Electroadhesive properties of polymer particles in contact with the photoconductor surface

The electroadhesive properties of polymer particles 5 to 30 μm in diameter have been assessed by the values of their individual charges after tearing off, and by the force of their adhesion to a solid surface. It has been established that the electroadhesion properties of polymer particles are largely determined by the donor-acceptor interaction between the main functional groups of polymers and the solid surface.

The electroadhesive properties of particles in contact with the surface of a photoconductor have been found to be affected by exposure to light. The spectral dependence of the adhesion force of particles and the variation in the distribution of the torn-off particles with regard to a charge sign under the effect of exposure to light are related to a variation in the density of the double electric layer at their interface with the solid surface.

The results obtained are interpreted on the basis of notions on the preponderant role of the forces of electrostatic nature, which are attributable to the effect of the double electric layer at the interface, in the adhesion interaction of the particles with the solid surface.     

The role of the pressing-on in the adhesion of elastic particles

One has carried out an analysis of the influence of the preliminary pressing-on on components of the adhesion force of different natures for the case of the contact of elastic particles with a rigid substrate. Two pressing-on variants are considered; as, - those realized under the effect of a dynamic and a static load. It has been shown that an increase in the adhesion of elastic particles to the surface resulting from the preliminary pressing-on is attributable to an increase in the adhesion force component due to a double electric layer in contact.     

Electrostatic free energy of interacting ionizable double layers

The electrostatic contribution to the interaction free energy of charge-regulating materials, similar as well as dissimilar, contains electric work as well as chemical work and can be obtained from an integration over the diffuse part of the double layer together with a summation of the surface contribution to the free energy over the two surfaces. Examples for the surface contribution are given for acid, base, zwitterionic, and amphoteric (1-pK and 2-pK) materials for a diffuse double layer and for the Stern-Gouy-Chapman model, with and without ion adsorption. For charge-regulating materials, the electrostatic contribution to the interaction free energy at contact (adhesion force of curved surfaces, or particles) is always finite and can be obtained from a simple calculation.     

UV光引发表面接枝两性离子水凝胶层的制备及抗细菌黏附性能

采用聚合和交联的SiO₂有机/无机杂化溶胶作为基材, 通过与两性离子单体层之间的过渡层, 在紫外光作用下引发杂化溶胶和两性离子单体溶液中的双键反应, 使生成的杂化层在基材和表面的两性离子聚合物之间形成辅助性黏接作用, 从而在基材表面构筑两性离子水凝胶层. 通过傅里叶红外光谱(FTIR)、 原子力显微镜(AFM)和接触角测试等方法对所制备的两性离子水凝胶层和杂化层的表面进行了表征. 以空白玻璃片为对照样品, 以金黄色葡萄球菌和大肠杆菌为试验菌, 研究了用两性离子凝胶层修饰的玻璃表面的抗细菌黏附性能. 结果表明, 在SiO₂杂化过渡层中引入线型-Si-(CH₂)₂-O-链段可有效提高杂化过渡层对基材的附着力, 并改善其柔韧性. 与对照样品相比, 用两性离子凝胶层修饰的玻璃表面具有优异的抗菌黏附性能.     

The influence of contact electrification on the adhesion of dielectric elastic spheres subjected to external loads before detachment

The influence of a static load on the adhesion of an elastic sphere to a rigid smooth surface has been investigated. The change in ratio of the electrostatic component of the adhesion force resulting from the formation of an electric double layer to the molecular one as a result of the contact pressure has been evaluated theoretically. The tearing-off force and the surface density of the charge forming in the contact between the silicone rubber sphere and a steel plate were determined simultaneously. It is shown that the observed increase in sticking force of the sphere after its compression may be explained by an increase in the electrostatic component of the adhesion force, which is proportional to the contact area.     

W/O型乳胶粒子表面电性的近代测试技术

采取近代表面电学测试技术对乳胶粒子表面电性进行微观测量，取得了一系列反映胶粒表面双电层结构的特征参量，证明表面扩散双电层的存在。为完善W／O型乳胶体系的稳定性理论提供了一定实验依据。     

Problems of adhesion

Many discrepancies in the theory of adhesion are connected with the confusion of processes of bond-forming and bond-breaking which have very different character. The former consumes several decimal orders of magnitude more work than would correspond to a reversible process.

The most important cause of this is the work needed to separate the parts of the electric double layer formed at the contact of two bodies. The corresponding electrostatic attraction plays the most important part in adhesion of solid bodies and especially of powder particles. It explains especially the photo controlled adhesion of powders. In contrast to this the separation of particles imbedded in a liquid may be realized nearly reversibly when the rate of process is not very high. The theory of adhesion (coagulation) of lyophobic colloid particles (the Derjaguin-Landau-Verwey-Overbeek theory) takes into consideration the Van der Waals forces and ionic-electrostatic interactions. Recently this theory has included in its scope the phenomena of repeptization.     

On the role of electrostatic forces in the adhesion of polymer particles to solid surfaces

Simultaneous measurements have been made of the adhesive force and double electric charge of particles after their removal from a metal surface. For the systems investigated, the adhesive force and charge on the particles increase with particle diameter according to a power law with an exponent close to 2. Such dependence can be explained on the basis of the electrostatic nature of the adhesive forces. A double electric layer exists at the interface between the particles and the metal surface. A calculation was made of the surface density of charge for the polyvinyl chloride particle-steel system.     

The influence of polymer structure and morphology on talc wettability

Advancing water contact angles were measured on freshly cleaved talc faces as well as on talc particles. The intrinsic hydrophobicity of talc was shown to be due to the dominance of the apolar components of the work of adhesion. Polyacrylamides and polysaccharides adsorb onto the surface of talc, displaying strikingly different morphologies. Adsorbed amount, apparent layer thickness, and polymer structure control talc wettability.     

Electrical phenomena accompanying the formation of new surfaces, and their role in adhesion and cohesion

Upon tearing off polymer films from metals and glasses phenomena are observed which testify to the apparition of high differences of potentials between the interfaces formed. In particular, if the film is stripped under vacuum, electron emission is observed with electron velocities of the order of kilovolts. These phenomena are due to division upon stripping of the double electric layer, formed upon close contact between the polymer and the substrate, and to retardation of its discharge. The same retardation of the discharge of the double layer may explain quantitatively both the high value of the work spent on tearing off the film, the dependence of the latter on the speed of stripping and on the pressure of surrounding gas. Similar phenomena were found to take place during the destruction of many crystalline (but not amorphous) solids and are explained by the formation and division of an alternating-sign double layer of mosaic structure.     

Effect of adsorbed polymers on electrophoresis of dispersed particles in strong electric fields

In this study, the effect of adsorbed non-ionic polyethylenoxides (PEO) and polyvinil-pyrrolidones (PVP) of different molecular mass on the electrophoresis of polystyrene, graphite and aluminum oxide particles both in weak (5–20 V/cm) and strong (50–400 V/cm) electric fields has been studied. The measurements in strong fields have been performed in short electric pulses using image analyzing equipment in which we have determined the deviation of particles from their normal sedimentation trajectory. We have shown that the adsorption of PEO and PVP strongly decreases the electrophoretic velocity (V_ef) of particles in weak electric fields, and this decrease is bigger the adsorbed amount is higher. This is explained by the shift of the shear plane toward solution due to polymer adsorption. At the same time the polymer adsorption only slightly changes the V_ef of particles in strong fields. It means that the non-linear (“cubic”) electrophoresis is independent of the position of the shear plane, i.e. the zeta-potential value. It proves our idea that the electrophoretic velocity in strong electric fields is determined mainly by the surface conductivity of particles, i.e. it is not a function of the electrokinetic potential but rather the Dukhin number that characterizes the polarization of the electric double layer.     

Polymer–TiO2 composite nanorattles via RAFT‐mediated emulsion polymerization

In this work, successful synthesis of polymer nanorattles containing titanium dioxide pigment particles in the centers of air voids is reported. The method used amphiphilic macro‐RAFT copolymers as stabilizers for pigment dispersion and the subsequent encapsulation of the pigment with polymer. The particles were first encapsulated by a water swellable hydrophilic layer, followed by a hard hydrophobic layer. Nanorattles were formed by swelling of hydrophilic polymer layers on the surface of the encapsulated pigment particles in a basic solution at elevated temperature. After swelling, the outer hard polymer shell was crosslinked to improve its strength. Air void sizes of the nanorattles were found to be controlled by swelling time, temperature, and the hydrophilic polymer layer thickness. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polarizability and complex conductivity of dilute suspensions of spherical colloidal particles with uncharged (neutral) polymer coatings

The polarizability of polymer-coated colloidal particles, as measured via dielectric relaxation spectroscopy, reflects on the degree to which convection, diffusion, and electromigration deform the equilibrium double layer. With a polymer coating, convection and electro-osmosis are resisted by hydrodynamic drag on the polymer segments. The electro-osmotic flow near the underlying bare surface is therefore diminished. Characteristics of the particles and the adsorbed polymer can, in principle, be inferred by measuring the frequency-dependent polarizability. In this work, "exact" numerical solutions of the electrokinetic equations are used to examine how adsorbed polymer changes the particle polarizability and, hence, the conductivity and dielectric constant increments of dilute suspensions. For neutral polymer coatings, the conductivity and dielectric constant increments are found to be very similar to those of the underlying bare particles, so the response depends mostly on the underlying bare particles. These observations suggest that dielectric spectroscopy is best used to determine the underlying surface charge, with characteristics of the coating inferred from the electrophoretic or dynamic mobility, together with the hydrodynamic radius obtained from sedimentation or dynamic light scattering. Addressed briefly are the effects of added counterions and nonspecific adsorption. The electrokinetic model explored in this work can be used to guide experiments (frequency and ionic strength, for example) to either minimize or maximize the sensitivity of the complex conductivity to the coating thickness or permeability.     

From Cd-rich to se-rich--the manipulation of CdSe nanocrystal surface stoichiometry

We report a protocol for manipulating the surface composition of CdSe nanocrystals. By combining the successive ion layer adhesion and reaction (SILAR) method developed by Li et al. J. Am. Chem. Soc. 2003, 125, 12567 with a phosphine-free selenium precursor, the surface stoichiometry of CdSe can be tunably altered from Cd- to Se-rich. By changing the overall surface stoichiometry, we demonstrate ligand binding to specific surface sites. Tertiary phosphines produce a dramatic enhancement in photoluminescence quantum yield of CdSe particles with Se-rich surfaces but have little effect on Cd-rich surfaces. Unpassivated selenium surface sites are also shown to be a cause of the photobrightening behavior of CdSe nanocrystals.     

Electrostatic double layer force between a sphere and a planar substrate in the presence of previously deposited spherical particles

A finite element model of the electrostatic double layer interaction between an approaching colloidal particle and a small region of a charged planar surface containing four previously deposited particles is presented. The electrostatic interaction force experienced by the approaching particle is obtained by solving the Poisson-Boltzmann equation with appropriate boundary conditions representing this complex geometry. The interaction forces obtained from the detailed three-dimensional finite element simulations suggest that for the many-body scenario addressed here, the electrostatic double layer repulsion experienced by the approaching particle is less than the corresponding sphere-plate interaction due to the presence of the previously deposited particles. The reduction in force is quite significant when the screening length of the electric double layer becomes comparable to the particle radius (kappaa approximately 1). The results also suggest that the commonly used technique of pairwise addition of binary interactions can grossly overestimate the net electrostatic double layer interaction forces in such situations. The simulation methodology presented here can form a basis for investigating the influence of several previously deposited particles on the electrostatic repulsion experienced by a particle during deposition onto a substrate.     

Polymerization of electric field-centered double emulsion droplets to create polyacrylate shells

Porous and hollow particles are widely used in pharmaceuticals, as solid phases for chromatography, as catalyst supports, in bioanalytical assays and medical diagnostics, and in many other applications. By controlling size, shape, and chemistry, it is possible to tune the physical and chemical properties of the particles. In some applications of millimeter-scale hollow shells, such as in high energy density physics, controlling the shell thickness uniformity (concentricity) and roundness (sphericity) becomes particularly important. In this work, we demonstrate the feasibility of using electric field-driven droplet centering to form highly spherical and concentric polymerizable double emulsion (DE) droplets that can be subsequently photopolymerized into polymer shells. Specifically, when placed under the influence of an ～6 × 10(4) V(rms)/m field at 20 MHz, DE droplets, consisting of silicone oil as the inner droplet and tripropylene glycol diacrylate with a photoinitiator in N,N-dimethylacetamide as the outer droplet, suspended in ambient silicone oil, were found to undergo electric field-driven centering into droplets with ≥98% sphericity and ～98% concentricity. The centered DE droplets were photopolymerized in the presence of the electric field. The high degrees of sphericity and concentricity were maintained in the polymerized particles. The poly(propylene glycol diacrylate) capsules are just within the sphericity requirements needed for inertial confinement fusion experiments. They were slightly outside the concentricity requirement. These results suggest that electric field-driven centering and polymerization of double emulsions could be very useful for synthesizing hollow polymer particles for applications in high energy density physics experiments and other applications of concentric polymer shells.     

The conditions governing the specific adsorption of counter-ions in the interaction of two parallel plate-like colloidal particles

Frens and Overbeek have proposed that during the Brownian collision of two colloidal particles in a hydrophobic sol, the surface charge density due to potential-determining (p.d.) ions remains virtually unchanged. It is argued here that the cause of this behaviour is the low concentration of p.d. ions in the diffuse layer. However, equilibrium can be maintained with respect to counter-ions adsorbed into the Stern region from the supporting electrolyte, because the concentration of such electrolyte in the dispersion medium is considerably greater than that of p.d. ions.A general expression is quoted from earlier work for the electric double layer interaction between two parallel plate-like particles in the case where surface charge due to p.d. ions is fixed, but where counter-ions adsorbed into the Stern region can equilibrate with ions of the same species in the diffuse layer. Incorporating discreteness-of-charge and ion-size effects into the adsorption isotherm of the counter-ions, the double layer interaction energy of the two plates is calculated at contact of the two outer Helmholtz planes (o.h.p.'s). It is shown that although this energy exceeds the classical expression obtained by assuming the potential at the o.h.p. to be independent of plate separation, it remains finite.     

dc Electrokinetics for spherical particles in salt-free concentrated suspensions including ion size effects

We study the electrophoretic mobility of spherical particles and the electrical conductivity in salt-free concentrated suspensions including finite ion size effects. An ideal salt-free suspension is composed of just charged colloidal particles and the added counterions that counterbalance their surface charge. In a very recent paper [Roa et al., Phys. Chem. Chem. Phys., 2011, 13, 3960-3968] we presented a model for the equilibrium electric double layer for this kind of suspensions considering the size of the counterions, and now we extend this work to analyze the response of the suspension under a static external electric field. The numerical results show the high importance of such corrections for moderate to high particle charges, especially when a region of closest approach of the counterions to the particle surface is considered. The present work sets the basis for further theoretical models with finite ion size corrections, concerning particularly the ac electrokinetics and rheology of such systems.     

Adhesion of nonplanar wrinkled surfaces

Topological patterns on polymer surfaces can significantly alter and control adhesion. In this study, the effect of surface wrinkles on a spherical surface on adhesion has been studied. Surface wrinkling induced by swelling of a crosslinked polydimethylsiloxane elastomer constrained by a stiff, thin surface layer (silicate) is used to produce topographic features of various length scales over a large curved area. By controlling the properties of the stiff layer and the applied strain conditions, surface wrinkles of varying amplitude and wavelength are obtained. The effect of wrinkle morphology on adhesion is quantified, and the results display a transition from enhancement of adhesion to decrease depending upon wrinkle dimensions. A simple phenomenological model is proposed that describes the change of adhesion behavior as a function of wrinkle morphology. Our results provide a critical understanding toward tuning the adhesion behavior of nonplanar surfaces consisting of periodic topographic structures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011