MEASUREMENT OF INTERFACIAL TENSION IN FLUID-FLUID SYSTEMS

J. Drelich Ch. Fang C.L. White Michigan Technological University, Houghton, Michigan

INTRODUCTION For more than a century, a variety of techniques have been used to measure interfacial tensions between immiscible fluid phases. A recent monograph by Rusanov and Prokhorov (1) provides a broad review of the technical literature on the interfacial tension techniques with detailed discussion of the theoretical bases and instrumentation. Additional valuable sources of information on the interfacial tension measurement methods include selected chapters in Refs. 2 5. In this article, we present a very brief overview of the most common techniques used in interfacial tension measurements. The reader is encouraged to explore Refs. 1 5 and references therein for further details. This article is organized as follows. Classical Interfacial Tension Measurement Methods reviews the methods that are used in surface chemistry laboratories. A short comparison of these techniques is presented at the end of the section. This comparison has been prepared to guide a selection of the experimental method for measurements of interfacial tension in liquid-fluid systems, including systems with surfactants, viscous liquids, or molten metals. Many of the industrial operations involve the liquid-fluid interfaces, for which the composition is constantly refreshed and does not reach equilibrium. The importance of such dynamic interfacial tensions is increasingly recognized to be essential to the understanding and control of interfacial processes in multiphase, multicomponent systems. Dynamic Interfacial Tension Measurements discusses a freshly created interface. In Measurement of Ultralow Interfacial Tension an example of: when the value of interfacial tension is significantly less than 1 mN/m is discussed. Ultralow interfacial tensions are common in the fluid systems of advanced technologies of liquid-liquid emulsification processes when effective surfactant solutions are used. Finally, in Microtensiomery, we discuss the methods of interfacial

tension measurements that have been applied (or have potential to be applied) to microinterfaces of microdroplets. Fundamental research on the interfacial properties of nanomaterials (materials and particles with microstructural features on the micrometer or nanometer scale) and droplets of micrometer-sized or nanometer-sized dimension will be an important challenge in the rapidly developing field of nanotechnology. CLASSICAL INTERFACIAL TENSION MEASUREMENT METHODS Fig. 1 shows a classification of common interfacial tension measurement methods, both classical and modern. Group I represents examples of techniques commonly used for direct measure of the interfacial tension with a microbalance. The techniques in group II are those in which interfacial tension can be determined from direct measurement of capillary pressure. Analysis of equilibrium between capillary and gravity forces is employed in the techniques of groups III and IV. Group III techniques rely on the balance between surface tension forces and a variable volume of liquid, whereas Group IV techniques fix the volume of a liquid drop and measure the distortion of that drop under the influence of gravity. Group V includes techniques where the shapes of fluid drops are distorted by centrifugal forces and are used to measure ultralow interfacial tensions. Group I: Direct Measurement Using a Microbalance Interfacial tension at fluid-fluid interfaces is a reflection of the excess energy associated with unsaturated intermolecular interactions at the interface. This excess energy tends to drive interfaces to adopt geometries that minimize the interfacial area, and this tendency can be interpreted as a physical force per unit length (i.e., a tension)

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Encyclopedia of Surface and Colloid Science Copyright D 2002 by Marcel Dekker, Inc. All rights reserved.

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Fig. 1 Classification of techniques for interfacial tension measurements that are discussed in this article.

applied in the plane of the interface. The excess energy per unit area (E/A) is numerically equal to this force per unit length (F/L), which is numerically equal to the interfacial tension (g). To directly measure interfacial tensions using a microbalance, a plate, ring, rod, or other probe of simple shape is brought into contact with the interface. If the probe is

completely wetted by one of the liquids, this liquid will adhere to the probe and climb as the result of capillary force, increasing the interfacial area and leading to a force tending to pull the probe toward the plane of the interface (Figs. 2 and 3). This restoring force is directly related to the interfacial tension and can be measured by a microbalance. The force (F) acting along the three-phase contact

Fig. 2 A schematic of the Wilhelmy plate method.

Fig. 3 Illustration of the ring method.

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line is exactly equal to the weight of the liquid meniscus standing above the plane of the fluid-fluid interface. This force, measured by the microbalance, is used to calculate the interfacial tension: g F p cos y
1

instruments use plates of standard dimensions so that measurements of the plate size and its weight are not required. Adsorption of organic compounds from the laboratory environment or test solutions can be a major source of experimental error when measuring surface tensions using the Wilhelmy plate method. Du Nouy ring method In this method, the interfacial tension relates to the force required to pull a wire ring off the interface (Fig. 3) (7, 8). As in the case of Wilhelmy plate, the ring is usually made up of platinum or platinum-iridium alloy of a radius (R) of 2 3 cm. The radius (r) of the wire ranges from 1/30 to 1/60 of that of the ring (9). Again, Eq. 1 describes in general the calculation procedure of the technique. Here, the perimeter ( p) of the three-phase contact line is equal to twice the circumference of the ring: p = 4pR. Because additional volume of liquid is lifted during the detachment of the ring from the interface, a correction factor ( f ) is required in Eq. 1 (8): g F f p cos y
2

where p is the perimeter of the three-phase contact line and y is the contact angle measured for the liquid meniscus in contact with the object surface. The two principal techniques used for direct measurement of interfacial tension using the microbalance are Wilhelmy plate and du Nouy ring methods. The Wilhelmy plate technique is used in both static and detachment modes, whereas du Nouy ring technique is strictly a de tachment technique. In the static measurement, the plate remains in contact with liquid during the entire cycle of interfacial tension measurement. If the instrument operates in the detachment mode, the interfacial tension is measured by measuring the force required to separate the ring or plate from contact with the interface. Wilhelmy plate technique A vertical thin plate is used in this technique (Fig. 2) (6). The commercial plates are made of roughened platinumiridium alloy or platinum. The metal plate must be cleaned from organic contaminants by an organic solvent and then flamed before the experiment. Both roughening and cleaning of the plate surface are used to maintain good wetting of the plate by the test liquid. It should be noted that materials other than platinum or platinum-iridium alloy, such as glass, mica, and steel (1, 5) have also been used. Nevertheless, good wetting of the test liquid to the plate is always necessary. The use of plates made of material other than metal is a must requirement in the case of certain liquids such as during the measurements of the interfacial tension between a heavy nonpolar liquid (i.e., carbon tetrachloride) and immisible, but lighter, polar liquid (i.e., water). For such systems, the plate should be hydrophobic. Several polymers, especially fluorinated polymers, can be used for this purpose. Adsorption and self-assembling of organic amines on the surface of the platinum plate could also be a solution to this problem. In the Wilhelmy plate method, the plate is put in a fixed position relative to the horizontal surface of the liquid (Fig. 2). Then, the force (F) vertically acting on the plate by the liquid meniscus is measured by using a microbalance. The force applied to the plate is equal to the weight of the liquid meniscus uplifted over the horizontal surface. By measuring this force, the interfacial tension can be calculated by using Eq. 1 where p = 2(L + t). Modern

The correction factor varies from about 0.75 to 1.05 and depends on the dimensions of the ring (R, r), its surface wettability (y), and difference in fluid density (Dr). The tabulated f values in relation to R/r (for y = 0) can be found in Ref. 8, and also calculated from the following approximate equation (10):  f 0:725 9:075 104 F 1:679r 0:04534 p3 DrgR3 R 1=2
3

The application range of Eq. 3 is: 0.045 DrgR3/F 7.5. The maximum force is measured by the microbalance (F ) and corresponds to detachment of the ring from the interface. The F value is measured experimentally and then Eq. 3 is used to calculate the correction factor f. The interfacial tension is then calculated from Eq. 2. The interfacial tension reading made by modern computerized instrumentation does not require separate calculation of f, since its calculation is incorporated in the software. The high-accuracy measurements with the ring method require that the plane of the ring remain parallel to the interface. The major error in this technique is caused by deformation of the ring, which is a very delicate probe and subject to inadvertent deformation during handling and cleaning. It is also important that perfect wettability of the ring surface by the denser fluid be maintained (y = 0). If perfect wetting is not achieved, additional correction of the instrument reading is needed. Poor wetting of ring by the

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denser fluid makes the measurement of interfacial tension impossible to carry out. In the case of special measurements requiring homemade rings, very large rings should be avoided to avoid the small value of the correction factor (see Eq. 3). If all of the necessary experimental precautions are observed, this method can guarantee higher accuracy than any other detachment method. Group II: Measurement of Capillary Pressure Interfacial tension is defined as the work required to create a unit area of interface at a constant temperature, pressure, and chemical potential. Because it is always positive for interfaces between immiscible phases, interfacial tension always tends to decrease the area of interface. This tendency gives rise to a pressure difference between fluids on either side of a curved interface, with the higher pressure on the concave side of the interface. This pressure difference results in phenomena such as a capillary rise, bubble and drop formation, etc. A formula describing the pressure difference (DP) across the curved interface is known as the Young-Laplace equation (11, 12):   1 1 DP g 4 R1 R2 where R1 and R2 are the radii of curvature. The pressure difference across a curved interface (DP) can be measured in a number of ways (e.g., using a pressure sensor or observing a capillary rise) and then be used to calculate g if the radii of curvature are known. The most common and probably one of the oldest methods in this group of interfacial tension measurement techniques is a

maximum bubble pressure method that is briefly described in the next paragraph. Modification of the maximum bubble pressure method based on a continuous measurement of varying pressure during growing bubble or drop is now a basic technique in examination of dynamic (not equilibrated) interfacial tension and is further discussed in Dynamic Interfacial Tension Measurements. Maximum bubble pressure This method is based on measuring the maximum pressure ( p ) to force a gas bubble out of a capillary into a liquid (Fig. 4) (13, 14). The measured pressure is the sum of capillary pressure (DP) caused by the interfacial tension and the hydrostatic pressure (rAghA) caused by the liquid column above the orifice of the capillary: DP p rA ghA
5

This pressure can be expressed as the height (h) of the column of an imaginary liquid of density (Dr = rA rB): h DP Drg
6

Sugden (13) derived an expression to relate h with the Laplace capillary constant a = 2g/(Drg) and the bubble meniscus:   r r  r  zc  b 1=2 7 X b a b 2 where X = a2/h, b = 2b2/a2, zc is the height of the bubble, and b is the curvature radius at the apex (lowest point of the bubble). Then he tabulated the minimum values of

Fig. 4 Maximum bubble pressure method. (A) A sequence illustrating the shape of bubble at three different stages of bubble growth. (B) Relationship between pressure inside the bubble and radius of the bubble.

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Measurement of Interfacial Tension in Fluid-Fluid System

X/r as dependent of a given value of r/a within the range 0 < r/a 1.5. Using this table, the surface tension can be calculated by following an iteration procedure. Direct and easier, but a little less accurate, calculation of the interfacial tension can be done by using the following equation (5): ! DPr 2rDrg rDrg2 1 g 8 2 3DP 6DP2 As further discussed in the next section; the maximum bubble and drop pressure technique or its modifications have been very useful in studying the dynamic interfacial tensions. This technique has also been attractive to examination of surface tension for molten metals (2). Group III: Analysis of the Balance Between Capillary and Gravity Forces Methods based on analysis of capillary effects, other than the shape of a drop or meniscus, such as capillary rise and drop volume or weight, are among the oldest surface tension measurement methods in use. A variety of modern instruments, usually fully automated and computerized (groups I, II, and IV), have replaced these methods in most laboratories. We provide a short review of two techniques that still might be attractive to researchers who have limited access to modern instrumentation. Capillary rise method The basis for the capillary rise method is to measure the height h of the meniscus in a round glass tube having the known inner radius r, as shown in Fig. 5 (2, 15). For small-diameter tubes (i.e., r < < h) the shape of the me-

Fig. 6 Schematic illustration of drop volume or weight method.

niscus is spherical, and the surface tension can be calculated by using the following equation: g Drghr 2 cos y
9

Since the glass tubes are easy to clean with acids, bases, and organic solvents, and because many of the liquids perfectly wet the glass surface, the cosy term in the above equation will often equal unity. If the shape of the meniscus is not spherical, Eq. 9 should be replaced with (15):   1 r r2 r3 0:1288 2 0:1312 3 g Drgrh 1 2 3h h h
10

The capillary rise method can be one of the most accurate techniques used to make surface tension measurements. Technical problems with the technique are related to fabrication of a uniform bare capillary tube and precise determination of its inside diameter. In addition, the capillary rise method is not very convenient for measuring the interfacial tension between two liquids. Drop volume or weight In this method, the weight or volume of a drop falling from a capillary with a radius r is measured (Fig. 6) (16, 17). The weight (W) of the drop falling off the capillary correlates with the interfacial tension through the following equation (5):   r W VDrg 2prgf p 11 3 V

Fig. 5 Illustration of the capillary rise method.

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where V is the drop volume, r is the radius of the capillary, and f is the correction factor required because only a portion of the drop volume is released from the capillary during detachment (2). The correction factor is a function of r/V1/3, and this correlation was empirically determined and tabulated by Harkins and Brown (17). It can also be calculated from the empirical function (5): r f p 3 V   r 0:167 0:193 p 3 V  3 r 0:0496 p 3 V   r :0489 p 3 V  2

from the end of the capillary before the drop reaches the critical size. In addition, the measurements in multicomponent solutions when adsorption occurs might not reflect equilibrium saturation of the solutes at the interface. Group IV: Analysis of Gravity-Distorted Drops Interfacial tension causes interfaces to behave as elastic membranes that always tend to compress the liquid. In the absence of other forces (e.g., in zero gravity), the liquid surface has a natural tendency to form spherical shapes to minimize the interfacial area per unit volume of liquid and thus, to minimize the excess energy of the interface. The shape of an interface in a gravitational field (Fig. 7) depends on the competition between the capillary and gravitational forces and can be described by the BashforthAdams equation (19):   sin f 1 2g g Drgz 13 x R1 b Eq. 13 is often expressed in a dimensionless form as: sin f 1 Drgb2 z 2 x=b R1 =b b g
14

12

Because of small volume of each drop, many drops need to be collected for the accurate measurement of drop weight or volume. In modern instrumentation, the volume of liquid and the number of droplets released from the capillary can be determined very precisely and thus the weight or volume of the individual drop is not difficult to calculate (18). Capillaries used in the drop weight or volume techniques are usually made of glass; however, metal capillaries are also used on occasion (1). Glass is wetted by many liquids, is transparent, and is relatively easy to clean. Capillary tubes specifically fabricated for routine interfacial tension measurements are now difficult to purchase in the U.S. market; however, glass capillaries can be produced relatively easily in glass workshops. The measurements of interfacial tension with the drop weight or volume technique are very simple but, unfortunately, sensitive to vibrations on the other side. Vibrations of the apparatus can cause premature separation of the drop

Fig. 7 Definition of dimensions and coordinates describing the sessile drop.

where g is the interfacial tension; Dr = A B equals the difference in density of fluids; R1 is the radius of curvature; x is the radius of rotation of point S around the z axis; f is the angle of R2 vector with the axis of symmetry; b is the radius of curvature at the apex of the curvature; and g is the acceleration due to gravity. Fig. 7 shows the details of drop geometry. The techniques of curved interface shape analysis are particularly attractive to researchers because they do not require advanced instrumentation. The experimental setup requires a camera with a low-magnification lens to record the shape of the drop. The interfacial tension can be easily calculated from the dimensions of the pendant drop, sessile drop, or liquid meniscus taken from the photographic picture and by using numerical solutions to the above equations. Modern instruments, however, use image analysis software whose role is to match the entire drop profile to the best fit of the theoretical curve (e.g., the BashforthAdams equation) describing the shape of the drop (14). These advances significantly improved the precision of the techniques and reduced the time of the measurement, providing an opportunity for examination of the interface aging process. Probably the most advanced software, axisymmetric drop shape analysis, was introduced by Neumann and co-workers (20). Since advanced instrumentation is not always available to researcher, a brief review

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Measurement of Interfacial Tension in Fluid-Fluid System

The pendant drop technique, as other interfacial tension measurement techniques, requires extreme cleanliness to obtain good quality and reproducible results. Here, the needle used for hanging the drop should be well cleaned and the climbing of the interface over the outer surface of the needle should be avoided. Needles made of stainless steel or glass that are relatively easy to clean with acids, bases, and organic solvents are most often used in surface chemistry laboratories. It is recommended that needles with a diameter that is less than 0.5 D be used (21). The diameter of the needle should not be too small, however, because this reduces the value of d and, consequently, the precision of interfacial tension determination. Sessile drop method
Fig. 8 Pendant drop.

of classical approaches of interfacial tension determination from the shape of the interface seems to be appropriate. Pendant drop method In a simple method, two parameters of the pendant drop that should be experimentally determined are the equatorial diameter D and the diameter d at the distance D from the top of the drop (Fig. 8) (21, 22). The interfacial tension is then calculated from the following equation (2, 21, 22): g DrgD2 H
15

This method is based on the analysis of the profile of the drop sitting on a solid substrate, as shown in Fig. 7 (24, 25). It is recommended that substrates used in sessile drop measurements be poorly wetted by the drop, i.e., they should have a contact angle larger than 90 degrees. In a simple experimental approach, one first needs to locate the equator of the drop, and then measure the height from the top of the drop to its equator (ze). For a very large sessile drop, an analytical expression for the interfacial tension is as follows (5): g Drgze2 2
17

The shape dependent parameter (H ) depends on a value of the shape factor S = d/D. Tables including the set of 1/H vs. S values are available in several references (1, 22). The values of 1/H can also be calculated from the following empirical formula (23): 1 B4 a B 3 S3 B2 S2 B1 S B0 H S
16

From a practical point of view, it is often difficult to precisely locate the equator of the drop and measure ze for many drops. Although the large drop is almost flat, locating the top of the drop is sometimes experimentally difficult. It should be recognized, however, that large drops are not required if tabulated dependencies of drop shape parameters, based on the Bashford-Adams analysis (Eq. 14) are used (19, 25). Practical Comments Most of the techniques reviewed in this section have been commercialized. Table 2 summarizes the accuracy, com-

where Bi (i = 0, 1, 2, 3, 4) and a are empirical constants for a certain range of S, which are shown in Table 1.

Table 1 Empirical constants for Eq. 16 Range of S 0.401 0.46 0.46 0.59 0.59 0.68 0.68 0.90 0.90 1.00 A 2.56651 2.59725 2.62435 2.64267 2.84636 B4 0.32720 0.31968 0.31522 0.31345 0.30715 B3 0 0 0 0 0.69116 B2 0.97553 0.46898 0.11714 0.09155 1.08315 B1 0.84059 0.50059 0.15756 0.14701 0.18341 B0 0.18069 0.13261 0.05285 0.05877 0.20970

Measurement of Interfacial Tension in Fluid-Fluid System Table 2 Accuracy and suitability of classic techniques used in interfacial tension measurements Accuracy mN=m $0.1 $0.1 0.1 0.3 <<0.1 Suitability for surfactant solutions Limited Limited Very good Very good Suitability for two-liquid systems Good Reduced accuracy Very good Very good, experimentally difficult Good Very good Very good Suitability for viscous liquids Very good Not recommended Not recommended Not recommended Suitability for melted metals Not recommended Not recommended Yes Not recommended

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Method Wilhelmy plate Du Nouy ring Maximum bubble pressure Capillary rise

Commercial availability Yes Yes Yes Not

Drop volume Pendant drop Sessile drop

0.1 0.2 $0.1 $0.1

Limited Very good Good

Not recommended Not recommended Very good

Yes Yes Yes

Yes Yes Not

mercial availability, and suitability of these techniques for various types of fluid-fluid systems. The accuracy of most of these techniques for pure liquid-gas systems is about 0.1 mN/m. The capillary rise technique is capable of significantly better accuracy than the others in Table 2. Most of the interfacial tension measurement techniques listed in Table 2, including the capillary rise method, have been successfully applied to liquid-liquid systems. Reduced accuracy of the detachment du Nouy ring method is associated with difficulties in calibrating the weight of the ring immersed in the less dense liquid. The same problem can be expected in the interfacial tension measurements using the Wilhelmy plate instrument. All techniques in Table 2 yield reduced accuracy when applied to liquid-liquid interfaces or when one or both of the liquids is viscous. The measurements with viscous liquids are always difficult to carry out due to problems with handling the liquid, injection of a liquid sample of the required volume into the instrument, low velocity liquid flow, and long time viscous effects during deformation of the interface. Two techniques are particularly recommended to examine the surface tension of viscous liquids: the Wilhelmy plate (not a detachment option!) and the sessile drop methods. In both techniques, samples can be equilibrated for several hours before the measurements are taken. It is important to recognize that any interfacial tension measurement can be strongly influenced by interfacially active solutes or impurities that are accidentally introduced into the fluid-fluid system or present on solid surfaces that act as part of the measurement system (1, 2). Any solid surfaces that make contact with liquids (e.g., plates, rings, and capillary tubes) must be carefully cleaned prior to making measurements. Furthermore, some interfacially active contaminants can be introduced

from the skin or breath of laboratory workers. Finally, it is important to note that interfacial tensions are influenced by temperature, which should be controlled and reported for all measurements. When using techniques that depend on a known wettability of a solid probe by one of the liquids, surface active solutes (whether present intentionally or as impurities) can seriously influence the interfacial tension measurements. Interfacially active solutes in a liquid phase can adsorb not only on the fluid-fluid interfaces but on the liquid-solid interfaces as well. This adsorption will affect wettability of the solid surface (the cosy term in Eqs. 1 and 2) and, therefore, influence the measured result. In principle, such effects can be eliminated by employing solid probes of alternate materials to which the solute does not adsorb, but plates and rings are not usually available in a wide range of alternative materials. Even when adsorption to solid-liquid interfaces is not a problem, it is important to allow fluid-fluid interfaces to achieve equilibrium before making a measurement. When equilibrium is achieved rapidly (within a few seconds), the drop volume technique may be suitable. If equilibration requires longer times, sessile drop, Wilhelmy plate, or other quasi-static techniques may be more appropriate. This consideration applies to any fluid-fluid system in which kinetically limited processes (adsorption, viscous flow, etc.) take place. Because of the relatively high temperatures involved and their reactivity with many gases and solids, surface tension measurements on liquid metals pose special challenges. The four principal techniques that have been employed are the maximum bubble pressure method, the sessile drop method, the drop volume or weight method, and the pendant drop method (26, 27). It is important that measurements on liquid metals be carried out in inert

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gas environment to avoid reactions with gases and other phases. Oxygen and other reactive gases are known to exert strong effects on the surface tension of selected metals, even when present in parts per million concentration (27).

DYNAMIC INTERFACIAL TENSION MEASUREMENTS In fluid-fluid systems containing interfacially active solutes, a freshly created interface will not generally be in compositional equilibrium with the two immiscible fluids it separates. It is only after solute redistribution from one or both phases (i.e., adsorption) has occurred that this interface will achieve its equilibrium state. It is sometimes important to measure the interfacial tension of freshly created interfaces, and such measurements yield what is known as dynamic surface tension. A detailed review of experimental techniques, theoretical background, and literature on the measurements of dynamic interfacial tensions was recently published by Dukhin et al. (3). Another valuable source of analysis of adsorption at the interface and dynamic interfacial tension is the book published by Joos (28).

Table 3 provides a characteristic time range for the selected interfacial tension measurement techniques. Of different techniques already discussed in this article, the capillary rise method is not recommended for dynamic interfacial tension measurements. The techniques discussed in the next sections are not very suitable for examination of dynamic effects at interfaces either. Interfacial tension changes that occur over time intervals of at least several seconds (and continue over several minutes, hours, or days) can be studied by using most of the classical techniques discussed in the previous section. For example, Fig. 9 shows the results of interfacial tension relaxation between bitumen and water of varying pH value recorded with the Wilhelmy plate instrument (30). In this bitumen-water system, the dynamic character of the interfacial tension is caused by diffusion of natural surfactants from the bitumen to interface and aqueous phase, and surfactant reaction with ions dissolved in water (31). As emphasized in the previous section, examination of the interfacial tension for surfactant solutions using classical techniques should be carried out with caution. Surfactants often adsorb on the solid surfaces of equipment used in measurements and change the wetting character-

Table 3 Characteristic time range for common interfacial tension measurement techniques Method Wilhelmy plate Time rangea >10 s Comments Some of the surfactants might alter the wetting properties of the plate, causing the change of measurement conditions (possible source of error) Same as above Strongly surface active chemicals might cause the release of pending drop before completion of the measurement Some of the surfactants might alter the wetting properties of a solid support substantially changing the shape of the sessile drop Hydrodynamic effects associated with releasing liquid volume and circulation of liquid inside the drop sometimes significantly reduce the accuracy of the interfacial tension measurements Difficulties with determination of the real surface age and problems with hydrodynamic effects in the vicinity of interface Not available commercially Not available commercially Not available commercially

Du Nouy ring Pendant drop Sessile drop

>30 s >10 s >10 s

Drop volume/weight

1 s 20 min

Maximum bubble pressure

1 ms 100 s

Growing drop/bubble Oscillating jetc Pulsating bubblec

a b

>10 msb 1 10 ms 5 ms 0.2 s

Based on Dukhin et al. (3). It is claimed by MacLeod and Radke (29) that the dynamics interfacial tension can be measured for several hours, although Ref. 3 specifies the upper limit as 600 s. c Methods not discussed in this article.

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Fig. 9 Dynamic interfacial tension measured between bitumen and water at 60C using the Wilhelmy plate technique. The pH values for water at the beginning (t = 0) and at the end of the measurements (t = 90 min) are listed in the figure legend. (The results are from Ref. 30.)

research area is just evolving, and the continued fundamental research will probably establish a better connection of dynamic interfacial phenomena with practical needs. Four basic techniques for measurements of the dynamic interfacial tension at short intervals include the maximum bubble pressure, growing drop (bubble), oscillating jet, and pulsating bubble methods (Table 3). Neither the oscillating jet technique nor the pulsating bubble technique is discussed in this article. Bases of these techniques are provided in Refs. 1 3 and references therein. The maximum bubble (drop) pressure method and its modifications have been the most popular techniques used in research conducted in recent years. Apparatus for making these measurements are also available commercially. The maximum bubble pressure technique was briefly described in Classical Interfacial Tension Measurement Methods. Following is a short description of a modification of the maximum bubble pressure technique that is suitable for dynamic surface tension measurements. Growing Drop (Bubble) Method Modern instrumentation permits the pressure inside a bubble or drop to be precisely and continuously measured as it forms and detaches from the end of a capillary (3, 29, 34, 35). The geometry of a drop or bubble can also be monitored during growth and detachment by using advanced videographic equipment. This ability to simultaneously monitor both pressure and geometry (size and shape) of bubbles or drops as they form allows dynamic interfacial tensions to be evaluated over a range of growth rates. Furthermore, the same experimental approach allows measurement of surface tensions using approaches normally applied to systems in (or near) equilibrium, such as the drop volume and maximum pressure drop techniques. Fig. 10 describes an experimental approach used by MacLeod and Radke (29) for measurement of dynamic interfacial tension using the growing drop technique. In

istics of a solid surface. This effect usually causes experimental problems in the Wilhelmy plate, du Nouy ring, and sessile drop techniques (see comments in Table 3). Short-time interfacial tension and wetting effects play important roles in high volume industrial processes such as froth flotation of particles and droplets, detergency, foam or froth generation, and stability (3). In these processes, dynamic interfacial tensions become more crucial to the success of the technology than the equilibrium (or near-equilibrium) interfacial tension. This issue has been emphasized in the literature (3, 32, 33), but straightforward links between dynamic interfacial tensions and (e.g., process efficiencies) have not yet been well established. This

Fig. 10

Schematic of the growing drop apparatus used by MacLeod and Radke. (From Ref. 29.)

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this apparatus, a liquid drop or gas bubble is formed and released from a capillary by using a precise micropump to carefully control the growth rate of the drop or bubble. A pressure transducer is used to simultaneously monitor and record the internal pressure in the drop or bubble, while its size and shape are recorded by using a video camera. These experiments can be carried out for a range of flow rates ranging from near equilibrium growth (very low flow rates) to highly nonequilibrium growth conditions (very rapid bubble or drop growth). Fig. 11 shows selected results of MacLeod and Radke (29) for growth of 0.25 mM aqueous decanol droplets for a range of droplet growth rates between 5 and 100 mm3/ min. The plots of interfacial tension vs. time show initially increasing, reaching a maximum, and then decreasing as a function of time. The positive slope of the g vs. t curves for t < 1 results from the depletion of decanol adsorption due to rapid expansion (stretching) of the interface when the bubble is small (see Fig. 4A). As the drop geometry proceeds beyond hemispherical shape (Fig. 4C), the relative rate of surface area growth decreases, allowing decanol from the bulk liquid to replenish the surface adsorption. The decrease in interfacial tension associated with this increase in adsorption yields the negative slope observed in the g vs. t curves for t > 1. As expected, the largest dynamic interfacial tensions, approaching those

for pure water, are observed for droplets formed at the highest capillary flow rates. Conversely, the lowest values (approaching the equilibrium interfacial tension for this solution) were observed for droplets growing at very slow rates. At drop formation times approaching 100 s, interfacial tensions for drops formed at all flow rates approach the equilibrium value for the 0.25 mM aqueous 1-decanol solution. The zero time for each measurement in Fig. 11 corresponds to the moment of detachment for the previous drop. Data points for a given capillary flow rate in Fig. 11 start at the time where the drop reaches a hemispherical shape (Fig. 4B), which also corresponds to the point at which the interfacial tension can be evaluated by using the maximum pressure method. Interfacial tension measurements using the drop-volume method are, of course, determined at the point where the drop detaches from the capillary and correspond to the last data point in the corresponding curve for the growing drop method. These two techniques, therefore, provide snapshots of the interfacial tension values in dynamic systems, and they bracket the family of curves determined by the growing drop method. The growing drop method provides the very important advantage of continuously recording the interfacial tension throughout the drop formation and allows the competing kinetic effects of interfacial stretching and solute transport for adsorption to be explored.

MEASUREMENT OF ULTRALOW INTERFACIAL TENSION Recovery of petroleum using tertiary oil recovery technology; cleaning of solid surfaces from dirt, grease, and oil; formulation of stable emulsions; in situ remediation of oil-contaminated soil with surfactant solutions; and other applications often rely on lowering the interfacial tension between immiscible liquids to ultralow values (much less than 1 mN/m) using surfactants. The measurements of such low interfacial tensions are extremely difficult to perform with classical interfacial tension measurement methods reviewed in Classical Interfacial Tension Measurement Methods or the dynamic techniques discussed in the previous section (e.g., see the accuracy values for methods shown in Table 2). For the measurements of ultralow interfacial tensions, the spinning drop technique has been developed at both laboratory and commercial scales (36 39). The basis of this technique is discussed in the following paragraph. An additional method designed for measurements of ultralow interfacial tensions was proposed by Lucassen (40) and is based on the analysis of the shape of the drop suspended

Fig. 11 Dynamic surface tension of 0.25 mM aqueous decanol solution droplets growing in air at 23C. Based on the experimental data presented by MacLeod and Radke. (From Ref. 29.)

Measurement of Interfacial Tension in Fluid-Fluid System

3163

Fig. 12 Schematic of the rotating drop method.

in liquid with a density gradient. The need for a strict control of liquid density limits this latter technique to relatively few applications. Spinning Drop Technique This technique relies on the fact that gravitational acceleration has little effect on the shape of a fluid drop suspended in a liquid, when drop and the liquid are contained in a horizontal tube spun about its longitudinal axis (Fig. 12) (36, 37). At low rotational velocities (o), the fluid drop will take on an ellipsoidal shape, but when o is sufficiently large, it will become cylindrical. Under this latter condition, the radius (r) of the cylindrical drop is determined by the interfacial tension, the density difference (Dr) between the drop and the surrounding fluid, and the rotational velocity of the drop. As the result, the interfacial tension is calculated from the following equation (38): g 1 3 r Dro2 4
18

metric techniques. Furthermore, the developing field of nanotechnology promises to yield novel structures on a nanometer scale, the interfaces of which are sure to be the subject of considerable study. The study of interfaces on the nanometer scale can be very important because they may exhibit properties that are very different from their macroscopic counterparts. For example, knowledge of partition and adsorption of surfactants and other interfacially active components of two-liquid systems is often crucial for the control of emulsion formulation and stability. It has recently been demonstrated that interfacial tension of microscopic droplets may differ significantly from the interfacial tension of macroscopic drops for the same surfactant solutions (42). This difference arises from dissimilar partitioning of surfactants into two immiscible liquids and is due to the effect of an enlarged interfacial area. In this regard, it becomes critical to conduct the study of interfacial phenomena, including the measurements of interfacial tension, on a length scale that is characteristic of the individual elements of the emulsion. Microtensiometry is the study of interfaces on very small particles and in finely dispersed systems. The micropipette technique, discussed first, is closely related to techniques depending on pressure differentials across curved interfaces that have already been presented. Techniques based on atomic force microscopy (AFM) offer the possibility of imaging nanometer-sized particles and directly measuring their interactions. AFM-based techniques are relatively new and still very much under development.

The spinning drop method has been very successful in examination of ultralow interfacial tensions down to 106 mN/m (39). For example, Fig. 13 shows the interfacial tension values for octane drops suspended in an aqueous phase saturated with ethoxylated alcohols (41). As shown in Fig. 13, the interfacial tension for the octane-waterCnE4 system varied from about 1 to 104 mN/m and depended on both temperature in the system and length of the hydrocarbon chain in the chemical structure of ethoxylated alcohol (Ref. 41 provides additional examples). The minimum in the interfacial tension vs. the temperature curve coincides with the phase inversion temperature, at which both hydrophilic and oleophilic natures of surfactant are in balance.

MICROTENSIOMETRY Criminology, biology, and pharmaceutical processing are among a number of fields in which material quantities of interest may be too small to apply conventional tensioFig. 13 The effect of temperature on interfacial tension measured between octane and aqueous phase saturated with CnE4. Graph based on the experimental data presented in Ref. 41.

3164

Measurement of Interfacial Tension in Fluid-Fluid System

Fig. 14 Illustration of micropipette techniques. (A) Based on analysis of pressure differences required to suck a microdroplet into the pipette. (B) Based on the examination of the force drop deformation relation.

Micropipette Technique (43 45) The micropipette technique was recently developed to directly measure interfacial tensions of micrometer-sized droplets. The technique was first used in examination of vesicles (43, 44) and next liquid droplets (42, 45). In this technique, the droplet is first captured at the tip of the glass micropipette and then sucked into the pipette (Fig. 14A). The interfacial tension is calculated from the minimum pressure, at which the droplet extends a hemispherical protrusion into the pipette, and by using the Laplace Eq. 4 in the following form (42):  Dp 2g 1 1 Rp Ro 
19

two-pipette technique, with a separation force applied between the pipettes to deform the droplet, has been used as shown in Fig. 14B (45). In the two-pipette technique, the separation force between the pipettes must also be measured, and the interfacial tension is calculated from the force drop deformation relation. Table 4 presents the results of interfacial tension measurements for water organic liquid systems determined with this technique. Atomic Force Microscopy The application of AFM permits roughness, heterogeneity, and interaction forces to be studied at submicroscopic scales that may extend down to molecular sizes. Among the most popular applications of the AFM are studies of interactions between substrates and colloidal particles. The AFM has not been established as a technique to measure interfacial tensions directly: however, it appears to have great potential for such measurements at the microscopic and submicroscopic levels. The technique is currently being evaluated as a tool for measuring the wetting properties of colloidal particles (48).

where Rp is the inner radius of the pipette and Ro is the radius of the exterior segment of the droplet; the dimensions of the pipettes internal diameter must be smaller than the diameter of the droplet. In the conventional technique shown in Fig. 14A, the large pressure difference required to draw the droplet into the pipette when the droplet does wet or adhere to the pipette surfaces, is a limitation. To avoid this limitation, a

Table 4 Results of interfacial tension measurements for the organic solvent microdroplets in water obtained with the micropipette technique and their comparison to the similar results measured for bulk two-liquid systems Interfacial tension measured for microdroplets [mN/m) 6.8 0.6 30.9 1.6 33.7 0.7 36.4 0.8 40.3 1.1 Interfacial tension measured for macrosystem [mN/m) 6.8 31.6 34.1 36.1 39.6

System Water-ethyl acetate Water-chloroform Water-benzene Water-toluene Water-hepto

(From Ref. 45.)

Fig. 15 Schematic of atomic force microscopy and its application to measurements of surface tension for microdroplets.

Measurement of Interfacial Tension in Fluid-Fluid System

3165 10. Zuidema, H.H.; Waters, G.W. Ring method for the determination of interfacial tension. Ind. Eng. Chem. Anal. Ed. 1941, 13, 312 313. Young, T. Miscellaneous Works; Peacock, G., Ed.; J. Murray: London, 1855; Vol. I, 418. de Laplace, P.S. Mechanique Celeste. Supplement to Book 10; 1806. Sugden, S. The determination of surface tension from the maximum pressure in bubbles. J. Chem. Soc. 1922, 121, 858 866. Rehbinder, P.A. Dependence of surface activity and surface tension of solutions upon temperature and concentration. Z. Phys. Chem. 1924, 111, 447 464. Lord Rayleigh, OM.; F.R.S. On the theory of the capillary tube. Proc. R. Soc. London, Ser. A 1916, 92, 184 195. Tate, T. On the magnitude of a drop of liquid formed under different circumstance. Phil. Mag. 1864, 27, 176 180. Harkins, W.D.; Brown, F.E. The determination of surface tension (free surface energy), and the weight of falling drops: the surface tension of water and benzene by the capillary height method. J. Am. Chem. Soc. 1919, 41, 499 525. Miller, R.; Hofmann, A.; Schano, K.H.; Halbig, A.; Hartmann, R. Measurement of surface and interfacial tensions with an automatic drop-volume tensiometer. Parfuem. Kosmet. 1992, 73, 390 397. Bashforth, F.; Adams, J.C. An Attempt to test the Theory of Capillary Action; Cambridge University Press: London, 1883. Lahooti, S.; del Rio, O.I.; Neumann, A.W.; Cheng, P. Axisymetric Drop Shape Analysis (ADSA). Applied Surface Thermodynamics; Neumann, A.W., Spelt, J.K., Eds.; Marcel Dekker, Inc.: New York, 1996; 441 507. Andreas, J.M.; Hauser, E.A.; Tucker, W.B. Boundary tension by pendent drops. J. Phys. Chem. 1938, 42, 1001 1019. Stauffer, C.E. The measurement of surface tension by the pendent drop technique. J. Phys. Chem. 1965, 69, 1933 1938. Misak, M.D. Equations for determining 1/H versus S values in computer calculations of interfacial tension by pendent drop method. J. Colloid Interface Sci. 1968, 27, 141 142. Quincke, G. Ueber die capillaritats-constanten des queck silbers. Ann. Phys. Chem. 1858, 4 (15), 1 48. Padday, J.F. The profiles of axially symmetric menisci. Trans. R. Soc. London 1971, A269, 265 293. Lang, G. Surface Tension of Liquid Elements. Handbook of Chemistry and Physics, 72nd Ed.; Lide, D.R., Ed.; CRC Press: Boca Raton, 1992; 133 145, Chapter 4. Eustathopoulos, N.; Nicholas, M.G.; Drevet, B. Wettability at High Temperatures; Pergamon: Amsterdam, 1999; Chapter 4. Joos, P. Dynamic Surface Phenomena; VSP: Zeist, The Netherlands, 1999.

AFM is a scanning probe technique based on measuring interaction forces between a cantilever tip and a specimen (Fig. 15). The force measurement is based on measuring the deflection of the cantilever, which has a known spring constant. The cantilever deflection is detected by the reflection of a laser beam as shown in the figure. Movement of the specimen under the cantilever tip (both in the horizontal plane for scanning, and vertically for force measurements) is controlled very precisely by a piezoelectric specimen stage (reverse systems with the piezoelectric stage attached to the cantilever holder are also in use). Interaction forces as small as 1pN (1012 N) can be measured between the probe tip and the specimen. Fig. 15 shows an approach for measuring the interfacial tension between a probe tip and a microscopic drop of liquid. The capillarity forces exerted on the tip by the liquid can be measured as it is inserted into the drop and as it is withdrawn and detaches from the drop. Calculation of surface tensions from these force-distance curves will depend on the shape of the probe tip, but the equations should be similar to those for classical macrodetachment techniques. A major challenge in using the AFM technique to measure interfacial tensions is fabrication of appropriate probe tips. Cylindrical tubes and spheres offer simple geometries and may present the best near-term options. Carbon nanotubes have recently been used as AFM tips, and may offer another promising approach (49).

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