Forces between mica surfaces in ethylene glycol

Measurements are presented of the force as a function of separation between two molecularly smooth mica surfaces immersed in ethylene glycol, and in solutions of lithium chloride and sulfuric acid in ethylene glycol. At surface separations greater than 3 nm the measured force is in very good agreement with double-layer theory, but at smaller separations there is an oscillatory solvation force which is superimposed on the double-layer repulsion. In contrast to the case in water, the adsorption of hydrogen ions at the mica surface does not markedly affect the short-range forces.

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.

The drainage of thin liquid films between solid surfaces

We present measurements of the thickness as a function of time of liquid films as they are squeezed between molecularly smooth mica surfaces. Three Newtonian, nonpolar liquids have been studied: octamethylcyclotetrasiloxane, n-tetradecane, and n-hexadecane. The film thicknesses are determined with an accuracy of 0.2 nm as they drain from ∼1 μm to a few molecular layers. Results are in excellent agreement with the Reynolds theory of lubrication for film thicknesses above 50 nm. For thinner films the drainage is slower than the theoretical prediction, which can be accounted for by assuming that the liquid within about two molecular layers of each solid surface does not undergo shear. In very thin films the continuum Reynolds theory breaks down, as drainage occurs in a series of abrupt steps whose size matches the thickness of molecular layers in the liquid. The presence of trace amounts of water has a dramatic effect on the drainage of a nonpolar liquid between hydrophilic surfaces, causing film rupture which is not observed in the dry liquids.

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are 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.

Molecular organization and viscosity of a thin film of molten polymer between two surfaces as probed by force measurements

Measurements are presented of the force between two molecularly smooth mica surfaces immersed in liquid poly(dimethylsiloxane) (Dow Corning 200 of nominal viscosity 50 cS) over a range of film thicknesses from 3 to 200 nm. There is a repulsion, attributed to conformational restrictions, when the polymer molecules are confined to a gap less than about 15 nm thick. In extremely thin films (<5 nm) the force is an oscillatory function of thickness with a repeat spacing corresponding to the width of the polymer molecule, which suggests that the polymer segments are arranged in layers near the solid surfaces. Dynamic force measurements show that the polymer has a viscosity equal to its bulk value even in very thin films, but a region next to each surface, only about one radius of gyration thick, does not flow. Saturation of the polymer with water destabilizes the film when it is very thin.

Experimental investigation of the dissolution of quartz by a muscovite mica surface : implications for pressure solution

Using the surface forces apparatus, which can measure small changes in thickness occurring even at essentially geological timescales, we have measured dissolution of quartz sheets when pressed against muscovite mica surfaces in aqueous electrolyte solution, but no dissolution is observed under dry conditions. It is postulated that the dissolved quartz may reprecipitate outside the contact junction as a fragile silica gel, which could be the main factor limiting the rate of further dissolution.

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.

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 forces due to structure in hydrocarbon liquids

Direct measurements of the force between two molecularly smooth mica sheets immersed in cyclohexane show not a monotonic van der Waals attraction, but an oscillatory function of distance, where the spacing between successive minima corresponds to the molecular diameter of cyclohexane. As surface separation increases the oscillations become less pronounced, and beyond 5 nm (typically seven or eight oscillations) they are no longer detected. These results accord with theoretical ideas on structural forces resulting from the inhomogeneous arrangement of molecules of the liquid near the solid surface. In n-octane the force law does not show the same pronounced oscillations, except at very small separations where repulsive barriers are found. These are attributed to the difficulty of removing the last layers of adsorbed molecules of the liquid from the mica surfaces, and they reduce the mice-mica adhesion significantly. Small amounts of water in the hydrocarbon liquids condense to form a bridge between the surfaces at small separations, causing a very strong adhesion between them. Some implications of these results for the stability of colloids in organic media are discussed.

Thin film drainage : hydrodynamic and disjoining pressures determined from experimental measurements of the shape of a fluid drop approaching a solid wall

Accurate measurements of the shape of a mercury drop separated from a smooth flat solid surface by a thin aqueous film reported recently by Connor and Horn (Faraday Discuss. 2003, 123, 193-206) have been analyzed to calculate the excess pressure in the film. The analysis is based on calculating the local curvature of the mercury/aqueous interface, and relating it via the Young-Laplace equation to the pressure drop across the interface, which is the difference between the aqueous film pressure and the known internal pressure of the mercury drop. For drop shapes measured under quiescent conditions, the only contribution to film pressure is the disjoining pressure arising from double-layer forces acting between the mercury and mica surfaces. Under dynamic conditions, hydrodynamic pressure is also present, and this is calculated by subtracting the disjoining pressure from the total film pressure. The data, which were measured to investigate the thin film drainage during approach of a fluid drop to a solid wall, show a classical dimpling of the mercury drop when it approaches the mica surface. Four data sets are available, corresponding to different magnitudes and signs of disjoining pressure, obtained by controlling the surface potential of the mercury. The analysis shows that total film pressure does not vary greatly during the evolution of the dimple formed during the thin film drainage process, nor between the different data sets. The hydrodynamic pressure appears to adjust to the different disjoining pressures in such a way that the total film pressure is maintained approximately constant within the dimpled region.

Double-layer and solvation forces measured in a molten salt and its mixtures with water

Measurements have been made of the force between molecularly smooth mica surfaces immersed in ethylammonium nitrate, which is a molten salt at room temperature, and in mixtures of this salt with water across the concentration range from 10 -4 M to that of the pure salt, which is 11.2 M. At low concentrations the salt behaves as a typical 1:1 electrolyte, and we measure an electrical double-layer force whose range decreases with increasing salt concentration. At high concentrations, above about 1 M, the double-layer force becomes so weak and short-ranged that it is completely dominated by a solvation force extending up to 5 nm. In the pure molten salt the solvation force is an oscillatory function of surface separation comparable to that measured in simple nonpolar liquids. No monotonic component of solvation force is found.

Forces due to structure in a thin liquid crystal film

Measurements of the force as a function of distance between two solids separated by a liquid crystal film give information on the structure of the film. We report such measurements for two molecularly smooth surfaces of mica separated by the nematic liquid crystal 4'-n-pentyl 4-cyanobiphenyl (5CB) in both the planar and homeotropic orientations at room temperature. The force is determined by measuring the deflection of a spring supporting one of the mica pieces, while an optical technique is used to measure the film thickness to an accuracy of ± (0.1-0.2) nm. The technique also allows the refractive indices of the nematic to be measured, and hence a determination of the average density and order parameter of the liquid crystal film as a function of its thickness. Three distinct forces were measured, each reflecting a type of ordering of the liquid crystal near the mica surfaces. The first one results from elastic déformation in the liquid crystal ; it was only observed in a twisted planar sample where the 5CB molecules are oriented in different directions at the two mica surfaces. The second, measured in both the planar and homeotropic orientations, is attributed to an enhanced order parameter near the surfaces. Both of these are monotonic repulsive forces measurable below 80 nm. Finally, there is a short-range force which oscillates as a function of thickness, up to about six molecular layers, between attraction and repulsion. This results from ordering of the molecules in layers adjacent to the smooth solid surface. It is observed in both the planar and homeotropic orientations, and also in isotropic liquids.

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.

Force amplification response of actin filaments under confined compression

Actin protein is a major component of the cell cytoskeleton, and its ability to respond to external forces and generate propulsive forces through the polymerization of filaments is central to many cellular processes. The mechanisms governing actin's abilities are still not fully understood because of the difficulty in observing these processes at a molecular level. Here, we describe a technique for studying actin–surface interactions by using a surface forces apparatus that is able to directly visualize and quantify the collective forces generated when layers of noninterconnected, end-tethered actin filaments are confined between 2 (mica) surfaces. We also identify a force-response mechanism in which filaments not only stiffen under compression, which increases the bending modulus, but more importantly generates opposing forces that are larger than the compressive force. This elastic stiffening mechanism appears to require the presence of confining surfaces, enabling actin filaments to both sense and respond to compressive forces without additional mediating proteins, providing insight into the potential role compressive forces play in many actin and other motor protein-based phenomena.