Other Surface Forces Measuring Techniques

Up to date, besides the SFA, several non-interferometric techniques have been developed for direct measurements of surface forces between solid surfaces. The most popular and widespread is atomic force microscopy, AFM [14]. This technique has been refined for surface forces measurements by introducing the colloidal probe technique [15,16], The AFM colloidal probe method is, compared to the SFA, rapid and allows for considerable flexibility with respect to the used substrates, taken into account that there is no requirement for the surfaces to be neither transparent, nor atomically smooth over macroscopic areas. However, it suffers an inherent drawback as compared to the SFA It is not possible to determine the absolute distance between the surfaces, which is a serious limitation, especially in studies of soft interfaces, such as, e.g., polymer adsorption layers. Another interesting surface forces technique that deserves attention is measurement and analysis of surface and interaction forces (MASIF), developed by Parker [17]. This technique allows measurement of interaction between two macroscopic surfaces and uses a bimorph as a force sensor. In analogy to the AFM, this technique allows for rapid measurements and expands flexibility with respect to substrate choice however, it fails if the absolute distance resolution is required. 

It is appropriate to mention here that the SFA and other techniques available for measuring surface forces have been reviewed before and the interested reader is referred to some excellent papers [9,18-20]. 

Since the beginning, the SFA technique experienced major interest from the scientific community, due to the opportunities that it has opened in surface chemical science. It has been used extensively for studying various systems, and along with this it has been developed to answer increasingly complex scientific questions. Today several types of the SFA are available, all suited for specific surface chemistry purposes. The SFA Mark II [4,5] and Mark IV [21] (see Fig. 2) were particularly designed for measuring forces acting normal to the surfaces. 

In fact, the SFA was initially developed for practically probing the DLVO theory, and DLVO forces were successfully measured in electrolyte solutions and colloidal systems [4,22]. However, the applications of the apparatus were not restricted to this. Detailed and accurate information was obtained on thickness and refractive index profiles of thin films [6], simple liquid molecular structuring 

the SFA was developed to suit an even broader range of measurements, and in 1985 Israelachvili reported a set-up of the SFA with vibrating upper surface suited for viscosity measurements of liquids confined between the surfaces [37]. 

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In this present chapter, we will describe the types of surface forces which can be expected in different types of systems (classified by conditions rather than as a description of different types of forces) and will concentrate primarily on three types of surface force measuring techniques. These are the SFA of Israelachvili (and as modified by others) (44-46), the AFM colloid probe technique (these two techniques are by far the most widely exploited), and the MASIF technique which provides high-resolution data from a purpose-built non-interferometric instrument. 

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. 

In this section, we present a few examples of instruments available for visual observation and imaging of colloids and surfaces, for measurement of sizes and for surface force measurements. Such a presentation can hardly be comprehensive in fact, that is not our purpose here. Throughout the book, we discuss numerous other techniques such as osmotic pressure measurements, light and other radiation scattering techniques, surface tension measurements,... 

The interferometric SFA has served as an invaluable tool in studying the hydrophobic attraction among other things due to the fact that it is the only technique available today that enables direct observation of occurrence of cavitation. For instance, recently Lin et al. [89] employed a dynamic surface forces measurement method to study interactions between DODAB LB coated surfaces. High-speed camera images of FECO revealed that there are no bubbles on the surfaces prior to contact. However, short-lived cavities, typically lasting 3 ps before disappearing, have been observed to form upon separation (Fig. 6). 

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. 

The forces measured between the AFM tip and the PCMA coated mica surface across a 1 cmc (8.3 X 10 3 M) SDS solution are shown in Figure 12. At repulsive double-layer force dominates the long-range interaction, whereas two pronounced steps with a periodicity of 40 A are observed at small separations. We can thus conclude that the adsorbed layer is heterogeneous both parallel and perpendicular to the surface. Two other surface force techniques, the MASIF and the SFA, were used to explore this further. 

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. 

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). 

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]. 

In addition, there are techniques developed in other fields of colloid science, which are not directly related to classical electrochemistry. In surface force experiments, for instance, the distance dependence of the electric double layer is measured precisely. This will be discussed later. 

If several nuclei could be observed in high-resolution NMR techniques to monitor similarities or differences in both chemical shifts or integrals, other parameters can be monitored by using LF 1H NMR. In this case, relaxation parameters are usually measured as intrinsic discriminating values. As pointed out in several studies, T2 relaxation decay has a multiexponential decay in both muscles and fish tissues. This suggests the presence of different "pools" in tissues and water distribution was assumed to be present in three distinct compartments, namely (a) "bound water," (b) "entrapped water," and (c) "free water." In those three pools, water acts with different relaxation times because it can be bound to proteins, involved in the conversion of muscle to meat and entrapped by weak surface forces, showing relaxation values in the range of 1-10,10-100, and 100-400 ms, respectively. 

Complementary to the SFA experiments, SFM techniques enabled direct, non-destructive and non-contact measurement of forces which can be as small as 1 pN. Compared to other probes such as optical tweezers, surface force balance and osmotic stress [378-380], the scanning force microscope has an advantage due to its ability in local force measurements on heterogeneous and rough surfaces with excellent spatial resolution [381]. Thus, a force-distance dependence measured from a small surface area provides a microscopic basis for understanding the macroscopic interfacial properties. Furthermore, lateral mapping... 

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. 

In order to understand the nature of surface forces which characterise the thermodynamic state of black foam films as well as to establish the CBF/NBF transition, their direct experimental determination is of major importance. This has been first accomplished by Exerowa et al. [e.g. 171,172] with the especially developed Thin Liquid Film-Pressure Balance Technique, employing a porous plate measuring cell (see Section 2.1.8). This technique has been applied successfully by other authors for plotting 11(A) isotherms of foam films from various surfactants solutions [e.g. 235,260,261]. As mentioned in Chapter 2, Section 2.1.2, the Pressure Balance Technique employing the porous ring measuring cell has been first developed by Mysels and Jones [262] for foam films and a FI(A) isotherm was... 

Since it utilizes a force instead of a current, the technique is capable of imaging both conducting and nonconducting materials. AFM can make three-dimensional quantitative measurements with a higher resolution and on a wider variety of materials than any other surface characterization methods. 

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