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BookChapt Surface Tension TP2
BookChapt Surface Tension TP2
IN FLUID-FLUID SYSTEMS
J. Drelich
Ch. Fang
C.L. White
Michigan Technological University, Houghton, Michigan
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 completely wetted by one of the liquids, this liquid will
per unit area (E/A) is numerically equal to this force per adhere to the probe and climb as the result of capillary
unit length (F/L), which is numerically equal to the in- force, increasing the interfacial area and leading to a force
terfacial tension (g). tending to pull the probe toward the plane of the interface
To directly measure interfacial tensions using a mic- (Figs. 2 and 3). This restoring force is directly related to
robalance, a plate, ring, rod, or other probe of simple shape the interfacial tension and can be measured by a micro-
is brought into contact with the interface. If the probe is balance. 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.
3154 Measurement of Interfacial Tension in Fluid-Fluid System
line is exactly equal to the weight of the liquid meniscus instruments use plates of standard dimensions so that
standing above the plane of the fluid-fluid interface. This measurements of the plate size and its weight are not re-
force, measured by the microbalance, is used to calculate quired. Adsorption of organic compounds from the labo-
the interfacial tension: ratory environment or test solutions can be a major source
of experimental error when measuring surface tensions
F using the Wilhelmy plate method.
g ¼ ð1Þ
p cos y
Du Noüy ring method
where p is the perimeter of the three-phase contact line and In this method, the interfacial tension relates to the force
y is the contact angle measured for the liquid meniscus in required to pull a wire ring off the interface (Fig. 3) (7, 8).
contact with the object surface. As in the case of Wilhelmy plate, the ring is usually made
The two principal techniques used for direct measure- up of platinum or platinum-iridium alloy of a radius (R)
ment of interfacial tension using the microbalance are of 2 –3 cm. The radius (r) of the wire ranges from 1/30 to
Wilhelmy plate and du Noüy ring methods. The Wilhelmy 1/60 of that of the ring (9).
plate technique is used in both static and detachment Again, Eq. 1 describes in general the calculation pro-
modes, whereas du Noüy ring technique is strictly a de- cedure of the technique. Here, the perimeter ( p) of the
tachment technique. In the static measurement, the plate three-phase contact line is equal to twice the circumfe-
remains in contact with liquid during the entire cycle of rence of the ring: p = 4pR. Because additional volume of
interfacial tension measurement. If the instrument ope- liquid is lifted during the detachment of the ring from the
rates in the detachment mode, the interfacial tension is interface, a correction factor ( f ) is required in Eq. 1 (8):
measured by measuring the force required to separate the
F
ring or plate from contact with the interface. g ¼ f ð2Þ
p cos y
Wilhelmy plate technique
The correction factor varies from about 0.75 to 1.05 and
A vertical thin plate is used in this technique (Fig. 2) (6). depends on the dimensions of the ring (R, r), its surface
The commercial plates are made of roughened platinum- wettability (y), and difference in fluid density (Dr). The
iridium alloy or platinum. The metal plate must be cleaned tabulated f values in relation to R/r (for y = 0) can be
from organic contaminants by an organic solvent and then found in Ref. 8, and also calculated from the following
flamed before the experiment. Both roughening and clean- approximate equation (10):
ing of the plate surface are used to maintain good wetting
1=2
of the plate by the test liquid. It should be noted that 9:075 104 F 1:679r
materials other than platinum or platinum-iridium alloy, f ¼ 0:725 þ þ 0:04534
p3 DrgR3 R
such as glass, mica, and steel (1, 5) have also been used. ð3Þ
Nevertheless, good wetting of the test liquid to the plate is
always necessary. The use of plates made of material other The application range of Eq. 3 is: 0.045 DrgR3/F
than metal is a ‘‘must’’ requirement in the case of certain 7.5. The maximum force is measured by the microbalance
liquids such as during the measurements of the interfacial (F ) and corresponds to detachment of the ring from the
tension between a heavy nonpolar liquid (i.e., carbon tet- interface. The F value is measured experimentally and
rachloride) and immisible, but lighter, polar liquid (i.e., then Eq. 3 is used to calculate the correction factor f. The
water). For such systems, the plate should be hydrophobic. interfacial tension is then calculated from Eq. 2. The in-
Several polymers, especially fluorinated polymers, can be terfacial tension reading made by modern computerized
used for this purpose. Adsorption and self-assembling of instrumentation does not require separate calculation of f,
organic amines on the surface of the platinum plate could since its calculation is incorporated in the software.
also be a solution to this problem. The high-accuracy measurements with the ring method
In the Wilhelmy plate method, the plate is put in a fixed require that the plane of the ring remain parallel to the
position relative to the horizontal surface of the liquid interface. The major error in this technique is caused by
(Fig. 2). Then, the force (F) vertically acting on the plate deformation of the ring, which is a very delicate probe and
by the liquid meniscus is measured by using a microba- subject to inadvertent deformation during handling and
lance. The force applied to the plate is equal to the weight cleaning. It is also important that perfect wettability of the
of the liquid meniscus uplifted over the horizontal surface. ring surface by the denser fluid be maintained (y = 0). If
By measuring this force, the interfacial tension can be perfect wetting is not achieved, additional correction of the
calculated by using Eq. 1 where p = 2(L + t). Modern instrument reading is needed. Poor wetting of ring by the
Measurement of Interfacial Tension in Fluid-Fluid System 3155
denser fluid makes the measurement of interfacial tension maximum bubble pressure method that is briefly described
impossible to carry out. In the case of special measure- in the next paragraph. Modification of the maximum bub-
ments requiring homemade rings, very large rings should ble pressure method based on a continuous measurement M
be avoided to avoid the small value of the correction factor of varying pressure during growing bubble or drop is now
(see Eq. 3). If all of the necessary experimental precau- a basic technique in examination of dynamic (not equi-
tions are observed, this method can guarantee higher ac- librated) interfacial tension and is further discussed in
curacy than any other detachment method. ‘‘Dynamic Interfacial Tension Measurements.’’
Maximum bubble pressure
Group II: Measurement of Capillary Pressure
This method is based on measuring the maximum pressure
Interfacial tension is defined as the work required to create
( p ) to force a gas bubble out of a capillary into a liquid
a unit area of interface at a constant temperature, pressure,
(Fig. 4) (13, 14). The measured pressure is the sum of
and chemical potential. Because it is always positive for
capillary pressure (DP) caused by the interfacial tension
interfaces between immiscible phases, interfacial tension
and the hydrostatic pressure (rAghA) caused by the liquid
always tends to decrease the area of interface. This ten-
column above the orifice of the capillary:
dency gives rise to a pressure difference between fluids on
either side of a curved interface, with the higher pressure DP ¼ p rA ghA ð5Þ
on the concave side of the interface. This pressure dif-
ference results in phenomena such as a capillary rise, This pressure can be expressed as the height (h) of the
bubble and drop formation, etc. A formula describing the column of an imaginary liquid of density (Dr = rA rB):
pressure difference (DP) across the curved interface is DP
known as the Young-Laplace equation (11, 12): h ¼ ð6Þ
Drg
1 1 Sugden (13) derived an expression to relate h with the
DP ¼ g þ ð4Þ
R1 R2 Laplace capillary constant a = 2g/(Drg) and the bubble
meniscus:
where R1 and R2 are the radii of curvature.
The pressure difference across a curved interface (DP) r r r zc b 1=2
can be measured in a number of ways (e.g., using a pres- ¼ þ ð7Þ
X b a b 2
sure sensor or observing a capillary rise) and then be used
to calculate g if the radii of curvature are known. The most where X = a2/h, b = 2b2/a2, zc is the height of the bub-
common and probably one of the oldest methods in this ble, and b is the curvature radius at the apex (lowest point
group of interfacial tension measurement techniques is a 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.
3156 Measurement of Interfacial Tension in Fluid-Fluid System
where V is the drop volume, r is the radius of the capillary, from the end of the capillary before the drop reaches the
and f is the correction factor required because only a critical size. In addition, the measurements in multicom-
portion of the drop volume is released from the capillary ponent solutions when adsorption occurs might not reflect M
during detachment (2). The correction factor is a function equilibrium saturation of the solutes at the interface.
of r/V1/3, and this correlation was empirically determined
and tabulated by Harkins and Brown (17). It can also be
Group IV: Analysis of
calculated from the empirical function (5):
Gravity-Distorted Drops
2 Interfacial tension causes interfaces to behave as elastic
r r r
f p
3
ffiffiffiffi ¼ 0:167 þ 0:193 p 3
ffiffiffiffi :0489 p
3
ffiffiffiffi membranes that always tend to compress the liquid. In the
V V V
3 absence of other forces (e.g., in zero gravity), the liquid
r surface has a natural tendency to form spherical shapes to
0:0496 p ffiffiffiffi ð12Þ
3
V minimize the interfacial area per unit volume of liquid and
thus, to minimize the excess energy of the interface. The
Because of small volume of each drop, many drops need shape of an interface in a gravitational field (Fig. 7) de-
to be collected for the accurate measurement of drop pends on the competition between the capillary and gra-
weight or volume. In modern instrumentation, the volume vitational forces and can be described by the Bashforth-
of liquid and the number of droplets released from the Adams equation (19):
capillary can be determined very precisely and thus the
weight or volume of the individual drop is not difficult to sin f 1 2g
g þ ¼ þ Drgz ð13Þ
calculate (18). x R1 b
Capillaries used in the drop weight or volume tech-
Eq. 13 is often expressed in a dimensionless form as:
niques are usually made of glass; however, metal capil-
laries are also used on occasion (1). Glass is wetted by sin f 1 Drgb2 z
many liquids, is transparent, and is relatively easy to clean. þ ¼ 2þ ð14Þ
x=b R1 =b g b
Capillary tubes specifically fabricated for routine inter-
facial tension measurements are now difficult to purchase where g is the interfacial tension; Dr = A B equals
in the U.S. market; however, glass capillaries can be pro- the difference in density of fluids; R1 is the radius of cur-
duced relatively easily in glass workshops. vature; x is the radius of rotation of point S around the z
The measurements of interfacial tension with the drop axis; f is the angle of R2 vector with the axis of symmetry;
weight or volume technique are very simple but, unfortu- b is the radius of curvature at the apex of the curvature; and
nately, sensitive to vibrations on the other side. Vibrations g is the acceleration due to gravity. Fig. 7 shows the de-
of the apparatus can cause premature separation of the drop tails 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, ses-
sile drop, or liquid meniscus taken from the photographic
picture and by using numerical solutions to the above
equations. Modern instruments, however, use image anal-
ysis software whose role is to match the entire drop profile
to the best fit of the theoretical curve (e.g., the Bashforth-
Adams 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, axi-
symmetric drop shape analysis, was introduced by Neu-
Fig. 7 Definition of dimensions and coordinates describing the mann and co-workers (20). Since advanced instrumen-
sessile drop. tation is not always available to researcher, a brief review
3158 Measurement of Interfacial Tension in Fluid-Fluid System
Range of S A B4 B3 B2 B1 B0
Table 2 Accuracy and suitability of classic techniques used in interfacial tension measurements
Accuracy
Suitability
for surfactant
Suitability
for two-liquid Suitability for Suitability for Commercial M
Method ½mN=m solutions systems viscous liquids melted metals availability
Wilhelmy plate 0.1 Limited Good Very good Not recommended Yes
Du Noüy ring 0.1 Limited Reduced accuracy Not recommended Not recommended Yes
Maximum bubble 0.1 – 0.3 Very good Very good Not recommended Yes Yes
pressure
Capillary rise <<0.1 Very good Very good, Not recommended Not recommended Not
experimentally
difficult
Drop volume 0.1 – 0.2 Limited Good Not recommended Yes Yes
Pendant drop 0.1 Very good Very good Not recommended Yes Yes
Sessile drop 0.1 Good Very good Very good Yes Not
mercial availability, and suitability of these techniques for from the skin or breath of laboratory workers. Finally, it is
various types of fluid-fluid systems. The accuracy of most important to note that interfacial tensions are influenced
of these techniques for pure liquid-gas systems is about by temperature, which should be controlled and reported
0.1 mN/m. The capillary rise technique is capable of for all measurements.
significantly better accuracy than the others in Table 2. When using techniques that depend on a known wet-
Most of the interfacial tension measurement techniques tability of a solid probe by one of the liquids, surface active
listed in Table 2, including the capillary rise method, have solutes (whether present intentionally or as impurities) can
been successfully applied to liquid-liquid systems. Re- seriously influence the interfacial tension measurements.
duced accuracy of the detachment du Noüy ring method Interfacially active solutes in a liquid phase can adsorb not
is associated with difficulties in calibrating the weight of only on the fluid-fluid interfaces but on the liquid-solid
the ring immersed in the less dense liquid. The same interfaces as well. This adsorption will affect wettability
problem can be expected in the interfacial tension mea- of the solid surface (the cosy term in Eqs. 1 and 2) and,
surements using the Wilhelmy plate instrument. All tech- therefore, influence the measured result. In principle, such
niques in Table 2 yield reduced accuracy when applied to effects can be eliminated by employing solid probes of
liquid-liquid interfaces or when one or both of the liquids alternate materials to which the solute does not adsorb, but
is viscous. plates and rings are not usually available in a wide range
The measurements with viscous liquids are always dif- of alternative materials.
ficult to carry out due to problems with handling the Even when adsorption to solid-liquid interfaces is not a
liquid, injection of a liquid sample of the required volume problem, it is important to allow fluid-fluid interfaces to
into the instrument, low – velocity liquid flow, and long – achieve equilibrium before making a measurement. When
time viscous effects during deformation of the interface. equilibrium is achieved rapidly (within a few seconds),
Two techniques are particularly recommended to examine the drop volume technique may be suitable. If equilibra-
the surface tension of viscous liquids: the Wilhelmy plate tion requires longer times, sessile drop, Wilhelmy plate,
(not a detachment option!) and the sessile drop methods. or other quasi-static techniques may be more appropriate.
In both techniques, samples can be equilibrated for se- This consideration applies to any fluid-fluid system in
veral hours before the measurements are taken. which kinetically limited processes (adsorption, viscous
It is important to recognize that any interfacial ten- flow, etc.) take place.
sion measurement can be strongly influenced by inter- Because of the relatively high temperatures involved
facially active solutes or impurities that are accidentally and their reactivity with many gases and solids, surface
introduced into the fluid-fluid system or present on solid tension measurements on liquid metals pose special chal-
surfaces that act as part of the measurement system (1, lenges. The four principal techniques that have been em-
2). Any solid surfaces that make contact with liquids ployed are the maximum bubble pressure method, the
(e.g., plates, rings, and capillary tubes) must be careful- sessile drop method, the drop volume or weight method,
ly cleaned prior to making measurements. Furthermore, and the pendant drop method (26, 27). It is important that
some interfacially active contaminants can be introduced measurements on liquid metals be carried out in inert
3160 Measurement of Interfacial Tension in Fluid-Fluid System
gas environment to avoid reactions with gases and other Table 3 provides a characteristic time range for the
phases. Oxygen and other reactive gases are known to exert selected interfacial tension measurement techniques. Of
strong effects on the surface tension of selected metals, different techniques already discussed in this article, the
even when present in parts per million concentration (27). capillary rise method is not recommended for dynamic
interfacial tension measurements. The techniques dis-
cussed in the next sections are not very suitable for exa-
DYNAMIC INTERFACIAL mination of dynamic effects at interfaces either.
TENSION MEASUREMENTS Interfacial tension changes that occur over time in-
tervals of at least several seconds (and continue over se-
In fluid-fluid systems containing interfacially active so- veral minutes, hours, or days) can be studied by using
lutes, a freshly created interface will not generally be in most of the classical techniques discussed in the previous
compositional equilibrium with the two immiscible fluids section. For example, Fig. 9 shows the results of inter-
it separates. It is only after solute redistribution from one facial tension relaxation between bitumen and water of
or both phases (i.e., adsorption) has occurred that this varying pH value recorded with the Wilhelmy plate ins-
interface will achieve its equilibrium state. It is sometimes trument (30). In this bitumen-water system, the dynamic
important to measure the interfacial tension of freshly character of the interfacial tension is caused by diffusion
created interfaces, and such measurements yield what is of natural surfactants from the bitumen to interface and
known as ‘‘dynamic surface tension.’’ A detailed review aqueous phase, and surfactant reaction with ions dissolved
of experimental techniques, theoretical background, and in water (31).
literature on the measurements of dynamic interfacial ten- As emphasized in the previous section, examination of
sions was recently published by Dukhin et al. (3). Another the interfacial tension for surfactant solutions using clas-
valuable source of analysis of adsorption at the interface sical techniques should be carried out with caution. Sur-
and dynamic interfacial tension is the book published by factants often adsorb on the solid surfaces of equipment
Joos (28). used in measurements and change the wetting character-
Table 3 Characteristic time range for common interfacial tension measurement techniques
Wilhelmy plate >10 s Some of the surfactants might alter the wetting properties
of the plate, causing the change of measurement
conditions (possible source of error)
Du Noüy ring >30 s Same as above
Pendant drop >10 s Strongly surface active chemicals might cause the release
of pending drop before completion of the measurement
Sessile drop >10 s Some of the surfactants might alter the wetting properties
of a solid support substantially changing the shape of
the sessile drop
Drop volume/weight 1 s – 20 min Hydrodynamic effects associated with releasing liquid
volume and circulation of liquid inside the drop
sometimes significantly reduce the accuracy of the
interfacial tension measurements
Maximum bubble pressure 1 ms – 100 s Difficulties with determination of the real surface age and
problems with hydrodynamic effects in the vicinity
of interface
Growing drop/bubble >10 msb Not available commercially
Oscillating jetc 1 – 10 ms Not available commercially
Pulsating bubblec 5 ms – 0.2 s Not available commercially
a
Based on Dukhin et al. (3).
b
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.
Measurement of Interfacial Tension in Fluid-Fluid System 3161
Fig. 10 Schematic of the growing drop apparatus used by MacLeod and Radke. (From Ref. 29.)
3162 Measurement of Interfacial Tension in Fluid-Fluid System
this apparatus, a liquid drop or gas bubble is formed and for pure water, are observed for droplets formed at the
released from a capillary by using a precise micropump to highest capillary flow rates. Conversely, the lowest values
carefully control the growth rate of the drop or bubble. A (approaching the equilibrium interfacial tension for this
pressure transducer is used to simultaneously monitor and solution) were observed for droplets growing at very slow
record the internal pressure in the drop or bubble, while rates. At drop formation times approaching 100 s, inter-
its size and shape are recorded by using a video camera. facial tensions for drops formed at all flow rates approach
These experiments can be carried out for a range of flow the equilibrium value for the 0.25 mM aqueous 1-decanol
rates ranging from near equilibrium growth (very low solution.
flow rates) to highly nonequilibrium growth conditions The zero time for each measurement in Fig. 11 cor-
(very rapid bubble or drop growth). responds to the moment of detachment for the previous
Fig. 11 shows selected results of MacLeod and Radke drop. Data points for a given capillary flow rate in Fig. 11
(29) for growth of 0.25 mM aqueous decanol droplets for start at the time where the drop reaches a hemispherical
a range of droplet growth rates between 5 and 100 mm3/ shape (Fig. 4B), which also corresponds to the point at
min. The plots of interfacial tension vs. time show ini- which the interfacial tension can be evaluated by using the
tially increasing, reaching a maximum, and then decrea- maximum pressure method. Interfacial tension measure-
sing as a function of time. The positive slope of the g vs. t ments using the drop-volume method are, of course, de-
curves for t < 1 results from the depletion of decanol termined at the point where the drop detaches from the
adsorption due to rapid expansion (stretching) of the capillary and correspond to the last data point in the
interface when the bubble is small (see Fig. 4A). As the corresponding curve for the growing drop method. These
drop geometry proceeds beyond hemispherical shape two techniques, therefore, provide ‘‘snapshots’’ of the in-
(Fig. 4C), the relative rate of surface area growth decrea- terfacial tension values in dynamic systems, and they
ses, allowing decanol from the bulk liquid to replenish the bracket the family of curves determined by the growing
surface adsorption. The decrease in interfacial tension as- drop method. The growing drop method provides the very
sociated with this increase in adsorption yields the negative important advantage of continuously recording the inter-
slope observed in the g vs. t curves for t > 1. As expected, facial tension throughout the drop formation and allows
the largest dynamic interfacial tensions, approaching those the competing kinetic effects of interfacial stretching and
solute transport for adsorption to be explored.
MEASUREMENT OF ULTRALOW
INTERFACIAL TENSION
MICROTENSIOMETRY
Criminology, biology, and pharmaceutical processing are Fig. 13 The effect of temperature on interfacial tension mea-
among a number of fields in which material quantities of sured between octane and aqueous phase saturated with CnE4.
interest may be too small to apply conventional tensio- 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) two-pipette technique, with a separation force applied bet-
ween the pipettes to deform the droplet, has been used as
The micropipette technique was recently developed to
shown in Fig. 14B (45). In the two-pipette technique, the
directly measure interfacial tensions of micrometer-sized
separation force between the pipettes must also be mea-
droplets. The technique was first used in examination of
sured, and the interfacial tension is calculated from the
vesicles (43, 44) and next liquid droplets (42, 45). In this
force –drop deformation relation. Table 4 presents the re-
technique, the droplet is first captured at the tip of the glass
sults of interfacial tension measurements for water – orga-
micropipette and then sucked into the pipette (Fig. 14A).
nic liquid systems determined with this technique.
The interfacial tension is calculated from the minimum
pressure, at which the droplet extends a hemispherical pro-
trusion into the pipette, and by using the Laplace Eq. 4 Atomic Force Microscopy
in the following form (42):
The application of AFM permits roughness, heterogeneity,
and interaction forces to be studied at submicroscopic
1 1
Dp ¼ 2g ð19Þ scales that may extend down to molecular sizes. Among
Rp Ro
the most popular applications of the AFM are studies of
where Rp is the inner radius of the pipette and Ro is the interactions between substrates and colloidal particles. The
radius of the exterior segment of the droplet; the dimen- AFM has not been established as a technique to measure
sions of the pipette’s internal diameter must be smaller interfacial tensions directly: however, it appears to have
than the diameter of the droplet. great potential for such measurements at the microscopic
In the conventional technique shown in Fig. 14A, the and submicroscopic levels. The technique is currently be-
large pressure difference required to draw the droplet into ing evaluated as a tool for measuring the wetting properties
the pipette when the droplet does wet or adhere to the pi- of colloidal particles (48).
pette surfaces, is a limitation. To avoid this limitation, a
AFM is a scanning probe technique based on measuring 10. Zuidema, H.H.; Waters, G.W. Ring method for the de-
interaction forces between a cantilever tip and a specimen termination of interfacial tension. Ind. Eng. Chem. Anal.
(Fig. 15). The force measurement is based on measuring
11.
Ed. 1941, 13, 312 – 313.
Young, T. Miscellaneous Works; Peacock, G., Ed.; J. Mur-
M
the deflection of the cantilever, which has a known spring
ray: London, 1855; Vol. I, 418.
constant. The cantilever deflection is detected by the ref-
12. de Laplace, P.S. Mechanique Celeste. Supplement to Book
lection of a laser beam as shown in the figure. Movement
10; 1806.
of the specimen under the cantilever tip (both in the ho- 13. Sugden, S. The determination of surface tension from the
rizontal plane for scanning, and vertically for force mea- maximum pressure in bubbles. J. Chem. Soc. 1922, 121,
surements) is controlled very precisely by a piezoelectric 858 – 866.
specimen stage (reverse systems with the piezoelectric 14. Rehbinder, P.A. Dependence of surface activity and sur-
stage attached to the cantilever holder are also in use). face tension of solutions upon temperature and concentra-
Interaction forces as small as 1pN (1012 N) can be mea- tion. Z. Phys. Chem. 1924, 111, 447 – 464.
sured between the probe tip and the specimen. 15. Lord Rayleigh, OM.; F.R.S. On the theory of the capil-
Fig. 15 shows an approach for measuring the in- lary tube. Proc. R. Soc. London, Ser. A 1916, 92, 184 –
terfacial tension between a probe tip and a microscopic 195.
16. Tate, T. On the magnitude of a drop of liquid formed un-
drop of liquid. The capillarity forces exerted on the tip by
der different circumstance. Phil. Mag. 1864, 27, 176 –
the liquid can be measured as it is inserted into the drop 180.
and as it is withdrawn and detaches from the drop. Cal- 17. Harkins, W.D.; Brown, F.E. The determination of surface
culation of surface tensions from these force-distance tension (free surface energy), and the weight of falling
curves will depend on the shape of the probe tip, but the drops: the surface tension of water and benzene by the
equations should be similar to those for classical macro- capillary height method. J. Am. Chem. Soc. 1919, 41,
detachment techniques. 499 – 525.
A major challenge in using the AFM technique to mea- 18. Miller, R.; Hofmann, A.; Schano, K.H.; Halbig, A.; Hart-
sure interfacial tensions is fabrication of appropriate probe mann, R. Measurement of surface and interfacial tensions
tips. Cylindrical tubes and spheres offer simple geometries with an automatic drop-volume tensiometer. Parfuem. Kos-
and may present the best near-term options. Carbon nano- met. 1992, 73, 390 – 397.
19. Bashforth, F.; Adams, J.C. An Attempt to test the Theory of
tubes have recently been used as AFM tips, and may offer
Capillary Action; Cambridge University Press: London,
another promising approach (49). 1883.
20. Lahooti, S.; del Rio, O.I.; Neumann, A.W.; Cheng, P.
Axisymetric Drop Shape Analysis (ADSA). Applied Sur-
REFERENCES face Thermodynamics; Neumann, A.W., Spelt, J.K., Eds.;
Marcel Dekker, Inc.: New York, 1996; 441 – 507.
1. Rusanov, A.I.; Prokhorov, V.A. Interfacial Tensiometry; 21. Andreas, J.M.; Hauser, E.A.; Tucker, W.B. Boundary ten-
Elsevier: Amsterdam, 1996. sion by pendent drops. J. Phys. Chem. 1938, 42, 1001 –
2. Adamson, A.W.; Gast, A.P. Physical Chemistry of Surfa- 1019.
ces, 6th Ed.; John Wiley & Sons, Inc.: New York, 1997. 22. Stauffer, C.E. The measurement of surface tension by the
3. Dukhin, S.S.; Kretzschmar, G.; Miller, R. Dynamics of pendent drop technique. J. Phys. Chem. 1965, 69, 1933 –
Adorption at Liquid Interfaces: Theory, Experiment, Appli- 1938.
cation; Elsevier: Amsterdam, 1995. 23. Misak, M.D. Equations for determining 1/H versus S
4. Hiemenz, P.C.; Rajagopalan, R. Principles of Colloid and values in computer calculations of interfacial tension by
Surface Chemistry, 3rd Ed.; Marcel Dekker, Inc.: New pendent drop method. J. Colloid Interface Sci. 1968, 27,
York, 1997. 141 – 142.
5. Sonntag, H. Koloidy; PWN: Warszawa, 1982. 24. Quincke, G. Ueber die capillaritäts-constanten des queck-
6. Wilhelmy, L. Ueber die abhängigkeit der capillaritäts- silbers. Ann. Phys. Chem. 1858, 4 (15), 1 – 48.
constanten des alkohols von substanz und gestalt des 25. Padday, J.F. The profiles of axially symmetric menisci.
benetzten fasten körpers. Ann. Phys. Chem. 1863, 4 (29), Trans. R. Soc. London 1971, A269, 265 – 293.
177 – 217. 26. Lang, G. Surface Tension of Liquid Elements. Handbook of
7. Lecomte du Noüy, P. A new apparatus for measuring sur- Chemistry and Physics, 72nd Ed.; Lide, D.R., Ed.; CRC
face tension. J. Gen. Physiol. 1919, 1, 521 – 524. Press: Boca Raton, 1992; 133 – 145, Chapter 4.
8. Harkins, W.D.; Jordan, H.F. A method for determination of 27. Eustathopoulos, N.; Nicholas, M.G.; Drevet, B. Wettabi-
surface and interfacial tension from the maximum pull on a lity at High Temperatures; Pergamon: Amsterdam, 1999;
ring. J. Am. Chem. Soc. 1930, 52, 1751 – 1772. Chapter 4.
9. Vold, R.D.; Vold, M.J. Colloid and Interface Chemistry; 28. Joos, P. Dynamic Surface Phenomena; VSP: Zeist, The
Addison-Wesley Publishing Co.: London, 1983. Netherlands, 1999.
3166 Measurement of Interfacial Tension in Fluid-Fluid System
29. MacLeod, C.A.; Radke, C.J. A growing drop technique for 39. Manual of the Spinning Drop Tensiometer Site 04; Krüss
measuring dynamic interfacial tension. J. Colloid Interface GmbH: Hamburg, Germany, 1995.
Sci. 1993, 160, 435 – 448. 40. Lucassen, J. The shape of an oil droplet suspended in an
30. Drelich, J. The Role of Wetting Phenomena in the Hot aqueous solution with density gradient. J. Colloid Interface
Water Process for Bitumen Recovery from Tar Sand. Sci. 1979, 70, 355 – 365.
Ph.D. Dissertation, The University of Utah: Salt Lake 41. Sottmann, T.; Strey, R. Ultralow interfacial tensions in
City, Utah, USA, 1993. water-n-alkane-surfactant systems. J. Chem. Phys. 1997,
31. Rudin, J.; Wasan, D.T. Mechanisms for lowering of in- 106, 8606 – 8615.
terfacial tension in alkali/acidic oil systems. Colloids Surf. 42. Yeung, A.; Dabros, T.; Masliyah, J. Does equilibrium
1992, 68, 81 – 94. interfacial tension depend on method of measurement? J.
32. Rosen, M.J. Surfactants and Interfacial Phenomena; Colloid Interface Sci. 1998, 208, 241 – 247.
Wiley-Interscience: New York, 1976. 43. Evans, E.; Skalak, R. Mechanics and Thermodynamics of
33. Dynamic Properties of Interfaces and Association Struc- Biomembranes; CRC Press, Inc.: Boca Raton, Florida,
tures; Pollai, V., Shah, D.O., Eds.; ACS Press: Champaign, 1980.
Illinois, 1996. 44. Evans, E.; Needham, D. Physical properties of surfactant
34. Passerone, A.; Liggieri, L.; Rando, N.; Ravera, F.; Ricci, bilayer membranes: thermal transitions, elasticity, rigidity,
E. A new experimental method for the measurement of the cohesion, and colloidal interactions. J. Phys. Chem. 1987,
interfacial tension between immiscible fluids at zero bond 91, 4219 – 4228.
number. J. Colloid Interface Sci. 1991, 146, 152 – 162. 45. Moran, K.; Yeung, A.; Masliyah, J. Measuring interfacial
35. Horozov, T.; Arnaudov, L. A novel fast technique for mea- tensions of micrometer-sized droplets: a novel microme-
suring dynamic surface and interfacial tension of surfactant chanical technique. Langmuir 1999, 15, 8497 – 8504.
solutions at constant interfacial area. J. Colloid Interface 46. Sarid, D. Scanning Force Microscopy; Oxford University
Sci. 1999, 219, 99 – 109. Press: New York, 1991.
36. Vonnegut, B. Rotating bubble method for the determina- 47. Wiesendanger, R. Scanning Probe Microscopy and Spec-
tion of surface and interfacial tensions. Rev. Sci. Instr. troscopy: Methods and Applications; Cambridge Univer-
1942, 13, 6 – 16. sity Press: Cambridge, Massachusettes, 1994.
37. Princen, H.M.; Zia, I.Y.Z.; Mason, S.G. Measurement of 48. Ecke, S.; Preuss, M.; Butt, H.-J. Microsphere tensiometry to
interfacial tension from the shape of a rotating drop. J. measure advancing and receding contact angles on indi-
Colloid Interface Sci. 1967, 23, 99 – 107. vidual particles. J. Adhesion Sci. Technol. 1999, 13, 1181 –
38. Couper, A.; Newton, R.; Nunn, C. A simple derivation of 1191.
Vonnegut’s equation for the determination of interfacial 49. Dai, H.; Hafner, J.H.; Rinzler, A.G.; Colbert, D.T.; Sma-
tension by the spinning drop technique. Colloid Polym. ley, R.E. Nanotubes as nanoprobes in scanning probe mic-
Sci. 1983, 261, 371 – 372. roscopy. Nature 1996, 384, 147 – 151.