The Effect of van der Waals Forces on the Deposition of Highly Dispersed Aerosol Particles on Ultrafine Fibers

The effect of van der Waals forces on the collection of highly dispersed aerosol particles with ultrafine fiber filters was studied theoretically. The capture coefficient was found from the numerical solution of the equation of convective diffusion with the account of the particle size, the effect of van der Waals forces acting between a particle and a fiber, and the gas slip effect at the surface of ultrafine fibers. It was shown that allowance being made for van der Waals forces markedly affects the capture coefficient within the maximal particle penetration range and that the radius of the most penetrating particles decreases with the rising effect of these forces.     

Diffusional Deposition of Heavy Submicron Aerosol Particles on Fibrous Filters

The deposition of Brownian submicron aerosol particles of high density in fibrous filters with allowance for interception effect, influence of gravitational, van der Waals forces, and the gas slip on the surface of ultrafine fibers was considered. Based on the numerical solution of the equation of convective diffusion in the field of external forces, the capture coefficient was calculated as a function of particle size and density, the angle between the vectors of gravity force, and the face flow velocity. It was shown that, for descending flow, the radius of most penetrating dense particles appeared to be noticeably smaller than for the ascending flow.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 352–356.Original Russian Text Copyright © 2005 by Kirsh.     

Anisotropy shift and Raman bandwidth studies in carbonyl containing molecule o-chlorobenzaldehyde: role of repulsive forces

The analysis of Raman anisotropy shift as a function of solvent concentration shows the weakening of pair interaction of the molecules due to the influence of solvent-induced perturbations. The present study deals with the effect of dielectric constant of the medium on the non-coincidence effect (anisotropy shift) and the role of van der Waals' volume on the anisotropic Raman bandwidth. The CO stretching vibration of o-chlorobenzaldehyde (OCBD) molecule was studied in various polar and non-polar solvents namely CCl4, CH3CN, C6H5Cl and CH3C6H5. The data on anisotropic bandwidth are interpreted using the van der Waals' volume within the framework of lineshape theory of Bratos and Tarjus, while the Onsager-Fr?hlich model on non-coincidence effect has been tested. Our study shows that the repulsive potential of the type e-alphaR is playing an important role in the OCBD-solvent interactions. The vanishing of anisotropy shift (non-coincidence effect) on dilution may be explained on the basis of repulsive forces playing a significant role in solute-solvent interactions.     

长程范德华力导向作用下胶体凝聚的计算机模拟

采用计算机模拟方法研究了长程范德华力在胶体凝聚过程中的作用, 发现由于胶粒间的范德华力是长程力, 它对胶粒或团簇运动将产生导向作用. 与不考虑导向作用的扩散控制团簇凝聚(DLCA)模型比较, 这种导向作用不仅加速了胶体的凝聚过程, 而且形成了更致密、分形维数更大的结构体. 研究还发现, 长程范德华力导向作用对胶粒的初始浓度非常敏感, 不论是在凝聚物的结构还是凝聚速率方面, 只有在胶粒初始浓度较低时, 该导向作用效应才明显. 其可能的原因是,在胶粒初始浓度较高时, 由于胶粒布朗运动的平均自由程很短而且位阻效应大, 从而使导向作用效应未能反映出来.     

On the nature of bonds between carbon atoms

The combined effect of conjugation and van der Waals' interaction has been calculated for carbon sp²-sp² single bonds of different lengths and for different molecular conformations. The bond shortening effect of conjugation is found to be comparable to that of hybridization. The attractive van der Waals' interaction, on the other hand, is always found to be small. It seems thus most improbable that this interaction should be the cause of the planarity of butadiene.     

A modeling approach to describe the adhesion of rough, asymmetric particles to surfaces

A combined theoretical and experimental study of the adhesion of alumina particles and polystyrene latex spheres to silicon dioxide surfaces was performed. A boundary element technique was used to model electrostatic interactions between micron-scale particles and planar surfaces when the particles and surfaces were in contact. This method allows quantitative evaluation of the effects of particle geometry and surface roughness on the electrostatic interaction. The electrostatic interactions are combined with a previously developed model for van der Waals forces in particle adhesion. The combined model accounts for the effects of particle and substrate geometry, surface roughness and asperity deformation on the adhesion force. Predictions from the combined model are compared with experimental measurements made with an atomic force microscope. Measurements are made in aqueous solutions of varying ionic strength and solution pH. While van der Waals forces are generally dominant when particles are in contact with surfaces, results obtained here indicate that electrostatic interactions contribute to the overall adhesion force in certain cases. Specifically, alumina particles with complex geometries were found to adhere to surfaces due to both electrostatic and van der Waals interactions, while polystyrene latex spheres were not affected by electrostatic forces when in contact with various surfaces.     

Mechanism of hydrodynamic separation of biological objects in microchannel devices

In this study, the separation mechanism employed in hydrodynamic chromatography in microchannel devices is analyzed. The main purpose of this work is to provide a methodology to develop a predictive model for hydrodynamic chromatography for biological macromolecules in microchannels and to assess the importance of various phenomenological coefficients. A theoretical model for the hydrodynamic chromatography of particles in a microchannel is investigated herein. A fully developed concentration profile for non-reactive particles in a microchannel was obtained to elucidate the hydrodynamic chromatography of these particles. The external forces acting on the particles considered in this model include the van der Waals attractive force, double-layer force as well as the gravitational force. The surface forces, such as van der Waals attractive force as well as the double-layer repulsive force, can either enhance or hinder the average velocity of the macromolecular particles. The average velocity of the particles decreases with the molecular radius because the van der Waals attractive force increases the concentration of the particles near the channel surface, which is the low-velocity region. The transport velocity of the particles is dominated by the gravity and the higher density enlarges the effect caused by gravity.     

Quantitative study of interactions between oxygen lone pair and aromatic rings: substituent effect and the importance of closeness of contact

Current models describe aromatic rings as polar groups based on the fact that benzene and hexafluorobenzene are known to have large and permanent quadrupole moments. This report describes a quantitative study of the interactions between oxygen lone pair and aromatic rings. We found that even electron-rich aromatic rings and oxygen lone pairs exhibit attractive interactions. Free energies of interactions are determined using the triptycene scaffold and the equilibrium constants were determined by low-temperature 1H NMR spectroscopy. An X-ray structure analysis for one of the model compounds confirms the close proximity between the oxygen and the center of the aromatic ring. Theoretical calculations at the MP2/aug-cc-pVTZ level corroborate the experimental results. The origin of attractive interactions was explored by using aromatic rings with a wide range of substituents. The interactions between an oxygen lone pair and an aromatic ring are attractive at van der Waals' distance even with electron-donating substituents. Electron-withdrawing groups increase the strength of the attractive interactions. The results from this study can be only partly rationalized by using the current models of aromatic system. Electrostatic-based models are consistent with the fact that stronger electron-withdrawing groups lead to stronger attractions, but fail to predict or rationalize the fact that weak attractions even exist between electron-rich arenes and oxygen lone pairs. The conclusion from this study is that aromatic rings cannot be treated as a simple quadrupolar functional group at van der Waals' distance. Dispersion forces and local dipole should also be considered.     

Retention index,connectivity index and Van der Waals' volume of alkanes (GLC)

Summary The relationships between retention index and Van der Waals' volume and between retention index and connectivity index have been studied for 58 different alkanes (C₁–C₉) on squalane. The correlation coefficient for the former is higher than for the latter. From these equations a linear relationship between Van der Waals' volume and connectivity index is obtained which indicates that the two parameters are equivalent. A simple method for calculating the Van der Waals' volume of alkanes is proposed.     

Van der Waals Emulsions: Emulsions Stabilized by Surface‐Inactive,Hydrophilic Particles via van der Waals Attraction

Surface‐inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil‐in‐water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil–water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion‐based technologies in practice.     

Effect of contact deformations on the adhesion of particles

A strict theory of reciprocal influence of the contact deformation and molecular attraction of a ball and a plane has been developed. It has been shown that despite the van der Waals' forces being capable of increasing the elastic contact area between the ball and the plane, the force that is required to overcome the molecular forces arising when the contact is broken does not increase thereby. In fact, it remains equal to the attraction force value that is determined when considering the point contact of a nondeformed ball with a plane.

In the absence of the electrostatic component, the adhesion force is equivalent to the first power of the ball radius and to the amount of work per unit area as required for affecting the equilibrium tearing-off of a flat surface of the same nature.     

Van der Waals Emulsions: Emulsions Stabilized by Surface‐Inactive,Hydrophilic Particles via van der Waals Attraction

Surface‐inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil‐in‐water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil–water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion‐based technologies in practice.     

聚合物的热压力系数及内压

本文将我们在前文中提出的修正van der Waals模型, 推广到了液态聚合物中, 从而建立了一个能在宽阔温度范围内准确计算聚合物热压力系数的关系式。式中ν和M分别为聚合物的比体积和链节的摩尔质量, A为聚合物的特性常数。对于本文考察的五种聚合物, 发现它们的链节大小均为聚合物的三个结构单元。     

Direct measurement of the binding force between microfabricated particles and a planar surface in aqueous solution by force-sensing piezoresistive cantilevers

We propose a force measurement method for evaluating the binding force between microscale flat surfaces in an aqueous solution. Using force-sensing piezoresistive cantilevers with sub-nanonewton force resolution, we have directly measured binding forces between SiO2-SiO2 microcontacts, which were created by gravity-driven random collision between microfabricated SiO2 cylindrical particles and a planar SiO2 substrate in a HCl solution. First, to examine our method we measured the pH dependence of the binding force. The binding forces were 12 and 5.8 nN at pH 1.0 and 2.0, respectively. As the pH increased, the binding force decreased and became zero at pH greater than 3.0. We confirmed that the bindings were based on the van der Waals' (VDW) force at pH 2.0 or less whereas a repulsive double-layer force acted between the surfaces at pH 3.0 or more. Second, the binding forces were categorized into a friction force or an adhesion force between the particles and the substrate. In the measurement, the friction force between the particle and the substrate was measured in the case when the particle slid on the substrate. On the contrary, the adhesion force was measured when the particle came off the substrate. Whether the particle slid or came off depended on the aspect ratio of the particle. We fabricated cylindrical particles with an aspect ratio of 0.03-2.0 and distinguished the friction force from the adhesion force by changing the aspect ratio of the particles. As a result, the friction force per unit contact area between SiO2-SiO2 flat surfaces was found to be 330 pN/microm2 +/- 20% when we used particles with a low aspect ratio (<0.1), and the adhesion force per unit contact area was 90 pN/microm2 +/- 20% for particles with a high aspect ratio (>0.4). For fluidic self-assembly that utilizes microscale surface contact in a liquid, our measurement method is an effective tool for studying and developing systems.     

Raman anisotropic bandwidth study of C=O stretching vibration of methyl isobutyl ketone: role of van der Waals' volume of the interacting systems

The bandwidth (FWHM) of the anisotropic component (Gamma(aniso)) of methyl isobutyl ketone (MIBK) for different concentrations of solvents varying from 10 to 90% was measured and was plotted as a function of solvent concentrations. In lower solvent concentration, the graph shows a curvature with a discontinuity which occurs between 40 and 60% and in higher solvent concentration, the graph shows a straight line for most of the solvents. In order to interpret the complicated behaviour we have taken into accounts the van der Waals' volume (V(w)) of the sphere of influence in solute dissolved in all solvents. Considering the role of van der Waals' volume in these systems the parameter Gamma(omega)=ln(Gamma(aniso)/V(w)) was plotted at different solvent concentrations. The graph shows a straight line for the entire region. In order to study the influence of screening effect on the bandwidth, the capacitances of the liquid mixture at different solvent concentrations varying from 10 to 90% were measured for all the solvents. The plot of capacitance at different solvent concentrations for each solvent shows a discontinuity around 50% of solvent concentration.     

Collision efficiencies of diffusing spherical particles: hydrodynamic,van der waals and electrostatic forces

A practical limitation of the application of Smoluchowski's classical estimate for the collisions probability of two diffusing spherical particles in Brownian motion is the non-consideration of interparticle forcves. For suspended particles in water such forces can arise from the disturbance the particle causes in the fluid (hydrodynamic forces), from the cloud of ions which surround an electrically charged particle (double layer forces) or they can be of molecular origin (van der Waals forces). In this paper corrections to Smoluckhowski's collision probability are computed when such forces operate Scoluchowski's collision probability are computed when such forces operate between two approaching particles of various sizes. Results for several values of the van der Waals energy of attraction and the ionic strength of the electrolyte are presented in a way convenient for particle collision modeling.     

Molecular intercalates

The paper deals with the relations between host lattices and guest molecules. Several types of interaction of the guest molecules and the host material are explained and some conclusions are made about the arrangement of various guest molecules in the van der Waals' gap.     

Colloid stability of thymine-functionalized gold nanoparticles

Gold nanoparticles surface-coated with thyminethiol derivatives containing long hydrocarbon chains have been prepared. The diameter of the particles is 2.2 and 7.0 nm, respectively, with a relatively narrow size distribution. Thyminethiol derivatives are attached to the gold particle surfaces with thymine moieties as the end groups. The colloid stability of the gold nanoparticles as a function of the type and concentration of monovalent salt, pH, and particle size was investigated in alkaline, aqueous solutions. The gold particles are stable in concentrated NaCl and KCl solutions, but are unstable in concentrated LiCl and CsCl solutions. The larger gold particles are more sensitive to salt concentration and aggregate at lower salt concentrations. The reversible aggregation and dispersion of the gold particles can be controlled by changing the solution pH. The larger gold particles can be dispersed at higher pH and aggregate faster than the smaller particles, due to stronger van der Waals forces between the larger particles. Hydration forces play an important role in stabilizing the particles under conditions where electrostatic forces are negligible. The coagulation of the gold nanoparticles is attributed to van der Waals attraction and reduced hydration repulsion in the presence of LiCl and CsCl.     

Capillary and van der Waals forces between uncharged colloidal particles linked by a liquid bridge

This work presents a theoretical study of the forces established between colloidal particles connected by means of a concave liquid bridge, where the solid particles are partially wetted by a certain amount of liquid also possessing a dry portion of their surfaces. In our analysis, we adopt a two-particle model assuming that the solids are spherical and with the same sizes and properties and that the liquid meniscus features an arc-of-circumference contour. The forces considered are the typical capillary ones, namely, wetting and Laplace forces, as well as the van der Waals force, assuming the particles uncharged. We analyze different parameters which govern the liquid bridge: interparticle separation, wetting angle, and liquid volume, which later determine the value of the forces. Due to the dual characteristic of the particles' surfaces, wet and dry, the forces are to be determined numerically in each case. The results indicate that the capillary forces are dominant in most of the situations meanwhile the van der Waals force is noticeable at very short distances between the particles.     

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.