I

Image Interactions repulsion and attraction between them. Three

main types of interactions can be identified: elec-
▶ Electrostatic Interactions trostatic, steric, and van der Waals. The electro-
static repulsion GE arises from the presence of
electrical double layers surrounding the particles
or droplets. The double layers arise from charge
Immobilization separation at the interface which produces
a surface charge that is compensated by unequal
▶ Deposition distribution of counterions (ions with opposite
▶ Particle Deposition charge to the surface) and co-ions (that have the
same charge sign as the surface). The surface
charge together with the compensating charge
forms the electrical double layer which will
Interaction Between Protein and have an extension (thickness) that increases
Polysaccharide with decrease of electrolyte concentration and
valency. When two particles or droplets approach
▶ Protein-Polysaccharide Interaction to a separation distance h that is smaller than
twice the double-layer thickness, repulsion
occurs as a result of the overlap of the double
Interaction Energy layers. Clearly, when the particles or droplets
have opposite surface charges, then the interac-
Tharwat Tadros tion between them becomes attractive. The
Wokingham, Berkshire, UK steric repulsion GS arises from the presence of
adsorbed nonionic surfactants or polymers.
The latter consist of an “anchor” chain that is
Synonyms insoluble in the medium and has a strong affinity
to the surface and a “stabilizing” chain that
Energy barrier is soluble in the medium and strongly solvated
by its molecules. The adsorbed layer is charac-
terized by a thickness d that is determined by
Definition the molecular weight of the stabilizing chain
and the salvation sheath. When the particles or
The interaction energy between particles or drop- droplets approach to a distance h that is smaller
lets in a dispersion gives a measure of the than 2d, strong repulsion occurs as a result of

T. Tadros (ed.), Encyclopedia of Colloid and Interface Science,

DOI 10.1007/978-3-642-20665-8, # Springer-Verlag Berlin Heidelberg 2013
I 634
two main effects: (a) unfavorable mixing, Gmix, of
the stabilizing chains when these are in good sol-
vent conditions and (b) reduction of configura-
tional on considerable overlap entropy that gives
an elastic term, Gel. Combination of Gmix and Gel
gives GS. The van der Waals attraction GA results
mainly from the London dispersion energy which
is due to charge fluctuation in the atoms or mole-
cules that form the particles or droplets. The van
der Waals attraction becomes very strong at short
distances of separation. Combination of GE with
GA gives GT which when plotted versus h shows an
energy maximum (barrier) at intermediate separa-
tion distances that prevents flocculation. Combina-
tion of Gs with GA gives GT which when plotted
versus h gives a small attractive minimum at h
2d
and when h <2d, very strong repulsion occurs, and
this ensures the colloid stability of the dispersion.
Cross-References
▶ Dispersions
▶ Emulsions
▶ Suspensions
Interaction Parameter
Tharwat Tadros
Wokingham, Berkshire, UK
Definition
The interaction parameter gives a measure of the
interaction between molecules, for example, sur-
factants or polymers, or between the molecule
and the medium in which it is dissolved. Various
interaction parameters can be described as
follows: (1) surfactant mixtures with no net inter-
action. This is the case when mixing two surfac-
tants with the same head group but with different
chain lengths. In analogy with the hydrophilic-
lipophilic balance (HLB) for surfactant mixtures,
one can also assume that the critical micelle
concentration, cmc, of a surfactant mixture
Interaction Parameter
(with no net interaction) to be an average of the
two cmcs of the single components. (2) Surfactant
mixtures with a net interaction, for example,
anionics and nonionics. The nonionic surfactant
molecules shield the repulsion between the
negative head groups in the micelle, and hence
there will be a net interaction between the two
types of molecules. Another example is the case
when anionic and cationic surfactants are mixed
whereby very strong interaction will take place
between the oppositely charged surfactant
molecules. To account for this interaction,
an interaction parameter b between the surfactant
molecules in the micelle A positive b value
means that there is a net repulsion between the
surfactant molecules in the micelle, whereas
a negative b value means a net attraction.(3) Poly-
mer-surfactant interaction. The interaction
between surfactants and water soluble polymers
results in some synergistic effects, for example,
enhancing the surface activity and stabilizing
foams and emulsions. (4) Interaction between
surfactant or polymers with the molecules of the
solvent in which they are dissolved: In the case
when there is no interaction between the mole-
cules and the solvent, the mixing is ideal and the
medium is referred to as theta-solvent. When the
molecules interact strongly with the solvent mol-
ecules, the mixing is nonideal and this can be
characterized by an interaction parameter
w < 0.5. When the polymer molecules are in
a poor solvent (worse than a theta-solvent),
polymer-polymer interaction becomes more
favorable than polymer/solvent interaction, and
this results in an interaction parameter w > 0.5.
Cross-References
▶ Foam
▶ Polymeric Surfactant
▶ Surfactants
Interface and Surface
▶ Colloids in Industries: Polymer Colloids
Interface, Liquid-liquid
Interface, Air-liquid
Tharwat Tadros
Wokingham, Berkshire, UK
Synonyms
Air-liquid interface
Definition
The air-liquid interface is that between air
(phase a) and liquid (phase b). The surface of
a liquid is the boundary between two bulk phases,
namely, liquid and air (or the liquid vapor).
An interface between two phases may be defined
providing a dividing line is introduced since the
interfacial region is not a layer that is one
molecule thick, but usually has a thickness d
with properties that are different from the two
bulk phases a and b. However, Gibbs introduced
the concept of a mathematical dividing plane Zs
in the interfacial region. In this model, the two
bulk phases a and b are assumed to
have uniform thermodynamic properties up to
Zs. Using the Gibbs model, it is possible to obtain
a definition of the surface tension g,
starting from the Gibbs-Deuhem equation:
P Liquid-liquid interface
dGs ¼ Ss dT þ Adg þ ni d mi where Gs is
the surface free energy, Ss is the entropy, A is
the area of the interface, and ni is the number of
moles of component i with chemical potential mi
at the interface. At constant temperature and
composition of the interface (i.e., in absence of
 s
any adsorption), g ¼ qG qA T;ni : It is obvious that
for a stable interface, g should be positive. In
other words, the free energy should increase if
the area of the interface increases; otherwise, the
interface will become convoluted, increasing the
interfacial area, until the liquid evaporates
(for A/L case). The surface tension, that is, the
force per unit length tangentially to the surface
measured in units of mNm1, is dimensionally
equivalent to an energy per unit area measured in
mJm2. For this reason, it has been stated that the
635 I
excess surface free energy is identical to
the surface tension, but this is true only for
a single component system, that is, a pure liquid
(where the total adsorption is zero). For polar
liquids such as water, the surface tension is
high, in the region of 72 mNm1, whereas for
nonpolar liquids such as hydrocarbons, g is
lower, in the region of 30 mNm1. Adsorption
of surfactants from aqueous solutions lowers g
from its value in pure water of 72 mNm1 to
a value in the region of 30–40 mNm1,
depending on the nature of the surfactant. Some
molecules such as fluorocarbon and silicone
surfactants can lower g to values 20 mNm1.
Cross-References
I
▶ Surfactants
▶ Wetting
Interface, Liquid-liquid
Tharwat Tadros
Wokingham, Berkshire, UK
Synonyms
Definition
The liquid-liquid interface is that between two
immiscible liquids (phase a and phase b). An
interface between two phases may be defined pro-
viding a dividing line is introduced since the inter-
facial region is not a layer that is one molecule
thick, but usually has a thickness d with properties
that are different from the two bulk phases a and b.
However, Gibbs introduced the concept of
a mathematical dividing plane Zs in the interfacial
region. In this model, the two bulk phases a and b
are assumed to have uniform thermodynamic
properties up to Zs. Using the Gibbs model, it is
possible to obtain a definition of the interfacial
I 636
tension g, starting from the Gibbs-Deuhem
P equa-
tion: dGs ¼  Ss dT þ Adg þ ni d mi where
Gs is the surface free energy, Ss is the entropy,
A is the area of the interface, and ni is the number
of moles of component i with chemical potential mi
at the interface. At constant temperature and com-
position of the interface
@ Gs  (i.e., in absence of any
adsorption): g ¼ @A T; ni : It is obvious that for
a stable interface, g should be positive. In other
words, the free energy should increase if the area
of the interface increases; otherwise, the interface
will become convoluted, increasing the interfacial
area, until the two “immiscible” phases dissolve in
each other. The interfacial tension, that is, the
force per unit length tangentially to the surface
measured in units of mNm1, is dimensionally
equivalent to an energy per unit area measured in
mJm2. For this reason, it has been stated that the
excess surface free energy is identical to the inter-
facial tension, but this is true only for a single
component system, that is, a pure liquid (where
the total adsorption is zero). For an aliphatic
hydrocarbon/polar liquid such as water interface,
the interfacial tension is high, in the region of
50 mNm1, whereas for an aromatic hydrocar-
bon/water, g is lower, in the region of
30 mNm1. Adsorption of surfactants from
aqueous solutions lowers g from its value of the
clean interface of 50 mNm1 to a value in
the region of 1–30 mNm1, depending on the
nature of the surfactant.
Cross-References
▶ Emulsions
▶ Surfactants
Interface, Solid-liquid
Tharwat Tadros
Wokingham, Berkshire, UK
Synonyms
Solid-liquid interface
Interface, Solid-liquid
Definition
The solid-liquid interface is that between a solid
(phase a) and a liquid (phase b). The solid can be
polar (high surface energy solid such as an
oxide), semipolar (intermediate surface energy
solid such as cellulose acetate), or nonpolar
(low surface energy solid such as hydrocarbon
solid or poly(tetrafluoroethylene). The liquid
can be polar (such as water or alcohol) or nonpo-
lar (such as hydrocarbon oil). One can define the
solid/liquid interfacial tension s as the energy per
unit area in mJm1, which depends on the nature
of the solid and the liquid. For a polar solid
dispersed in a polar liquid, charge separation
may take place resulting in the formation of an
electrical double layer. A surface charge so can
be defined that is compensated by unequal distri-
bution of counterions and co-ions. The diffuse
double layer charge sd is equal in magnitude
but opposite in sign to so. A nonpolar surface
is not easily wetted by a polar liquid such as
water, and in this case, a surfactant (wetting
agent) is added to render the surface hydrophilic
by orientation of the surfactant molecule with
the hydrocarbon tail in contact with the
nonpolar surface and the polar head group (ionic
or polar nonionic) pointing toward the bulk solu-
tion. For a nonpolar surface in contact with
a nonpolar liquid, wetting can be spontaneous
and no surfactant is required in this case. The
solid/liquid interfacial tension can reach low
values. Polar (high surface energy surface) solids
are not easily wetted by nonpolar liquids,
and a surfactant is needed to disperse the
polar particles in a nonpolar liquid. In this
case, the polar head group of the surfactant
becomes attached to the polar surface, leaving
the nonpolar hydrocarbon chain pointing toward
the nonpolar medium.
Cross-References
▶ Dispersions
▶ Surfactants
▶ Wetting
Interfacial Dynamics Methods
Interfacial and Bulk Rheology of
Food Systems
▶ Food Rheology
Interfacial Dynamics Methods
A. Javadi1, N. Mucic1, M. Karbaschi2,
J. Y. Won1, V. B. Fainerman3, A. Sharipova4,
E. V. Aksenenko5, V. I. Kovalchuk6,
Nina M. Kovalchuk1,6, A.V. Makievski7,
J. Kr€agel1 and R. Miller1
1
Max Planck Institute of Colloids and Interfaces,
Potsdam/Golm, Germany
2 I
Sharif University of Technology, Teheran, Iran
3
Donetsk Medical University, Donetsk, Ukraine
4
International Postgraduate Institute “Excellence
Polytech” of Kazakh National Technical
University, Almaty, Kazakhstan
5
Institute of Colloid Chemistry and Chemistry of
Water, Kiev, Ukraine
6
Institute of Biocolloid Chemistry, Kiev,
Ukraine
7
SINTERFACE Technologies, Berlin, Germany
Keywords
Capillary pressure tensiometry; Dilational
viscoelasticity; Drop profile analysis; Dynamic
surface tension; Interfacial tension; Liquid film
stability; Maximum bubble pressure tensiometry;
Oscillating drops and bubbles
Definition
Dynamic surface and interfacial tensions are the
easiest to measure properties of liquid interfaces.
Required by many modern technologies, short-
time data are very important. The bubble pressure
tensiometry is a classical method and provides
data for the shortest adsorption times, even
down to milliseconds. For interfaces between
two immiscible liquids, the capillary pressure
637 I
tensiometry is the most promising technique.
Combination of this technique with complemen-
tary drop and bubble profile analysis provides a
very large time range of adsorption studies tools.
The surface/interfacial relaxation behavior,
i.e., the reaction of an interfacial layer to external
perturbations, can be quantitatively studied by
oscillating drops and bubbles.
Overview
All modern technologies dealing with liquids, for
instance, emulsification or foaming, are of very
dynamic character. Originally, all of these
methods were bases on an empirical basis. Now,
however, we have reached a state were any
increase in their efficiency requires a solid scien-
tific basis. The development of such a scientific
foundation needs serious efforts. From
a formulation point of view, a quantitative anal-
ysis of the effects of emulsifiers, foaming agents,
and additives becomes increasingly important,
i.e., possibilities for the measurement of their
interfacial properties are very essential.
Among the measurable quantities of dynamic
interfacial layers easiest accessible are the sur-
face and interfacial tensions, for the measurement
of which a large number of tensiometers exist.
This frequently applied methodology allows
a quantitative characterization of liquid inter-
faces. Looking back into the history, the ring
and plate tensiometry were the first methods
that had been systematically applied. These
essentially static or quasi-static methods are still
in use, mainly due to the yet valid standards
elaborated in the past for their proper application
(e.g., the standards of the American Society for
Testing and Materials – ASTM). The ring and
plate tensiometers are still used in many labora-
tories due to the mentioned standard reasons.
However, for many applications, they are by far
not optimal measurement tools although nowa-
days all instruments are operated by modern
computers. In particular for liquid-liquid inter-
face, problems of wetting arise and cannot be
easily controlled or avoided, so that the measured
quantities can be affected by systematic errors.
I 638
The enormous progress in the development of
electronic sensors and powerful computers,
gained mainly over the last 25 years, created
a basis for new and very efficient experimental
methods. One of the important items is, for exam-
ple, the accurate pressure sensor which gives
access to measurements of the pressure in drops
or bubbles with an accuracy of few Pascal with
a stable signal over hours. Another impressive
building block of modern instruments in fluid
science is the piezo actuator, which allows
making volume changes in the range of
nanoliters. Moreover, the development of the
video technique allows recording all situations
in an experiment and provides the necessary
information for a quantitative analysis. This
requires high-performance computers as the anal-
ysis of high-resolution images is a quite time-
consuming job. And in cases where a standard
video technique is insufficient, also high-speed
video recording with 105 frames per second is
available, even with a sufficient high resolution.
Here of course computers of very high capacity
are needed, in addition to efficient image analysis
procedures in order to handle the enormous
amount of data.
The advent of modern drop profile instruments
was actually coming with the availability of the
first electronic video cameras. Their quality was
yet not sufficient for accurate measurements, and
the acquired images had to be corrected
according to a mechanically produced calibrated
grid. Also the data handling was not as easy as it
is now. For example, to transfer the image of
a pendant drop from the camera via a frame grab-
ber into a computer, extract the drop profile
coordinates and then fit the Gauss-Laplace
equation to this profile was the job for a so-called
work station. These days video cameras are of
extremely high quality, have very high resolu-
tion, and can even provide many thousand frames
per second. This makes drop and bubble profile
tensiometry presently the most frequently used
method in surface science laboratories. And work
stations have been completely replaced by
normal PCs, and even laptops do the job of
image acquisition and fitting, and all this even
in fractions of a second.
Interfacial Dynamics Methods
A second group of measuring techniques,
complementary to the drop and bubble profile
methods is the capillary pressure tensiometry.
This type of tensiometers works in the range of
short adsorption times. The most popular and
obviously the method with access to the shortest
adsorption times of less than 1 ms is the maxi-
mum bubble pressure tensiometry. Since about
20 years now, there are commercial instruments
available that are based on this principle and
provide short-time adsorption data at the
solution-air interface. There are also capillary
pressure tensiometers for studies of interfaces
between two immiscible liquids. They can even
be applied to interfaces between two liquids of
the same density or liquid systems under micro-
gravity conditions. The drawback here is, in com-
parison with the bubble pressure tensiometry,
that the much higher viscosity of the liquids, as
compared to gas, leads to additional problems to
be solved. The shorter the time for the measured
interfacial tension is, the larger are the contribu-
tions by the hydrodynamics. Hence, an accurate
separation of liquid flow effects from the interfa-
cial effects being the main target of such
measurements is required.
In addition to the time dependent surface and
interfacial tensions, the dilational rheology pro-
vides another set of interfacial parameters suit-
able for the characterization of dynamic liquid
interfaces. This family of experimental instru-
ments is based on small-amplitude interfacial
perturbations. The subsequent relaxation pro-
cesses are recorded in terms of changes in the
surface/interfacial tension. Knowledge on the
dilational viscoelasticity is of great importance
for understanding the dynamic processes going
on in interfacial layers. In the 1960s, the surface
wave damping methods were the most important
tools. Now, the oscillating drop and bubble
methods are most often applied. While slow
oscillations can be studied via drop profile anal-
ysis tensiometry, for higher frequencies, the cap-
illary pressure tensiometers are the only suitable
instruments.
There are also other interfacial techniques
available to quantitatively study changes of the
interfacial properties. For example, optical
Interfacial Dynamics Methods
methods, such as interfacial ellipsometry, provide
information on the properties of interfacial layer;
however, due to the rather complex measuring
procedures, the time resolution is often low, and
more than 10 measurements per hour are pres-
ently difficult to perform. The same is true for
nonlinear optical methods like sum frequency or
second harmonic generation instruments.
Very spectacular are the recently designed
microfluidic devices. Some are able, for example,
to produce series of drops or bubbles under very
controlled conditions. It is even thought that
piling up such microfluidic devices could allow
the production of designed emulsions or disper-
sions via these principles. Most of the
microfluidic devices, however, are not equipped
with measuring technique and therefore work
only in a qualitative way. The drop-drop manip-
ulation tool, presented at the end of this manu-
script, is equipped with capillary pressure sensors
and piezo translators as fine dosing systems.
Therefore, this method can be seen as
a microfluidic device with the possibility of quan-
titative investigations. It allows studies of
elementary processes in foams or emulsions,
such as the coalescence between two drops or
two bubbles, respectively. Also asymmetric
systems can be investigated by looking after the
interaction between a drop and a bubble, as it is
the case in reality in foamed emulsions – ice
cream, for example.
It is the subject of future work to reach yet
shorter times and higher frequencies of perturba-
tion, which are needed for highly dynamic pro-
duction processes. This, however, entails not only
the need of fast data acquisition but requires also
to solve very complex theoretical problems,
such as the combination of matter transfer and
liquid flow pattern. Both topics are closely
linked in experiments at very short times or
high-frequency perturbations. The separation of
the interfacial effects from the integral measuring
signals becomes a most difficult task. The
utilization of a high-speed and high-resolution
video technique will surely allow us to achieve
the mentioned goals and to get a quantitative
knowledge of the relevant interfacial dynamics
properties.
639 I
Introduction
Dynamic interfacial properties are gaining more
and more interest due to the many fields of appli-
cation. Increasing the efficiency of a technology
is typically linked with increased speed. For tech-
nologies including liquids, this entails faster
formation of interfaces in general, and of droplets
and bubbles in the case of emulsion and foam
systems. Hence, the trend is to go to shorter and
shorter adsorption times.
This general trend in technologies creates
strong demands on the fundamental analysis of
interfaces and on the availability of experimental
tools. The most versatile group of experimental
methods is tensiometry. It is the easiest and most
frequently applied methodology for the quantita-
I
tive characterization of liquid interfaces.
Looking back into history, we had ring and
plate tensiometry as classical methods. These
mainly static or quasi-static methods were used
in the past, and many standards were elaborated
for their proper application, such as the ASTM
(American Society for Testing and Materials)
standards. The ring and plate tensiometry are
still used in many laboratories, due to the exis-
tence of these standards; however, for most of the
applications, they are by far not optimal any more
although operated by modern computers.
Developments in electronics and increase in
computer capacity over the last decades created
the basis for new advanced experimental
methods. This is true for accurate pressure sen-
sors but also for video technique. While first drop
profile instruments were equipped with electronic
cameras, the images of which had to be corrected
according to a calibrated grid (see Cheng et al.
1990), these days, the video cameras are of
extremely high quality, high resolution, and can
even provide several thousand frames per second.
Due to these facts, the variety of tensiometry
methods has been reduced now to mainly two
techniques which complement each other and
cover a broad time interval – drop and bubble
profile analysis tensiometry and capillary
pressure tensiometry. The capillary pressure ten-
siometry can even be applied for interfaces
between two immiscible liquids of the same
I 640
density or under microgravity conditions
(Kovalchuk et al. 2010).
For the characterization of liquid interfaces,
the dilational rheology provides another set of
interfacial parameters which are of great impor-
tance for understanding the dynamic interfacial
processes. While in the past, surface wave
damping methods were the most important
tools, presently, the oscillating drop and bubble
methods are most often applied. Slow oscillations
can be studied via drop profile analysis tensiom-
etry, while for higher frequencies, the capillary
pressure tensiometers are suitable.
There are also other interfacial techniques
available which give access to changes in the
interfacial properties, such as ellipsometry; how-
ever, due to the time consumable measuring
procedures, the resolution is of the order of 10
measurements per hour.
Very spectacular are nowadays the microfluidic
techniques, which allow producing liquid disperse
systems under very controlled conditions. It is
even thought that piling up such microfluidic
devices could allow the production of designed
emulsions or dispersion via microfluidic principles
(Shah et al. 2008). The microfluidics is usually not
equipped with measuring technique. The finally
presented drop-drop interaction tool, however, is
equipped with capillary pressure technique and
piezo translators as fine dosing systems. This
method can be seen as a microfluidic tool on the
level of quantitative investigations.
This entry gives a summary of the traditional
as well as state of the art tools for the character-
ization of liquid interfaces, including the two
complementary methods of drop profile analysis
and capillary pressure tensiometry as present
workhorses in surface and interfacial science.
Dynamic Surface Tension
For investigating liquid interfaces, there are
several methods available; however, to study the
dynamics, the arsenal is not very large. Dynamic
surface tensions are the most suitable and best
developed methods to measure surface properties
as a function of time, even at very short
Interfacial Dynamics Methods
adsorption times. While drop and bubble
methods are the workhorses in the modern labs
now, the traditional classical methods like ring
and plate tensiometry are less and less applied.
Classical Methods
There are a number of classical tensiometry
methods which were a must in the past for every
surface science laboratory. The oldest procedure is
possibly the plate tensiometry which measures the
force (weight) of a liquid meniscus formed spon-
taneously when the plate is brought into contact
with the liquid. Due to his significant contributions,
the method is also called Wilhelmy plate method,
as summarized by Rusanov and Prokhorov (1996).
A similar protocol was proposed by the French
physicist Pierre Lecomte du No€uy (1925), who
measured the maximum force (weight) required
to raise a ring from the surface of a liquid. Both
methods are still in practice (see Lunkenheimer
1982; Wu et al. 1999; Richter and Vollhardt
2006) but less and less efficient as compared to
modern methodologies. For contact angle studies,
however, the Wilhelmy plate technique is yet often
applied (Smedley and Coles 2005).
One more relatively old method is the drop
volume tensiometry proposed by Tate (1864).
It determines the volume of drops detaching
from a capillary of given diameter. Knowing the
radius of the capillary and the liquid’s density, it
is possible to calculate the surface tension. This
method is still used because it allows accurate
measurements even for liquid/liquid systems,
although the available time window is rather nar-
row (see Javadi et al. 2011a).
In summary, we can conclude that classical
methods are still in use, but most of the require-
ments can be covered much better with drop and
bubble methods as described further below.
Maximum Bubble Pressure Tensiometry
More than 150 years ago, Simon (1851) was the
first who proposed the maximum bubble pressure
method for measuring the surface tension of
liquids. Caused by the fast development of elec-
tronics and computers, the maximum bubble
pressure technique became quickly a classical
method in interfacial science and provides
Interfacial Dynamics Methods
Gas inflow L at pressure P
Solution
Interfacial Dynamics Methods, Fig. 1 Scheme of
a bubble pressure experiment
experiments at the shortest adsorption times now.
After Simon, the pioneers doing the most impor-
tant steps toward the existing instruments now
commercially available are Mysels (1990),
Kloubek (1968), and most of all Fainerman
(1979) who made the method a standard (Miller
2011) for dynamic surface tensions in the range
of milliseconds (Fainerman 1990) and even
below (Fainerman et al. 2006).
The theory which describes the diffusion-
controlled adsorption kinetics of surfactants at
a liquid surface was first derived by Ward and
Tordai (1946). This theory is summarized in
Section 3 of the article ▶ Surfactant Adsorption
Kinetics; in this section, we particularize to the
experimental studies only.
The main principle of the maximum bubble
pressure tensiometry is rather easy and can be
practiced in any laboratory with a simple con-
struction, such as a capillary connected with
a gas supply and a manometer for pressure mea-
surement (cf. Fig. 1). However, reproducible
experiments for a quantitative analysis of the
adsorption mechanism taking place at the bubble
surface during the growth and separation of
a bubble require rather sophisticated instruments,
and not all instruments on the market fulfill these
requirements (Meissner et al. 2004).
The design of a typical bubble pressure tensi-
ometer includes a gas supply, a gas flow control
641 I
Pmax
Pressure
tI td
Time
Interfacial Dynamics Methods, Fig. 2 Stages of bub-
ble formation and definition of bubble lifetime and dead
time
I
unit, a capillary, a pressure sensor, and a proxim-
ity electronic to control the experimental proce-
dure and to monitor the data. A comprehensive
description of all experimental details was given
recently in Fainerman and Miller (2011). The
main problem to be solved, along the accurate
measurement of the maximum pressure in the
bubble as a function of bubble lifetime, is the
analysis of the time intervals between two suc-
cessive bubbles. The time interval between two
bubbles tb consists of the lifetime tl and the dead
time td (cf. Fig. 2). The lifetime tl is the period
from the beginning of a bubble formation, right
after the detachment of the old bubble, until the
moment of maximum pressure. This maximum
pressure is established when the bubble reaches
its hemispherical size. The dead time is then the
remaining period from the moment of maximum
pressure until the bubble detachment. The higher
the bubble frequency and the shorter the bubble
dead time, the shorter can be the lifetimes
reached by such an experimental setup.
The measured maximum pressure Pmax corre-
lates with the surface tension g in a simple
relationship:
2g
Pmax ¼  Drgh; (1)
rcap
where rcap is the capillary radius, Dr is the den-
sity difference between the liquid and the gas, g is
I 642
Interfacial Dynamics
Methods, Fig. 3 The
dependence of dynamic 70
surface tension of Triton
X-100 solutions at room
temperature for different
concentrations: 5  105 60
(1), 104 (2), 2  104 (3),
5  104 (4), 103 (5), and
2  103 mol/l (6), γ [mN/m]
according to Fainerman and
Miller (2004) 50
40
30
0.001
the gravity constant, and h is the immersion depth
of the capillary into the liquid. Under highly
dynamic conditions, additional terms have to be
considered in addition, such as the aerodynamic
resistance of the capillary, and the effects of
viscous and inertia effects of the liquid
(Kovalchuk and Dukhin 2001). If the capillaries
are too large, i.e., have a radius of rcap > 100 mm,
a correction of the non-sphericity of the bubble
shape has to be considered:
rcap  Pmax
g¼f
2
where f is a correction factor that depends mainly
on the capillary diameter and the surface tension,
as shown, for example, by Bendure (1971).
There is much systematic work on the quanti-
fication of the aerodynamic, viscous, and inertia
effects performed recently and summarized in
Fainerman and Miller (2011). Therefore, these
problems will not be discussed here, although
they are of extraordinary importance for reaching
shortest adsorption times. Instead, we want to go
a bit more into the detail of determining the dead
time accurately, even at high bubble frequencies.
Kloubek (1972) proposed for this case that the
dead time can be assumed to be equal to the
Interfacial Dynamics Methods
1
2
3
4
5
6
0.01 0.1 1 10 100
t1 [S]
bubble time. A much more suitable procedure
was proposed by Fainerman (1992) who analyzed
the dependence of pressure as a function of gas
flow rate P (L) and found a sharp transition from
a gas jet to a separate bubble regime. The sharp
transition at Pc and Lc defines the critical moment
where bubble time tb and dead time td are really
identical. From here, the dead time can be
calculated much more accurately:
LPc
td ¼ tb : (3)
Lc P
(2)
Figure 3 shows the dynamic surface tensions
for six different Triton X-100 concentrations.
These are typical short-time data that can be
used for the analysis of the adsorption kinetics
of a surfactant at the water/air interface. It was
demonstrated by Fainerman and Miller (2004)
that even for a technical surfactant like Triton
X-100, the adsorption kinetics can be described
by a diffusion controlled mechanism. The analy-
sis of long-time adsorption data (not shown here)
cannot be described by such a simple adsorption
model because the various compounds adsorb at
the surface and provide a rather complex picture.
In the end, however, each component would
possibly follow again a diffusion mechanism.
Interfacial Dynamics Methods 643 I
Interfacial Dynamics
Methods,
Fig. 4 Dynamic surface 70
1
tension for C14EO8
solutions as a function of 2
the effective surface
lifetime; labels correspond 60 5
to the surfactant
10

γ [mN/m]
concentrations given as
multiples of the CMC 20
(1.1  105 mol/l); 50
according to Fainerman 50
et al. (2006) 100
200
40

30
0.0001 0.001 0.01 0.1 1 10 100
t [S] I

In Fig. 4, the dynamic surface tensions are where T is the temperature and R is the gas law
shown as measured by bubble pressure tensiom- constant. Model calculations require the rate
etry for micellar solutions of C14EO8 as functions constant of fast micelle dissolution kf as extra
of the effective lifetime (Fainerman et al. 2006). parameter, which is available from studies of
The analysis shows that this type of nonionic various authors using ultrasonic and thermal
surfactants adsorbs according to a diffusional relaxation, stopped flow, and other techniques
adsorption mechanism. as summarized by Fainerman and Miller (2011).
A linearized theory to analyze dynamic surface Hence, by a comparison of the experimental
tension curves was first outlined by Fainerman dependencies given in Fig. 4 with calculations,
(1981). An approximation for the change in it can be verified whether the model of fast
adsorption with time G(t) for the mechanism of micelle dissolution/formation is valid.
fast micelle dissolution/formation for short adsorp-
tion times was derived by Fainerman et al. (2006): Bubble Profile Tensiometry
Profile analysis tensiometry (PAT) allows mea-
 1=2     suring the surface/interfacial tension of liquids
Dt 2 c0  cCMC
G ¼ 2cCMC 1þ kf t ; (4) via the analysis of the shape of a buoyant or
p 3 cCMC
pendant drop or bubble formed at the tip of
a capillary. The method is suitable for both
where c0 is the total surfactant concentration, D is liquid–gas and liquid-liquid interfaces, and appli-
the diffusion coefficient of surfactant monomers, cable to systems ranging from molten metals to
cCMC ¼ CMC, and kf is the fast micelle pure organic solvents and diluted and concen-
dissolution/formation constant. Equation 4 was trated solutions. There is also no limitation with
derived under the assumption kf·t«1. With respect to the magnitude of surface or interfacial
P ¼ g0  g ¼ RTG; i.e., in the range of low tension, accessible in a broad range of tempera-
surface coverage, Eq. 4 can be transformed to: tures and external pressures (see Neumann and
 1=2     Spelt 1996). For measurements at constant inter-
Dt 2 c0  cCMC
P ¼ 2RTcCMC 1þ kf t ; facial area, the time window ranges from about
p 3 cCMC 1 s up to hours and days so that even extremely
(5) slow processes can be followed.
I 644
Dosing System
Video Camera
Light Source
PC with Integrated Frame Sample
Grabber
Interfacial Dynamics Methods, Fig. 5 Main elements
of a drop profile analysis tensiometer
The concept of the instrumentation looks
rather simple. A profile analysis tensiometer
(PAT) consists of a dosing system driven by
a computer software, a measuring chamber, and
a CCD camera (see Fig. 5). The dosing system
produces a drop of the test liquid (or a bubble in
the test liquid) at the tip of an appropriate capil-
lary. The capillary should provide a good wetting
such that axisymmetric drops/bubbles are
formed. Usually metal and plastic capillaries are
used, depending on the type of surfactant solu-
tions studied. Another important part of the
PAT is the measuring chamber with a glass
cuvette in which the respective capillary sits.
The glass cuvette contains the second immiscible
fluid. For drops in air, the cuvette contains some
of the liquid at the bottom in order to provide
a saturated atmosphere for minimizing evapora-
tion from the surface of the studied drop. In this
section, we mainly deal with the liquid–gas inter-
face, while further below, we will discuss the
peculiarities of liquid-liquid interfaces. Note, for
the methodology nothing is changed, except that
the density difference between the two fluids is
smaller, in some cases even very small so that the
drops can become spherical (see later).
Liquid-air interfaces in PAT experiments can
be established in two ways, either by using
a pendant drop or by immersing an air bubble
into the liquid contained in the cuvette. For low
concentrated solutions, experiments with
a bubble formed in the solution are preferred
over a single drop in air. The reason is that due
to the very small volume to surface area ratio in
the drop configuration, a depletion of surfactant
molecules from the bulk due to adsorption at the
drop surface can happen. Such depletion is
Interfacial Dynamics Methods
essentially negligible for the bubble configura-
tion. This phenomenon is well described, for
example, by Fainerman et al. (2008), and the
surfactant depletion can even be used to quantify
the amount of adsorbed molecules.
The measurement step consists of recording
the drop/bubble image by a CCD camera, with
a subsequent transfer via a digitizing board to
a computer, and thereafter the analysis of
the drop/bubble profile in order to fit it by the
Gauss-Laplace equation and obtain the
corresponding surface tension. Figure 6 shows
the definition of the profile coordinates (x and z)
and other parameters (R1, R2, s and y) of a drop or
bubble. The extracted profile coordinates are
compared with drop profiles calculated from the
Gauss-Laplace equation (Neumann and Spelt
1996), and via a best fit routine, the value of the
surface tension g as only free parameter
is obtained.
The point (xi, zi) refers to the polar angle y
with the arc length s, measured from the drop
apex. R1 and R2 are the two principal radii of
curvature at the apex. For axisymmetric profiles,
the two radii become identical R1 ¼ R2 ¼ R0. The
standard form of the Gauss-Laplace equation
(also called Young-Laplace equation by some
authors) describes the mechanical equilibrium
of the interface between two homogeneous fluids.
Padday (1969) has shown routines for solving
this equation, which can be presented in the
following parametric form:
dx
¼ cos y (6)
ds
dz
¼ sin y (7)
ds
dy 2 Drgz sin y
¼   : (8)
ds R0 g x
Here, Dr is the difference between the densities
of the two fluids, and g is the acceleration due to
gravity.
In the meantime, various algorithms have
been developed for all calculation routines
required to make the profile analysis a method
Interfacial Dynamics Methods 645 I
z

Gauss Laplace
PAT Equation

dx R2
R1
dz
ds (xI,zI)
Θ
x

Interfacial Dynamics Methods, Fig. 6 Definition of the coordinate system for a liquid drop and the schematic how
the surface tension is obtained by a fitting routine

Interfacial Dynamics
Methods,
Fig. 7 Dynamic surface
tension of C10EO4 solutions
measured by the drop
profile method at
different concentrations
(mol/l): 105 ( ), 2  105
( ), 3  105 ( ),
5  105 ( ), 104 ( ),
2  104 ( ), 3  104 ( ),
5  104 ( ), and
7  104 ( ), according to
Schulze-Schlarmann et al.
(2005)

for determining accurately the surface tension,
including edge detection to get the drop/bubble
profile coordinates, optimization procedures for
finding the optimum value of the only free param-
eter, the surface tension g, and accurate solution
of the Gauss-Laplace equation (see also Zholob
et al. 2011).
As experimental example, we see in Fig. 7 the
dynamic surface tension measured for aqueous
C10EO4 solutions using the drop profile tensiom-
etry. From the curves, it is visible that PAT is not
suitable for measuring the short-time values,
i.e., t < 2 s, and only the long-time adsorption
dynamics of C10EO4 can be recorded. In a recent
work by Mucic et al. (2011a), it was analyzed for
which type of surfactants and in which solution
concentration interval the profile analysis tensi-
ometry is the best choice. It was also shown that
the use of a complementary set of methods,
consisting of the maximum bubble pressure and
drop profile tensiometry, covers the broadest time
interval of about eight orders of magnitude which
is most suitable for many practical problems in
adsorption kinetics.
Dynamic Interfacial Tension
Similarly to liquid/gas surfaces, for the interface
between two liquids, the measurement of
I 646
Interfacial Dynamics Methods, Fig. 8 Pendant water
droplet in three different fluids representing a large,
medium, and low density difference Dr (air, hexane, and
silicon oil), respectively. (a) Water drop in air, drop
volume 9 mm3, Dr ¼ 996.8 kg/m3, g ¼ 72.3 mN/m
interfacial tension is the most efficient tool for
studies of the dynamics of their interfacial
properties.
Capillary Pressure Tensiometry
Almost all traditional and common experimental
techniques for measuring the surface/interfacial
tension are based on the existence of a consider-
able buoyancy force and its competition with the
surface/interfacial tension force. However, for
liquid-liquid interfaces, in particular for condi-
tions of a low density difference, these techniques
fail to measure correct values. Under micrograv-
ity condition, this problem is true for any inter-
face. As an example, Fig. 8 shows the shape of a
pendant water droplet at a capillary tip immersed
in three different media: air, hexane, and silicon
oil (350 CP). Clearly with decreasing density
difference, i.e., decreasing gravity force pulling
downward, the interfacial tension contribution is
increased significantly, and as this force tends to
minimize the surface area, the drop shape tends
more and more to a spherical shape. The calcula-
tion of interfacial tension from a spherical shape
is either largely erratic or even almost impossible.
The increase of the drop volume might help to
improve interfacial tension measurements;
however, there are practical limitations for
making experiments with extra large droplets
and also cannot completely eliminate the original
errors. The problems in dynamic experiments are
Interfacial Dynamics Methods
(b) Water drop in hexane, drop volume 9 mm3,
Dr ¼ 338 kg/m3, g ¼ 51 mN/m (c) Water drop in silicon
oil (350 cP), drop volume 8 mm3, Dr ¼ 33 kg/m3, g ¼ 40
mN/m
much higher, as drop shape deformations, viscos-
ity effects, drag forces, and respective instabil-
ities become larger with increasing drop size.
These are the main reasons for having the capil-
lary pressure techniques as alternative to profile
tensiometry for which the pressure jump across
the interface is measured and yields the
surface/interfacial tension values accurately via
the Laplace equation in its simplest form,
Pcap ¼ 2g(t)/r(t). As the basis of measurements
does not depend on the determination of the
accurate drop profile, this technique is a great
tool for experiments under highly dynamic
conditions (range of 1,000 to 0.001 s).
History of Experimental Capillary Pressure Setups
The history of the development of experimental
setups goes back to the beginning of the 1990s
(Passerone et al. 1991; Nagarajan and Wasan
1993; MacLeod and Radke 1994; Zhang et al.
1994; Liggieri et al. 1995). However, from the
first version of such instrument for slowly chang-
ing interfaces to fast dynamic conditions realized
by the present generation of setups, there was
a long way with several problems to be solved,
including hardware/software and data analysis, as
summarized recently (Kr€agel et al. 2005; Javadi
et al. 2006, 2009, 2010a; Ravera et al. 2010a, b;
Kovalchuk et al. 2010, 2011). The schematic
view of a recently developed capillary pressure
setup (ODBA, SINTERFACE Technologies) is
Interfacial Dynamics Methods 647 I
Processor

Interface Control Box

Data and Drop Image Monitoring

Inlet Valve

Pressure
Chamber
Pressure
Piezo Drive Sensor

Syring I
Pump

Capillary
Tip
Light Source CCD Camera
Solution Reservoir

External cell

Interfacial Dynamics Methods, Fig. 9 Schematic of the capillary pressure setup ODBA (Javadi et al. 2010a)

shown in Fig. 9 (Javadi et al. 2010a). A droplet
is formed at the tip of a capillary, and a sensor
measures the pressure differences between the
pressure chamber and the surrounding atmo-
sphere. By the use of a syringe pump or piezo
drive, growing and oscillating drop experiments
can be performed (see further below).
The cell containing the external fluid phase
can be open to the atmosphere or designed as
a closed chamber. For a closed cell, the geometry
and compressibility of the solid walls, sealings,
and other parts contribute significantly to the total
measured pressure and should be considered
quantitatively in the data analysis. In addition,
the range of drop volume changes should be
controlled carefully to avoid sudden high
overpressure which may damage the sensitive
pressure sensor. Therefore, the version of
a closed cell is used just for special purposes,
and the open cell configurations are more
common. Depending on the capillary tip and
pressure sensor arrangement, mainly two differ-
ent configurations might be considered for the
setup (Fig. 10). At a first glance, the differences
appear rather little; however, the applicability to
gas/liquid and liquid/liquid systems can be sig-
nificantly different. The main differences are
seen in the hydrodynamic contributions and the
compressibility effects. The configuration B is
a closed cell, but it is open to the atmosphere
through phase 2, while the configuration A is
linked to the atmosphere via the fluid phase 1.
The main benefit of configuration B is for
gas/liquid interfaces for which phase 2 is air,
and the hydrodynamic contribution of the air
flow inside the narrow capillary is small. How-
ever, for this configuration, any growing drop
(in gas) experiments are impossible.
I 648
Interfacial Dynamics a b
Methods, Fig. 10 Two
different configurations of
phase 2
recently developed
PIEZO-
capillary pressure setups: PISTON
A - ODBA configuration;
B - CPT configuration
(Kovalchuk et al. 2011)
phase 1
Elementary Experiments and Calibration
Procedures
The measured total pressure includes different
contributions indicated below and should be
evaluated accurately:
PðtÞ ¼ Phyd þ Pvisc þ Pinertial þ Pdrag þ Pcap ;
(9)
where the terms in the right hand side correspond
to the hydrostatic pressure, viscosity effects
inside the tip, inertial effects, the drag force
of second phase on the growing drop, and the
capillary pressure term as our main target,
respectively.
The hydrostatic pressure of the liquid column
between the pressure sensor and droplet position
should also be corrected considering the immer-
sion depth of the droplet in the external phase.
Firstly, some basic experiments should be
performed under static conditions with pure
liquids, and the results should fulfill the Laplace
equation from small to big droplets (Fig. 11). This
is important for testing the pressure sensor’s
accuracy, the applied zero reference parameters
and offset, and the capturing of drop images. For
very small or very big droplets, a small disagree-
ment might be observed because of wettability
issues, optical distortions, and deformation from
sphericity at large volumes. Some additional
effects can arise due to impurities in the studied
solvent system. These matters can be checked
using cycling experiments with several expan-
sions/contractions of a drop (Figs. 11, 12).
Interfacial Dynamics Methods
phase 2
PRESSURE
SENSOR
PRESSURE
phase 1 SENSOR
PISTON
PIEZO-
Hydrodynamic Effects
Dynamic experiments can be performed via two
different growing/oscillating experimental pro-
tocols. Figure 13 shows an experimental exam-
ple of a growing water drop in silicon oil
(viscosity 1,000 cP). A water drop with the size
of about 1 mm3, firstly at static conditions, is
subsequently expanded during 50 s to a size of
12 mm3. During this process, the capillary pres-
sure decreased from 120 Pa to about 50 Pa,
while the measured interfacial tension shows
a constant value of about 39 mN/m. Such behav-
ior is expected for a pure solvent system (Javadi
et al. 2011b). Regarding the low density differ-
ence for this system, the capillary pressure tech-
nique is the most suitable (and almost only)
experimental method for these kinds of mea-
surements. For fast dynamic conditions due to
the viscous flow of liquid in the system and
especially inside the narrow capillary tip, the
hydrodynamic pressure loss can be significant
and should be measured separately and consid-
ered accurately in any further data analysis
(Javadi et al. 2006, 2010a; Kovalchuk et al.
2011). Figure 14 shows an example for the
water flow through a typical capillary tip (inter-
nal diameter 0.5 mm and length 3 mm) when the
capillary tip is immersed in water in order to
avoid any interfacial effects (Javadi et al.
2006). The results demonstrate a hydrodynamic
pressure loss from 10 to several hundred
Pascal (depending on the flow rate) which are
considerable values in comparison with the cap-
illary pressure values that are in the range
Interfacial Dynamics Methods 649 I
Interfacial Dynamics 400
Methods,
Drop expansion path
Fig. 11 Dependence of
capillary pressure on drop Drop Contraction path
radius as calibration 350
experiment of a capillary
pressure setup (ODBA) for

Capillary Pressure (pascal)

quasi-static water drops
in air 300

ΔP = 2γ/r
250

200

150 I

100
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
1/R

80 DP is the hydrodynamic pressure loss, L is the

Drop Expansion Path capillary length, m is the dynamic viscosity, Q is
78
Drop Contraction Path
the mass flow rate, rcap is the capillary radius,
76
and r is the fluid density. Up to a considerable
Surface Tension (mN/m)

74 expanding drop rate, the drag force and inertial

72 terms are negligible, which simplifies the esti-
70 mation of viscosity effects for the subsequent
68
analysis of data for surfactant solutions (Javadi
et al. 2010a).
66
The capillary pressure Pcap increases signifi-
64 cantly with decreasing drop radius. This can be
62 achieved using smaller capillary tip radii.
60
However, the given approximation shows a dra-
0.4 0.5 0.6 0.7 0.8 0.9 matic increasing in the hydrodynamic contribu-
Drop Radius (mm)
tion with decreasing capillary tip size. For
Interfacial Dynamics Methods, Fig. 12 Surface experiments with higher flow rates, the results
tension values for different drop radii as calibration exper- can deviate from such simple approximation sig-
iment of a capillary pressure setup (ODBA) for nificantly because of emerging turbulence effects
quasi-static water drops in air
or nonstationary conditions so that more accurate
calculations or direct computational simulations
of 50–500 Pa (depending on the drop size). are required (Javadi et al. 2006; Kovalchuk et al.
The results show a good agreement with a sim- 2000). Therefore, capillary tip size and design are
plified momentum balance equations such as important issues for the capillary pressure
Hagen-Poiseuille (DP ¼ 8mLQ/prrcap4) where technique.
I 650 Interfacial Dynamics Methods

Interfacial Dynamics 140 14

1
Methods,
Fig. 13 Change in
120 12
capillary pressure P(t)
(1) and corresponding g(t)
(2) as a function of time for 100 10
a water drop in silicone oil

γ [mN/m] P[Pa]
1,000 cP (density 80 8

V [mm3]
0.968 g/cm3) with changing
drop size (3)
60 6
2
40 4

20 3 2

0 0
0 50 100 150 200
t [S]

600 detachment is monitored which transforms to

Expermental Data, Cap. Tip 0.5 mm a small new drop growing at the tip. For the
Theoretical Model
500 whole process, a constant interfacial tension of
Viscous Pressure Loss (pascal)

about 51 mN/m for the water/hexane interface is

400 observed over a wide range of flow rates. This
covers a total drop formation time of 1–100 s,
300 which in turn corresponds to dynamic interfacial
tensions measured with a time resolution of about
200 0.01 s. The technique is also applicable for
measurements in the millisecond range via
100
a calculation of drop size from the applied flow
rate or by using a high-speed video camera.
Figure 16 shows the dynamic interfacial
20 40 60 80
measurements of water drop in a hexane solution
of 104 mol/l Span80. Different protocols are
Flow rate (mm3/sec)

Interfacial Dynamics Methods, Fig. 14 Measurements presented in this figure:

of hydrodynamic pressure loss as a function of flow rate Stages a–b: pre-aged growing drop (PGD)
using the capillary pressure setup (ODBA), comparison Stages c–d: continuously growing drop (CGD)
with the Hagen-Poiseuille law (dotted line) (Javadi et al.
2006) Stages e–f: stop growing drop (SGD)
Each protocol has its own benefits and com-
plexities or limitations (Javadi et al. 2010a). The
Measurements Under Dynamic Conditions easiest protocol for getting dynamic interfacial
When all basic calibrations and a relevant tension values for a regular surfactant solution
estimation of the hydrodynamic effects are at medium or high solution concentrations is
performed, for a wide range of flow rates and SGD, as the hydrodynamic effect is vanished
drop expanding rates, a constant interfacial after stopping the flow. The main limitation
tension should be observed for the pure system might be the residual hydrodynamic instability
as it is illustrated in Fig. 15. In this figure, first effects on the droplet after stopping the flow.
a big droplet (2 mm radius) close to its However, recent capillary pressure experiments
Interfacial Dynamics Methods 651 I
Interfacial Dynamics
Methods,
Fig. 15 Dynamic
interfacial tension (filled
symbols) and drop radius
(open symbols) for pure,
the water/hexane interface
as a function of
dimensionless time t*,
using the CGD (Continuous
Growing Drop) protocol
with different flow rates of
0.85 ( ), 2 ( ), 4.8 ( ), 8.5
( ), and 16.7 ( ) mm3/s
(dimensionless time
calculated by using a
selected flow rate as
reference)

Preaged Growing Drop (PGD) Continuously Growing Drop (CGD) Stop Growing Drop (SGD)

OD=1mm

drop
t=0 water d
a
b e
Static drop
adsorption reaches equilibrium c hexane + 10−4 mol/l Span80
f
40
t=0 d
35
30 e
ST [mN/m]

25 c
20
b
15
a
10 f
5
0 25 50 75 100 125 150 175 200 225 250 275 300 325 350 375 397
Time [sec]

first drop detachment last drop detachment Static drop

Interfacial Dynamics Methods, Fig. 16 Protocols of solution: stages a–b: pre-aged growing drop (PGD); stages
capillary pressure tensiometry for measuring dynamic c–d: continuously growing drop (CGD); and stages e–f:
interfacial tensions water drop in Span80 104 mol/l hexane stop growing drop (SGD) protocol (Javadi et al. 2010a)
I 652
Interfacial Dynamics
Methods,
Fig. 17 Dynamic
interfacial tension of
a water drop in hexane ( )
and solution of 104 mol/l
Span80 using the capillary
pressure analyser (ODBA)
with the SGD experimental
protocol at two different
flow rates 0.42 ( ) and 16.7
( ) mm3/s
with a high-speed video camera (up to 5,000 fps)
demonstrate negligible hydrodynamic instabil-
ities up to a rather high liquid flow rate. Clearly,
this limitation depends on the capillary tip size
and design and the fluid properties such as
viscosity ratio of the two phases and compress-
ibility effects (e.g., 25 mm3/s water in hexane
for an inner capillary tip diameter of 0.5 mm).
Figure 17 shows an example using this protocol
for a water drop in a hexane solution of
104 mol/l Span80 (SGD for two different flow
rates 0.42 and 16.7 mm3/s). This figure underlines
the need of applying high flow rates to generate
a fresh interface (negligible pre-adsorbed surfac-
tants) in short-time dynamic interfacial tension
measurements.
Drop Profile Tensiometry
The drop profile tensiometry is a technique
quite similar to the bubble profile tensiometry
explained in paragraph Bubble Profile Tensiom-
etry and Fig. 5. Therefore, in this section, atten-
tion is paid essentially to experimental results
obtained at water–oil interfaces.
Interfacial Dynamics Methods
The theory of the diffusion-controlled adsorp-
tion of a surfactant at the interface between two
immiscible liquids allowing for the transfer
of surfactant through the interface is summarized
in the entry ▶ Surfactant Adsorption Kinetics.
Here, we concentrate on experimental
studies only.
From the dynamic point of view, there is no
significant difference in the surfactant adsorption
between water-air and water–oil interfaces.
Namely, the diffusion controlled kinetics applies
in most cases for both interfaces (Fainerman et al.
2010; Javadi et al. 2010b). On the other hand, at
the water–oil interface the adsorption layer is in
contact with the oil molecules that enhance sur-
factants activity (Pradines et al. 2010), and thus
considerable changes in the interfacial tension
are observed already at much lower concentra-
tions than at the water-air interface.
Sodium dodecyl sulfate (SDS), the most
frequently used surfactant, hydrolyzes in an
aqueous solution and dodecanol is produced.
Dodecanol is a highly surface active compound;
thus, it competes with SDS molecules at the
Interfacial Dynamics Methods
75
65
55
γ [mN/m]
45
35
25
0.0001 0.001 0.01 0.1
t [S]
Interfacial Dynamics Methods, Fig. 18 Dynamic sur-
face tension of SDS at the water-air interface in presence
of 0.01 mol/l NaCl at various concentrations (the curves
are labelled by the SDS concentration in mmol/l) mea-
sured by bubble profile (open symbols) and maximum
interface. At the water-air interface, these two
molecules form a mixed adsorption layer, while
at the water-hexane interface the dodecanol mol-
ecules, being much more hydrophobic, transfer to
the hexane phase. Consequently, the interfacial
tension is determined mainly by SDS adsorption.
This phenomenon is shown in Figs. 18 and 19.
The kinetic curves in Fig. 18 exhibit a surface
tension plateau in between two adsorption
processes: the first one due to the adsorption of
SDS and the second one due to the increasing
adsorption of dodecanol. Dodecanol is a much
stronger surfactant than SDS, but because of its
much lower concentration, the dodecanol mole-
cules reach the surface very slowly, and there-
fore, the respective effects appear much later. At
the water-hexane interface, there is no any indi-
cation that after adsorption any remarkable
amount of dodecanol remains at the interface, as
it is shown in Fig. 19. Obviously dodecanol is
transferred into the nonpolar hexane phases due
to the partition coefficient between hexane and
water of K ¼ ch/cw of about 6,700 (Javadi et al.
2010b). That is why the equilibrium interfacial
653 I
0.2
0.5
1
2
10
5
1 10 100 1000 10000
I
bubble pressure tensiometry (filled symbols); theoretical
curve for the concentration of 2 mmol/l was calculated
using the model presented in Miller et al. (2003, 2004);
according to Fainerman et al. (2010)
tension is determined exclusively by the adsorp-
tion of SDS and is reached during much shorter
time than at the water/air interface.
It is noteworthy that the adsorption behavior of
surfactants soluble in both liquid phases depends
not only on the partition coefficient but also on the
ratio between the volumes of the two liquid phases.
With the increase of this ratio of the phase
initially free from surfactants (acceptor phase) to
that of the phase initially containing the surfactants
(donor phase), more surfactant is transferred to the
acceptor phase resulting in the increase of the
equilibrium interfacial tension. The equilibrium
concentration in the donor phase can be found
from the mass balance equation (Liggieri
et al. 1997):
cd;0
cd;eq ¼ ; (10)
1 þ K VVda
where cd,eq and cd,0 are the equilibrium and initial
concentration in donor phase, respectively,
K ¼ ca/cd is partition coefficient, ca is the final
concentration in the acceptor phase, and Vd and
I 654 Interfacial Dynamics Methods

Interfacial Dynamics
Methods,
Fig. 19 Dynamic
interfacial tension of SDS
at the water/hexane
interface in presence of
0.01 mol/l of phosphate
buffer (pH 7) at various
SDS concentrations, as
measured by drop
profile tensiometry at
water/hexane interface:
(1) 5  106 mol/l,
(2) 105, (3) 104,
(4) 2  104, (5) 5  104,
(6) 103, (7) 2  103,
and (8) 5  103 mol/l,
according to Javadi et al.
(2010b)

55
50
50
a
b 45
45 c
d
40
γ (mN/m)

γ (mN/m)

40 35

30
a
35
25 b
c
20
30
0 500 1000 1500 2000
15
t (s) 0 2000 4000 6000 8000
t (s)
Interfacial Dynamics Methods, Fig. 20 Experimental
dynamic interfacial tension obtained for C13DMPO at the Interfacial Dynamics Methods, Fig. 21 Experimental
water/hexane interface with an aqueous solution drop in dynamic interfacial tension obtained for C13DMPO at the
hexane, theoretical curves: (a) c0 ¼ 105 mol/l, (b) c0 ¼ 2 water/hexane interface with a drop of hexane in the aque-
 105 mol/l, (c) c0 ¼ 3  105 mol/l, and (d) c0 ¼ 5  ous solution, theoretical curves: (a) c0 ¼ 1.5  105 mol/l,
105 mol/l, according to Liggieri et al. (1997) (b) c0 ¼ 2.3  105 mol/l, and (c) c0 ¼ 5.3 105 mol/l,
according to Liggieri et al. (1997)

Va are the volumes of the donor and acceptor
phases, respectively.
In Fig. 20, the adsorption behavior of
C13DMPO at the interface of an aqueous solution
drop immersed in hexane is shown. It is seen that
surfactants continuously adsorb at the interface
and then transfer into the oil phase until the
minimum interfacial tension is attained. After-
ward, an increase in the interface tension occurs
which indicates the depletion of surfactant in the
drop due to the ongoing transfer process. Con-
trary to this phenomenon, in Fig. 21, the results
for the opposite situation are shown. Now a single
drop of hexane is immersed into the aqueous
Interfacial Dynamics Methods
Interfacial Dynamics
Methods, Fig. 22 Photo
of a coaxial double
capillary (Sinterface
Technologies, Berlin,
Germany) and the
schematic illustrating the
drop formation at the tip
(Kotsmar et al. 2008)
solution; therefore, the molecules adsorb from
the solution around the drop and transfer into
the oil drop. Depletion effects do not occur due
to sufficiently small volume of the oil phase ini-
tially free from surfactants. Thus, no minima
exist in the plots shown in Fig. 21, and a smooth
interfacial tension decrease is observed.
Double Capillary
The double capillary technique was first proposed
by Wege et al. (1999, 2002) and Cabrerizo-
Vı́lchez et al. (1999) and provided now interest-
ing protocols for studies of dynamic interfacial
phenomena. The key element of this technique,
shown in Fig. 22, is the coaxial double capillary
which allows the exchange of the liquid inside
a single drop without any direct interfacial per-
turbation. These two capillaries are connected to
separate injection systems. A droplet is formed at
the tip of the outer capillary. One syringe
connected to the inner capillary injects small
quantities of a fluid into the drop (master), while
the other one (slave) is connected to the outer
capillary and sucks liquid out of the drop in
order to keep the total drop volume constant.
When liquid flows into the drop, the active
control loop realizes any drop volume growths
and balances its size via the outer capillary. Thus,
even during a continuous inflow of liquid, the size
of the drop can be kept almost constant.
The operation of the master–slave system is
governed by the software which controls the
655 I
measurement of the surface tension by drop pro-
I
file analysis tensiometry and the recording of the
digital images of the drop over time. The software
provides measurements for the selection of the
liquid flow rate.
In literature, several applications of the double
capillary technique to dynamic surface studies
are reported. For example, Fainerman et al.
(2008) studied the adsorption characteristics of
nonionic surfactants by drop profile tensiometry.
The evaporation of solvent in long-time experi-
ments results in a decrease of the drop volume,
and the loss is compensated by the supply of the
pure solvent through the inner channel of the
coaxial capillary. So, the total surfactant amount
in the drop can be kept constant during the whole
experiment.
Kotsmar et al. (2008) discussed the formation
of mixed protein/surfactant adsorption layers
studied by the drop profile analysis tensiometry,
equipped with a coaxial double capillary system.
The adsorption experiments were performed with
different types of molecules sequentially at the
same surface/interface. Initially, a first exchange
of the initial protein containing subphase against
a pure pH 7 buffer solution was performed. Then,
a second exchange of the subphase against
a C12DMPO solution at different surfactant con-
centrations was made. This causes the protein
adsorption layer structure to be modified by the
surfactant molecules, leading to the formation of
protein/surfactant complexes. At the final stage,
I 656
80
Fresh interface of
75 Protein Solution
70
65
Equilibrium
γ [mN/m]
60
55
50
45
40
35
0 5000
Interfacial Dynamics Methods, Fig. 23 Dynamic sur-
face tensions measured for a sequential adsorption made
by the coaxial double capillary. The numbers refer to
periodic drop oscillation experiments at different stages
of the surface layer: 1 – equilibrium adsorbed layer of
a buffer solution is used to remove all molecules
yet existing in the bulk of the drop. Such inter-
esting protocol which is suitable to find out the
conditions under which a pre-adsorbed protein
can be replaced from a liquid interface by
a respective surfactant is illustrated schemati-
cally in Fig. 23. Throughout all the stages of the
experiment, the dynamic surface tension is mea-
sured for the study of the adsorption/desorption
process during the drop-bulk exchange.
Ferri et al. (2010) reviewed experimental and
theoretical works regarding studies with the
double capillary technique. In another recent
work by Javadi et al. (2011c), the coaxial double
capillary system is qualitatively analyzed with
respect to the efficiency of the drop volume
exchange process, experimentally, and via CFD
simulations. For this aim, the subphase of a pure
water drop is exchanged by a surfactant solution
to allow the surfactant molecules to be adsorbed
without any perturbation by a convective flow.
The CFD simulations support the analysis of data
extracted from the experiments and to predict the
concentration and flow fields during the drop
exchange process. Figure 24 represents the con-
centration fields predicted by CFD simulations as
compared with the experimentally visualized
concentration fields for a pulse-like liquid
Interfacial Dynamics Methods
Exchange with
Bulk exchange Surfactant
with buffer solution
4
1 2
3
10000 15000 20000
t [sec]
b-casein; 2 – adsorbed layer of b-casein remained after
washing with the solvent (buffer solution); 3 – rich sur-
factant + protein mixed layer; and 4 – diluted adsorbed
layer washed out with buffer solution (Kotsmar et al.
2008)
injection. A good agreement between the exper-
iments and the simulations is achieved.
The hydrodynamic conditions in the applica-
tion of the coaxial double capillary system can
change with small changes in the properties of the
injected liquid (Javadi et al. 2010c). When
1.5 wt% ethanol is added to the dye solution,
the density becomes slightly less than that of
water. The results for such situation are presented
in Fig. 25. A small difference in the density
between the drop bulk and the injected solution
can result in a quick reverse flow of the injected
liquid, and less than half of the droplet is involved
in the exchange process, while the bottom part of
the bulk remains stagnant. Even a continuation of
this liquid exchange over long times cannot
provide a complete bulk exchange.
Regarding the optimum geometry (immersion
depth, capillary tip sizes, etc.) or the optimum
operating condition (pulse-like flow with differ-
ent flow rates, time intervals, etc.) to ensure the
minimum perturbation in an efficient drop
volume exchange process, the condition can
vary from case to case, depending on the
corresponding phenomena and the physical prop-
erties of the system to be studied.
For the evaluation of subphase concentration
in the experiments by double capillary system,
Interfacial Dynamics Methods 657 I

0.0031
0.0029
0.0027
0.0026
0.0024
0.0022
0.0021
0.0019
0.0017
0.0016
0.0014
0.0012
0.0011
0.0009
0.0007
0.0006
0.0004
0.0002
0.0001

t=0.2 s t=1.2 s t=4.0 s

Interfacial Dynamics Methods, Fig. 24 Comparison of dye injection into a drop: experimental snapshots (top) and I
CFD simulation (bottom) for dt ¼ 0.2 s, dV ¼ 0.1 mm3/pulse, according to Javadi et al. (2011c)

0 0 0

−0.0005 −0.0005 −0.0005

−0.001 −0.001 −0.001

Y

−0.0015 −0.0015 −0.0015

−0.002 −0.002 −0.002

−0.0025 −0.0025 −0.0025

−0.001−0.0005 0 0.0005 0.001 0.0015 −0.001−0.0005 0 0.0005 0.001 0.0015 −0.001−0.0005 0 0.0005 0.001 0.0015
X X X

t=0.5 s t=2 s t=4 s

Interfacial Dynamics Methods, Fig. 25 Comparison 0.3 mg/ml + 1.5 % ethanol (density slightly lower than
of dye injection into a drop: experimental snapshots (top) that of water), for dt ¼ 0.2 s, dV ¼ 0.1 mm3/pulse,
and CFD simulations (bottom) for a dye solution of according to Javadi et al. (2010c)

different algorithms are introduced, based on computational fluid dynamics (CFD) as powerful
simplified assumptions like well-mixed assump- computational tool in prediction of fluid velocity,
tion which results in a rough estimation. pressure, and concentration fields could be
For a well estimation of the concentration, considered as a reliable tool.
I 658
Interfacial Dynamics
Methods, Fig. 26 Dg-
responses to different
sinusoidal
DA-perturbations at
0.02 Hz frequency for an
aqueous solution of 2 %
poly(sodium
4-styrenesulfonate),
according to Loglio et al.
(2011)
Interfacial Relaxation Measurements
Besides the dynamics of adsorption of surfactants
at freshly formed liquid interfaces, also the
response of a surface layer to external perturba-
tions is an important property of adsorption
layers. Methods for measuring this mechanical
interfacial response, also called dilational visco-
elasticity or interfacial relaxation, are mainly
based on surface/interfacial tension measure-
ments. The most frequently used methods today
are oscillating drops/bubbles using the profile
analysis or capillary pressure tensiometry to
follow the relaxation process during harmonic
perturbations. As these techniques cannot reach
very high frequencies, the capillary wave
damping method complements the drop/bubble
methods very well with frequencies up to about
1,000 Hz.
Slow Oscillations
The profile analysis tensiometer (PAT) is the
instrument which allows oscillation of a drop or
bubble in order to obtain information about the
adsorption layer viscoelasticity. However, in
contrast to similar studies with small spherical
drops (ODBA), it is limited to slow oscillations
(0.001–0.1 Hz). At higher oscillation frequen-
cies, the drop or bubble does not retain
a Laplacian shape which further on results in
physically unrealistic data.
Interfacial Dynamics Methods
The theory of the oscillation behavior of
interfacial tension is summarized in the entry
▶ Surfactant Adsorption Kinetics. In this
section, we focus on experimental studies only.
Measurements of the viscoelasticity by using
PAT is based on the surface tension response to
drop or bubble perturbations. That means oscil-
lations of the drop/bubble surface area are input
information and the resulting surface tension
oscillations are the output information. If har-
monic sinusoidal oscillations of the drop surface
area are generated for drops of pure solvents
(without any surfactant), the surface tension
remains constant, i.e., the amplitude of the output
signal is equal to zero as pure solvents do not
have any dilational elasticity and viscosity. On
the contrary, if the drop is formed from
a surfactant solution, there will be different time
shifts and amplitudes of the resulting surface
tension oscillations depending on the frequency
of generated oscillations and the surfactant con-
centration of the solution. The changes in surface
tension as output signal are then to be analyzed to
gain the dilational viscoelasticity parameters
(Loglio et al. 2001). As an example, in Fig. 26,
the surface tension response to sinusoidal surface
area oscillations at three different amplitudes is
shown. It is seen that the amplitude of surface
tension oscillations is proportional to the ampli-
tude of surface area oscillations providing the
value of the surface dilational viscoelastic
Interfacial Dynamics Methods 659 I
Interfacial Dynamics a 60
Methods,
Fig. 27 Experimental
dependencies of the 50
viscoelastic modulus (a)
and phase angle (b) on the
oscillation frequency 40

|E| [mN/m]
measured by the buoyant
bubble method for the
30
TX45 solutions at various
concentrations: 1 (1), 2 (2), 2
5 (3), 10 (4), 20 (5), 50 (6), 20 3
and 100 (7) mol/l, according 4
to Fainerman et al. (2009) 1
10 5
6
7
0
0.001 0.010 0.100 1.000
f [Hz]
b 60 I

50 7

40 6
φ [degrees]

5
4
30 3

2
20

1
10

0
0.001 0.010 0.100 1.000
f [Hz]

modulus independent of the oscillation ampli-
tude, see Eq. 41 in the entry ▶ Adsorption Kinet-
ics of Surfactants.
Figure 27 illustrates the experimental data on
surface rheology obtained for Triton X-45
solutions with the buoyant bubble method. The
dependencies of the viscoelasticity modulus and
phase angle on oscillation frequency for various
Triton X-45 concentrations are rather similar to
those obtained for solutions of other surfactants
(Lucassen and Giles 1975; Mucic et al. 2011b)
and predicted by the theory: the modulus
increases with increasing frequency, whereas
the phase angle decreases. The expressions for
the viscoelasticity modulus |E| and phase angle f
between stress (dg) and strain (dA) in the case of
diffusion controlled adsorption kinetics are
presented in the entry ▶ Adsorption Kinetics of
Surfactants, Eqs. (44) therein.
PAT used as a slow oscillation method
(0.001–0.1 Hz) is suitable for studies of mole-
cules with a slow adsorption relaxation process;
particularly, it is the method of choice for low
concentrated solutions. Then, however, the
depletion of bulk concentration might be
a problem when the experiment is based on
I 660
a single drop. In order to avoid this problem, one
should perform the experiments with the bubble
configuration. Another solution would be the use
of the double capillary and supplying sufficient
solution to the drop until the adsorption equilib-
rium is established. This methodology was sum-
marized by Kotsmar et al. (2009a).
The adsorption behavior of protein-surfactant
mixtures recently became a very important issue
in the food-related industries. In Fig. 28, an
example of the viscoelasticity of mixed
BCS/C12DMPO solutions is shown. The concen-
tration of BCS is kept constant (106 mol/l) while
the C12DMPO concentration is changed. The idea
behind these experiments is to follow the replace-
ment of protein molecules from the water/air
interface via the interaction with surfactants,
formation of protein-surfactant complexes, and
final competition.
According to Kotsmar et al. (2009b), for all
studied frequencies, the elasticity for mixed
BCS/C12DMPO adsorption layers starts from
the corresponding value for the pure BCS and
decreases with increasing C12DMPO concentra-
tion up to about 4  105 mol/l. At higher con-
centrations, the values increase, pass through
a maximum, and finally decrease. From the
dotted line on, the obtained values are very
close to those measured for the surfactant alone.
Thus, in this concentration region, the surfactant
dominates the surface layer, in agreement with
the results from previous studies using different
methods (Kotsmar et al. 2008, 2009c).
Fast Oscillations
The experimental setup shown in Fig. 9 was
originally developed to perform drop and bubble
oscillations at high frequencies. The first exper
iment of this kind was proposed by Kretzschmar
and Lunkenheimer (1970). Since then, this meth-
odology was further improved and is now in
many aspects superior to all capillary wave
damping techniques (Noskov 2010) for the appli-
cable frequency range up to 500 Hz (Andersen
et al. 2006). Drop/bubble profile tensiometry was
first used for transient relaxation studies
(Miller et al. 1993) and low frequency oscilla-
tions (Benjamins et al. 1996). The oscillating
Interfacial Dynamics Methods
Interfacial Dynamics Methods, Fig. 28 Dilational vis-
coelastic modulus |E| of mixed BCS/C12DMPO at a fixed
BCS concentration of 106 mol/l as a function of
C12DMPO concentration, measured at different oscilla-
tion frequencies: 0.005 Hz ( ), 0.01 Hz ( ), 0.02 Hz ( ),
0.04 Hz ( ), and 0.1 Hz ( ); curves are only guides for the
eye; according to Kotsmar et al. (2009b)
drop/bubble tensiometry based on capillary pres-
sure measurements is the most suitable technique
now for oscillations in a broad frequency interval
and has been used for studies of various surfac-
tant systems.
The experimental protocol consists of the
formation of a drop/bubble which is then left for
a respective period of time to establish the
adsorption equilibrium at the interface. This
equilibration time depends on the concentration
and surface activity of the surfactant to be studied
(Mucic et al. 2011b). Then, by an accurate dosing
system (in our case a piezo translator shown in
Fig. 9), harmonic volume changes and, conse-
quently, area changes are generated. The ampli-
tudes are kept sufficiently small, typically below
10 % of the drop/bubble area, in order to remain
in the range of a linear perturbation response. The
frequency of these oscillations can go down to
about 0.1 Hz or less and is limited from above by
the hydrodynamics of the liquid similarly to the
growing drop protocol discussed above.
The hydrodynamics of the oscillatory flow
inside the capillary tip for high frequencies can
be more complex than for constant flow rates
(Javadi et al. 2006). Therefore, in addition to the
discussed regular hydrodynamic effects, extra
Interfacial Dynamics Methods
phenomena and related limitations such as the
hydrodynamic relaxation time th ¼ rc2 =u should
be considered, where rc is the capillary tip radius
and u is the kinematic viscosity of the fluid in the
capillary. If the period of oscillation is smaller
than the hydrodynamic relaxation time, the
velocity profile across the capillary cannot be
stationary, and the pressure drop in the capillary
is no longer described by the Poiseuille law
(Kovalchuk et al. 2000). For very high frequen-
cies also due to inertia, viscosity, and gravity
effects, drops might start to oscillate with over-
tones so that a clear analysis of the measured
pressure signal becomes impossible. The
frequency limits depend strongly on the absolute
drop size and the geometry of the capillary. With
decreasing capillary diameter, i.e., the radius of
the liquid drop, it will be possible to perform
experiments at higher frequencies with less drop
deformation problems. Note, however, that han-
dling smaller and smaller droplets will lead to
problems with temperature and drop size controls
which are difficult to solve. And also the hydro-
dynamic effects can increase dramatically.
Therefore, the optimization of the capillary tip
size and design is a very important issue. Via the
analysis of fast video recordings, it is possible to
determine the frequency limits for a given exper-
imental situation, defined by the density and
viscosity of the two fluids, and the absolute size
of the drop/bubble (Javadi et al. 2011c).
Experimental Examples for Pure Solvents and
Surfactant Solution
The simplest way of testing the highest reliable
frequency for oscillation experiments is to
perform experiments with pure solvents. Any
observed changes in the capillary pressure P(t)
should be compensated by the changes in R(t)
such that the final g(t) is independent of time,
i.e., the viscoelasticity of the liquid interface
should be zero.
As an example, the details of a drop oscillation
experiment at room temperature of 23–24  C are
shown in Fig. 29. For a pure water drop in pure
hexane, a phase shift of p is observed which is
expected, as the maximum/minimum drop size
and capillary pressure appear in opposite
661 I
moments for drops bigger than a hemispherical
size. For a CTAB (cetyl trimethyl ammonium
bromide) solution in addition to the changes in
drop curvature, the extra contributions to the cap-
illary pressure values appear due to changes in
the surface layer coverage caused by drop surface
area expansions and contractions. The observed
phase shift between measured capillary pressure
P(t) and area A(t) can be also described by the
pressure relaxation model described as below.
This demonstrates that a simple direct data anal-
ysis of oscillating drop experiments can lead to
erroneous conclusions, and only via the shown
theory, a physically reasonable interpretation of
experimental data is possible.
The results of interfacial tension and capillary
pressure during oscillating drops for an aqueous
I
drop of a 104 mol/l CTAB solution in hexane are
shown in Fig. 30 together with the result of the
surfactant-free system. The obtained results show
how the interfacial tension variations are consid-
erable for the CTAB solution as compared to pure
system, where we can observe a negligible
variation.
Theoretical Basis for the Oscillating Drop
Technique
The hydrodynamic basis for oscillation experi-
ments in a measuring device, similar to the above
mentioned experimental setup ODBA, is
discussed in detail by Kovalchuk et al. (2011).
Despite growing drop experiments which allow
just to subtract the hydrodynamic effects directly
from the measured total pressure, for oscillating
experiments, the extraction of the capillary pres-
sure term requires a much more sophisticated
procedure because of the existing phase shifts
between the different pressure contributions.
The dynamic response of the considered measur-
ing system is a complex response which includes
not only the viscoelasticity of the interfacial layer
but also a number of other contributions, such as
the hydrodynamics of the fluid flow through the
capillary and the flow in the bulk around
the meniscus, the elastic contribution due to
changes in the meniscus curvature, and the elastic
contributions stemming from the finite compress-
ibility of the liquid and the cell deformability
I 662 Interfacial Dynamics Methods

a 333 1.12
1.1
328
1.08

Drop area [mm2]

323 1.06
CP [Pa]

1.04
318
1.02
313 1
0.98
308
0.96
303 0.94
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
t [s]

b 150 1.1

1.08
145
1.06

Drop area [mm2]

140
1.04
CP [Pa]

135 1.02

1
130
0.98
125
0.96

120 0.94
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
t [s]

Interfacial Dynamics Methods, Fig. 29 Drop area A(t) (bottom) in hexane, drop volume 0.12 mm3, oscillation
( ) and capillary pressure P(t) ( ) during oscillations of frequency 10 Hz
a pure water drop (top) and CTAB solution 10-4 mol/l

70 Pressure 350

60
300
50
g (t) 250
g [mN/m]

40 pure water /hexane

P [Pa]

−4
10 mol/l CTAB in water /hexane
Interfacial Dynamics 30
g (t) 200
Methods,
Fig. 30 Capillary pressure 20
P(t) and interfacial tension
150
g(t) during oscillation of 10
a drop of water and
104 mol/l aqueous CTAB Pressure
0 100
solution in hexane, drop
0 0.2 0.4 0.6 0.8 1
volume 0.12 mm3,
oscillation frequency 10 Hz t [s]
Interfacial Dynamics Methods
Zhv Zhi Zm Zsv Zse
m for viscous and inertia effects in the bulk
Zc
Interfacial Dynamics Methods, Fig. 31 Equivalent
scheme showing the connections of different complex
resistances acting in drop/bubble oscillation experiments
(Kovalchuk et al. 2002, 2011). For small-
amplitude harmonic oscillations, the response of
the system is linear and all contributions can be
characterized by respective complex resistances
as shown in Fig. 31 (Javadi et al. 2011b).
The response of the system as a whole can be
characterized by the complex resistance
(impedance):
Z ¼ dP=dVDrv ; (11)
where dP is the pressure variation in the cell
(at constant atmospheric pressure) measured by
the pressure sensor, and dVDrv is the volume
variation applied via the piezo translator. The
response of the system can be described by the
total resistance:
 1
1 1
Z¼ þ : (12)
Zc Zhv þ Zhi þ Zm þ Zse þ Zsv
The viscoelastic contribution of the interfacial
layer depends on the meniscus geometry and is
composed of two terms:
Zs ¼ Zse þ Z sv ; (13)
where Zse ¼ (2er/a0)∙(dlnA/dVm) and
Zsv ¼ (2iod/a0)∙(dlnA/dVm) are the complex
resistances arising from the surface dilatational
elasticity, er, and viscosity, d, respectively. Here,
o ¼ 2pf is the angular frequency of the generated
oscillation, f is the frequency in Hz, a0 is the
radius of curvature of the meniscus at equilib-
rium, and dlnA/dVm is a geometric coefficient
describing the variation of the surface area A of
the meniscus as a function of its volume Vm.
663 I
The hydrodynamic contribution accounts
phases inside the capillary and around the
meniscus. Under quasi-stationary conditions
(for relatively slow oscillations, see Kovalchuk
et al. 2001), these effects can be considered
separately:
Zh ¼ Zhr þ Zhi ; (14)
where Zhv ¼ ioG1 and Zhi ¼ o2 G2 are the
complex resistances describing the viscous and
inertia contributions, respectively. Following
Kovalchuk et al. (2004), the hydrodynamic coef-
ficients can be approximated by G1 ¼ 81 l pa4C
 . qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
and G2 ¼ 4r1 l 3pa2C þ r2 p 2 h20 þ a2C ,
where 1 and r1 are the dynamic viscosity and I
density of the fluid inside the capillary, r2 is the
density of the fluid around the meniscus, aC and
l are the inner capillary radius and the length of
the thinnest inner part of the capillary (or the
effective capillary length, accounting also for
entrance effects), and h0 is the equilibrium
drop/bubble height (with respect to the capillary
cut off). We neglect here the viscous effects in the
liquid around the meniscus as their contribution is
usually small for liquids having a viscosity
similar to that of water (Alexandrov et al. 2009).
The second term in the expression for G2
describes the contribution of the added mass of
liquid around the meniscus. This effect is most
important for bubbles oscillating in a liquid.
The elastic resistance of the meniscus arises
due to variations of the capillary pressure with
changes in the radius of curvature a (at constant
interfacial tension g):
2g da
Zm ¼ : (15)
a20 dVm
Here, the geometry coefficient da=dVm
describes the variation of a(Vm). One more con-
tribution arises due to the finite liquid compress-
ibility in the cell and deformability of the cell
walls (Kovalchuk et al. 2000, 2002). For rela-
tively small pressure amplitudes and not very
high frequencies (corresponding to the acoustic
I 664 Interfacial Dynamics Methods

wave lengths, much larger than the cell size), this (K ¼ B1 ¼ dlnV/dP is the bulk compressibil-
contribution is described by the resistance: ity), dVc =dP is the coefficient describing the var-
iation of the internal volume of the cell as
Bef
Zc ¼  ; (16) a function of pressure (i.e., deformability of the
Vc walls), and VGas and BGas are the volumina of the
where Vc is the total volume of liquid in the cell air bubble and the bulk elasticity of air.

1 The complex resistances involved
and Bef ¼ B 1 þ VBc dVdP
c
þ B VGas
Vc BGas is the effec- in Eqs. 13–15) are connected in series, whereas
tive cell elasticity including the elastic response the resistance Zc, describing the intrinsic elastic-
of the liquid, the cell walls, and any gas bubbles, ity of the cell, is connected in parallel to the other
occasionally entrapped into the cell. Here, B is resistances. Hence, the total complex resistance is
the bulk elasticity of the liquid given by

2 31
Vc 1
Z ¼ 4  5 : (17)
Bef ioG1  o2 G2  2g2
a
da
dVm þ 2e
a0
r d ln A
dVm þ 2io
a0
d d ln A
dVm
0

For pure solvents without surfactants the
dynamic surface viscoelasticity is zero and the
complex resistance is reduced to
2 31
V 1
Z0 ¼ 4 5 ; (18)
c
 some mechanical properties of the interface have
Bef ioG1  o2 G2  2g20 dV
da
a m
0 to be taken into account for a correct understand-
where g0 is the interfacial tension of the surfactant
free system.
Figures 32 (a) and (b) illustrate drop oscilla-
tion experiments obtained with the capillary pres-
sure setup ODBA at different frequencies. Also
data from hydrodynamic experiments without
a drop, i.e., with the capillary immersed into the
same liquid, are shown for comparison. It is seen
that the experimental data follow the theoretical
predictions discussed above. The phase angle
given by the argument of the complex resistance
Z is more sensitive to the surface viscoelasticity
than its modulus; however, the experimental
error of its determination is higher.
Wave Damping Methods
Capillary waves are known since antiquity. Aris-
totle (384–322 BC) and Pliny the Elder
(23–79 AD), for example, described the damping
of waves by the presence of oil films at a water
surface. Benjamin Franklin (Franklin and
Brownrigg 1774) was possibly the first to per-
form real experiments using the wind to generate
waves, and Lamb (1932) already assumed that in
addition to the viscosity and surface tension also
ing the damping of capillary waves. Levich
(1941) improved the understanding by formulat-
ing the tangential forces at the liquid surface as
a boundary condition, i.e., he introduced the
Plateau–Gibbs–Marangoni effect and by this the
dynamic surface elasticity. The development of
the capillary wave theories was mainly com-
pleted by Lucassen (1968a) who found the exis-
tence of longitudinal waves as an unexpected side
result of his theoretical analysis of capillary
waves. Their existence was almost immediately
confirmed experimentally (Lucassen 1968b).
The introduction of the laser technique into
surface science then showed that the spectral
shape of scattered light is directly related to the
damping coefficient of capillary waves and can
be applied for the determination of the surface
rheological properties (Langevin 1992). One of
the advantages of this so-called surface quasi-
elastic light scattering method (SQELS) is its
noninvasive character. In addition, very high
Interfacial Dynamics Methods 665 I
Interfacial Dynamics a Experiment: Theory:
Methods, 105
- Run 1 1 -εr = 0
Fig. 32 Modulus
- Run 2 2 -εr = 70 mN/m
(a) and argument (b) of the
complex resistance Z as - Run 3
3 - with out
functions of frequency for - Run 4
104 meniscus
drop oscillations: Run 1 to - with out
3 – pure water drops meniscus
(different applied
mod(Z), Pa/mm3
amplitudes), Run 4 – drop,
containing a surfactant; 2
theoretical curves 1 and 2 103
are for surface elasticities er
of 0 and 70 mN/m, 1
respectively; drop base
radius ab ¼ 0.25 mm, the
102
meniscus height
h0 ¼ 0.65 mm, the capillary
radius and length were 3
aC ¼ 0.15 mm and
lef ¼ 3.3 mm, respectively; 101
Bef/VA ¼ 3.24104 Pa/mm3; I
10−1 100 101 102
experimental data from
hydrodynamic experiments Frequency, Hz
without drop and the
respective theoretical Experiment: Theory:
curves are given for - Run 1 1 -εr = 0
comparison b
1 - Run 2 2 -εr = 70 mN/m
0 - Run 3
3 - with out
- Run 4
meniscus
- with out
meniscus

−1
agr(Z), rad

3
−2

2
−3

10−1 100 101 102

Frequency, Hz

perturbation frequencies of up to 2 MHz can be
reached (Sakai et al. 1991). A great drawback,
however, is that with SQELS negative dilational
surface viscosities have been obtained which
contradicts with the second law of thermodynam-
ics (Noskov and Loglio 1998).
In the beginning, the method of capillary wave
damping was mainly applied to insoluble mono-
layers at low oscillation frequencies ( 1 kHz).
Initially the obtained results were most of all used
to confirm the theories derived and for many
systems there was good quantitative agreement
I 666
Interfacial Dynamics
Methods,
Fig. 33 Schematic setup Pin Hole
of an ellipsometer,
according to Motschmann
and Teppner (2001) Laser
Quarter
Wave
Plate
(Lucassen and Hansen 1966). However, for some
spread polymer layers, the damping coefficient
showed unexpected maxima at certain surface
coverages. These phenomena initially only
explained conformational transitions in the
monolayer, but later, it was demonstrated that
the dependence of the damping coefficient on
surface coverage is particularly sensitive to any
details in the surface equation of state (Ahmad
1983).
The last becomes evident in particular in stud-
ies of surfactants of high surface activity. For
example, the adsorption kinetics of the cationic
surfactant DoTAB (dodecyl trimethyl ammo-
nium bromide) show a diffusion exchange of
matter mechanism only if the data analysis is
based on the correct equation of state, i.e.,
a modified to the Frumkin model (Stenvot and
Langevin 1988). Similar results were obtained
also for the famous anionic surfactant SDS
(sodium dodecyl sulphate) (Noskov et al. 1990).
The methods of capillary wave damping are
still practiced in studies of various interfacial
systems (Noskov 2009; Monroy et al. 2009;
Maestro et al. 2011); however, despite its excel-
lent frequency spectrum, the lack of automated
instruments makes it difficult in use.
Ellipsometry
Ellipsometry is an optical tool used typically for
polymer layers. The principle of ellipsometry of
liquid interfacial layers is rather easy explained.
A light with a defined state of polarization is sent
to the interface from which it is reflected. The
Interfacial Dynamics Methods
Polarizer Photo Diode
Pin Hole
Analyzer
Sample
reflected light beam has typically a different
polarization. Ellipsometers are built such that
the angle of incident light can be tuned in
a certain range and that the reflected light can be
picked up by a sensor and its polarization
analyzed (Motschmann and Teppner 2001).
Experiments at the Water/Air Surface
Surfactant adsorption layers have a thickness of
the order of 1 nm which is insufficient so far to get
accurate data. In this case, it is impossible to
separate the thickness of the layer from the infor-
mation on the adsorbed amount. However, the
ellipsometric angle can be assumed proportional
to the adsorbed amount so that the change in
adsorption can be studied.
A typical ellipsometer has the optical elements
shown in Fig. 33.
The applicability of the method to interfacial
layers depends strongly on the refractive indices
of the adjacent bulk phases. For the water/air
interface, the difference between the refractive
indices of the two fluids is rather large:
nAir ¼ 1.0002 and nWater ¼ 1.3330 at 20  C.
Battal et al. (2003) used this technique for
measuring the adsorption of cationic surfactants
and compared with tensiometry data. Also Stocco
et al. (2010) studies this type of surfactants as
foaming agent and used ellipsometry data for
a better understanding of the foam stability of
the respective aqueous solutions.
Ritacco et al. (2010) studied the equilibrium
and dynamic surface properties of aqueous
trisiloxane solutions. The results in Fig. 34 show
how experimental data are in good agreement
with those calculated from an adsorption
Interfacial Dynamics Methods 667 I
Interfacial Dynamics 1,E−06
Methods,
Fig. 34 Adsorption values
for trisiloxane surfactant 8,E−07
with 8 ethylene oxide units,
circles – data from

Γ [mol/m2]
ellipsometry, 6,E−07
rhombus – calculated from
isotherm, according to
4,E−07
Ritacco et al. (2010)

2,E−07

0,E+00
1,E−08 1,E−07 1,E−06 1,E−05 1,E−04 1,E−03 1,E−02 1,E−01 1,E+00
C [mol/m3]

a b I

Laser Laser oil

Photo Diode Photo Diode

water
Sample Sample

Interfacial Dynamics Methods, Fig. 35 Scheme of an (b) using a cylindrical cell mounted exactly in the center
ellipsometer for studies at the water/oil interface: (a) using of the instrument, according to Stocco et al. (2011)
wave guides, according to Benjamins et al. (2002);

isotherm with model parameters obtained from
fitting to an experimental surface tension
isotherm.
This experiment demonstrates nicely that
there are protocols which allow quantitative
ellipsometry experiments also of standard surfac-
tant adsorption layers.
Experiments at the Water/Oil Interface
The use of ellipsometry is more difficult at the
interface between two liquids. First of all, the
difference in the refractive index of the two fluids
is much smaller than for the liquid/gas interface.
For example, the index of hexane is 1.3749, of
silicone oil 1.403 (independent of viscosity,
i.e., degree of polymerization), of tetradecane
1.428, of sunflower oil (SFO) 1.4646, or of
MCT (medium chain triglyceride, often used as
synthetic SFO) 1.4485. While experiments at the
water/hexane interface appear extremely diffi-
cult, studies of the interface to tetradecane,
SFO, or MCT appear feasible.
In addition to the difficulty given by the
smaller refractive index, it is also more difficult
from an experimental point of view to study the
liquid/liquid interface by optical methods with
tuneable angle of incidence for the light beam.
Obviously Benjamins et al. (2002) were the first
to propose an arrangement which allowed
a defined access of the interface without passing
the light through the surface of the oil when
coming from top. They used a light guide for
bringing the light beam directly to the water/oil
interface and a second guide for picking the
reflected light up for analysis. In Fig. 35, the
principle setup is shown.
I 668
1.5
Γ ⫻ 106 [mol/m2]
1.0
0.5
10−6 10−5 10−4 10−3
C [wt.%]
Interfacial Dynamics Methods, Fig. 36 Change of
adsorption G as a function of bulk concentration of an
oxyethylated octadecanol C18EO50 at three different
water/oil interfaces, according to Benjamins et al. (2002)
Another design was recently proposed by
Stocco et al. (2011) who use a cylindrical cell,
filled partly by the aqueous and partly by the oil
phase. As the light passes this cylinder cell
perpendicularly, the beam can directly reach the
interface, becomes reflected, and leaves the cell
to the sensor again perpendicularly. This arrange-
ment requires an accurate positioning of the cell
in the center of the ellipsometer so that the light
source and the sensor can be moved around the
central point located at the interface.
With these experimental details, ellipsometry
is also applicable to the interface between two
liquids, as it was demonstrated by experiments
on an oxyethylated alcohol C18EO30 by
Benjamins et al. (2002). Figure 36 presents
some results of these studies.
Direct Drop-Drop and Bubble-Bubble
Interactions
The drop and bubble micro manipulator
(DBMM) is a novel tool for the quantitative anal-
ysis of the interaction between two droplets or
two bubbles or even between a single droplet and
a bubble in a liquid medium. The DBMM was
constructed as an extra module for the drop
profile analysis tensiometer PAT-1. It consists
of two identical cells, each one being a capillary
pressure tensiometer. To this end, it is identical to
Interfacial Dynamics Methods
the so-called oscillating drop and bubble pressure
analyzer ODBA which consists mainly of the
pressure sensor, the piezoelectric translator, and
the syringe dosing system, as described in detail
by Javadi et al. (2010b). Such type of experiments
was qualitatively performed by Ata (2008) with
a simple arrangement consisting just of two cap-
illaries at the tips of which bubbles were formed
and manually brought into contact. The more
generalized instrument DBMM, commercially
10−2
available now, was recently discussed by Loglio
et al. (2011) from a conceptual point of view. The
schematic setup of the DBMM is given in Fig. 37
and a corresponding photo in Fig. 38. The piezo
drive on each side provides an exact drop size
control and drop oscillations in a broad frequency
range.
The capillaries of the two cells are mounted in
such a way that their tips are located opposite to
each other. At both tips, drops or bubbles can be
formed with a controlled volume. The exact posi-
tioning of one drop (bubble) against the other can
be arranged by an accurate xyz micrometer stage.
The principle of the DBMM is shown schemati-
cally in Fig. 37.
There are two independent dosing systems on
either side of the instrument. The crude syringe
pump (ILS, St€utzerbach, Germany) has an accu-
racy between 5 ml up to 500 ml, depending on the
used syringe size. Each side of the DBMM has an
additional fine dosing system realized by a piezo
translator P-843.40 (Physik Instrumente,
Germany). This accurate dosing system,
improved by placing a moving rod of 1 mm in
diameter (instead of originally 5 mm), provides
a volume for a full stroke of 60 mm of only 50
picolitre, and a further reduction to 10 pl appears
feasible. The range available by the pressure sen-
sor PDCR-4000 (GE-Druck, Germany) is up to
7,000 Pa, with a possible 10 times overload pres-
sure. We limited the maximum total pressure to
a value of 10,000 Pa by a software setting, in
order to avoid any damage. The accuracy of the
sensors for a single reading is  5 Pa and can be
increased by averaging several readings, which
goes of course on the expense of the data acqui-
sition rate. More details of the various elements
of the setup are summarized by Won et al. (2011).
Interfacial Dynamics Methods 669 I
Interfacial Dynamics Extension Volume
Methods,
Fig. 37 Schematic of the
drop bubble micro
manipulator DBMM with
its main elements
xyz Stage Drop 2
PS1 PS2

Drop 1

Piezo 1 Piezo 2

Dosing 1 Dosing 2

I
Interfacial Dynamics
Methods, Fig. 38 Photo
of the drop bubble micro
manipulator DBMM;
left – in working position
with the two piezo drives on
the left and the xyz
micrometer stage on the
right; right – slipped up to
see two capillary holders
and two cylinders covering
the pressure sensors

As mentioned above, the whole DBMM mod-
ule has to be mounted onto the measuring cell of
a drop and bubble profile tensiometer PAT-1, as
shown in Fig. 38. There is also a stand-alone
version which includes only the main parts of
PAT. The standard version is equipped with
a standard video camera, which can be replaced
also by a fast video camera providing the same
high pixel resolution (better than 1,280  1,024)
at 1,000 fps or more (at reduced resolution).
As emphasized in many publications on single
drop and bubble experiments, the capillary is
a rather small part in each setup; however, it is
surely the most important part. In our setup, we
use capillary holders from Eppendorf for fixing
the two capillaries. Therefore, the outer diameter
of all capillaries at one end is 1.0 mm. The tips of
the capillaries are of different material, particular
shape, and diameter according to the planned
application. Eppendorf also provides respective
micro-capillaries from glass with customer
design, which are not disposable due to the
costs, are therefore, not suitable for routine
work in the lab. Our capillaries are designed
from various materials; the easiest to machine
are steel tubes taken from medical injection
needles, cut with blunt ends, and bended such
that the two capillaries can approach each other
to a certain distance. In this way, the two formed
drops/bubble meet each other at the poles, in
contrast to the arrangement used by Ata (2009),
who positioned the capillaries in a vertical way.
This was done because the formed bubbles were
loaded by heavy particles and an axisymmetric
geometry for each bubble was given only in this
way. Also glass capillaries with 1-mm outer
diameter are accessible without problems, and
they have the enormous extra advantage that
I 670
a b 240
220
200
Pressure (P)
180
c
160
140
120
10
Interfacial Dynamics Methods, Fig. 39 Two water droplets in air; the pressure and surface tension of pure
water, left cell
their tips can be easily designed with tailored
smaller orifices. They can be made with very
sharp or blunt tips, depending on the liquids to
be studies. The wetting of glass capillaries can be
adjusted by hydrophobization (inside or outside).
The capillaries used can have identical or differ-
ent tip shapes and diameters. Also the size of the
drops/bubbles can be chosen according to
the target with an identical or different size.
The software routines of the instrument provide
exact data of the radius of the drops at both sides
and the respective capillary pressures in real time.
The acquired values can be recorded with
a selected data acquisition rate. Also a video
movie can be recorded simultaneously with the
standard of 25 fps (or higher frame rates in case
a high-speed camera is used). Once the two drops
of a desired size are formed, the xyz-stage allows
moving the first drop toward the second drop until
both are positioned properly: just opposite to each
other or out of a common symmetry axis,
depending on the scientific aim of the study.
To demonstrate the functionality of the
DBMM, we show here only few selected exper-
iments. One experimental protocol is to measure
the capillary pressure before and during coales-
cence for systems containing surfactants,
proteins, and their mixtures. The target of these
studies is to understand which surface layer
Interfacial Dynamics Methods
Pressure 100
Surface Tension
Surface Tension (mN/m)
80
60
20 30 40
Time (s)
composition prevents droplets or bubbles from
coalescence. Furthermore, a thin film is created
when the droplets (or bubbles) contact each other.
The life time of such thin films will be controlled
by the properties of the present adsorption layers.
The simplest experiment for demonstration
reasons is the approach of two water droplets
against each other, in air or hexane system,
without any added surfactant. Studies for air
bubbles have been performed in aqueous solu-
tions containing food proteins such as b-casein
(BCS) and b-lactoglobulin (BLG), and different
types of added surfactants.
The following figures show results from
experiments with two water droplets in air
(Fig. 39), two air bubbles in a BLG solution
(Fig. 40), and one hexane droplet and one air
bubble in pure water (Fig. 41). Shown is the
time interval at which coalescence between the
two droplets or bubbles occurs. During the
approach, radius, volume, surface area, pressure,
and the surface/interfacial tension of the droplets
are recorded. The measuring signal and the
pictures which were taken before and after
coalescence are shown. When the two pure
water droplets get in contact, coalescence hap-
pens within 0.3 s and the pressure decreases
immediately (see Fig. 39). Of course, the shown
surface/interfacial tension is of physical meaning
Interfacial Dynamics Methods 671 I
a b 500 200
Pressure
Surface Tension 180

400 160

140

Surface Tension (mN/m)

300 120

Pressure (P)
100

200 80
c 60

100 40

20

0 0

−20
175 180 185 190 195 200 205 210

Interfacial Dynamics Methods, Fig. 40 Two air bubbles in an aqueous BLG (106 mol/l); the pressure and surface I
tension was measured in the left cell

Interfacial Dynamics
Methods, Fig. 41 One
droplet of hexane (left) and
one air bubble (right) in
pure water

only before coalescence. For the two air bubbles in
the aqueous BLG solution, the coalescence also
happens very quickly (t ¼ 0 on the time axis
corresponds to the start of the experiment and not
to the moment of contact) but with delay of few
seconds after contact (Fig. 40). This shows that the
formed BLG adsorption layer was not sufficient to
provide the bubbles from coalescence.
In Fig. 41, we see the asymmetric scenario of
a hexane droplet in contact with an air bubble in
pure water, when coalescence does not happen.
Instead, the bubble is engulfed by the drop and
continues to exist even after it is detached from
the capillary.
As this new methodology is very new, more
experimental work has to be done in order to
I 672 Interfacial Dynamics Methods

evaluate its real potential. It appears that it can
develop into a valuable tool for a quantitative
characterization of the stability of foams, emul-
sions, and also more complex systems like
foamed emulsions.
will surely allow to achieve the mentioned goals
and to get a quantitative knowledge of these
interfacial dynamics properties.
List of Symbols

A area
Summary c surfactant bulk concentration
c0 total surfactant concentration
To meet the requirements of many modern tech- c subsurface concentration
nologies, a quantitative knowledge on the cCMC critical micelle formation
involved interfacial properties is required. This concentration
applies essentially to the dynamics of fluid inter- cd,0 initial concentration in donor phase
faces, which are subject to changes due to the (Eq. 10)
large deformations of liquid interfaces during cd,eq equilibrium concentration in donor
many technological processes. This is true for phase (Eq. 10)
emulsification or foaming or during the transport D diffusion coefficient
of these systems through pipes, etc. For rather dA strain
slow processes, it is easy to measure the dg stress
corresponding properties by means of quasi- |E| viscoelasticity modulus
static methods. Here, drop and bubble profile f correction factor in Eq. (2)
tensiometry and ellipsometry provide excellent g gravity constant
data. Hence, the amount adsorbed and the reply h immersion depth of the capillary
to slow deformations can be investigated easily. into the liquid
We describe here, however, also the experi- K partition coefficient between two
mental tools for short adsorption time and media
high-frequency perturbation data, which are kf micelle formation rate constant
accessible only since recently. At the present L gas flow rate
state of the art, data in the millisecond range l capillary length
are measurable but using capillary pressure Lc critical gas flow rate
techniques with drops and bubbles. In addition, nAir refractive indices of air
the dilational rheology at frequencies up to nWater refractive indices of water
100 Hz, even at interfaces between two immisci- P pressure
ble liquids is available via experiments with Pc pressure at critical gas flow rate
oscillating drops and bubbles. Pcap capillary pressure (Eq. 9)
It is the subject of future work, to reach still Pdrag pressure caused by the drag force
shorter times and higher frequencies, which are (Eq. 9)
needed for highly dynamic production processes. Phyd hydrostatic pressure (Eq. 9)
This, however, entails not only the need of fast Pinertial pressure caused by inertial effects
data acquisition but also requires to solve very (Eq. 9)
complex theoretical problems, such as the com- Pmax maximum pressure
bination of matter transfer and liquid flow Pvisc pressure caused by viscosity effects
pattern. Both are closely linked in experiments inside the capillary tip (Eq. 9)
at very short times or high-frequency perturba- Q volumetric flow rate
tions. The separation of the interfacial effects R gas law constant
from the integral measuring signals becomes R(t) drop radius
a most difficult task. The utilization of R1, R2,R0 parameters of the drop geometry
a high-speed and high-resolution video technique (Fig. 6)
Interfacial Dynamics Methods 673 I
r radial coordinate Andersen A, Örtegren J, Koelsch P, Wantke KD,
rcap capillary radius Motschmann H (2006) Oscillating bubble SHG on
surface elastic and surface viscoelastic systems: new
s parameter of the drop geometry insights in the dynamics of adsorption layers. J Phys
(Fig. 6) Chem B 110:18466–18472
T temperature Ata S (2008) Coalescence of bubbles covered by particles.
t time Langmuir 24:6085–6091
Ata S (2009) The detachment of particles from coalescing
tb bubble time bubble pairs. J Colloid Interface Sci 338:558–565
td dead time Battal T, Shearman GC, Valkovska DS, Bain CD,
tl lifetime Darton RC, Eastoe J (2003) Determination of the
Va volume of the acceptor phase, dynamic surface excess of a homologous series of
cationic surfactants by ellipsometry. Langmuir
Eq. (10) 19:1244–1248
Vd volume of the donor phase, Eq. (10) Bendure RL (1971) Dynamic surface tension determina-
x drop profile coordinate (Fig. 6) tion with the maximum bubble pressure method.
z drop profile coordinate (Fig. 6) J Colloid Interface Sci 35:238–248
Benjamins J, Cagna A, Lucassen-Reynders EH
G surface concentration (1996) Viscoelastic properties of triacylglycerol/
g surface and interfacial tension water interfaces covered by proteins. Colloids Surf
g0 surface and interfacial tension of the A 114:245–254
Benjamins JW, Jönsson B, Thuresson K, Nylander T (2002) I
pure system
New experimental setup to use ellipsometry to study
DP hydrodynamic pressure loss liquid-liquid and liquid–solid interfaces. Langmuir
Dr density difference between two 18:6437–6444
fluids Cabrerizo-Vı́lchez MA, Wege HA, Holgado-Terriza JA,
y parameter of the drop geometry Neumann AW (1999) Axisymmetric drop shape anal-
ysis as penetration Langmuir balance. Rev Sci Instrum
(Fig. 6) 70:2438–2444
m dynamic viscosity Cheng P, Li D, Boruvka L, Rotenberg Y, Neumann AW
P surface pressure (¼ g0  g) (1990) Automation of axisymmetric drop shape anal-
r fluid density ysis for measurements of interfacial tensions and con-
tact angles. Colloids Surf 43:151–167
f phase angle du No€uy PL (1925) An interfacial tensiometer for univer-
sal use. J General Physiol 7:625–633
Fainerman VB (1979) Measurement of the dynamic sur-
Acknowledgments The work was financially supported face tension of solutions by the method of the maximal
by a project of the DFG SPP 1506 (Mi418/18-1), the pressure in a bubble. Colloid J (Russ) 41:79–83
European Space Agency (ESA FASES MAP AO-99-052 Fainerman VB (1981) Kinetics of surfactant adsorption
and PASTA), and the German Space Agency (DLR from micellar solutions (theory). Colloid J (Russ)
50WM1129). 43:94–100
Fainerman VB (1990) On the surface tension measure-
ment by the bubble pressure method in the millisecond
range. Colloid J (Russ) 52:921–927
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Interfacial Tension
Tharwat Tadros
Wokingham, Berkshire, UK
Definition
The interfacial tension g between two immiscible
liquids in the absence of any adsorption is the
change of the free energy Gs with interfacial
area A at constant
 Gs temperature and constant com-
position: g ¼ @@A T;ni
. The value of g depends on
the nature of the two immiscible liquids. For an
alkane-water system, g is
50 mNm1; for an
aromatic oil-water interface, g is
30 mNm1;
and for a polar oil (such as hexanol)-water inter-
face, g is
15 mNm1. Any adsorption at the
interface, in particular surfactant molecules, will
lower g to an extent depending on the nature of the
oil and surfactant, reaching values in the region of

1–10 mNm1. The reduction in g with surfactant
Interfacial Tension 677 I
addition is important for formation of emulsions, reach
104–102 mNm1. These ultralow
whereby the total interfacial energy is reduced, interfacial tensions are important for the formu-
thus facilitating the process of emulsification lation of microemulsions.
(which will require less energy). Interfacial
tension gradients produced during emulsifica- Cross-References
tion stabilize the emulsion droplets against
coalescence during the process. Combination ▶ Emulsion Formation
of surfactant molecules can lower g to very ▶ Emulsion Stabilization
low values, and in some cases, g can ▶ Surfactants