Surface force apparatus measurement techniques

As shown in Equation 10.4, the depression of the melting point of a given confined solvent is related to the geometry of the pores of the confining material. In principle, measurement of AT can give access to the pore size. Three main techniques have been developed to measure porosity in solids via the use of the Gibbs-Thomson equation thermoporosimetry, NMR cryporometry and surface force apparatus. These techniques are secondary methods since they require pre-... 

The surface forces apparatus measures the forces between surfaces of macroscopic dimensions. The requirement that large areas be brought to very small separations imposes demanding requirements on the flatness of the surfaces used and by far the majority of experiments with the SFA have used freshly cleaved mica as a surface that can be relied upon to be atomically smooth over macroscopic areas. The technique of scanning force microscopy allows the force between a tip of small radius of eurvature and virtually any kind of surface to be measured. In addition, the tip can be scanned over the surface to provide an image, which can be of very high resolution, of the force as a function of position. The drawbacks of the technique are that it is difficult to... 

Several properties of the filler are important to the compounder (279). Properties that are frequentiy reported by fumed sihca manufacturers include the acidity of the filler, nitrogen adsorption, oil absorption, and particle size distribution (280,281). The adsorption techniques provide a measure of the surface area of the filler, whereas oil absorption is an indication of the stmcture of the filler (282). Measurement of the sdanol concentration is critical, and some techniques that are commonly used in the industry to estimate this parameter are the methyl red absorption and methanol wettabihty (273,274,277) tests. Other techniques include various spectroscopies, such as diffuse reflectance infrared spectroscopy (drift), inverse gas chromatography (igc), photoacoustic ir, nmr, Raman, and surface forces apparatus (277,283—290). 

The surface forces apparatus (Section 2.3) enables the estimation of a surface energy term, Fq (Eq. 9), providing sufficiently smooth surfaces can be produced. In recent years Chaudhury, Pocius and colleagues have made a valuable contribution to the field of adhesion by developing the technique to study energies of adhesion and of surface energies of polymers [81-85]. These SFA results provide alternatives to values based on traditional destructive tests or contact angle measurements. 

Other, similar methods for measuring surface-surface interactions, which come under the generic heading of surface force apparatus, include the crossed-filament method. This utilizes a beam deflection technique similar to that now being used in some AFMs for the measurement of surface displacement [94]. Another technique for displacement measurement used in a similar SFA is that of a capacitance transducer. Both techniques suffer the criticism that separation is not measured at the point of interest, i.e., the gap between the two surfaces as measured in the FECO technique. 

The surface forces apparatus (SEA) can measure the interaction forces between two surfaces through a liquid [10,11]. The SEA consists of two curved, molecularly smooth mica surfaces made from sheets with a thickness of a few micrometers. These sheets are glued to quartz cylindrical lenses ( 10-mm radius of curvature) and mounted with then-axes perpendicular to each other. The distance is measured by a Fabry-Perot optical technique using multiple beam interference fringes. The distance resolution is 1-2 A and the force sensitivity is about 10 nN. With the SEA many fundamental interactions between surfaces in aqueous solutions and nonaqueous liquids have been identified and quantified. These include the van der Waals and electrostatic double-layer forces, oscillatory forces, repulsive hydration forces, attractive hydrophobic forces, steric interactions involving polymeric systems, and capillary and adhesion forces. Although cleaved mica is the most commonly used substrate material in the SEA, it can also be coated with thin films of materials with different chemical and physical properties [12]. 

The second device with which surface forces can be measured directly and relatively universally is the atomic force microscope (AFM) sometimes also called the scanning force microscope (Fig. 6.8) [143,144], In the atomic force microscope we measure the force between a sample surface and a microfabricated tip, placed at the end of an about 100 //,m long and 0.4-10 //,m thick cantilever. Alternatively, colloidal particles are fixed on the cantilever. This technique is called the colloidal probe technique . With the atomic force microscope the forces between surfaces and colloidal particles can be directly measured in a liquid [145,146], The practical advantage is that measurements are quick and simple. Even better, the interacting surfaces are substantially smaller than in the surface forces apparatus. Thus the problem of surface roughness, deformation, and contamination, is reduced. This again allows us to examine surfaces of different materials. 

The JKR theory predicts correct contact radii for relative soft surfaces with effective radii larger than 100 /an. This was shown in direct force measurements by the surface forces apparatus [217, 218] or specifically designed systems. For smaller spheres it was verified using the colloidal probe technique [219],... 

Example 11.4. McGuiggan et al. [492] measured the friction on mica surfaces coated with thin films of either perfluoropolyether (PFPE) or polydimethylsiloxane (PDMS) using three different methods The surface forces apparatus (radius of curvature of the contacting bodies R 1 cm) friction force microscopy with a sharp AFM tip (R 20 nm) and friction force microscopy with a colloidal probe (R 15 nm). In the surface force apparatus, friction coefficients of the two materials differed by a factor of 100 whereas for the AFM silicon nitride tip, the friction coefficient for both materials was the same. When the colloidal probe technique was used, the friction coefficients differed by a factor of 4. This can be explained by the fact that, in friction force experiments, the contact pressures are much higher. This leads to a complete penetration of the AFM tip through the lubrication layer, rendering the lubricants ineffective. In the case of the colloidal probe the contact pressure is reduced and the lubrication layer cannot be displaced completely. 

Until fairly recently, the theories described in Secs. II and III for particle-surface interactions could not be verified by direct measurement, although plate-plate interactions could be studied by using the surface forces apparatus (SFA) [61,62]. However, in the past decade two techniques have been developed that specifically allow one to examine particles near surfaces, those being total internal reflection microscopy (TIRM) and an adapted version of atomic force microscopy (AFM). These two methods are, in a sense, complementary. In TIRM, one measures the position of a force-and torque-free, colloidal particle approximately 7-15 fim in dimension as it interacts with a nearby surface. In the AFM method, a small (3.5-10 jam) sphere is attached to the cantilever tip of an atomic force microscope, and when the tip is placed near a surface, the force measured is exactly the particle-surface interaction force. Hence, in TIRM one measures the position of a force-free particle, while in AFM one measures the force on a particle held at a fixed position. 

The advent of the atomic force microscope has allowed surface properties at nearly molecular length scales to be measured directly for the first time. Recently, a method has been proposed whereby a small ( 3.5 /nn) particle is attached to the cantilever tip of the commercially available, Nanoscope II AFM [67,68]. The particles are attached with an epoxy resin. When the cantilever tip is placed close to a planar surface, the AFM measures directly the interaction force between the particle and the surface. A primary difference between this technique and the surface forces apparatus (SFA) is the size of the substrates, since the SFA generally requires smooth surfaces approximately 2 cm in diameter. Other differences are discussed by Ducker et al. [68]. For our purposes, it suffices to note that the AFM method explicitly incorporates the particle-wall geometry that is the focus of this chapter. 

Intercalated compounds offer a unique avenue for studying the static and dynamic properties of small molecules and macromolecules in a confined environment. More specifically, layered nanocomposites are ideal model systems to study small molecule and polymer dynamics in restrictive environments with conventional analytical techniques, such as thermal analysis, NMR, dielectric spectroscopy and inelastic neutron scattering. Understanding the changes in the dynamics due to this extreme confinement (layer spacing < Rg and comparable to the statistical segment length of the polymer) would provide complementary information to those obtained from traditional Surface-Force Apparatus (SFA) measurements on confined polymers (confinement distances comparable to Rp [36]. 

A more recently developed force measurement technique, coined the liquid surface force apparatus (LSFA), brings a drop made from a micropipette close to a flat liquid/liquid interface [29-32]. A piezo electric drive is used to change the position of the micropipette while the deflection of the pipette and the radius of the drop are recorded with piezo motion. The drop radius and thus the film thickness between the two liquid/liquid interfaces are recorded using interferometry. The method requires a calibration of the interferometer, where the drop must come into contact with the other liquid interface. The distance resolution of the film is about 1 nm at a 50-nm separation and 5 nm at a separation of 10 nm. This is a very robust technique where the authors have proposed attaching a particle to the end of the pipette instead of a drop [29]. In comparing this method to AFM, the only drawback of the LSFA is the weaker distance resolution. It is important point out that both methods required a contact point for distance calibration. 

In the last 40 years, techniques to directly measure surface forces and force laws (force vs. separation distance between surfaces) have been developed such as the surface forces apparatus (SFA) [6] and AFM. Surface forces are responsible for the work required when two contacting bodies (such as an AFM tip in contact with a solid surface) are separated from contact to infinite distance. Although the physical origin of all relevant surface forces can be derived from fundamental electromagnetic interactions, it is customary to group these in categories based on characteristic features that dominate the relevant physical behavior. Thus, one speaks of ionic (monopole), dipole—dipole, ion—dipole interactions, electrostatic multipole forces (e.g., quadrupole), induced dipolar forces, van der Waals (London dispersive) interactions, hydrophobic and hydrophilic solvation, structural and hydration forces,... 

Basically two different types of experimental approaches have been used to study the boundary shp local (direct) [45,60] and effective (indirect) methods [49-52,61]. The first group of methods is based on apphcation of optical techniques using tracer particles or molecules to determine the flow field. These techniques have a resolution of less than lOOnm, so they cannot distinguish small differences in slip lengths. The effective methods assume the boundary conditions (Eq. 18) or similar ones to hold at the substrate surface and infer the slip length by measuring macroscopic quantities. These methods have been the most popular so far and they include atomic force microscopy (AFM), surface force apparatus (SEA), capillary techniques, and QCM. 

Compared with other direet foree measurement techniques, a unique aspect of the surface forces apparatus (SFA) is to allow quantitative measurement of surface forces and intermolecular potentials. This is made possible by essentially three measures (i) well defined contact geometry, (ii) high-resolution interferometric distance measurement and (iii) precise mechanics to control the separation between the surfaces. 

We have not discussed in detail experiments on interaction between surfaces mediated by a polymer solution. There exist now many experiments probing the interaction between two surfaces in a polymer solution both when the polymer adsorbs and when the polymer is grafted. The earliest experiments were performed using a surface forces apparatus and measuring the interactions between mica surfaces [38]. More recently, experiments have been performed using other techniques such as atomic force microscopy... 

The overall conclusion was that adhesion energetics in liquids could be readily undCTStood by this technique. However, the adhesion forces varying with separation were not easy to measure by this method, because of the large deformations across the contact. Force measurement required the surface force apparatus of Israelachvili, to maintain the surfaces in rigid cylindrical form and to keep a known gap between the surfaces. 

Several properties of surfaces have origins that are very sensitive to the surface, but are essentially macroscopic in character. Examples include adhesion, surface tension and the contact angle. Techniques to measure these properties are not discussed in this chapter, but rather are mentioned in connection with discussions of the property involved elsewhere in this book. However, surface properties can also be probed at a microscopic level for example the forces between surfaces at microscopic separations may be probed using the surface forces apparatus (SFA). The scanning force microscope... 

Measurement of interfacial forces thus offers the potential to study the factors involved in protein repellence or adsorption. Force measurements on adsorbed and grafted PEG layers have been reported, using both the surface forces apparatus (SFA) and the colloid-probe atomic force microscopy (AFM) technique. - Adsorbed PEG layers show responses due to relaxation processes,... 

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