A theoretical approach for estimation of ultimate size of bimetallic nanocomposites synthesized in microemulsion systems

In this research a new idea for prediction of ultimate sizes of bimetallic nanocomposites synthesized in water-in-oil microemulsion system is proposed. In this method, by modifying Tabor Winterton approximation equation, an effective Hamaker constant was introduced. This effective Hamaker constant was applied in the van der Waals attractive interaction energy. The obtained effective van der Waals interaction energy was used as attractive contribution in the total interaction energy. The modified interaction energy was applied successfully to predict some bimetallic nanoparticles, at different mass fraction, synthesized in microemulsion system of dioctyl sodium sulfosuccinate (AOT)/isooctane.     

Estimation of the Hamaker constants by sedimentation field-flow fractionation

van der Waals forces are one of several forces that control the adhesion between two materials. These forces are important to quantify in adhesion studies because they are always present and are always attractive. The major problem in calculating the van der Waals interaction between colloidal particles is that of evaluating the Hamaker constant. Hence, an accurately determined Hamaker constant for a given material is needed when interfacial phenomena such as adhesion are discussed in terms of the total potential energy between a particle and a substrate. In this paper, a new simple and accurate methodology for the estimation of the Hamaker constant is introduced. The results are in good agreement with those values found in literature.     

van der Waals interaction between internal aqueous droplets and the external aqueous phase in double emulsions

A mathematical model for analyzing the van der Waals interaction between the internal aqueous droplets (W(1)) and the external aqueous phase (W(2)) of double emulsions has been established. The effects of Hamaker constants of the materials forming the system, especially those of the two different adsorbed surfactant layers with uniform density (A(1) and A(2)), on the van der Waals interaction were investigated. The overall van der Waals interaction across the oil film is a combined result of four individual parts, that is, W(1)-W(2), A(1)-A(2), W(1)-A(1), and A(2)-W(2) van der Waals interaction, and it may be either attractive or repulsive depending on many factors. It was found that the overall van der Waals interaction is dominated by the W(1)-W(2) interaction at large separation distances between the W(1)/O and O/W(2) interfaces, while it is mostly determined by the A(1)-A(2) interaction when the two interfaces are extremely close. Specifically, in the cases when the value of the Hamaker constant of the oil phase is intermediate between those of W(1) and W(2) and there is a thick oil film separating the two interfaces, a weak repulsive overall van der Waals interaction will prevail. If the Hamaker constant of the oil phase is intermediate between those of A(1) and A(2) and the two interfaces are very close, the overall van der Waals interaction will be dominated by the strong repulsive A(1)-A(2) interaction. The repulsive van der Waals interaction at such cases helps stabilize the double emulsions.     

On possible microscopic origins of the swelling of neutral lipid bilayers induced by simple salts

It was recently suggested that the swelling of neutral multilipid bilayers upon addition of a salt can be simply explained only by the electrolyte screening of the van der Waals attractions, while assuming that the hydration force and the repulsion due to thermal undulations of membranes are unaffected by the salt. While we agree that the screening of the van der Waals interactions plays a role, we suggest that the increase in the hydration force upon addition of a salt has also to be taken into account. In a statistical model, which accounts for the membrane undulations, parameters could be found to explain the multibilayer swelling even when the van der Waals attraction is considered unaffected by the electrolyte screening. These results point out that the decrease by a factor of three of the Hamaker constant upon addition of a salt, suggested recently to be responsible for the swelling of neutral multilipid bilayers, is perhaps too large, and a smaller decrease in Hamaker constant, coupled with the above mentioned effects might explain the swelling.     

Microflotation Suppression and Enhancement Caused by Particle/Bubble Electrostatic Interaction

The processes of attachment and detachment of small or medium-sized particles to relatively large bubbles during microflotation are considered in terms of the heterocoagulation theory. Calculations are made for the conditions that the surface potentials are of similar sign and constant, that one of the surface potentials is small, that hydrophobic attraction is absent, and that there are no surface deformations. Under these conditions bubble-particle aggregates may form as a result of an electrostatic attraction which exceeds the repulsive van der Waals force at intermediate distances. Next to electrostatic and van der Waals forces, hydrodynamic and gravitational forces are considered. These forces may overcome the electrostatic repulsion at large distances and promote particle bubble attachment. Strong electrostatic attraction at small distances, arising at a large difference of the surface potentials of the bubble and the particle and of low electrolyte concentrations, can prevent subsequent detachment by hydrodynamic and gravitational forces. With increasing electrolyte concentration the electrostatic barrier increases and the attractive electrostatic force diminishes. As a result, a critical electrolyte concentration for microflotation exists. Above this concentration attachment may still occur but it is followed by detachment. At lower electrolyte concentrations the electrostatic attractive force prevents the detachment. The dependence of the critical electrolyte concentration on the values of the bubble and particle potentials and the Hamaker constant is calculated. The critical concentration does not depend on particle or bubble size if the absolute values of the total detachment force and the total pressing force coincide, which is the case for Stokes and potential flow. For every electrolyte concentration lower than the critical value there are two critical particle sizes that limit the flotation possibility. For small particle sizes attachment is impossible because the pressing force is smaller than the electrostatic barrier. For large particle sizes detachment cannot be prevented because the detachment force exceeds the maximum electrostatic attraction. A microflotation domain of intermediate particle sizes exists in which irreversible heterocoagulation occurs. Copyright 2001 Academic Press.     

Effective van der Waals surface energy of self-assembled monolayer films having systematically varying degrees of molecular fluorination

The systematic variation of the van der Waals surface energy with fluorination for a series of self-assembled monolayers (SAMs) generated by the adsorption of partially fluorinated alkanethiols onto the surface of gold is examined experimentally and theoretically. The surface energy is elucidated on the basis of an effective Hamaker constant, which is obtained as a combination of the respective Hamaker constants of fluorocarbons and hydrocarbons; the fraction depends on the degree of fluorination. The good agreement between experiment and theory is discussed. In addition, the Hamaker constants of various liquids contacted on the well-defined hydrophobic surfaces are interpreted using modified Lifshitz theory.     

Stable van der Waals-induced deformations of the air-water interface. Theoretical predictions and a suggestion for an experiment

This article concerns the stability of the air-water interface subjected to a 2D attractive van der Waals stress. The physical problem models the setup of a Wilhelmy plate experiment prior to three-phase contact line formation. We present and employ an unambiguous condition to quantify the stability limit in terms of the distance of closest approach of a solid cylindrical plate of parabolic cross section to the fluid surface as a function of the strength of the van der Waals surface force and plate geometry. A numerical study spanning 4 orders of magnitude of the Hamaker constant and nearly 6 orders of magnitude of solid geometry characterizes the dependence of the stability limit on these physical parameters. Comparisons are also made with a previously published analytical condition guaranteeing a stable deformation of the fluid interface. A possible experiment for testing the theory is also described. Used together with the theory, the technique could be used as an independent means of determining system properties such as the surface tension or Hamaker constant.     

Deflection and pull-in instability of nanoscale beams in liquid electrolytes

An elastic beam suspended horizontally over a substrate in liquid electrolyte was subjected to electric, osmotic, and van der Waals forces. The problem, which is governed by four non-dimensional parameters, was solved using the finite element method. The sum of the electric and osmotic forces, the electrochemical force, is usually attractive. However, the electrochemical force can be repulsive for a narrow range of the ion concentration, the initial separation and surface potentials. Furthermore, the beam deflection is not a monotonic function of the applied surface potentials, the bulk ion concentration, or the initial separation between the beam and the substrate. As these parameters are increased monotonically, the beam bends up and then down. The pull-in voltage increases as the bulk ion concentration increases. The pull-in voltage of a double-wall carbon nanotube suspended over a graphite substrate in liquid can be less than or greater than the pull-in voltage in air, depending on the bulk ion concentration. The critical separation between the DWCNT and the substrate increases with the bulk ion concentration. However, for a given bulk ion concentration, the critical separation is independent of the electric potentials. Furthermore, the critical separation is approximately equal in liquid and air.     

Superlubricity using repulsive van der Waals forces

Using colloid probe atomic force microscopy, we show that if repulsive van der Waals forces exist between two surfaces prior to their contact then friction is essentially precluded and supersliding is achieved. The friction measurements presented here are of the same order as the lowest ever recorded friction coefficients in liquid, though they are achieved by a completely different approach. A gold sphere attached to an AFM cantilever is forced to interact with a smooth Teflon surface (templated on mica). In cyclohexane, a repulsive van der Waals force is observed that diverges at short separations. The friction coefficient associated with this system is on the order of 0.0003. When the refractive index of the liquid is changed, the force can be tuned from repulsive to attractive and adhesive. The friction coefficient increases as the Hamaker constant becomes more positive and the divergent repulsive force, which prevents solid-solid contact, gets switched off.     

Influence of the subsurface composition of a material on the adhesion of staphylococci

Controlling the interface between bacteria and solid materials has become an important task in biomedical science. For a fundamental and comprehensive understanding of adhesion it is necessary to seek quantitative information about the involved interactions. Most studies concentrate on the modification of the surface (chemical composition, hydrophobicity, or topography) neglecting, however, the influence of the bulk material, which always contributes to the overall interaction via van der Waals forces. In this study, we applied AFM force spectroscopy and flow chamber experiments to probe the adhesion of Staphylococcus carnosus to a set of tailored Si wafers, allowing for a separation of short- and long-range forces. We provide experimental evidence that the subsurface composition of a substrate influences bacterial adhesion. A coarse estimation of the strength of the van der Waals forces via the involved Hamaker constants substantiates the experimental results. The results demonstrate that the uppermost layer is not solely responsible for the strength of adhesion. Rather, for all kinds of adhesion studies, it is equally important to consider the contribution of the subsurface.     

Experimental determination of energy barrier to particle detachment

The estimation of energy barrier to detachment of particles from a substrate was carried out. Detachment processes of 4 m polyethylene particles from a quartz wall under the gravitational force in aqueous solutions were investigated by a direct observation technique. The magnitude of energy barriers was experimentally determined by the temperature dependence of the rate constant of detachment and was compared with that estimated theoretically from the superposition of electrostatic and London—van der Waals energies calculated using the experimental electrokinetic potentials and Hamaker constants, respectivley. Both were in fairly good agreement.     

Nonadditivity in van der Waals interactions within multilayers

Working at the macroscopic continuum level, we investigate effective van der Waals interactions between two layers within a multilayer assembly. By comparing the pair interactions between two layers with effective pair interactions within an assembly we assess the significant consequences of nonadditivity of van der Waals interactions. This allows us to evaluate the best numerical estimate to date for the Hamaker coefficient of van der Waals interactions in lipid-water multilamellar systems.     

Effect of surface treatment on the Hamaker constant of intermediate modulus carbon fibers

The Hamaker constant of unsized intermediate modulus carbon fibers was evaluated by contact angle measurement following the Fowkes theory of interfacial energetics. The effects of a surface treatment (performed by the manufacturer) and an oxygen plasma treatment (performed by us), both of oxidizing nature, proved to slightly increase the value of the Hamaker constant to a level that enhanced by about 9% the Lifshitz-van der Waals contribution to the theoretical adhesion force between the fiber and an epoxy matrix. A possible explanation of the observed increase of the Hamaker constant is the higher contribution to the overall Lifshitz-van der Waals interaction of Keesom (orientation) and Debye (induction) forces.     

Wetting: Inverse Dynamic Problem and Equations for Microscopic Parameters

Movement of a liquid meniscus in a low-diameter capillary while it is being filled or emptied is considered. The liquid is nonvolatile. Assuming low Reynolds number and low capillary number, the liquid-gas interface shape is studied. Angles of inclination of this boundary to the solid near the contact line are small. Consideration is given to the inverse problem in wetting dynamics: to establish an analytic expression for the universal constant that influences the dynamics of a three-phase contact line. Inverse relations for microscopic parameters in terms of macroscopic measured values obtained in experiments with a meniscus moving through a capillary are derived. The inverse relations are substantiated independently. To do so, numerical experiments for a van der Waals liquid have been carried out, using the de Gennes model of partial wetting. General formulas for microparameters agree well with numerical experiments. The article provides the similarity criterion which influences the wetting in the case of a van der Waals liquid meniscus. The inverse dynamic problem for both an advancing and a receding meniscus is solved. A relation for the critical speed of meniscus recession is proposed. Two contact angles for a meniscus are discussed. Behavior of dynamic contact angles in the vicinity of the critical speed is studied. One of the angles is shown to vanish at less than the critical speed, and the other one, exactly at the critical speed. In the case of an advancing meniscus the equations for microparameters are valid for both partial and complete wetting. The proposed inverse expression for complete wetting allows determination of the maximum precursor film thickness and its dependence on the motion speed (also determination of the Hamaker constant in the case of a van der Waals liquid). Copyright 2000 Academic Press.     

Influence of surface properties of particles on their adhesion and removal

The effect of surface properties of particles on their adhesion and removal was investigated using an immersed system consisting of nylon particles and a quartz plate. The nylon particles were dyed with a reactive dye in order to change their properties and were used for the adhesion and removal experiments in comparison with undyed particles. The electrokinetic potentials of the particles were measured by micro-electrophoresis and the Hamaker constants were independently evaluated using experimental values of dispersive component of surface free energy determined by the Wilhelmy technique. The experimental results were used for the discussion of particle adhesion and removal on the basis of the heterocoagulation theory. The differences in adhesion and removal efficiencies between dyed and undyed particles were explained in terms of the electrostatic and dispersive van der Waals interaction by considering the differences in thier properties, the electrokinetic potential and the Hamaker constant, due to dyeing.     

Yield stress and zeta potential of nanoparticulate silica dispersions under the influence of adsorbed hydrolysis products of metal ions--Cu(II), Al(III) and Th(IV)

The effects of hydrolysable Cu2+, Al3+ and Th4+ ions on the zeta potential and yield stress behaviour of silica dispersions were evaluated as a function of pH and metal ions concentration. Silica dispersion remained dispersed at its point of zero charge (pzc) of pH approximately 2.0 (CR1). Adsorbed hydrolysis products of Cu2+ and Al3+ caused the dispersion to display two further points of charge reversal (CR2 and CR3) at moderate ions concentration. CR2 occurred near the pH for the formation of the first hydrolysis product. This pH is about 2.8 for Al3+ and 5.0 for Cu2+. For all three metal ions, CR3 approached the pzc of the metal hydroxides at complete surface coverage. At CR3, the dispersions displayed a maximum yield stress. As many as three type of attractive forces; bridging, charged patch and van der Waals, may account for the maximum yield stress at low surface coverage. At complete coverage, only the van der Waals force is in play--the adsorbed hydrolysis products must have increased significantly the effective Hamaker constant of silica. With Al3+ the yield stress was absent at CR2 because particle bridging and charged patch attraction are unimportant as the silica surface charge is near zero. Adsorption of strongly hydrolysed Th4+ ions at pH<2.0 caused the dispersion to display only one pzc (CR3).     

Direct numerical simulation of aerosol coagulation with van der Waals forces

The van der Waals interaction energy has been computed for a large number of silver and water particle pairs in the range of 1 to 15 nm radius by first calculating the exact, retarded Hamaker factor for semi-infinite bodies and then applying a geometric correction for sphericity. The enhancement of particle collision rates has been deduced from these calculations. These values for the collisional enhancement were used in a direct numerical simulation of the coagulation of silver and water aerosols. Despite the size dependence of the van der Waals enhancement factors, the aerosol size distributions quickly attained nearly self-preserving forms.     

The bridging force between two plates by polyelectrolyte chains

The interaction between particles in a colloidal system can be significantly affected by their bridging by polyelectrolyte chains. In this paper, the bridging is investigated by using a self-consistent field approach which takes into account the van der Waals interactions between the segments of the polyelectrolyte molecules and the plates, as well as the electrostatic and volume exclusion interactions. A positive contribution to the force between two plates is generated by the van der Waals interactions between the segments and the plates. This positive (repulsive) contribution plays an important role in the force when the distances between the plates are small. With increasing van der Waals interaction strength between segments and plates, the force between the plates becomes more repulsive at small distances and more attractive at large distances. When the surfaces of the plates have a constant surface electrical potential and a charge sign opposite to that of the polyelectrolyte chains, the force between the two plates becomes less attractive as the bulk polyelectrolyte concentration increases. This behavior is due to a higher bulk counterion concentration dissociated from the polyelectrolyte molecules. At short distances, the force between plates is more repulsive for stiffer chains. A comparison between theoretical and experimental results regarding the contraction of the interlayer separation between the platelets of vermiculite clays against the concentration of poly(vinyl methyl ether) was made.     

The effect of surface modification on the stability characteristics of poly(N-isopropylacrylamide) latices under Brownian and flow conditions

The stability of thermoreversible microgel particles of poly(N-isopropylacrylamide) having carboxylate surface charge groups has been studied in the presence of electrolyte and non-adsorbing polymer. Methylation of the surface charge groups leads to a decrease in the electrophoretic mobility of the particles and also the interparticle electrostatic repulsive potential, resulting in the material becoming more susceptible to flocculation. The Hamaker constant of the microgel particles increases with the decrease in the hydrodynamic size of the particles following heating. This brings about an increase in the van der Waals attractive energy which results in the particles aggregating in the presence of sufficient electrolyte. Under conditions of flow through membranes, where shearing forces are operative, the flocculation observed following the heating of the dispersions results in the blockage of pores.