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Tension Superficial Tecnicas
Tension Superficial Tecnicas
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
3152
3153
Fig. 1 Classification of techniques for interfacial tension measurements that are discussed in this article.
3154
F
p cos y
F
f
p cos y
1=2
3
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
3155
DP
Drg
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
niscus is spherical, and the surface tension can be calculated by using the following equation:
g
Drghr
2 cos y
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
W VDrg 2prgf p
11
3
V
f p
3
V
0:167 0:193 p
3
V
3
r
0:0496 p
3
V
:0489 p
3
V
2
12
3157
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
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DrgD2
H
17
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).
15
Drgze2
2
16
Practical Comments
Most of the techniques reviewed in this section have been
commercialized. Table 2 summarizes the accuracy, com-
B4
B3
B2
B1
B0
0.401 0.46
0.46 0.59
0.59 0.68
0.68 0.90
0.90 1.00
2.56651
2.59725
2.62435
2.64267
2.84636
0.32720
0.31968
0.31522
0.31345
0.30715
0
0
0
0
0.69116
0.97553
0.46898
0.11714
0.09155
1.08315
0.84059
0.50059
0.15756
0.14701
0.18341
0.18069
0.13261
0.05285
0.05877
0.20970
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Method
Accuracy
mN=m
Suitability
for surfactant
solutions
Suitability
for two-liquid
systems
Suitability for
viscous liquids
Suitability for
melted metals
Commercial
availability
Wilhelmy plate
Du Nouy ring
Maximum bubble
pressure
Capillary rise
0.1
0.1
0.1 0.3
Limited
Limited
Very good
Good
Reduced accuracy
Very good
Very good
Not recommended
Not recommended
Not recommended
Not recommended
Yes
Yes
Yes
Yes
<<0.1
Very good
Not recommended
Not recommended
Not
Drop volume
Pendant drop
Sessile drop
0.1 0.2
0.1
0.1
Limited
Very good
Good
Very good,
experimentally
difficult
Good
Very good
Very good
Not recommended
Not recommended
Very good
Yes
Yes
Yes
Yes
Yes
Not
3160
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 Characteristic time range for common interfacial tension measurement techniques
Method
Time rangea
Wilhelmy plate
>10 s
Du Nouy ring
Pendant drop
>30 s
>10 s
Sessile drop
>10 s
Drop volume/weight
1 s 20 min
1 ms 100 s
Growing drop/bubble
Oscillating jetc
Pulsating bubblec
>10 msb
1 10 ms
5 ms 0.2 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
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
3161
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
Schematic of the growing drop apparatus used by MacLeod and Radke. (From Ref. 29.)
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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
1 3
r Dro2
4
18
3163
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 tensio-
Fig. 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
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.
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).
System
Water-ethyl acetate
Water-chloroform
Water-benzene
Water-toluene
Water-hepto
(From Ref. 45.)
Interfacial tension
measured for
microdroplets
[mN/m)
Interfacial tension
measured for
macrosystem
[mN/m)
6.8 0.6
30.9 1.6
33.7 0.7
36.4 0.8
40.3 1.1
6.8
31.6
34.1
36.1
39.6
Fig. 15 Schematic of atomic force microscopy and its application to measurements of surface tension for microdroplets.
3165
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11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
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