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.     

Influence of surface roughness on dispersion forces

Surface roughness occurs in a wide variety of processes where it is both difficult to avoid and control. When two bodies are separated by a small distance the roughness starts to play an important role in the interaction between the bodies, their adhesion, and friction. Control of this short-distance interaction is crucial for micro and nanoelectromechanical devices, microfluidics, and for micro and nanotechnology. An important short-distance interaction is the dispersion forces, which are omnipresent due to their quantum origin. These forces between flat bodies can be described by the Lifshitz theory that takes into account the actual optical properties of interacting materials. However, this theory cannot describe rough bodies. The problem is complicated by the nonadditivity of the dispersion forces. Evaluation of the roughness effect becomes extremely difficult when roughness is comparable with the distance between bodies. In this paper we review the current state of the problem. Introduction for non-experts to physical origin of the dispersion forces is given in the paper. Critical experiments demonstrating the nonadditivity of the forces and strong influence of roughness on the interaction between bodies are reviewed. We also describe existing theoretical approaches to the problem. Recent advances in understanding the role of high asperities on the forces at distances close to contact are emphasized. Finally, some opinions about currently unsolved problems are also presented.     

Dynamic adhesion behavior of micrometer-scale particles flowing over patchy surfaces with nanoscale electrostatic heterogeneity

The dynamic adhesion behavior of micrometer-scale silica particles is investigated numerically for a low Reynolds number shear flow over a planar collecting wall with randomly distributed electrostatic heterogeneity at the 10-nanometer scale. The hydrodynamic forces and torques on a particle are coupled to spatially varying colloidal interactions between the particle and wall. Contact and frictional forces are included in the force and torque balances to capture particle skipping, rolling, and arrest. These dynamic adhesion signatures are consistent with experimental results and are reminiscent of motion signatures observed in cell adhesion under flowing conditions, although for the synthetic system the particle–wall interactions are controlled by colloidal forces rather than physical bonds between cells and a functionalized surface. As the fraction of the surface (Θ) covered by the cationic patches is increased from zero, particle behavior sequentially transitions from no contact with the surface to skipping, rolling, and arrest, with the threshold patch density for adhesion (Θ_crit) always greater than zero and in quantitative agreement with experimental results. The ionic strength of the flowing solution determines the extent of the electrostatic interactions and can be used to tune selectively the dynamic adhesion behavior by modulating two competing effects. The extent of electrostatic interactions in the plane of the wall, or electrostatic zone of influence, governs the importance of spatial fluctuations in the cationic patch density and thus determines if flowing particles contact the wall. The distance these interactions extend into solution normal to the wall determines the strength of the particle–wall attraction, which governs the transition from skipping and rolling to arrest. The influence of Θ, particle size, Debye length, and shear rate is quantified through the construction of adhesion regime diagrams, which delineate the regions in parameter space that give rise to different dynamic adhesion signatures and illustrate selective adhesion based on particle size or curvature. The results of this study are suggestive of novel ways to control particle–wall interactions using randomly distributed surface heterogeneity.     

The effect of surface roughness on the adhesion of solid surfaces for systems with and without liquid lubricant

We present molecular dynamics results for the interaction between two solid elastic walls during pull-off for systems with and without octane (C(8)H(18)) lubricant. We used two types of substrate--flat and corrugated--and varied the lubricant coverage from approximately 1/8 to approximately 4 ML (monolayers) of octane. For the flat substrate without lubricant the maximum adhesion was found to be approximately three times larger than for the system with the corrugated substrate. As a function of the octane coverage (for the corrugated substrate) the pull-off force first increases as the coverage increases from 0 to approximately 1 ML, and then decreases as the coverage is increased beyond monolayer coverage. It is shown that at low octane coverage, the octane molecules located in the substrate corrugation wells during squeezing are pulled out of the wells during pull-off, forming a network of nanocapillary bridges around the substrate nanoasperities, thus increasing the adhesion between two surfaces. For greater lubricant coverages a single capillary bridge is formed. The adhesion force saturates for lubricant coverages greater than 3 ML. For the flat substrate, during pull-off we observe discontinuous, thermally activated changes in the number n of lubricant layers (n-1-->n layering transitions), whereas for the corrugated substrate these transitions are "averaged" by the substrate surface roughness.     

Charge heterogeneity of surfaces: mapping and effects on surface forces

The DLVO theory treats the total interaction force between two surfaces in a liquid medium as an arithmetic sum of two components: Lifshitz–van der Waals and electric double layer forces. Despite the success of the DLVO model developed for homogeneous surfaces, a vast majority of surfaces of particles and materials in technological systems are of a heterogeneous nature with a mosaic structure composed of microscopic and sub-microscopic domains of different surface characteristics. In such systems, the heterogeneity of the surface can be more important than the average surface character. Attractions can be stronger, by orders of magnitude, than would be expected from the classical mean-field DLVO model when area-averaged surface charge or potential is employed. Heterogeneity also introduces anisotropy of interactions into colloidal systems, vastly ignored in the past. To detect surface heterogeneities, analytical tools which provide accurate and spatially resolved information about material surface chemistry and potential — particularly at microscopic and sub-microscopic resolutions — are needed.Atomic force microscopy (AFM) offers the opportunity to locally probe not only changes in material surface characteristic but also charges of heterogeneous surfaces through measurements of force–distance curves in electrolyte solutions. Both diffuse-layer charge densities and potentials can be calculated by fitting the experimental data with a DLVO theoretical model. The surface charge characteristics of the heterogeneous substrate as recorded by AFM allow the charge variation to be mapped. Based on the obtained information, computer modeling and simulation can be performed to study the interactions among an ensemble of heterogeneous particles and their collective motions. In this paper, the diffuse-layer charge mapping by the AFM technique is briefly reviewed, and a new Diffuse Interface Field Approach to colloid modeling and simulation is briefly discussed.     

Combined depletion and electrostatic forces in polymer-induced membrane adhesion: a theoretical model

We develop a semi-quantitative analytical theory to describe adhesion between two identical planar charged surfaces embedded in a polymer-containing electrolyte solution. Polymer chains are uncharged and differ from the solvent by their lower dielectric permittivity. The solution mimics physiological fluids: It contains 0.1 M of monovalent ions and a small number of divalent cations that form tight bonds with the headgroups of charged lipids. The components have heterogeneous spatial distributions. The model was derived self-consistently by combining: (a) a Poisson-Boltzmann like equation for the charge densities, (b) a continuum mean-field theory for the polymer profile, (c) a solvation energy forcing the ions toward the polymer-poor regions, and (d) surface interactions of polymers and electrolytes. We validated the theory via extensive coarse-grained Molecular Dynamics (MD) simulations. The results confirm our analytical model and reveal interesting details not detected by the theory. At high surface charges, polymer chains are mainly excluded from the gap region, while the concentration of ions increases. The model shows a strong coupling between osmotic forces, surface potential and salting-out effects of the slightly polar polymer chains. It highlights some of the key differences in the behaviour of monomeric and polymeric mixed solvents and their responses to Coulomb interactions. Our main findings are: (a) the onset of long-ranged ion-induced polymer depletion force that increases with surface charge density and (b) a polymer-modified repulsive Coulomb force that increases with surface charge density. Overall, the system exhibits homeostatic behaviour, resulting in robustness against variations in the amount of charges. Applications and extensions of the model are briefly discussed.     

Hydrophobic forces and hydrogen bonds in the adhesion between retinoid-coated surfaces

Interactions between hydrophobic chains of lipid monolayers and interactions between hydrophilic headgroups of lipid bilayers (with or without a molecular recognition step) are now well documented, especially for commonly used lipids. Here, we report force measurements between a new class of fluorinated lipid layers whose headgroups (synthetic ligands of retinoid receptors) display a very unusual polar/apolar character and can interact via a combination of hydrophobic forces and hydrogen bonds. Although these two interactions produce adhesion and are therefore not easily distinguishable, we show that it is possible to extract both contributions unambiguously. Experiments are performed both in pure water, where the adhesion is a combination of hydrophobic forces and hydrogen bonds, and in Tris buffer, where the hydrophobic effect is the dominant short-range attractive force. The contribution of hydrophobic forces scaled down to molecular interactions is deduced from force versus distance profiles, and the same value is found independently in pure water and Tris buffer, about 1 kBT. We also show that retinoid lipid layers attract each other through a very long-range (100 nm) exponential force, which is insensitive to the pH and the salinity. The origin of this long-range attraction is discussed on the basis of previously proposed mechanisms.     

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.     

Correction of random surface roughness on colloidal probes in measuring adhesion

Atomic force microscopes (AFM) are commonly used to measure adhesion at nanoscale between two surfaces. To avoid uncertainties in the contact areas between the tip and the surface, colloidal probes have been used for adhesion measurements. We measured adhesion between glass spheres and silicon (100) surface using colloidal probes of different radii under controlled conditions (relative humidity of < 3%, temperature of 25 +/- 1 degrees C). Results showed that the adhesion forces did not correlate with the radii of the spheres as suggested by elastic contact mechanics theories. Surface roughness and random surface features were found on the surfaces of the colloidal probes. We evaluated various roughness parameters, Rumpf and Rabinovich models, and a load-bearing area correction model in an attempt to correct for the roughness effects on adhesion, but the results were unsatisfactory. We developed a new multiscale contact model taking into account elastic as well as plastic deformation in a successive contacting mode. The new model was able to correct for most of the surface roughness features except for surface ridges with sharp angular features, limited by the spherical asperity assumption made in the model.     

Effect of surface roughness and softness on water capillary adhesion in apolar media

The roughness and softness of interacting surfaces are both important parameters affecting the capillary condensation of water in apolar media, yet are poorly understood at present. We studied the water capillary adhesion between a cellulose surface and a silica colloidal probe in hexane by AFM force measurements. Nanomechanical measurements show that the Young's modulus of the cellulose layer in water is significantly less (~7 MPa) than in hexane (~7 GPa). In addition, the cellulose surface in both water and hexane is rather rough (6-10 nm) and the silica probe has a comparable roughness. The adhesion force between cellulose and silica in water-saturated hexane shows a time-dependent increase up to a waiting time of 200 s and is much (2 orders of magnitude) lower than that expected for a capillary bridge spanning the whole silica probe surface. This suggests the formation of one or more smaller bridges between asperities on both surfaces, which is confirmed by a theoretical analysis. The overall growth rate of the condensate cannot be explained from diffusion mediated capillary condensation alone; thin film flow due to the presence of a wetting layer of water at both the surfaces seems to be the dominant contribution. The logarithmic time dependence of the force can also be explained from the model of the formation of multiple capillary bridges with a distribution of activation times. Finally, the force-distance curves upon retraction show oscillations. Capillary condensation between an atomically smooth mica surface and the silica particle show less significant oscillations and the adhesion force is independent of waiting time. The oscillations in the force-distance curves between cellulose and silica may stem from multiple bridge formation between the asperities present on both surfaces. The softness of the cellulose surface can bring in additional complexities during retraction of the silica particle, also resulting in oscillations in the force-distance curves.     

Friction and adhesion forces of Bacillus thuringiensis spores on planar surfaces in atmospheric systems

The kinetic friction force and the adhesion force of Bacillus thuringiensis spores on planar surfaces in atmospheric systems were studied using atomic force microscopy. The influence of relative humidity (RH) on these forces varied for different surface properties including hydrophobicity, roughness, and surface charge. The friction force of the spore was greater on a rougher surface than on mica, which is atomically flat. As RH increases, the friction force of the spores decreases on mica whereas it increases on rough surfaces. The influence of RH on the interaction forces between hydrophobic surfaces is not as strong as for hydrophilic surfaces. The friction force of the spore is linear to the sum of the adhesion force and normal load on the hydrophobic surface. The poorly defined surface structure of the spore and the adsorption of contaminants from the surrounding atmosphere are believed to cause a discrepancy between the calculated and measured adhesion forces.     

Numerical study of the interplay of monomer-surface electrostatic and non-electrostatic interactions in the adsorption of weak polyelectrolytes on oppositely charged surfaces

The adsorption of weak polybase on oppositely charged planar surfaces has been investigated numerically by using the self-consistent field theory (SCFT). Particular attention was paid to the interplay of monomer-surface electrostatic and non-electrostatic interactions in the adsorption behaviors of weak polybase. In this study, the strength of monomer-surface non-electrostatic interactions was set to be no more than the thermal energy k _B T. It was found from the numerical study that in the regime of low surface charge density of the substrate and low pH or high bulk degree of ionization, both the screening-enhanced and screening-reduced salt effects emerge. On the contrary, in the opposite regime, only the screening-reduced salt effect was observed. Moreover, the overall charge neutrality inside the adsorption layer was analyzed. The underlying mechanism governing the adsorption behaviors of weak polybase on oppositely charged surfaces was elucidated.     

Capillary forces: influence of roughness and heterogeneity

A formalism is described to calculate capillary forces between solid surfaces analytically. Assumptions are that the liquid menisci (1) have a much larger extension parallel to the gap than normal and (2) are formed by capillary condensation and are in equilibrium with the vapor. To calculate capillary forces, first the gap between the two surfaces is described by a height distribution function. Roughness is considered with an asperity distribution function. Both distributions can at least in principal be measured by light, electron, or atomic force microscopy or grazing incidence X-ray reflectivity. The total capillary force versus distance or vapor pressure is obtained by a convolution of both distributions and an integration. The formalism is applied to calculate the capillary force between rough spherical particles. In addition, a method to consider surface heterogeneity is suggested.     

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.     

Impact of surface forces on wetting of hierarchical surfaces and contact angle hysteresis

The influence of the long-range surface forces on the wetting of multi-scale partially wetted surfaces is discussed. The possibility of partial wetting is stipulated by a specific form of the Derjaguin isotherm. Equilibrium of a liquid meniscus inside a cylindrical capillary is used as a model. The interplay of capillary and disjoining pressures governs the equilibrium of the liquid in the nano- and micrometrically scaled pores constituting the relief of the surface. It is shown that capillaries with a radius smaller than a critical one will be completely filled by water, whereas the larger capillaries will be filled only partially. Thus, small capillaries will show the Wenzel type of wetting behavior, while the same liquid inside the large capillaries will promote the Cassie-Baxter type of wetting. Consideration of disjoining/conjoining pressure allows explaining of the “rose petal effect”, when a high apparent contact angle is accompanied with a high contact angle hysteresis.     

Control of adhesion and surface forces via potential-dependent adsorption of pyridine

The orientation and extent of adsorption of pyridine on a gold electrode is known to depend on applied potential and is well characterized. By use of the electrochemical surface forces apparatus, we measured the potential dependence of the double-layer interactions and adhesive forces between a gold electrode and a mica surface for different pyridine concentrations. We observed that, unlike mica-mica interactions, the gold-mica interactions were strongly affected by the presence of small concentrations of pyridine. We are able to reach high negative surface potentials (as determined by applying Derjaguin-Landau-Verway-Overbeek theory to our force measurements), which is similar to what is observed in the absence of pyridine. This demonstrates the electronic nature of the forces measured and shows that pyridine does not displace potential-determining ions on the surface. At positive potentials, where the interaction between gold and mica is attractive, pull-off measurements are a strong function of applied potential. The major effect of the presence of pyridine is on the observed shift in the potential of zero force (PZF), moving it to more negative potentials. This effect is caused by the strong dipole of the pyridine molecule. When the applied potential is cast as a deviation from the PZF, the effect of pyridine is to reduce adhesion between gold and mica. We modeled the potential-dependent adhesion of this system using an electrocapillary framework developed previously, and in doing so, we establish the relationship between the gold-liquid and gold-mica surface energies. In addition, we show that pyridine adsorption affects the capacitance of the gold-mica interface.     

Structural and adhesion properties of surfaces functionalized with polyelectrolytes and polystyrene particles

Surfaces functionalized with polystyrene particles and polyelectrolytes were used to investigate the morphological and adhesion properties of composite substrates. Atomic force microscopy (AFM) studies showed that surfaces with non-homogeneous topography have non-homogeneous adhesion properties. In addition, the homogeneity of the adhesion properties is dependent upon the chemical species used to functionalize the surface. Force volume (FV) imaging was utilized to map the adhesion of the fabricated substrates with high-resolution. The FV studies revealed that the hydrophobicity of the surface is not uniform despite the fact that the surface was functionalized with the same polyelectrolyte. The analysis methodology we report here opens the possibility to design better surfaces for future tissue engineering applications.     

Interaction of hydrogen chloride with ice surfaces: the effects of grain size, surface roughness, and surface disorder

Characterization of the interaction of hydrogen chloride (HCl) with polar stratospheric cloud (PSC) ice particles is essential to understanding the processes responsible for ozone depletion. The interaction of HCl with ice was studied using a coated-wall flow tube with chemical ionization mass spectrometry (CIMS) between 5x10(-8) and 10(-4) Torr HCl and between 186 and 223 K, including conditions recently shown to induce quasi-liquid layer (QLL) formation on single crystalline ice samples. Measurements were performed on smooth and rough (vapor-deposited) polycrystalline ice films. A numerical model of the coated-wall flow reactor was used to interpret these results and results of studies on zone-refined ice cylinders with grain sizes on the order of several millimeters (reported elsewhere). We found that HCl adsorption on polycrystalline ice films typically used in laboratory studies under conditions not known to induce surface disordering consists of two modes: one relatively strong mode leading to irreversible adsorption, and one relatively weak binding mode leading to reversible adsorption. We have indirect experimental evidence that these two modes of adsorption correspond to adsorption to sites at crystal faces and those at grain boundaries, but there is not enough information to enable us to conclusively assign each adsorption mode to a type of site. Unlike what was observed in the zone-refined ice study, there was no strong qualitative contrast found between the HCl uptake curves under QLL versus non-QLL conditions for adsorption on smooth and vapor-deposited ices. We also found indirect evidence that HCl hexahydrate formation on ice between 3x10(-7) and 2x10(-6) Torr HCl and between 186 and 190 K is a process involving hydrate nucleation and propagation on the crystal surface, rather than one originating in grain boundaries, as has been suggested for ice formed at lower temperatures. These results underscore the dependence of the HCl-ice interaction on the characteristics of the ice substrate.     

Investigation on the adhesion of polymer particles to the surface of a semiconductor

In this work the role of electrostatic forces in the adhesion of particles of dielectrics to a solid surface was studied. The experiment consisted in measuring simultaneously the force of adhesion and the charges of the electric double layer arising upon contact. The measurements were made with specially developed units—a pneumatic adhesiometer and a charge-spectrometer. The objects of study were polymer powders used in electrography, whose adhesion to thin layers of selenium samples were varied by varying the illumination and were estimated by their volume resistance in the dark and in the light. The shift in the Fermi level of the selenium caused by the change in the output work is accompanied by a change in adhesion of the particles. Experiments on the separation of polymer particles and films from selenium surface on illumination revealed spectral dependence of adhesion. In accordance with the electronic theory of adhesion, the effects observed may be attributed to the change in charge density of the electric double layer.