Surface force-distance

Compared witii other direct force measurement teclmiques, 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 tliree measures (i) well defined contact geometry, (ii) high-resolution interferometric distance measurement and (iii) precise mechanics to control the separation between the surfaces. 

The measurement of surface forces calls for a rigid apparatus that exhibits a high force sensitivity as well as distance measurement and control on a subnanometre scale [38]. Most SFAs make use of an optical interference teclmique to measure distances and hence forces between surfaces. Alternative distance measurements have been developed in recent years—predominantly capacitive techniques, which allow for faster and simpler acquisition of an averaged distance [H, 39, 40] or even allow for simultaneous dielectric loss measurements at a confined interface. 

The accurate and absolute measurement of the distance, D, between the surfaces is central to the SFA teclmique. In a typical experiment, the SFA controls the base position, z, of the spring and simultaneously measures D, while the spring constant, k, is a known quantity. Ideally, the simple relationship A F(D) = IcA (D-z ) applies. Since surface forces are of limited range, one can set F(D = go) = 0 to obtain an absolute scale for the force. Furthennore, SF(D = cc)/8D 0 so that one can readily obtain a calibration of the distance control at large distances relying on an accurate measurement of D. Therefore, D and F are obtained at high accuracy to yield F(D), the so-called force versus distance cur >e. 

Frantz P, Agrait N and Salmeron M 1996 Use of capacitance to measure surface forces. 1. Measuring distance of separation with enhanced spacial and time resolution Langmuir 12 3289-94... 

When the film thickens beyond two or three molecular layers, the effect of surface structure is largely smoothed out. It should therefore be possible, as Hill and Halsey have argued, to analyse the isotherm in the multilayer region by reference to surface forces (Chapter 1), the partial molar entropy of the adsorbed film being taken as equal to that of the liquid adsorptive. By application of the 6-12 relation of Chapter 1 (with omission of the r" term as being negligible except at short distances) Hill was able to arrive at the isotherm equation... 

Fig. 8. (i) Surface force.s apparatus (SFA). The force between the two surfaces is measured by measuring the deflection of the leaf spring on which one of the surfaces is mounted. The distance between the surfaces is determined by measuring the wavelengths of interference fringes. 

Fig. 1. Schematic diagram illustrating the mechanical instability for (a) a weak spring (spring constant k) a distance D from the surface, experiencing an arbitrary surface force (after [19]) and (b) the experimentally observed force-distance curve relative to the AFM sample position (piezo displacement) for the same interaction.

Even the void fraction together with particle size distribution does not provide all of the necessary information on the kind of flow. The mutual forces between distinct particles depend not only on the distance between the particles but also on the surface properties of the particles. The strength of the attractive forces between particles depends on conditions. For instance, the moisture content of the solid is essential for determining the attractiv c forces between particles, especially for hydroscopic materials such as wood. Airflow between particles usually tends to separate particles, whereas the surface forces, adhesion forces, tend to bring them together. 

The surface force apparatus (SFA) is a device that detects the variations of normal and tangential forces resulting from the molecule interactions, as a function of normal distance between two curved surfaces in relative motion. SFA has been successfully used over the past years for investigating various surface phenomena, such as adhesion, rheology of confined liquid and polymers, colloid stability, and boundary friction. The first SFA was invented in 1969 by Tabor and Winterton [23] and was further developed in 1972 by Israela-chivili and Tabor [24]. The device was employed for direct measurement of the van der Waals forces in the air or vacuum between molecularly smooth mica surfaces in the distance range of 1.5-130 nm. The results confirmed the prediction of the Lifshitz theory on van der Waals interactions down to the separations as small as 1.5 nm. 

Force curve gives the relationship between the z-piezo displacement and the cantilever deflection as shown in Figure 21.10b. When a cantilever approaches to a stiff sample surface, cantilever deflection. A, is equal to the z-piezo displacement, z — Zo- The value of zo is defined as the position where the tip-sample contact is realized. On the other hand, z-piezo displacement becomes larger to achieve the preset trigger value (set point) of the cantilever deflection in the case of an elastic sample due to the deformation of the sample itself. In other words, we can obtain information about a sample deformation, 8, from the force-distance curve of the elastic surface by the following relationship ... 

NR with standard recipe with 10 phr CB (NR 10) was prepared as the sample. The compound recipe is shown in Table 21.2. The sectioned surface by cryo-microtome was observed by AFM. The cantilever used in this smdy was made of Si3N4. The adhesion between probe tip and sample makes the situation complicated and it becomes impossible to apply mathematical analysis with the assumption of Hertzian contact in order to estimate Young s modulus from force-distance curve. Thus, aU the experiments were performed in distilled water. The selection of cantilever is another important factor to discuss the quantitative value of Young s modulus. The spring constant of 0.12 N m (nominal) was used, which was appropriate to deform at rubbery regions. The FV technique was employed as explained in Section 21.3.3. The maximum load was defined as the load corresponding to the set-point deflection. 

The ratio (p/G) has the units of time and is known as the elastic time constant, te, of the material. Little information exists in the published literature on the rheomechanical parameters, p, and G for biomaterials. An exception is red blood cells for which the shear modulus of elasticity and viscosity have been measured by using micro-pipette techniques 166,68,70,72]. The shear modulus of elasticity data is usually given in units of N m and is sometimes compared with the interfacial tension of liquids. However, these properties are not the same. Interfacial tension originates from an imbalance of surface forces whereas the shear modulus of elasticity is an interaction force closely related to the slope of the force-distance plot (Fig. 3). Typical reported values of the shear modulus of elasticity and viscosity of red blood cells are 6 x 10 N m and 10 Pa s respectively 1701. Red blood cells typically have a mean length scale of the order of 7 pm, thus G is of the order of 10 N m and the elastic time constant (p/G) is of the order of 10 s. 

Surface forces measurement is a unique tool for surface characterization. It can directly monitor the distance (D) dependence of surface properties, which is difficult to obtain by other techniques. One of the simplest examples is the case of the electric double-layer force. The repulsion observed between charged surfaces describes the counterion distribution in the vicinity of surfaces and is known as the electric double-layer force (repulsion). In a similar manner, we should be able to study various, more complex surface phenomena and obtain new insight into them. Indeed, based on observation by surface forces measurement and Fourier transform infrared (FTIR) spectroscopy, we have found the formation of a novel molecular architecture, an alcohol macrocluster, at the solid-liquid interface. 

FIG. 8 Force-distance dependence for surfaces covered with fluorocarbon amphiphile 1 in pure water (1) and in aqueous solutions containing 0.7 mg/L poly (styrenesulfonate) (2) and 7.0 g/L poly (styrenesulfonate) (3). The molecular weight of the polymer is 5 X ICP. Lines are drawn as a visual guide. 

Although the DMT theory attempts to incorporate distance-dependent surface interactions into the adhesion problem, it does not take into account the effect surface forces have on the elastic deformation. In other words, it does not predict the neck formation predicted by JKR. 

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]. 

Here Tq is the unit vector perpendicular to the z-axis, and r is its distance to the point q. From this equation it follows that the sum of the two true forces represents the centripetal force. In other words, the distribution of the attraction and surface forces per unit volume ... 

Now we demonstrate one interesting feature of the magnitude of the surface force as a function of the latitude. First, assuming that the fluid Earth is almost a sphere with a radius a, we can represent the distance r as r — a cos 1. Then, Equation (2.18) has the form... 

FIGURE 6.9 Dependence of viscoelastic parameters on solvent quality. The (A) static force, (B) drag coefficient at 10 kHz, (C) dynamic spring constant, and (D) dispersion parameter are shown as a function of the surface-sphere distance. The results for water, propanol, and a 50/50 water/propanol mixture are given. Reprinted with permission from Benmouna and Johannsmann (2004). 

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