Surface maximum bubble method

The maximum bubble pressure method is good to a few tenths percent accuracy, does not depend on contact angle (except insofar as to whether the inner or outer radius of the tube is to be used), and requires only an approximate knowledge of the density of the liquid (if twin tubes are used), and the measurements can be made rapidly. The method is also amenable to remote operation and can be used to measure surface tensions of not easily accessible liquids such as molten metals [29]. 

Hsu and Berger [43] used the maximum bubble pressure method (MBP) to study the dynamic surface tension and surface dilational viscosity of various surfactants including AOS and have correlated their findings to time-related applications such as penetration and wetting. A recent discussion of the MBP method is given by Henderson et al. [44 and references cited therein]. 

Surface tension of the nonpolarized ITIES was investigated by using the drop-weight [2,3,29], maximum bubble pressure [30] and pendant drop [4] methods. The latter method... 

There are numerous other methods for measuring surface tension that we do not discuss here. These include (a) the measurement of the maximum pressure beyond which an inert gas bubble formed at the tip of a capillary immersed in a liquid breaks away from the tip (the so-called maximum bubble-pressure method) (b) the so-called drop-weight method, in which drops of a liquid (in a gas or in another liquid) formed at the tip of a capillary are collected and weighed and (c) the ring method, in which the force required to detach a ring or a loop of wire is measured. In all these cases, the measured quantities can be related to the surface tension of the liquid through simple equations. The basic concepts involved in these methods do not differ significantly from what we cover in this chapter. The experimental details may be obtained from Adamson (1990). 

Several other methods for determining 7 —notably, the maximum bubble pressure, the drop weight, and the DuNouy ring methods (see Section 6.2) —all involve measurements on surfaces with axial symmetry. Although the Bashforth-Adams tables are pertinent to all of these, the data are generally tabulated in more practical forms that deemphasize the surface profile. 

Figure D3.5.6 Adsorption kinetics of a small molecule surfactant. Surface tension of polyoxyethylene (10) lauryl ether (Brij) at the air-water interface decreases as time of adsorption increases. Brij concentration is 0.1 g/liter, as measured by the drop volume technique and the maximum bubble pressure method (UNITD3.6).

Bendure, R.L. 1971. Dynamic surface tension determination with maximum bubble pressure method. J. Colloid Interface Sci. 37 228-238. 

An almost overwhelmingly large number of different techniques for measuring dynamic and static interfacial tension at liquid interfaces is available. Since many of the commercially available instruments are fairly expensive to purchase (see Internet Resources), the appropriate selection of a suitable technique for the desired application is essential. Dukhin et al. (1995) provides a comprehensive overview of currently available measurement methods (also see Table D3.6.1). An important aspect to consider is the time range over which the adsorption kinetics of surface-active substances can be measured (Fig. D3.6.5). For applications in which small surfactant molecules are primarily used, the maximum bubble pressure (MBP) method is ideally suited, since it is the only... 

In the Maximum-bubble-pressure method the surface tension is determined from the value of the pressure which is necessary to push a bubble out of a capillary against the Laplace pressure. Therefore a capillary tube, with inner radius rc, is immersed into the liquid (Fig. 2.9). A gas is pressed through the tube, so that a bubble is formed at its end. If the pressure in the bubble increases, the bubble is pushed out of the capillary more and more. In that way, the curvature of the gas-liquid interface increases according to the Young-Laplace equation. The maximum pressure is reached when the bubble forms a half-sphere with a radius r/s V(j. This maximum pressure is related to the surface tension by 7 = rcAP/2. If the volume of the bubble is further increased, the radius of the bubble would also have to become larger. A larger radius corresponds to a smaller pressure. The bubble would thus become unstable and detach from the capillary tube. 

Fundamental knowledge about the behavior of charged surfaces comes from experiments with mercury. How can an electrocapillarity curve of mercury be measured A usual arrangement, the so-called dropping mercury electrode, is shown in Fig. 5.2 [70], A capillary filled with mercury and a counter electrode are placed into an electrolyte solution. A voltage is applied between both. The surface tension of mercury is determined by the maximum bubble pressure method. Mercury is thereby pressed into the electrolyte solution under constant pressure P. The number of drops per unit time is measured as a function of the applied voltage. 

Viscosity and density of the component phases can be measured with confidence by conventional methods, as can the interfacial tension between a pure liquid and a gas. The interfacial tension of a system involving a solution or micellar dispersion becomes less satisfactory, because the interfacial free energy depends on the concentration of solute at the interface. Dynamic methods and even some of the so-called static methods involve the creation of new surfaces. Since the establishment of equilibrium between this surface and the solute in the body of the solution requires a finite amount of time, the value measured will be in error if the measurement is made more rapidly than the solute can diffuse to the fresh surface. Eckenfelder and Barnhart (Am. Inst. Chem. Engrs., 42d national meeting, Repr. 30, Atlanta, 1960) found that measurements of the surface tension of sodium lauryl sulfate solutions by maximum bubble pressure were higher than those by DuNuoy tensiometer by 40 to 90 percent, the larger factor corresponding to a concentration of about 100 ppm, and the smaller to a concentration of 2500 ppm of sulfate. 

A new method of surface tension determination has been developed which is continuous, automated, compatible with computer data acquisition systems, and capable of monitoring flowing process streams. The method is a variant of the well-known maximum bubble pressure technique. To illustrate the principles, we will describe the simplest initial configuration of the instrument here. Further details and a description of a refined version of the instrument will be reported later. 

Methods. All experiments were performed at 25°C. Critical micelle concentrations were determined using the maximum bubble pressure method on a SensaDyne 6000 surface tensiometer. Dry nitrogen was used as the gas source for the process and was bubbled through the solution at a rate of 1 bubble/sec. Cmc s measured using the Wilhemy plate method were in agreement with those obtained from the bubble tensiometer however, the bubble pressure method was used since it is less susceptible to error due to impurities and the nitrogen environment makes pH control easier. 

The Young-Laplace equation forms the basis for some important methods for measuring surface and interfacial tensions, such as the pendant and sessile drop methods, the spinning drop method, and the maximum bubble pressure method (see Section 3.2.3). Liquid flow in response to the pressure difference expressed by Eqs. (3.6) or (3.7) is known as Laplace flow, or capillary flow. 

For foams, it is the surface tension of the foaming solution that is usually of most interest. For this, the most commonly used methods are the du Noiiy ring, Wilhelmy plate, drop weight or volume, pendant drop, and the maximum bubble pressure method. For suspensions it is again usually the surface tension of the continuous phase that is of most interest, with the same methods being used in most cases. Some work has also been done on the surface tension of the overall suspension itself using, for example, the du Noiiy ring and maximum bubble pressure methods (see Section 3.2.4). 

Hogness,1 Burdon,2 Bircumshaw, and Sauerwald have done a great deal to render accurate measurements possible the best method is probably the maximum bubble pressure method, but the measurement of sessile drops (see Chap. IX), and of drop volumes, are also useful. Metals always have a very high surface tension. Table X gives typical results. 

There are static and dynamic methods. The static methods measure the tension of practically stationary surfaces which have been formed for an appreciable time, and depend on one of two principles. The most accurate depend on the pressure difference set up on the two sides of a curved surface possessing surface tension (Chap. I, 10), and are often only devices for the determination of hydrostatic pressure at a prescribed curvature of the liquid these include the capillary height method, with its numerous variants, the maximum bubble pressure method, the drop-weight method, and the method of sessile drops. The second principle, less accurate, but very often convenient because of its rapidity, is the formation of a film of the liquid and its extension by means of a support caused to adhere to the liquid temporarily methods in this class include the detachment of a ring or plate from the surface of any liquid, and the measurement of the tension of soap solutions by extending a film. 

Measurements on molten metals. The maximum bubble pressure method has proved one of the most satisfactory, but sessile drops, and drop-volumes have also been used with success.2 The principal difficulty lies in the proneness of metals to form skins of oxides, or other compounds, on their surfaces and these are sure to reduce the surface tension. Unless work is conducted in a very high vacuum, a freshly formed surface is almost a necessity if the sessile bubble method is used, the course of formation of a surface layer may, if great precautions are taken, be traced by the alteration in surface tension. Another difficulty lies in the high contact angles formed by liquid metals with almost all non-metallic surfaces, which are due to the very high cohesion of metals compared with their adhesion to other substances. 

Only the two first methods allow measurement of the temperature coefficient of the surface energy. The maximum bubble pressure technique is well-adapted for metals with low and intermediate melting points and specially for oxidizable metals, while the sessile drop technique has been applied with success to measure ctlv values up to 1500°C. The drop weight method is particularly useful for very high melting-point metals because it avoids liquid contact with container materials. This is also true for the recently developed levitation drop technique that analyses the oscillation spectrum of a magnetically levitated droplet. 

Equipment. A Brookfield synchro-lectric viscometer, serial no. 758, is used to measure viscosity in the range of 0-100,000 cP. Sugden s double capillary modification of the maximum bubble pressure method is used to determine surface tensions. The apparatus is calibrated with benzene and is checked by determining the surface tension of chloroform at 25°C, which is found to be 23.5 dyn cm"1 (26.5 dyn cm 1) (35). 

In the method of the Jailing meniscus a liquid-wetted tapering tube is placed vertically in a reservoir, as in fig. 1.26. Inside the tube liquid is held by the capillary pressure. The tube is now moved upwards - or the liquid in the vessel downwards - to increase the hydrostatic pressure head, and this is continued until the liquid in the capillary collapses. From the hydrostatic head the Laplace pressure is obtained and from that the surface tension. The method is very simple and may be considered as the counterpart of the maximum bubble pressure technique there are also similarities to the situation sketched in fig. 1.8a. The idea is rather old... 

A variant is the micro-pipette method, which is also similar to the maximum bubble pressure technique. A drop of the liquid to be studied is drawn by suction into the tip of a micropipette. The inner diameter of the pipette must be smaller than the radius of the drop the minimum suction pressure needed to force the droplet into the capillary can be related to the surface tension of the liquid, using the Young-Laplace equation [1.1.212). This technique can also be used to obtain interfacial tensions, say of individual emulsion droplets. Experimental problems include accounting for the extent of wetting of the inner lumen of the capillary, rate problems because of the time-dependence of surfactant (if any) adsorption on the capillary and, for narrow capillaries accounting for the work needed to bend the interface. Indeed, this method has also been used to measure bending moduli (sec. 1.15). 

Table 1.2. Surface tensions of water in mN m , obtained by various investigations using different techniques. Temperatures in degrees Celsius. Abbreviations for methods CR = capillary rise, WP = Wilhelmy plate, DNR = Du Nouy ring, DM = other detachment method or object in the surface. HD = hanging (pendent) drop, SD = sessile drop, MBP = maximum bubble pressure DW = drop weight.

In the maximum bubble pressure method, the interval between two bubbles ( the lifetime of one bubble) is the only measure of the age of the growing surface. Such intervals can nowadays be varied between milliseconds and several hours. Modem pressure transdueers allow small pressures to be measured rapidly and accurately. The trend is that the mcudmum pressure increases with increasing flow rate, as expected. 

Figure 1.30. Surface tension of a 6.2 mM solution of purified sodium dodecyl sulfate. Maximum bubble pressure method. (Redrawn from K.J. Mysels, Colloids Surf. 43 (1990) 241.) Discussion of the regions I and II in the text.

Fedor (1990), and Fedor et al. (1991). The density, surface tension, electrical conductivity, and viscosity have been measured at the temperature of 1573 K and in a relatively wide concentration range. The density and surface tension were measured by means of the maximum bubble pressure method using a device similar to that described in Section 6.2.2. The viscosity was measured using the rotational method, and the electrical conductivity, by means of the two-electrode method. 

Density measurement by the method of maximum bubble pressure is essentially the same as the measurement of surface tension. However, the precision of this method in the density measurement of molten salts is far below the method of hydrostatic weighing and is used only exceptionally. On the other hand, this method is used with an advantage at higher temperatures to measure simultaneously density and surface tension of the oxide systems. 

The surface tension of this system was measured by Lubyova et al. (1997) using the maximum bubble pressure method. The values of constants a and b of the temperature dependency of surface tension, a = a —bt, obtained using the linear regression analysis, together with the values of the standard deviations of approximation, and the values of the surface tension at 823°C for the investigated KF-KBF4 melts are given in Table 6.1. 

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