Direct measurement of surface forces due to charging of solids immersed in a nonpolar liquid

Direct measurements of a long-range force between charged solid surfaces in a nonpolar liquid are presented for the first time. Measurements were made between mica surfaces in solutions of the anionic surfactant sodium di-2-ethylhexylsulfosuccinate (AOT) at millimolar concentrations in n-decane using a surface force apparatus which has been modified to improve its sensitivity for detecting a weak and long-range force. Modifications include a magnetic drive system, the use of a weak cantilever spring with the apparatus mounted in a vertical configuration, and a detailed consideration of the interference optics to allow accurate measurements of surface separations up to several micrometers. The results show a repulsion that is well fitted by theoretical curves based on a model in which only counterions enter the calculation, in other words, in the absence of a reservoir of ions in the solvent. Fitting the theory to the data allows an estimate of the mica surface charge density of ∼1 mC/m². A mechanism for surface charging of mica in this solution is proposed, which includes a role for trace amounts of water that are inevitably present and adsorbed surface aggregates of AOT. The relevance of the results to previously observed charge stabilization of colloids in nonaqueous solvents is discussed.

Measurement of surface forces between mica sheets immersed in aqueous quaternary ammonium ion solutions

Forces between mica surfaces immersed in Me4NBr, Pr4NBr, and Pe4NBr solutions over a wide concentration range are reported (Me = methyl, Pr = propyl, Pe = pentyl). In each case the cation adsorbs quite strongly onto the negatively charged mica surface and determines the double-layer potential. However, this strong adsorption does not cause complete neutralization of the negative lattice charge apparently because of packing constraints due to the large size of these ions. Adsorption of Me4N+ ions gives rise to a short-range (<2 nm) repulsive force similar to that previously observed between bilayers of CTAB and may be due to the residual hydration of these ions. The large rations also, unexpectedly, give rise to short-range repulsive forces but of a somewhat different nature. In this case, the repulsive forces can be explained by assuming that the large adsorbed ions shift the plane of charge a distance of one ion diameter from the mica surface. At all but very high concentrations these larger ions could be displaced from the mica surfaces on forcing them together. No evidence of any “hydrophobic attraction” was observed between surfaces containing these adsorbed ions. Previous studies on coagulation are discussed in the light of our results.

The 'wimple' : rippled deformation of a fluid drop caused by hydrodynamic and surface forces during thin film drainage

It is well-known that hydrodynamic pressures in a thin draining liquid film can cause inversion of the curvature of a drop or bubble surface as it approaches another surface, creating a so-called “dimple”. Here it is shown that a more complicated rippled shape, dubbed a “wimple”, can be formed if a fluid drop that is already close to a solid wall is abruptly pushed further toward it. The wimple includes a central region in which the film remains thin, surrounded by a ring of greater film thickness that is bounded at the outer edge by a barrier rim where the film is thin. This shape later evolves into a conventional dimple bounded by the barrier rim, which then drains in the normal way. During the evolution from wimple to dimple, some of the fluid in the thicker part of the film ring flows toward the central region before eventually draining in the opposite direction. Although the drop is pressed toward the wall, the central part of the drop moves away from the wall before approaching it again. This is observed even when the inward push is too small to create a wimple.

The influence of surface forces on thin film drainage between a fluid drop and a flat solid

An experiment is described in which a mica surface is driven towards a mercury drop immersed in aqueous electrolyte. Under appropriate conditions, hydrodynamic pressure in the aqueous film creates a classical dimple in the mercury drop. The use of optical interferometry and video recording to monitor the shape of the drop and the thickness of the aqueous film with sub-nanometre resolution yields a high density of precise data showing the formation and evolution of the dimple as the film drains. Variation of electrical potential applied to the mercury phase allows control of the surface forces acting between the drop and the mica surface, so that the effect of surface forces on the film drainage process is highlighted. It is found that the film thickness at the centre of the dimple and the lateral extent of the dimple are not significantly affected by surface forces. On the other hand, the minimum film thickness at the edge of the dimple is sensitive even to weak surface forces. Since this minimum film thickness is a major determinant of the film drainage rate, it is shown that surface forces have an important effect on the overall drainage process.

Surface forces and their action in ceramic materials

A descriptive account is given of the surface forces acting between two solids. Different contributions to the force are outlined, with particular attention paid to the underlying mechanisms, and how they are affected by the nature of the medium between the surfaces. This is followed by a discussion of the areas of ceramic science and engineering in which surface forces play a role.

Direct measurement of surface forces between sapphire crystals in aqueous solutions

Measurements are presented of the electrical double layer and van der Waals forces between the (0001) surfaces of two single-crystal sapphire platelets immersed in an aqueous solution of NaCl at pH values from 6.7 to 11. The results fit the standard Deryaguin-Landau-Verwey-Overbeek (DLVO) theory, with a Hamaker constant of 6.7 × 10−20 J. These are the first measurements made using the Israelachvili surface forces apparatus without mica as a substrate material, and they demonstrate the possibility of using this technique to explore the surface chemistry of a wider range of materials.

Measuring surface forces to explore surface chemistry : mica, sapphire and silica

In this paper measurements of the forces acting between two solid surfaces separated by a thin liquid film are discussed. By investigating these forces in a range of different liquids and solutions, it is possible to acquire an understanding of the surface properties of the solid material. The surface of mica has been studied extensively in this way, and the results obtained are reviewed to illustrate how the surface force measurements can give surface chemical information. Recent measurements on two other materials, sapphire and silica, which are of greater practical interest are also discussed.

Attractive forces between surfaces : what can and cannot be learned from a jump-in study with the surface forces apparatus?

We study theoretically the dynamics of film thinning under the action of an attractive surface force near the point of a jump instability. Our approach is illustrated by modeling van der Waals and hydrophobic attractive forces. The main result is that with the hydrophobic force law reported previously it is often impossible to establish the jump separation with any certainty. The surfaces instead approach slowly from a distance which is much larger than the point where an actual jump is expected. We conclude that an attractive force measured by the static jump technique is overestimated, and we formulate principles of a new dynamic jump method. The use of this new technique would permit direct measurements of attractive forces at separations below the static jump distance down to contact of the surfaces.

The boundary lubrication of chemically grafted and cross-linked hyaluronic acid in phosphate buffered saline and lipid solutions measured by the surface forces apparatus

High molecular weight hyaluronic acid (HA) is present in articular joints and synovial fluid at high concentrations; yet despite numerous studies, the role of HA in joint lubrication is still not clear. Free HA in solution does not appear to be a good lubricant, being negatively charged and therefore repelled from most biological, including cartilage, surfaces. Recent enzymatic experiments suggested that mechanically or physically (rather than chemically) trapped HA could function as an “adaptive” or “emergency” boundary lubricant to eliminate wear damage in shearing cartilage surfaces. In this work, HA was chemically grafted to a layer of self-assembled amino-propyl-triethoxy-silane (APTES) on mica and then cross-linked. The boundary lubrication behavior of APTES and of chemically grafted and cross-linked HA in both electrolyte and lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) solutions was tested with a surface forces apparatus (SFA). Despite the high coefficient of friction (COF) of μ ≈ 0.50, the chemically grafted HA gel significantly improved the lubrication behavior of HA, particularly the wear resistance, in comparison to free HA. Adding more DOPC lipid to the solution did not improve the lubrication of the chemically grafted and cross-linked HA layer. Damage of the underlying mica surface became visible at higher loads (pressure >2 MPa) after prolonged sliding times. It has generally been assumed that damage caused by or during sliding, also known as “abrasive friction”, which is the main biomedical/clinical/morphological manifestation of arthritis, is due to a high friction force and, therefore, a large COF, and that to prevent surface damage or wear (abrasion) one should therefore aim to reduce the COF, which has been the traditional focus of basic research in biolubrication, particularly in cartilage and joint lubrication. Here we combine our results with previous ones on grafted and cross-linked HA on lipid bilayers, and lubricin-mediated lubrication, and conclude that for cartilage surfaces, a high COF can be associated with good wear protection, while a low COF can have poor wear resistance. Both of these properties depend on how the lubricating molecules are attached to and organized at the surfaces, as well as the structure and mechanical, viscoelastic, elastic, and physical properties of the surfaces, but the two phenomena are not directly or simply related. We also conclude that to provide both the low COF and good wear protection of joints under physiological conditions, some or all of the four major components of joints—HA, lubricin, lipids, and the cartilage fibrils—must act synergistically in ways (physisorbed, chemisorbed, grafted and/or cross-linked) that are still to be determined.

Recent advances in the surface forces apparatus (SFA) technique

The surface forces apparatus (SFA) has been used for many years to measure the physical forces between surfaces, such as van der Waals (including Casimir) and electrostatic forces in vapors and liquids, adhesion and capillary forces, forces due to surface and liquid structure (e.g. solvation and hydration forces), polymer, steric and hydrophobic interactions, bio-specific interactions as well as friction and lubrication forces. Here we describe recent developments in the SFA technique, specifically the SFA 2000, its simplicity of operation and its extension into new areas of measurement of both static and dynamic forces as well as both normal and lateral (shear and friction) forces. The main reason for the greater simplicity of the SFA 2000 is that it operates on one central simple-cantilever spring to generate both coarse and fine motions over a total range of seven orders of magnitude (from millimeters to ångstroms). In addition, the SFA 2000 is more spacious and modulated so that new attachments and extra parts can easily be fitted for performing more extended types of experiments (e.g. extended strain friction experiments and higher rate dynamic experiments) as well as traditionally non-SFA type experiments (e.g. scanning probe microscopy and atomic force microscopy) and for studying different types of systems.

The electrochemical surface forces apparatus : the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Theoretical Models for Surface Forces and Adhesion and Their Measurement Using Atomic Force Microscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)