and Overbeek (DLVO) energy interaction. Rippled sphere model was used to survey van der Waals attraction energy and repulsive double-layer interaction energy between nanoparticles. The effect of particle size, asperity size, number of asperities, and concentration was studied for different orientations. Spherical coordinates were used to evaluate the effect of changes in orientation under controlled conditions. Surface element integral method was used to calculate DLVO energy interactions between rough particles at specific orientations. The DLVO energy results show that a change in orientation significantly affected the stability of the nanoparticles. The stability of dispersion varied as the contact surface between nanoparticles changed.

Consequences of shifted ion adsorption equilibria due to nonelectrostatic interaction potentials in electrical double layers

Abstract Consistent incorporation of nonelectrostatic interactions in the chemical potential for electrical double layers at interfaces interacting across electrolytes under the constant potential or charge regulation boundary conditions has recently been presented for the case of ionic dispersion potentials. This gives rise to shifted adsorption equilibria, and thereby a shift in the predicted surface electrostatic potential. It also results in an additional component previously unaccounted for in the total double layer interaction force. The new force component due to ionic dispersion can be repulsive or attractive and can in some cases exceed entropic repulsion in magnitude. The altered force leads to the need to recalibrate electrostatic surface potentials and equilibrium constants when fitting to experimental force data. We explore the implications and consequences for model systems of mica surfaces, to illustrate the effect of salt concentration, and cellulose surfaces to illustrate the effect of pH. The final example is the more complex, asymmetric system of crude oil and glass interacting across salt solutions of varying concentration and pH. The DLVO theory augmented by ionic dispersion potentials is used to fit measured data for ζ-potentials of oil and glass, from which the calculated disjoining pressure isotherms are compared to measured macroscopic oil–glass adhesion data.

Lateral capillary interactions between colloids beneath an oil-water interface that are driven by out-of-plane electrostatic double-layer interactions.

We study the lateral capillary interactions between colloids beneath an oil-water interface that lead to closely packed two-dimensional self-assembled colloidal crystals. These capillary forces are caused by the overlap of deformed interfaces above colloids on a solid substrate. The interface deformation is due to the electrostatic disjoining pressure between the charged particles and the charged oil-water interface. It is notable that the short-range (i.e., on the nanometer scale) and out-of-plane electrostatic double-layer interactions, which occur through an aqueous phase, can generate the long-range lateral capillary attraction (i.e., on the micrometer scale).

Temperature dependence of aging kinetics of hectorite clay suspensions

The aging of salt-free hectorite suspensions with different concentrations (cL=2.9, 3.2 and 3.5wt%) stored for 2days or 4days was studied by rheology at different temperatures. The evolution of storage and loss moduli G′ and G″ during aging followed aging time–temperature superposition. The temperature dependence of the shift factor aT, which reflected the aging kinetics, was interpreted by the reaction-limited colloidal aggregation (RLCA) mechanism with counterion condensation in calculating the double-layer interaction of the charged clay particles. Temperature dependence of the plateau modulus and yield stress of the suspension aged for 800s was modeled with the soft glassy rheology (SGR) theory. The estimated noise temperature x indicated that the sample aged at higher temperature corresponded to a deeper quench in the nonergodic state. Under larger amplitude of oscillatory shear, the suspension exhibited a strain rate-frequency superposition (SRFS). The shearing eliminated the effects of aging and heating.