Surfaces separation measurement

Fig. 15. Force nomalised by radius as a function of surface separation measured on approach (A) and separation (A). The separation curve is graphically offset by 5mN/m for clarity. The picture shows magnified region of the surface forces curve. The inset shows the entire surface forces curve. Reprinted with permission from Ref. [159]. 2004 American Chemical Society.

Figure 20.10. Force normalized by radius as a function of surface separation measured between mica surfaces across aqueous Nal solutions, with concentrations of 0.3mM ( ), 3mA/ ( ) and 30mM (A). The lines are theoretically calculated DLVO forces using constant-charge boundary conditions, with Debye lengths in accordance with the electrolyte concentration and surface charge densities (surface potentials on isolated surfaces) of 4.1 mC/m (74 mV) 15 mC/m (81 mV) and 34 mC/m (66 mV), respectively (112)...

Routine production tests are performed, approximately once per month on each producing well, by diverting the production through the test separator on surface to measure the liquid flowrate, water cut, and gas production rate. The wellhead pressure (also called the flowing tubing head pressure, FTHP) is recorded at the time of the production test, and a plot of production rate against FTHP is made. The FTHP is also recorded continuously and used to estimate the well s production rate on a daily basis by reference to the FTHP vs production rate plot for the well. 

A major advance in force measurement was the development by Tabor, Win-terton and Israelachvili of a surface force apparatus (SFA) involving crossed cylinders coated with molecularly smooth cleaved mica sheets [11, 28]. A current version of an apparatus is shown in Fig. VI-4 from Ref. 29. The separation between surfaces is measured interferometrically to a precision of 0.1 nm the surfaces are driven together with piezoelectric transducers. The combination of a stiff double-cantilever spring with one of a number of measuring leaf springs provides force resolution down to 10 dyn (10 N). Since its development, several groups have used the SFA to measure the retarded and unretarded dispersion forces, electrostatic repulsions in a variety of electrolytes, structural and solvation forces (see below), and numerous studies of polymeric and biological systems. 

Fig. VI-4. Illustration of the surface force apparatus with the crossed-cylinder geometry shown as an inset. The surface separations are determined from the interference fringes from white light travelling vertically through the apparatus. At each separation, the force is determined from the deflection in the force measuring spring. For solution studies, the entire chamber is filled with liquid. (From Ref. 29.)...

Other SFA studies complicate the picture. Chan and Horn [107] and Horn and Israelachvili [108] could explain anomalous viscosities in thin layers if the first layer or two of molecules were immobile and the remaining intervening liquid were of normal viscosity. Other inteipretations are possible and the hydrodynamics not clear, since as Granick points out [109] the measurements average over a wide range of surface separations, thus confusing the definition of a layer thickness. McKenna and co-workers [110] point out that compliance effects can introduce serious corrections in constrained geometry systems. 

The molecular constants that describe the stnicture of a molecule can be measured using many optical teclmiques described in section A3.5.1 as long as the resolution is sufficient to separate the rovibrational states [110. 111 and 112]. Absorption spectroscopy is difficult with ions in the gas phase, hence many ion species have been first studied by matrix isolation methods [113], in which the IR spectrum is observed for ions trapped witliin a frozen noble gas on a liquid-helium cooled surface. The measured frequencies may be shifted as much as 1 % from gas phase values because of the weak interaction witli the matrix. 

The well defined contact geometry and the ionic structure of the mica surface favours observation of structural and solvation forces. Besides a monotonic entropic repulsion one may observe superimposed periodic force modulations. It is commonly believed that these modulations are due to a metastable layering at surface separations below some 3-10 molecular diameters. These diflftise layers are very difficult to observe with other teclmiques [92]. The periodicity of these oscillatory forces is regularly found to correspond to the characteristic molecular diameter. Figure Bl.20.7 shows a typical measurement of solvation forces in the case of ethanol between mica. 

Energy of Adhesion. The iaterfacial energy between two mutually insoluble saturated Hquids, A and B, is equal to the difference in the separately measured surface energies of each phase ... 

See 2-3.1. Electrical conduction through solids takes place both through the bulk material and over the surface. In most cases surfaces have different physical and chemical properties than the bulk, for example due to contamination or moisture. Volume and surface resistivity can be separately measured for solid materials such as antistatic plastic sheet. Powders represent a special case since although both surface and bulk conduction occur, their contributions cannot be individually measured and the volume or bulk resistivity of a powder includes surface effects. 

If, for the purpose of comparison of substrate reactivities, we use the method of competitive reactions we are faced with the problem of whether the reactivities in a certain series of reactants (i.e. selectivities) should be characterized by the ratio of their rates measured separately [relations (12) and (13)], or whether they should be expressed by the rates measured during simultaneous transformation of two compounds which thus compete in adsorption for the free surface of the catalyst [relations (14) and (15)]. How these two definitions of reactivity may differ from one another will be shown later by the example of competitive hydrogenation of alkylphenols (Section IV.E, p. 42). This may also be demonstrated by the classical example of hydrogenation of aromatic hydrocarbons on Raney nickel (48). In this case, the constants obtained by separate measurements of reaction rates for individual compounds lead to the reactivity order which is different from the order found on the basis of factor S, determined by the method of competitive reactions (Table II). Other examples of the change of reactivity, which may even result in the selective reaction of a strongly adsorbed reactant in competitive reactions (49, 50) have already been discussed (see p. 12). 

Hill et al. [117] extended the lower end of the temperature range studied (383—503 K) to investigate, in detail, the kinetic characteristics of the acceleratory period, which did not accurately obey eqn. (9). Behaviour varied with sample preparation. For recrystallized material, most of the acceleratory period showed an exponential increase of reaction rate with time (E = 155 kJ mole-1). Values of E for reaction at an interface and for nucleation within the crystal were 130 and 210 kJ mole-1, respectively. It was concluded that potential nuclei are not randomly distributed but are separated by a characteristic minimum distance, related to the Burgers vector of the dislocations present. Below 423 K, nucleation within crystals is very slow compared with decomposition at surfaces. Rate measurements are discussed with reference to absolute reaction rate theory. 

FIGURE 9.4 The direct force measurement apparatus shown here ean measure the forees between two eurved molecularly smooth surfaces in liquids. Mica surfaces, either raw or eoated, are the primary surfaees used in this apparatus. The separation between the surfaces is measured by optieal teehniques to better than 10 nm. The distance between the two surfaces is controlled by a three-stage meehanism that ineludes a voltage-driven piezoelectric crystal tube supporting the upper mica surface this crystal tube can be displaced less than 10 nm in a controlled fashion. A force-measuring spring is attached to the lower mica surface and its stiffness can be varied by a factor of 1,000 by shifting the position of a movable clamp. Reprinted with permission from Proc. Natl. Acad Sci. USA, 84, July 1987, 4722. 

Another remarkable feature of thin film rheology to be discussed here is the quantized" property of molecularly thin films. It has been reported [8,24] that measured normal forces between two mica surfaces across molecularly thin films exhibit oscillations between attraction and repulsion with an amplitude in exponential growth and a periodicity approximately equal to the dimension of the confined molecules. Thus, the normal force is quantized, depending on the thickness of the confined films. The quantized property in normal force results from an ordering structure of the confined liquid, known as the layering, that molecules are packed in thin films layer by layer, as revealed by computer simulations (see Fig. 12 in Section 3.4). The quantized property appears also in friction measurements. Friction forces between smooth mica surfaces separated by three layers of the liquid octamethylcyclotetrasiloxane (OMCTS), for example, were measured as a function of time [24]. Results show that friction increased to higher values in a quantized way when the number of layers falls from n = 3 to n = 2 and then to M = 1. 

Fig. 9—Forces between mica surfaces in a process of separation, measured on SFA. Showing a linear increase in adhesion force, followed by a sudden separation and vibration [7].

Surface forces measurement directly determines interaction forces between two surfaces as a function of the surface separation (D) using a simple spring balance. Instruments employed are a surface forces apparatus (SFA), developed by Israelachivili and Tabor [17], and a colloidal probe atomic force microscope introduced by Ducker et al. [18] (Fig. 1). The former utilizes crossed cylinder geometry, and the latter uses the sphere-plate geometry. For both geometries, the measured force (F) normalized by the mean radius (R) of cylinders or a sphere, F/R, is known to be proportional to the interaction energy, Gf, between flat plates (Derjaguin approximation). 

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. 

All the analytical methods mentioned to separate, identify, and quantify chlorophylls and derivatives consume time, money, and samples. As alternatives, industries have been employing non-destructive methods for surface color measurements that are not only indirectly related to chlorophyll content, but may also estimate the pigments directly in tissues, leaving the sample intact and enabling serial analyses in a relatively short time. Eood color affects consumer acceptance and is an important criterion for quality control. Color vision is a complex phenomenon that depends on both the total content and number of pigments and also on absorption, reflectance and emission spectra of each compound present. 

Figure 5.6 Capacity versus potential measurements on the lifting of surface reconstruction of Au(lOO) in 0.1 M H2SO4 [Kolb, 1996]. Whereas below 0.55 V the sohd curve of Au(100)-hex more or less coincides with separate measurements on Au(l 11) (dashed curve), increasing the potential above +0.55 V lifts the reconstruction and gives Au(100)-(1 x 1) (dotted curve).

The SH signal directly scales as the square of the surface concentration of the optically active compounds, as deduced from Eqs. (3), (4), and (9). Hence, the SHG technique can be used as a determination of the surface coverage. Unfortunately, it is very difficult to obtain an absolute calibration of the SH intensity and therefore to determine the absolute number for the surface density of molecules at the interface. This determination also entails the separate measurement of the hyperpolarizability tensor jS,-, another difficult task because of local fields effects as the coverage increases [53]. However, with a proper normalization of the SH intensity with the one obtained at full monolayer coverage, the adsorption isotherm can still be extracted through the square root of the SH intensity. Such a procedure has been followed at the polarized water-DCE interface, for example, see Fig. 3 in the case of 2-( -octadecylamino)-naphthalene-6-sulfonate (ONS) [54]. The surface coverage 6 takes the form ... 

Contact angle measurements for a water droplet on an asphaltene modified borosilicate surface confirmed that low concentrations of TFSA molecules change the wettability of the surface from fractionally-wet to water-wet. Table II shows the results of the contact angle measurements all reported results are the average of 10 separate measurements, none of which varied from the mean by more than 5° As the concentration of the TFSA... 

A sharp decrease in adsorption enthalpy between 10 and 30% surface coverage of SAL can also be seen in Figure 2. This decrease may indicate that only a small number of surface sites are favorably oriented for SAL-goethite bond formation, although possible SAL-SAL interactions on the surface may also have an effect. Separate measurements of SAL adsorption on goethite, gave relatively small adsorption maxima (when compared to the phosphate and fluoride adsorption maxima discussed above) of 22 and 11 pmol/g at pH 4.8 and 6.3, respectively, in either 0.001 M NaN0 or 0.001 M KC1 06). J... 

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