Surface viscosity effect

The surface viscosity effect on terminal velocity results in a calculated drag curve that is closer to the one for rigid spheres (K5). The deep dip exhibited by the drag curve for drops in pure liquid fields is replaced by a smooth transition without a deep valley. The damping of internal circulation reduces the rate of mass transfer. Even a few parts per million of the surfactant are sometimes sufficient to cause a very radical change. 

With quantitative relationships among surface velocity, the geometric parameters, the substrate fluid viscosity, and the floor speed, this arrangement not only demonstrates surface viscosity effects but also provides a means for its measurement. 

With respect to the rheological parameters fliey come to the conclusion that surface elasticity effects are superior to surface viscosity effects. This, however, apphes to pure surfactant layers and may be different for pure protein or mixed surfactant/protein adsorption layers. It has been stressed also by Langevin (26), in her review on foams and emulsions, fliat studies on the dynamics of adsorption and dilational rheology studies for mixed systems, in particular surfactant-polymer systems, are desirable in order to understand these most common stabilizing systems. 

Let us first consider the case of System II (surfactant inside the drops, Fig. 15b) in which case the two drops approach each other like drops from pure liquid phases (if only the surface viscosity effect is negligible). Therefore, to estimate the velocity of approach of such two aqueous droplets one can use the following approximate expression, which directly follows from Eq. (49) for 1 ... 

The complete mathematical expression for the double layer incorporating the Stern layer is quite complex and will not be given here. However, its existence and related effects are quite significant for practical studies of electro-kinetic phenomena discussed below because it is if/s that is actually being estimated in such procedures. When a charged particle moves relative to an electrolyte solution, or a solution moves relative to a charged surface, viscosity effects dictate that only that portion of the electrical double layer up to (approximately) the Stern layer will move. The ions in the Stern layer will remain with the surface. The dividing line between movement with the solution and that with the surface is referred to as the shear plane (Fig. 5.6). The exact... 

The drop in pressure when a stream of gas or liquid flows over a surface can be estimated from the given approximate formula if viscosity effects are ignored. The example calculation reveals that, with the sorts of gas flows common in a concentric-tube nebulizer, the liquid (the sample solution) at the end of the innermost tube is subjected to a partial vacuum of about 0.3 atm. This vacuum causes the liquid to lift out of the capillary, where it meets the flowing gas stream and is broken into an aerosol. For cross-flow nebulizers, the vacuum created depends critically on the alignment of the gas and liquid flows but, as a maximum, it can be estimated from the given formula. 

Rizzuti et al. [Chem. Eng. Sci, 36, 973 (1981)] examined the influence of solvent viscosity upon the effective interfacial area in packed columns and concluded that for the systems studied the effective interfacial area a was proportional to the kinematic viscosity raised to the 0.7 power. Thus, the hydrodynamic behavior of a packed absorber is strongly affected by viscosity effects. Surface-tension effects also are important, as expressed in the work of Onda et al. (see Table 5-28-D). 

The effective surface viscosity is best found by experiment with the system in question, followed by back calculation through Eq. (22-55). From the precursors to Eq. (22-55), such experiments have yielded values of [L, on the order of (dyn-s)/cm for common surfactants in water at room temperature, which agrees with independent measurements [Lemhch, Chem. Eng. ScL, 23, 932 (1968) and Shih and Lem-lich. Am. Inst. Chem. Eng. J., 13, 751 (1967)]. However, the expected high [L, for aqueous solutions of such sldn-forming substances as saponin and albumin was not attained, perhaps because of their non-newtonian surface behavior [Shih and Lemhch, Ind. Eng. Chem. Fun-dam., 10, 254 (1971) andjashnani and Lemlich, y. Colloid Inteiface ScL, 46, 13(1974)]. 

In large tubes, as well as in tubes of a few millimeters in diameter, two-phase flow patterns are dominated in general by gravity with minor surface tension effects. In micro-channels with the diameter on the order of a few microns to a few hundred microns, two-phase flow is influenced mainly by surface tension, viscosity and inertia forces. The stratified flow patterns commonly encountered in single macro-channels were not observed in single micro-channels. 

This has been verified for polydimethylsiloxanes added to crude oils. The effect of the dilatational elasticities and viscosities on crude oil by the addition of polydimethylsiloxanes is shown in Table 21-1. Under nonequilibrium conditions, both a high bulk viscosity and a surface viscosity can delay the film thinning and the stretching deformation, which precedes the destruction of a foam. There is another issue that concerns the formation of ordered structures. The development of ordered structures in the surface film may also stabilize the foams. Liquid crystalline phases in surfaces enhance the stability of the foam. 

The superficial gas velocity Og is G/A, where A is the horizontal cross-sectional area of the empty vertical foam column. Also, g is the acceleration of gravity, p is the liquid density, p is the ordinary liquid viscosity and p, is the effective surface viscosity. 

Figure 8. The effect of surface viscosity on the critical capillary pressure.

The dynamic surface tension of a monolayer may be defined as the response of a film in an initial state of static quasi-equilibrium to a sudden change in surface area. If the area of the film-covered interface is altered at a rapid rate, the monolayer may not readjust to its original conformation quickly enough to maintain the quasi-equilibrium surface pressure. It is for this reason that properly reported II/A isotherms for most monolayers are repeated at several compression/expansion rates. The reasons for this lag in equilibration time are complex combinations of shear and dilational viscosities, elasticity, and isothermal compressibility (Manheimer and Schechter, 1970 Margoni, 1871 Lucassen-Reynders et al., 1974). Furthermore, consideration of dynamic surface tension in insoluble monolayers assumes that the monolayer is indeed insoluble and stable throughout the perturbation if not, a myriad of contributions from monolayer collapse to monomer dissolution may complicate the situation further. Although theoretical models of dynamic surface tension effects have been presented, there have been very few attempts at experimental investigation of these time-dependent phenomena in spread monolayer films. 

In order to verify the importance of surface tension, a large amount of data has been collected for bubble formation in liquids having different surface tension but nearly constant viscosity. Liquids of both low and high viscosity have been used. The equation is seen to agree excellently with the data obtained over a wide range of flow rates. It was also observed that for highly viscous liquids the surface-tension effects become negligible at much smaller flow rates. 

The influence of orifice geometry is closely associated with that of overall surface-tension force. From Sections IV and V, however, it is evident that the surface-tension effects are limited to small flow rates, the actual value of the flow rate where the effect becomes absent being dependent on viscosity... 

A high proportion of the complex phenomena shown by emnlsions and foams, which are common when petroleum enters the environment, can be traced to these induced surface-tension effects. Dissolved gases, even hydrocarbon gases, lower the surface tension of oils, but the effects are less dramatic and the changes probably result from dilution. The matter is of some importance in environmental issues because the viscosity and surface tension of the petroleum govern the amount of oil that migrates or can be recovered under certain conditions. 

The steep thermal gradient along the tube means that any variation in the sample position (e.g. because of pipetting, or spreading due to surface tension and viscosity effects) will alter the atomization peak shape. Peak area integration will help to minimize this problem, as will a rapid heating ramp and isothermal operation (see Sections 3.6.2 and 3.6.3). 

The pressures inside and outside of the void are effectively equal until the resin viscosity becomes so high that viscous effects become important. As the resin proceeds toward solidification, the pressure in the void can rise significantly above the resin pressure. Surface tension effects are also negligible for voids larger than 100 pm. 

The presence of a thermodynamically incompatible polysaccharide in the aqueous phase can enhance the effective protein emulsifying capacity. The greater surface activity of the protein in the mixed biopolymer system facilitates the creation of smaller emulsion droplets, i.e., an increase in total surface area of the freshly prepared emulsion stabilized by the mixture of thermodynamically incompatible biopolymers (see Figure 3.4) (Dickinson and Semenova, 1992 Semenova el al., 1999a Tsapkina et al., 1992 Makri et al., 2005). It should be noted, however, that some hydrocolloids do cause a reduction in the protein emulsifying capacity by reducing the protein adsorption efficiency as a result of viscosity effects. 

Figure 8.12 illustrates the effect of complex formation between protein and polysaccharide on the time-dependent surface shear viscosity at the oil-water interface for the system BSA + dextran sulfate (DS) at pH = 7 and ionic strength = 50 mM. The film adsorbed from the 10 wt % solution of pure protein has a surface viscosity of t]s > 200 mPa s after 24 h. As the polysaccharide is not itself surface-active, it exhibited no measurable surface viscosity (t]s < 1 niPa s). But, when 10 wt% DS was introduced into the aqueous phase below the 24-hour-old BSA film, the surface viscosity showed an increase (after a further 24 h) to a value around twice that for the original protein film. Hence, in this case, the new protein-polysaccharide interactions induced at the oil-water interface were sufficiently strong to influence considerably the viscoelastic properties of the adsorbed biopolymer layer. 

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