Surface apparatus

Figure 26.14 Schematic view of a molecular beam-surface apparatus, dedicatedtomeasuringquantum-stateresolved translational energy distribution for the product of a surface reaction. Two types of measurement can be taken (i) integral TOF distribution (i.e. non-state resolved) when one uses a quadrupole mass spectrometer (ii) state-re-solved TOF distribution when one uses laser excitation either to collect spedfic LIF or ion mass signals from REMPI detection. Reproduced from Hasselbrink et al, J. Chem. Phys., 1990, 92 3154, with permission of the American Institute of Physics...

Since the 1980s, the surface science community has developed techniques that probe the structure, composition, mechanical properties, and dynamics of surfaces at high pressure. The research activity on in situ surface characterization will be covered in Part 111. Several examples of high-pressure surface apparatuses are shown in Eig. 1.8. These include (a) high-pressure SFG vibration spectroscopy, (b) high-pressure STM, (c) high-pressure XPS, and (d) atomic force microscopy (AFM). 

Diffuse-reflection measurements are often used to study in situ reactions on catalyst surfaces. Apparatus for such studies are also commereially available, which make it possible to elevate the sample temperature in vacuum or in a stream of an appropriate gas. 

In this work, a microwave interferometric method and apparatus for vibration measurements is described. The principle of operation is based on measurement of the phase of reflected electromagnetic wave changing due to vibration. The most important features of the method are as follows simultaneous measurement of tlie magnitude and frequency of the rotating object high measurement accuracy weak influence of the roll diameter, shape and distance to the object under test. Besides, tlie reflecting surface can be either metallic or non-metallic. Some technical characteristics are given. 

Fig. 11-13. Apparatus for measuring the time dependence of interfacial tension (from Ref. 34). The air and aspirator connections allow for establishing the desired level of ftesh surface. IV denotes the Wilhelmy slide, suspended from a Cahn electrobalance with a recorder output.

The surface viscosity can be measured in a manner entirely analogous to the Poiseuille method for liquids, by determining the rate of flow of a film through a narrow canal under a two-dimensional pressure difference Ay. The apparatus is illustrated schematically in Fig. IV-7, and the corresponding equation for calculating rj is analogous to the Poiseuille equation [99,100]... 

For example, a wall or apparatus surface. For example, a colloidal particle. 

It has long been known that the form of a curved surface of mercury in contact with an electrolyte solution depends on its state of electrification [108, 109], and the earliest comprehensive investigation of the electrocapillary effect was made by Lippmann in 1875 [110]. A sketch of his apparatus is shown in Fig. V-10. 

Fig. V-17. Schematic diagram for the apparatus for measurement of Vobs (see text). The vibrating reference electrode is positioned close to the surface of a AgN03 solution in which there is an Ag electrode, which, in turn, is in electrical contact with the reference electrode. (From Ref. 196.)...

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.)...

While evidence for hydration forces date back to early work on clays [1], the understanding of these solvent-induced forces was revolutionized by Horn and Israelachvili using the modem surface force apparatus. Here, for the first time, one had a direct measurement of the oscillatory forces between crossed mica cylinders immersed in a solvent, octamethylcyclotetrasiloxane (OMCTS) [67]. 

The modification of the surface force apparatus (see Fig. VI-4) to measure viscosities between crossed mica cylinders has alleviated concerns about surface roughness. In dynamic mode, a slow, small-amplitude periodic oscillation was imposed on one of the cylinders such that the separation x varied by approximately 10% or less. In the limit of low shear rates, a simple equation defines the viscosity as a function of separation... 

The surface forces apparatus (Section VI-3C) has revealed many features of surfactant adsorption and its effect on the forces between adsorbent surfaces [180,181]. A recent review of this work has been assembled by Parker [182]. 

Friction can now be probed at the atomic scale by means of atomic force microscopy (AFM) (see Section VIII-2) and the surface forces apparatus (see Section VI-4) these approaches are leading to new interpretations of friction [1,1 a,lb]. The subject of friction and its related aspects are known as tribology, the study of surfaces in relative motion, from the Greek root tribos meaning mbbing. 

Klein and co-workers have documented the remarkable lubricating attributes of polymer brushes tethered to surfaces by one end only [56], Studying zwitterionic polystyrene-X attached to mica by the zwitterion end group in a surface forces apparatus, they found /i < 0.001 for loads of 100 and speeds of 15-450 nm/sec. They attributed the low friction to strong repulsions existing between such polymer layers. At higher compression, stick-slip motion was observed. In a related study, they compared the friction between polymer brushes in toluene (ji < 0.005) to that of mica in pure toluene /t = 0.7 [57]. 

The surface forces apparatus of crossed mica cylinders (Section VI-4D) has provided a unique measurement of friction on molecular scales. The apparatus is depicted in Fig. VI-3, and the first experiments involved imposing a variation or pulsing in the sepa-... 

The force between two adjacent surfaces can be measured directly with the surface force apparatus (SEA), as described in section BT20 [96]. The SEA can be employed in solution to provide an in situ detennination of the forces. Although this instmment does not directly involve an atomically resolved measurement, it has provided considerable msight mto the microscopic origins of surface friction and the effects of electrolytes and lubricants [97]. 

Kumacheva E 1998 Interfacial friction measurements in surface force apparatus Prog. Surf. Sc/. 58 75... 

Blakely D W, Kozak E I, Sexton B A and Somor]ai G A 1976 New instrumentation and techniques to monitor chemical surface reactions over a wide pressure range (10 to 10 Terr) in the same apparatus J. Vac. Sc/. Technol. 13 1091... 

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. 

Interactions between macromolecules (protems, lipids, DNA,.. . ) or biological structures (e.g. membranes) are considerably more complex than the interactions described m the two preceding paragraphs. The sum of all biological mteractions at the molecular level is the basis of the complex mechanisms of life. In addition to computer simulations, direct force measurements [98], especially the surface forces apparatus, represent an invaluable tool to help understand the molecular interactions in biological systems. 

Luckham P F and Manimaaran S 1997 Investigating adsorbed polymer layer behaviour using dynamic surface forces apparatuses—a review Adv. Coiioid interface Sc/. 73 1 -46... 

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