Current Opinion in Colloid & Interface Science 15 (2010) 217228

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Current Opinion in Colloid & Interface Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c o c i s

Interfacial dilational rheology by oscillating bubble/drop methods

Francesca Ravera a,, Giuseppe Loglio b, Volodymyr I. Kovalchuk c
a
b
c

CNR Istituto per l' Energetica e le Interfasi, 16149 Genoa, Italy

University of Florence, 50019 Sesto Fiorentino (Firenze), Italy
Institute of Bio-Colloid Chemistry, Vernadsky str. 42, 03142 Kiev, Ukraine

a r t i c l e

i n f o

Article history:
Received 17 February 2010
Received in revised form 21 April 2010
Accepted 22 April 2010
Available online 5 May 2010
Keywords:
Dilational viscoelasticity
Oscillating drops and bubbles
Drop shape
Capillary pressure tensiometry
Interfacial tension
Interfacial rheology

a b s t r a c t
Dilational rheology represents a powerful tool to investigate equilibrium and dynamic properties of simple
and more complex interfacial layers containing surfactants, proteins, polymers or micronano sized particles.
Concerning the experimental techniques for dilational rheology, drop/bubble tensiometers based on the
acquisition of the drop/bubble prole and capillary pressure tensiometers are especially effective.
This article focuses on oscillating drop/bubble methodologies where harmonic variations of the interfacial
area are utilized for the measurement of the dilational viscoelasticity in the frequency domain. The
increasing efciency of these techniques of the last ten years is due, from one side, to the implementation of
advanced instrumentations which make faster the drop/bubble control and the data acquisition and, on the
other side, to the application of new theoretical approaches for data acquisition and interpretation.
A critical analysis of such drop/bubble instruments is presented where their potentialities and limitations are
underlined. Moreover, recent improvements in the denition of calculation methods based on the modelling
of the experimental set up are reviewed together with some examples of experimental studies based on the
utilisation of such methodologies.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
The study of the mechanical properties of liquid interfaces has a
large relevance for many technological and natural processes
involving multiphase systems characterised by a high specic area
such as liquid lms, emulsions or foams.
Being these systems in most practical cases subjected to dynamic
conditions, dynamic interfacial tension and interfacial rheology, are
important characteristics which may be the driving force for their
evolution and the key-feature for stability [14].
Interfacial rheology relies with surface modication induced by
mechanical forces, like shear or dilational stresses [5,6]. Much
information on this topic can be found in the recent book [7]. In
case of dilational, or compression/expansion, rheology, the stress is
the variation of the interfacial tension while the corresponding
surface modication is the area change. Dilational rheology is of
special signicance for systems containing surfactants or, more in
general, for composite interfacial layers where the interfacial tension
changes due to surface relaxation processes or diffusion. For these
systems a viscoelastic modulus, or dilational viscoelasticity, can be
attributed to the interface characterizing its dynamic response to
expansions/compressions.

Corresponding author. CNR-IENI, via De Marini 6, 16149 Genova, Italy.

E-mail address: f.ravera@ge.ieni.cnr.it (F. Ravera).
1359-0294/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2010.04.001

Moreover, the close link existing between the dynamic properties

of the interfacial layers and the adsorption mechanisms makes
dilational rheology a unique tool to access the characteristics of the
transport and the kinetic processes determinant for the adsorption reequilibration and the physicochemical properties of the involved
surfactant-interface system. However to obtain qualitative and
quantitative information about such adsorption mechanisms, it is
necessary to adopt accurate and effective experimental methods, to
access broad scales of time, and to interpret the rheological data by
means of appropriate theoretical models.
Concerning the experimental techniques for dilational rheology, which
is the main topic of this article, the methods utilising oscillating bubbles
and drops are especially effective. In this eld during the last decade
several progresses have been made either by upgrading and adapting
existing tensiometric techniques or developing new methodologies.
Bubble/drop methods derive from classical methods, originally
conceived for interfacial tension measurements that, own to the
technological advances, have enlarged their potentialities. Such
techniques in fact have become increasingly efcient due to the
implementation of advanced instrumentations which make faster the
drop/bubble control and the data acquisition [810]. Moreover the
application of new theoretical approaches has allowed the acquired
data to be interpreted also under dynamic conditions [1113]. The
implementation of modern control techniques provides, for example,
a better dynamic performance in measuring the response of interfacial
tension to area variations, improving the accuracy of dilational viscoelasticity measurements.

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F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

Due to their versatility and their always better applicability to both

liquidliquid and liquidair interfaces, bubble/drop techniques are today
widely employed for dilational rheology investigations [14,15]. Moreover, because the relaxation processes responsible for the dynamic
behaviour of uid interfaces, like diffusion exchange, surface re-arrangement of the adsorbed molecules, etc., occur over a broad time-scale,
an important point for the advancement in this kind of investigation is to
access broad work frequency ranges. In many experimental works this
enlargement of the frequency range is obtained by coupling different
tensiometers, appropriate for different scales of time.
This article focuses on oscillating drop/bubble methodologies
where harmonic variations of the interfacial area are utilized for
dilational rheology investigations in the frequency domain. Such
methods have been employed for many experimental studies,
implemented in commercial or in laboratory developed drop/bubble
tensiometers [16,17].
In the following a critical analysis of such drop/bubble instruments
is presented where their potentialities and limitations are underlined
especially concerning the evaluation of the dilational viscoelasticity
versus frequency. Recent improvements in the denition of calculation methods based on the modelling of the experimental set up are
reviewed together with some examples of experimental studies based
on the utilisation of such methodologies.
2. Experimental techniques for interfacial tension and
dilational rheology
Two main types of bubble/drop techniques characterized by two
different ways of monitoring the interfacial tension are here referred
as: one is based on the analysis of the drop prole [14] and the other
one on the capillary pressure measurement [18]. Both techniques
exploits the relationship existing for uid interfaces between the
interface curvature, the pressure difference across them and their
interfacial tension, as stated by the Laplace equation.
Thus, in both cases the capillary pressure inherent to a curved
interface is important. However, the interfacial tension response ,
which is necessary to calculate the dilational viscoelasticity, is obtained
in different ways. In case of drop/bubble prole tensiometry sufciently
large drops and bubbles are used (usually larger than 1 mm in diameter)
which are well deformed due to gravity. Accordingly the main curvature
appears not constant and the capillary pressure varies along the
interface. In this case the local pressure difference across the interface
can be obtained from the drop/bubble shape. In the case of pressure
tensiometry the drops and bubbles used are small and practically not
deformed in the gravity eld. The shape of the liquid meniscus appears
very close to a spherical shape and the capillary pressure in different
points at the interface is almost constant. This allows one to measure this
unique capillary pressure directly by a pressure sensor.
These techniques are effective for liquidliquid and liquidair
interfaces and can be used according to different methodologies to
investigate different dynamic aspects of the interfacial properties.
Concerning the dilational viscoelasticity measurements, as each
tensiometer works properly in a given time scale, their coupling is very
effective to cover a quite broad frequency range. These methods are
limited in frequency by the onset of non radial oscillations [11] and also by
other uodynamic effects which, as better discussed in the following, may
set a limit between 100 and 1000 Hz, depending on the experimental setup and conditions. Therefore, for higher frequencies, drop/bubble
tensiometers are not longer appropriate and other methods such as
those based on capillary waves damping are instead preferable [19].

Under gravity conditions, a bubble or a drop of one liquid inside

another uid assumes a shape which minimises the total energy of the
system. Such shape is determined by a combination of surface tension
and gravity effects: surface forces tend to make drops and bubbles
spherical whereas gravity tends to vertically elongate or squeeze
them. At each point of the surface of a drop/bubble, under mechanical
equilibrium condition, the relation between the pressure difference
across the interface, the surface tension and the surface curvature is
provided by the Laplace equation [20].
For axis-symmetric menisci, the Laplace equation together with
the pressure dependence on the drop height, due to the gravity eld,
lead to a set of three rst-order differential equations (Bashforth
Adams [21]) in terms of geometrical parameters of the drop/bubble.
d
sin
= 2
z
x
d s

d x
= cos
d s

d z
= sin
d s

where s = s / b, x = x / b and z = z / b are the dimensionless arc length,

horizontal and vertical coordinates, respectively, normalized by the
curvature radius at the drop apex b, is the angle of the tangent to the
prole, and is a dimensionless parameter (Fig. 1). The boundary
conditions for this set of equations are
x 0 = 0; z0 = 0;

0 = 0

The numerical integration of such set of equations provides the

prole of a meridian section of the drop/bubble. Such theoretical prole
results to be dependent on a dimensionless shape factor, = gb2 / ,
where g is the gravity acceleration, the density difference, b the
curvature radius at the drop apex and the interfacial tension. This
factor is important because relates the drop deformation due to gravity
effect to the interfacial tension. The strategic aim is to determine this
parameter from the comparison of calculated and measured proles and
subsequently to nd interfacial tension [20,2224].
According to its working principle, there are then two fundamental requirements for the application of this technique: the two
involved uids must have an appreciable density difference and the
interface must be not far from the mechanical equilibrium.
In fact if the liquids are isodense the drop is spherical whatever
is the interfacial tension which then results undetermined. The dimensionless shape factor gives an estimation of the level of drop
deformation due to gravity effect and in practice determine the

2.1. Drop/bubble prole tensiometry

The drop/bubble prole tensiometry (DPT) is a well-established
technique for determining the mechanical properties of liquidgas
and liquidliquid interfaces.

Fig. 1. The meniscus prole and (x, z) coordinate system.

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

measurement accuracy. In many practical cases, with the most common acquisition systems, accurate data are obtained for || N 0.1. In
contrast, for the capillary pressure measurements the shape factor
should be smaller than this limit.
The requirement of mechanical equilibrium of the interface
implies that only slow variation of the surface area can be applied
to obtain accurate measurements. DPT is then commonly used for
measuring interfacial tension at constant area to investigate for
example adsorption kinetics or during slow variations of the surface
area to investigate interfacial rheology at low frequency.
On the other side the advantages of the DPT are numerous. Only
very small amounts of the liquid are required, just enough to form one
drop. It is suitable for both liquidvapour and liquidliquid interfaces,
and applicable to materials ranging from organic liquids to molten
metals [25] and from pure solvents to concentrated solutions.
Operating at constant interfacial area, the time scale ranges from
parts of a second up to hours and even days so that even extremely
slow processes can be easily followed.
Under periodic perturbation of interfacial area, the technique
allows the acquisition of the interfacial tension response for
frequencies spanning some decades in the low frequency range, i.e.
10 510 1 Hz. At faster oscillations, as better discussed in the
following, a frequency threshold appears when the interface is no
more in mechanical equilibrium.
A typical DPT (see Fig. 2) is composed by a cell where a drop or a
bubble is formed inside the other uid, at the tip of a vertical or of a Ushaped capillary. According to the densities of the two adjoining
phases, variant congurations are possible, namely pendant/emerging
drops, sessile drops and captive/emerging bubbles. The drop/bubble is
continuously monitored by a video-camera coupled to a computer
and its prole is acquired in an automatic way in order to calculate the
surface tension by means of a numerical tting procedure.
Modern versions of DPT and in particular some commercial tensiometers offer the option of controlling the interfacial area and all the
geometrical characteristics of a drop (or of a bubble) as a function of
time, by a feed-back loop comparing the observed drop area-value
with the set-value in a pre-dened time-line. This feature is an essential instrumental tool for studying the dynamic interfacial tension
and the interfacial responses to controlled area perturbations.
The implementation of this control task led to a large improvement of the technique, allowing for example to investigate adsorption
kinetics under really constant surface area conditions. At the same
time it has been a key step for the utilisation of DPT for dilational
rheology investigation.
Different algorithms and procedures have been proposed and are
available to obtain interfacial tension from drop/bubble prole
measurements [14,23,24,26,27]. In particular, in the axisymmetric
drop shape analysis (ADSA) of Rotenberg et al. [24] a tting procedure was developed which is based on minimization of the error
function dened by the deviation of the theoretical curve from the
experimental prole. In this procedure the parameter , the coor-

219

dinates of the drop apex x0 and z0, and the curvature at the drop apex
b are used as adjustable parameters. Such procedure requires precise
edge detection from the acquired images of a drop (or bubble) and
accurate solution of the equation sets (1)(3).
For so formulated mathematical problem, Eqs. (1)(4), there is no
direct analytical solution in the general case. For some limiting situations it is possible to nd approximate solutions, e.g. for extremely
large or extremely small sessile drops [28]. In [29] an elliptical
solution was proposed which in fact is also a sort of approximate
solutions. The most popular way, however, is to obtain a numerical
solution and various algorithms were proposed for this purpose
[23,24,28,30].
Conventional algorithms use the arc length along the drop prole
as independent variable to t the calculated prole coordinates to the
experimental shape in vertical, horizontal or normal direction. For
small almost spherical drops this technique leads to rather large
errors. Zholob et al. in [31] have proposed to transform the equation
sets (1)(3) into a second order differential equation by using polar
coordinates with the origin of the coordinate system located in the
drop (bubble) centre and with the polar angle used as independent
variable. This allows to improve the accuracy without a signicant
increase of computation times.
A critical aspect in drop/bubble shape analysis is an accurate edge
detection procedure. The edge detection methods are continuously
improved to provide better sensitivity, resistance against noise and to
minimize possible errors [32]. The derivative algorithms analysing the
variation of light intensity near the edge are the most popular way to
develop of an edge detector. In particular, in gradient edge detections
the position of the local maximum of the gradient across an edge is
assumed to be the drop edge coordinate. The edge detection can be
improved by using special correction and smoothening procedures
[8]. In [33] an alternative approach was proposed that eliminates
independent edge detection and suggests combining the image
processing tasks with the comparison with the theoretical shape.
This method takes into account that the extracted edge prole should
be a Laplacian drop prole. Thus, this method also includes an edge
detection, but in a more sophisticated way. In [31] it was proposed to
approximate the brightness gradient along the direction normal to the
drop prole by normal distribution curve



xx0 2
Gx = Gm exp

Then the parameter x0, obtained by tting the experimental points

according to Eq. (5), can be accepted as the best edge coordinate. This
allows to avoid multiple local maxima detection and to increase the
accuracy of edge detection.
For the fundamental physical and mathematical principles for DPT,
very shortly above summarised, the reader is directed to the
textbooks [20,22]. It is also worth calling attention to recent progress
on the determination of interfacial tension for drop/bubbles with
nearly spherical shape, as described in Ref. [8] where all possible
error sources are investigated by a systematic scrutiny of the software
and hardware components of the measurement scheme.
2.2. The capillary pressure tensiometry
The capillary pressure tensiometry (CPT) exploit in a direct way
the Laplace equation being based on the direct measurement of the
pressure difference across the interface of a spherical, or nearlyspherical, drop/bubble. Indeed, according to the Laplace equation,
such pressure, P, is directly linked to the interfacial tension

Fig. 2. Scheme of a typical DPT set up with control of the meniscus dimensions.

P=

2
0
+P
R

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F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

where R is the drop radius (or the curvature radius at the apex of the
drop) and P0 can be either an hydrostatic constant or a uid-dynamic
term, depending on the adopted experimental methodology. The
interfacial tension can be then inferred from the above relationship by
knowing P, R and P0 versus the time.
A typical CPT is composed by two chambers connected by a
capillary tube, as schematically sketched in Fig. 3. One of the chambers
is closed and contains both the pressure sensor and a piezoelectric
rod. The latter is utilised to control the volume of the drop (or
bubble) formed at a tip of a glass capillary. A video camera allows for a
continuous monitoring of the drop. Sub-millimetric droplets are
typically utilised to obtain measurable capillary pressure values,
which are typically of the order of a hundred Pascal. The drop radius is
either measured by direct imaging or calculated from the injected
liquid volume, if the compressibility of the closed phase is known. The
other cell either is open to atmospheric pressure or, if closed, contains
another pressure sensor. Practically, two congurations are usually
utilized as sketched in Fig. 3, in which the closed cell may contain
either the liquid phase forming the drop or the liquid surrounding the
drop.
Technical details about this kind of tensiometer can be found in
Refs. [17,18,34,35]. An important characteristics of this technique is
that it does not require gravity deformed droplet but it works
preferably with spherical interfaces, which makes it suitable both for
liquidliquid and liquidair systems, using either small drops or small
density difference.
The CPT has been widely utilised in many experimental investigations of adsorbed layers based on the measurement of equilibrium
and dynamic interfacial tension and of the dilational visco-elasticity
[34], both at water/air and water/oil interfaces. Moreover, this tensiometer is also the core of an apparatus (FAST Facility for Adsorption and Surface Tension) utilised for studies about surfactant
adsorption at liquidliquid and liquidair system under weightlessness conditions (microgravity) [36,37] on board the Space Shuttle.
The CPT is a versatile technique which can be used according to
different experimental methodologies, to investigate dynamic and
equilibrium aspects of pure and composite surfactant systems. For
example, according to the growing drop experiment, the drop volume
is continuously increased while the pressure is measured. If the
surface tension is constant, the Laplace equation provides a linear
relationship between the pressure and the curvature and the interfacial tension can be obtained from the slope of the pressurecurvature straight line [38]. By this method it is possible to measure
both the interfacial tension of pure systems and equilibrium interfacial tension of surfactant systems presenting adsorption kinetics fast
with respect to the drop growing rate. The method has also been
proposed to investigate adsorption kinetics [39]. This method does
not require the direct drop imaging, being possible to calculate the
drop curvature from the volume rate.
The growing drop experiments are also used for side measurements in dilational studies [34] to evaluate the compressibility of the
system.

The equilibrium interfacial tension can be easily obtained in a CPT

according to the pressureradius step method [34]. For a certain
number of different drop volumes, the drop radius and the pressure
are measured after adsorption equilibration. Interpreting the pressure-curvature data the equilibrium surface tension is calculated from
the slope of the tting straight-line, according to the Laplace equation.
This method is used for equilibrium adsorption studies versus the
surfactant bulk concentration to access the adsorption isotherm of
the system, and also for side measurements in the framework of
rheological studies to evaluate the interfacial tension of the reference
state.
Rheological studies can be performed in the CPT where the
response of the interfacial tension to small amplitude perturbation of
the surface area are investigated. These perturbations can be aperiodic
functions, such as in the stress-relaxation experiment [40], or periodic
with different shapes of the forced signal, such as pulsed, trapezoidal
or sinusoidal [41]. As better explained in the following, when
used according to the oscillating drop/bubble method the CPT is an
effective tool to measure the dilational viscoelasticity at relatively
high frequency.
In this method harmonic perturbations are applied to the drop/
bubble interfacial area by means of controlled displacement of liquid
volume while the oscillating pressure response, related to the
response of the interfacial tension, is acquired.
3. The dilational viscoelasticity
The dilational viscoelasticity, or complex viscoelastic modulus, is
the quantity expressing the relationship between the surface
modication of an interfacial layer and the related dilational stress.
Due to its connection with the dynamic characteristics of the interfacial layers, this quantity is very signicant especially as regards its
dependence on the frequency of the area perturbation.
The dilational stress of an adsorbed layer is the variation of the
interfacial tension from its initial value 0 to a generic value at the
time t, i.e. = (t) 0 while the related surface deformation is the
expansion/contraction of the surface area A. For purely elastic
dilational behaviour, the surface stress is proportional to the relative
area variation, = A / A0 = (A(t) A0) / A0. However the interfacial
layer may have a viscous behaviour due, for example, to the occurring
of relaxation phenomena. Thus in general the dilational stress can be
written as the sum of two terms: one purely elastic, proportional to
and the second one, a viscous term, proportional to the rate of surface
deformation [5,6] that is the rate of the area variation, = d/dt [5]. A
general expression for the dilational viscoelasticity is then

= E0 +

where the coefcients E0 and are termed as the dilational surface

elasticity and viscosity, respectively.
Eq. (7) leads to a denition of the complex dilational visco-elastic
modulus, or the dilational viscoelasticity, E. For a low amplitude
harmonic perturbation of frequency , in fact, the area perturbation
can be expressed as A = ei2t which, introduced in Eq. (7), gives
E=

Fig. 3. Sketch of the measurement cell of a capillary pressure tensiometer according to

two possible congurations. In both cases the closed part of the cell is equipped by a
pressure sensor and a piezoelectric driver.

= E0 + i2
A = A0

The dilational viscoelasticity E is then a frequency dependent

complex quantity, where the real part ER E0 is the dilational elasticity
and the imaginary part EI = 2 is directly related to the dilational
viscosity. It is important to notice that whatever area modication one
assumes, provided that it is a low amplitude perturbation, it can be
expressed, according to the Fourier formalism for linear systems, as a
superposition of harmonic components in the domain of frequency.

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

Moreover, when a purely harmonic perturbation is applied to the

surface, the interfacial tension and the other quantities inuenced by
this perturbation present also a harmonic variation at the same
frequency.
From these considerations it is clear the importance of knowing
the feature of E(). Under linear conditions, in fact, from Eq. (7), the
response of the interfacial tension to an arbitrary area variation of the
adsorbed layer is given by [42],
t
t = 0 E td

where is the inverse Fourier transform of E. Thus the complex

modulus E() can be considered as the transfer function of the
interfacial layer which is assumed to be a linear system. Eq. (9)
evidences that the interfacial tension response of an interfacial layer
can be assessed in a way as accurate as large is the frequency range
where E() is determined.
From practical aims Eq. (9) has been used in the interpretation of
experiments involving non-harmonic perturbations of the interfacial
area, like trapezoidal or rectangular variation in stress-relaxation
experiments [41,43].
On the other side the direct determination of E() is considered
very useful by many authors to access both the equilibrium
adsorption properties and the re-equilibration mechanisms of such
disturbed layer which are at the basis of its dynamic behaviour. In fact
several theoretical approaches are available in literature correlating
the E() feature to diffusion exchange, surface re-organisations and
other kinetics processes eventually occurring in the interfacial layer.
These theoretical approaches provide expressions of E() in terms of
the principal parameters related to the thermodynamics and the
kinetics of the adsorption layers. Such expressions can then be tted
to the experimentally acquired dilational data providing such
thermodynamic and kinetic parameters as best t values.
One example of this is the classical Lucassenvan den Tempel
approach [44] which, assuming diffusion controlled adsorption,
provides an expression of the dilational viscoelasticity in terms of a
characteristic frequency D and the high frequency limit elasticity, or
Gibbs elasticity,
related
to the thermodynamics of the adsorption


d
. D is related to the diffusion coefcient of
layer EG =
d ln eq
surfactant in the bulk and to the adsorption
 2 thermodynamic
dc
D
. This classical
characteristics of the system, i.e. D = 2
d eq
model is well known and widely used also today for surfactant
systems both at liquidair and liquidliquid interfaces. Moreover
introducing into the expression of E, more sophisticate thermodynamic models considering, for example, different possible molecular
states in the adsorption layer, such as molecular re-orientation or
surface aggregation [45,46], or two-dimensional compressibility
[47,48], the behaviour of some surfactant layers at increasing surface
coverage [11,49,50] can be described as well as multicomponent
systems such as ionicnonionic surfactants, surfactant-polymers and
surfactants-proteins [51,52]. The possibility to describe such more
complex systems is important for practical applications because of the
wide utilisation of these mixtures in modern technologies, to obtain
effects that cannot be obtained by single components.
Nevertheless for systems containing polymers or proteins for
which the kinetic transformations of the adsorbed layer have often
very long characteristic times, a diffusion controlled model is sometime not appropriate to describe the experimental dilational results.
This can happen even for some common surfactants, especially at
wateroil interfaces [12], subjected to kinetic processes in the
adsorbed layer, like molecular re-orientation [12], aggregation [53],
or chemical reactions [6]. It is then necessary to take into account not
only new surface isotherms but also multiple kinetic processes with
and without diffusion exchange with the bulk. Extensions of the

221

Lucassen van den Tempel equation are available in literature especially concerning insoluble layers, polymers and proteins [54,55,56].
In Ref. [57] a general approach to calculate E() is proposed, where
diffusion is considered together with other kinetic surface processes.
Such approach can be applied to any relaxation process described by a
linear rate equation. In fact for its application the only requirement is
that the system has linear behaviour. This is usually true for surfactant
adsorbed layers and in general for interfacial layer not far from the
equilibrium.
The E() feature provided by this approach depends, in particular,
on the characteristic frequency of the surface kinetic process. It has
been applied so far to soluble and insoluble surfactant systems [54]
and also, more recently, for interpreting rheological data obtained
with mixed surfactant nanoparticle systems, in order to better
investigate the relaxation process inside the mixed interfacial layer
[58].
It is important to underline that from the theoretical studies about
the relation between the E() feature and the dynamic characteristics
of the layer, it is well established that particular features of E() are
present around those frequency related to the characteristic times of
the system [54]. For example a maximum in the imaginary part EI and
an inexion point in the real part ER can appear when they are
acquired versus the frequency. This means that to effectively
investigate the dynamics of the interfacial layer the experimental
tool must provide access to time scales comparable to the characteristic time of the specic surface phenomena.
4. The oscillating drop/bubble methods
4.1. The principle of the measurement method
Drop/bubble tensiometers are particularly suitable to investigate
the dynamic behaviour of the adsorbed layers when they are used
according to the oscillating drop/bubble methodology [5962] to
measure the visco-elasticity versus frequency.
The instruments described in Section 2, allow precise measurements of this complex quantity for various types of uid interfaces
and quite broad frequency ranges are obtained by their coupling due
to the different time scales at which they preferably work [62,63].
According to this method, harmonic oscillations of the drop or
bubble surface area result in periodic expansion and compression
of the adsorption layer at the interface. Any deviation from equilibrium initiates various relaxation processes at the interface and
in the adjacent bulk solution. As a result the interfacial tension
varies periodically with the same frequency and with a certain
delay with respect to the external disturbance. As explained in
Section 3, for small-amplitude harmonic perturbations of the surface area the magnitude and phase of the interfacial tension
response is directly related to the dilational viscoelasticity through
Eq. (8) or (9).
Whatever is the tensiometer employed, in order to get the
frequency trend of the dilational viscoelasticity, the oscillating drop
experiments are usually performed by applying a frequency sweep to
the surface area A. Thus for each frequency it holds:
A = A + A sin 2t
0

10

where A0 is the reference surface area and the amplitude of the area
oscillations.
The harmonic response of the surface tension reads
0

sin 2t +
= +

11

where 0 is the equilibrium reference surface tension and the

amplitude of the surface tension oscillations. The phase shift between the area perturbation and the response of the interfacial

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F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

tension, is the phase of the complex dilational modulus. In fact,

according to Eq. (8),

E=

exp i
A = A0

12

Eq. (12) provides an expression for E in terms of quantities that can

be determined experimentally as frequency functions, either in a
direct way or by an appropriate calculation procedure, depending on
the utilized tensiometer.
When the oscillating drop/bubble method is applied in a DPT,
against time is directly acquired while a controlled harmonic perturbation is applied to the surface area. The amplitudes and and
the phase shift are obtained as amplitudes and phase of the components of frequency , extracted by the experimental signals via DFT
(Discrete Fourier Transform) algorithms as explained in details in
Refs. [6466].
At each frequency the complex dilational viscoelasticity is then
calculated according to Eq. (12). In Fig. 4 data acquired during the
surface oscillation are reported as an example with the extracted
theoretical harmonics utilised for the calculation of E.
When oscillating drop/bubble techniques are applied in a CPT the
measurable quantities are the pressure inside the closed cell and the
elongation of the piezoelectric rod which, due to the compressibility
of the system does not necessarily correspond to the variation of the
drop volume. In fact, while at low frequency the geometrical
characteristics of the drop (radius and surface area) can be directly
measured by imaging techniques, such direct acquisition of the drop
prole variation becomes more and more unreliable at increasing
frequencies. To get dilational viscoelasticity for frequency of the order
of 1 Hz and higher, a specic experiment theory is necessary allowing
for the calculation of E() from the acquired signals. Such theory must
account for hydrodynamic effects and consider also the inuence of
the cell plus liquids compressibility on the drop behaviour [1113].
Hereafter some specic worth noting aspects of the oscillating
drop/bubble techniques are discussed separately. These aspects
concern some intrinsic limitations of the instruments and also the
practical procedures allowing for the optimization of the instrument
performance.
4.2. Treatment of the oscillatory experimental signals
One practical problem connected with the oscillating drop/bubble
is the treatment of the real oscillating signals, that are the surface
tension and surface area, in the case of DPT, and the pressure and
piezo volume for CPT. As a matter of fact, even under experimental
conditions ensuring the linearity of the system, a real output signal

may contain harmonics with frequencies different from that imposed

due, for example, to some external disturbances (drift or low and high
frequency noise) or to a weak non linearity of the system [65].
For this reason it is preferable to adopt a procedure of harmonics
extraction with respect to a tting procedure with a sinusoidal function which, when the experimental signal contains other frequency
components, may denitely ensue in meaningless amplitude and
phase values. The mathematical procedure for the harmonics extraction based on the Discrete Fourier analysis, is hereafter summarized.
The component at frequency of a generic experimental signal g(t)
presenting a phase is
0

g = g + g sin 2t +

13

Considering the discretisation of this experimental signal, at the

generic time tj, using the Fourier series expansion, one obtains






gj = A cos 2tj + B sin 2tj
where A =

1
N

gk 2 cos 2tk , B =

k=1

14
1
N

gk 2 sin 2tk , N is the

k=1

number of experimental points and gk is the measured value at the

time tk. Thus one obtains,
g =

p
A2 + B 2

= arctan

15

 
B
A

16

In a typical oscillating drop experiment the oscillating signal is

acquired for a number of cycles sufcient to warrant the achievement
of stationary oscillations and a signicant statistics.
The validity of the linearity hypothesis is of crucial importance for
such analysis because the magnitude of the dilational modulus, which
is a transfer function, should be independent of the oscillation amplitude. In [65,66] the total harmonic distortion (THD) parameter was
proposed for a quantitative estimation of the goodness of the linearity
hypothesis in oscillation experiments with drops and bubbles. It can
be dened as

THD =

1 = 2
a22 + a23 + + a2n
a1

17

where a1 is the amplitude value at the fundamental frequency and a2,

a3, , an amplitude values of the higher harmonics. Under condition
of periodic oscillations with different amplitudes at the same frequency, the THD parameter shows the existence of a linearity range in
the relationship between an imposed interfacial area variation and the
resulting interfacial tension response.
4.3. Applicability limits for DPT measurements

Fig. 4. Example of acquired surface tension () and surface area () by the oscillating
drop method in the DPT, at = 0.02 Hz.

The condition of the mechanical equilibrium of the drop/bubble to

have Laplacian prole is very important especially when a DPT is used
for dilational rheology measurements, i.e. when periodic oscillation
are applied to the surface area.
Increasing the frequency of the area perturbation in fact a threshold may be overcome where the interface is no more at mechanical
equilibrium as shape distortion occurs due to viscous forces and to
triggering of drop/bubble normal oscillation modes [67,68].
About this upper limit in the frequency range, specic investigations have shown [69] that, for amplitude of the area oscillations
below 10%, the drop can be considered at mechanical equilibrium for
frequencies below 1 Hz. This condition holds for waterair systems
while for more viscous liquids or liquidliquid interfaces, the limit
frequency reduces to about 0.1 Hz.

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

Similar results on this frequency limit are found in Ref. [68] where
the effects of oscillating a viscous oil drop in water, on the drop prole
based measurements, is experimentally explored.
In this work, by comparing the experimental results to a model
oscillating spherical drop, it has been found that the viscous effects
can lead to an artefact in the surface tension measurement, i.e. the
acquired is actually an effective surface tension. This comparison
provides also a criterion under which viscous forces can be neglected, which is Ca b 0.002, where Ca is the capillary number, or the
ratio between viscous and capillary forces, dened as Ca = V/
a2 where is the viscosity difference between the two uid
phases, V the amplitude of volume oscillation and a the capillary
radius.
4.4. Determination of the dilational viscoelasticity by CPT measurements
As previously mentioned an important critical point of the oscillating drop method using CPT is the calculation of the dilational
visco-elasticity from the acquired pressure signal due to the
difculty in applying directly the Laplace equation when increasing
frequency. This is essentially due to two basic reasons. The rst is
the technical limitations in the rate of the image acquisition which
in practice makes very difcult the measurement of the drop/bubble
radius and area when increasing the oscillation frequency. This is
even more important if one considers that the relationship between
the imposed volume variation, Vpz, and that of the droplet/bubble
Vm is affected by the system compressibility. The second reason is
the presence of dynamic contributions to the measured pressure
besides the capillary pressure. Also this second effect increases
while increasing the frequency and strongly depends on the
physical characteristics of the uids, such as viscosity and density
and also on the geometry of the specic experimental cells and
capillaries.
Thus, in contrast to the case of DPT, when the CPT is used the
interfacial area variation A and the respective interfacial tension
response , which are necessary to calculate the dilational
viscoelasticity according to Eq. (8), are not directly measured. They
should be found in an indirect way from the known volume variation
produced by the piezo-actuator Vpz and the measured pressure
variation inside the closed cell P (Fig. 3).
In practice, when oscillating drop experiments are performed in a
CPT, a sinusoidal voltage signal is applied to the piezoelectric rod
proving a variation of its volume, Vpz,
Vpz = Vpz + V pz sin 2t
0

variation. According to the volume balance [15,70] the meniscus

volume variation can be expressed as
Vm =

Vpz +

V0
P
Bef

!
20

1
where P = P P0 is the pressure variation, Bef = B 1 + VB0 dVdPCell
is
the effective (intrinsic) cell elasticity, B is the bulk elasticity of the
liquid in the cell and dVCell/dP is the coefcient characterizing the
elastic properties of the cell subjected to a pressure variation.
Different signs before the brackets in Eq. (20) correspond to two
congurations shown in Fig. 3.
As we can see from Eq. (20), the meniscus volume variation Vm
depends on both the externally applied volume variation Vpz and
pressure variation P. In his turn, the pressure variation in the cell
depends on the meniscus volume variation, as the last determines the
degree of the capillary pressure variation related to the meniscus
interface and, additionally, the ow velocity in the capillary responsible for the hydrodynamic pressure drop. Thus, there is interdependency between two unknown quantities: Vm and P. The
solution of the respective set of equations for volume and pressure
balances allows to express these two quantities through the applied
external disturbance Vpz with account for both the effective
elasticity of the cell and the complex resistance (impedance) of the
capillary with the attached meniscus [15,70]. The complex resistance
of the capillary includes the contribution of the meniscus interface
what we are looking for. Thus, by measuring the response, which is
either Vm or P, to the known disturbance Vpz, one can get the
complex resistance from which the information about the interfacial
tension variation can be obtained.
Usually, under the conditions of fast oscillations (up to several
hundred Hz), it is much easier to measure the pressure variation P as
a response than Vm. In order to obtain correct information about the
interfacial tension variation the contribution of hydrodynamic effects
in the bulk phases and that of the viscous stresses at the interface
should be accounted for. Usually the approximation of quasistationary incompressible uid ow inside the capillary is used for
this aim which is valid for not very high oscillation frequencies as
discussed below. As a result the dilational viscoelasticity E can be
expressed as [36,47,70]
2
3
!1
V pz i
a0 dVm 4
V0
20 da 5
2
E=
21

e +
iG1 + G2 + 2
2 d ln A
Bef
a0 dVm
P

18

and the pressure inside the closed part of the cell is measured by the
pressure sensor as response of this harmonic perturbation. The component of frequency of the pressure signal presents in general a
phase shift with respect to Vpz, that is
0
P = P + P sin 2t +

223

19

, P and are extracted by the experimental

The amplitudes Vpz
signals via DFT Fourier-series expansion algorithm. Thus an oscillating
drop experiment provides for each frequency , a set of Vpz, P, data.
The problem is then to calculate the complex modulus E from these
experimentally acquired quantities.
By assumption of a spherical shape of the meniscus (i.e. drop or
bubble) the interfacial area variation A can be calculated from the
variation of the meniscus volume Vm. The last, however, is different
from Vpz = Vpz V 0pz because the real liquid in the cell is characterized by a non-zero bulk compressibility. As well the deformation of
the cell walls can also contribute to the difference between Vpz and
Vm when the walls are not sufciently rigid. Neglecting of these
effects can result in erroneous determination of the interfacial area

where = 2 is the angular frequency, G1 and G2 are the coefcients

describing the viscous and inertial contributions, a0 and 0 are the
equilibrium meniscus curvature radius and equilibrium interfacial
tension, and da/dVm and dlnA/dVm are the geometric coefcients
describing the variation of the meniscus curvature radius a and the
interfacial area with the meniscus volume Vm.
The viscous contribution is determined mainly by the uid ow
inside the capillary (according to Poiseuille law) because the length of
the capillary is usually mach larger than its internal radius. In the
recent study by Alexandrov et al. [71] the contribution from viscous
stresses acting at the interface was analyzed, and it was shown that it
is signicant only in the case of highly viscous liquids (by two orders
of magnitude higher than water). Considering different approaches
for the contribution of viscous stresses at the interface the authors
proposed a respective correction which is based on exact numerical
solution of the hydrodynamic problem of an expanding/contracting
spherical drop attached to a capillary in an outer uid phase.
The inertia contribution is determined by both the inertia of the
uid ow inside the capillary and the inertia of the added mass of the
uid surrounding the meniscus [15,70]. When the uid inside the
capillary is a liquid (in case of an oscillating drop) then the ow inside

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F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

the capillary gives the main contribution. However for a gas owing
through the capillary (i.e., for the oscillating bubble conguration) the
main contribution comes from the added mass of liquid surrounding
the meniscus because of its higher density. It should be noted that the
entrance regions of the capillary can also give corrections to the
coefcients G1 and G2. Thus, the determination of the coefcients G1
and G2 is an important problem.
To handle this problem several approaches have been proposed
depending on the experimental conditions and on the investigated
systems. In some rheological studies using CPT for measuring the
dilational modulus [15,34,50], reference measurements on pure
systems (zero dilational viscoelasticity) without surfactants have
been used in order to obtain the hydrodynamic coefcients G1 and G2,
which are necessary to extract from the experimentally acquired
pressure signal the capillary pressure term from which it is possible to
directly evaluate the surface tension variation and consequently the
dilational viscoelasticity. This approach however is mainly limited by
the difculties to rely on the perfect equivalence of the experimental
conditions of the reference measurements, especially concerning the
drop/bubble geometry or the effect of different lling of the
experimental cell. Alternative to such calibration experiments is to
calculate the coefcients G1 and G2 according to the uid dynamics
approaches. This way can also be difcult especially when the
meniscus is slightly deformed due to gravity. The optimal way
depends on the conditions of the experiment. In particular, under
microgravity conditions the direct calculation of the coefcients can
be preferable, because in this case the meniscus has a spherical shape
[13,36,70]. The same concerns also the geometric coefcients da/dVm
and dlnA/dVm which can be much easier calculated for spherical
menisci.
One of the most important problems connected with the data
interpretation is originated by the compressibility of the closed phase
(cell plus liquid) which, in general, cannot be neglected because of the
large ratio between the droplet and the cell volume.
In the method proposed in Refs. [12,54] the expression to calculate
E from the acquired pressure and piezo volume signals has been found
assuming a particular modelling of the closed part of the measurement cell simulating the compressibility, C = 1/Bef, of the system (cell
plus liquids): the real system is considered equivalent to an incompressible liquid containing an amount of gas of volume Vg, related to
the pressure P through the perfect gas law. A relationship between
this equivalent volume and the compressibility C can be easily found
according to the denition of this latter, i.e.
C=

0
1 V
1 Vg

V P Patm V 0

important experimental parameter which can inuence the quality

of the experiment.
In other approaches [15,49], severe assumption on the feature of
the E() are used, such as a diffusion controlled adsorption mechanisms, which make the methods good only for particular classes of
systems reducing, as a matter of fact, the generality of the techniques.
The systematic quantitative analysis of the simulated pressure
signals proposed in ref. [64] allowed for the evaluation of the effect of
the most critical experimental parameters like the compressibility,
the capillary size and the uid properties.
In Fig. 5 an example of experimentally acquired P(v) and () are
reported as obtained with a CPT used in Refs. [34,35,58]. The
corresponding ER() and EI() are also reported as calculated by using
the approach presented in Ref. [64]. The curves in Fig. 5b were
obtained by tting a theoretical curve determined according to a
general model which takes into account both diffusion and internal
reorganization of the interface [54,57]. This model which is an extension of the Lucassen van den Tempel model, allows the characteristic frequencies of the dynamic processes involved in adsorption
to be obtained. In this case 0 = 3.1 Hz and k = 73.7 Hz were found as
characteristic frequencies for the diffusion transfer and kinetic process internal to the adsorbed layer, respectively.
4.5. Applicability limits for CPT measurements
The calculation method described in the previous section to derive
E() for CPT oscillating drops/bubbles, has been obtained under some
conditions depending on the cell-capillary geometry and on the
properties of the used uids, which, as a matter of fact, set a frequency
limitation in the applicability of this approach.
The applicability of Eq. (21) requires two conditions to be fullled
for the uid inside the capillary related to two approximations done in
the calculation [72]: the incompressibility approximation which, for
geometrical parameters typical of the used tensiometers is usually
satised, even for air owing in the capillary, and the quasi stationary

22

where V0 is the volume of the closed phase (phase 2 in the conguration 1 and phase 1 in the conguration 2). Thus using the
present model, the compressibility can be expressed through the ratio
between the effective gas volume and the total volume of the closed
phase.
To evaluate this effective volume side experiments exploiting
growing bubbles or drops are usually adopted as explained in details
in Refs. [34,64].
An important coefcient is da/dVm which describes the variation of
the meniscus curvature radius a with the meniscus volume Vm. It
changes its sign when the meniscus grows to a size larger than
hemisphere. Therefore the behaviour of the meniscus becomes qualitatively different for the menisci smaller and larger than hemisphere.
In particular, a meniscus smaller than hemisphere is always stable,
however a meniscus larger than hemisphere can become unstable
depending on certain critical conditions [11,15]. As well the shape of
the amplitude- and phase shift-frequency characteristics becomes
qualitatively different for the menisci smaller and larger than hemisphere [11]. Thus, the optimal equilibrium meniscus size is an

Fig. 5. P(v) and () acquired during oscillating bubble experiment in conguration 2

for C12E6 (3.5 5 M) (a), and the corresponding ER() and EI() (b). The theoretical
curves in a are calculated using E() obtained according to a mixed kinetic model [57].
Experimental data of Ref. [64].

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

approximation of the ow inside the capillary which is instead quite

important stating, as a matter of fact, an upper limit for the work
frequency, that is v b / (a2), where a is the capillary radius and and
are the viscosity and density of the uid inside the capillary,
respectively. As an example, with a capillary radius of 0.02 cm, one
obtains typically limit frequencies around 20 Hz and 100 Hz for drops
and bubbles respectively.
Limitations for the geometry of the capillary arise also from
another condition which concerns the compressibility of the closed
cell. In fact, for small capillary and nite compressibility the system
becomes unstable when the drop curvature approaches its maximum
value (hemispherical drop/bubble). This instability manifests as an
explosive growing of the drop when it is subjected to a continuous
incrementing of its volume. This phenomenon and the conditions for
the occurring of this explosive drop growing are well known for many
years [73,74] and are analyzed in detail in a recent work on CPT [64].
The onset of this instability is independent of the frequency, but it can
be very important even at very slow oscillations when small drops
and small capillary radius are used.
Other important studies on the applicability of the oscillating
bubble method in CPT are reported in Refs. [67,75],where the conditions for the deformation of the bubble shape when the oscillation
frequency increases are analyzed.
The assumption for the dynamic bubble shape to be governed by
the static YoungLaplace equation alone is one essential assumption
for dilational rheology measurements in CPT and, in fact, in most
experimental studies the bubble is considered to remain nearly
spherical during oscillations. In Ref. [67], these assumptions are
critically analyzed by solving the NavierStokes and continuity
equations governing the ow of a liquid surrounding an oscillating
bubble using a rigorous nite element method and by the comparison
with experimentally obtained data. Conditions for nearly spherical
oscillating bubbles are found out depending on the geometry of the
experimental cell and on the uid properties like viscosity and surface
tension. For example, it is found that for a bubble oscillating in a
standard CPT chamber with moderate volume amplitudes and not too
low surface tension, the forcing frequency must be smaller than
100 Hz, for viscosity of the surrounding liquid not higher than 0.1 Pa s.
In ref. [75] extensions of this study are presented including the
effect of strong convection and of the liquid/air surface properties on
the onset of prole distortion at increasing frequency.
4.6. Drop image acquisition at high frequency
Typical digital CCD-cameras, as well as special traditional analogic
CCD-cameras, offer the feature of acquiring image sequences with
selectable values of exposure time and of frame rate. When a CCDcamera with such image-acquisition characteristics is adopted in CPT
instrumentation, the technique of the spectrum translation/compression (SCT) [76] can be optionally implemented during high frequency drop oscillations.
The adoption of this technique allows the characteristics of a real
high frequency oscillations, i.e. amplitude and shape, to be well reconstructed in a frequency-compressed spectrum, where each
component is translated towards lower frequencies.
Essentially the SCT measurement technique is based on subsampling the acquired images, at a properly adjusted rate, lower than
that required for representing the cycle characteristics.
In mathematical terms, the sampling operation is expressed by the
sifting property of a nite series of equally spaced Dirac delta
functions.

+ n=Q

tnts It dt = Ints ;

n = 0

n = 1; 2; ; i; Q

23

225

where I(t) = I0sin(2t) and ts is the sampling acquisition period. In

order to optimise the effectiveness of this technique for the reconstruction of the periodic real signal, it is important to assume a
suitable relationship between ts and the frequency of the real signal.
For the general case of a multi-harmonic periodic signal, constituted by a fundamental frequency 0 and N harmonics, we have:
It =

n = N

an exp 2in0 t

24

The mathematical operator of Eq. (23) transforms each of the n

components of the periodic oscillation at frequency = n0 into a
component of the new spectrum at frequency,
t;n =

K+ n

25

where is a fraction of the period of the fundamental component, i.e.

0 b b 1/N, and K is an integer relating the acquisition rate s to 0 such
as s = 0 / (K + ).
As better explained in Ref. [76], the requirement for an
appropriate sub-sampling of the experimental signal states that, for
each value of n, an integer Zn must exist such that the following
condition is satised,
0bn0 Zn s

s
2

26

The observation of the actual properties and behaviour of highfrequency oscillations provided by the DSC can have an important role
in data analysis and interpretation of typical high frequency
oscillating drop/bubble experiments. In particular this technique is
effective to check the onset of critical hydrodynamic effects and
allows the intrinsic elasticity of the liquid/cell system as a function of
frequency to be evaluated by comparison of the liquid volume, as
displaced by a piezo-actuator, and the actually-observed drop
volume-amplitude oscillation. Hence the SCT may result an advantageous procedure for the determination of reliable values of interfacial
dilational visco-elasticity in high-frequency ranges.
5. Review of experimental results
There are several experimental studies in literature concerning the
dilational rheology of surfactant adsorption layers and most of them
are based on experimental techniques exploiting oscillating drops/
bubbles for measuring the dilational viscoelasticity versus frequency.
In many experimental studies the frequency dependence of the
dilational viscoelasticity is used to access dynamic adsorption mechanisms, such as diffusion, molecular re-orientation, surface aggregation, which in turn depend on molecular characteristics of the
surfactant molecules. As mentioned above, such surface processes
can be accessed provided that their characteristic frequencies are
within the experimentally available frequency range and appropriate
theoretical models are utilised for interpreting the experimental data.
To this aim, in most experimental studies, the dilational viscoelasticity
is measured by coupling the drop/bubble prole technique with the
capillary pressure techniques. In this way a frequency range from 0.01
to 100 Hz is commonly obtained for water/air interfaces allowing for
the detection of kinetics processes with characteristic time of the
order of 10 2 s and higher.
Examples of these studies are in Ref. [54] concerning polyoxyethylene glycol ethers (CiEj) investigated at water/air and water/
hexane interfaces and on other kind of non-ionic surfactants and
surfactant mixture [77]. These studies proved that the dilational
rheology can be considered an effective tool for accessing the kinetics
of a surface process, even if for more deepen understanding it is

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F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

necessary a contemporaneous investigation of equilibrium properties,

adsorption kinetics and surface rheology.
This experimental approach, that is measuring E() in order to
address the dynamics of the surface processes, is applied also to more
complex systems, like proteins, mixture of surfactants and protein or
polymers with amphiphilic character.
The principal characteristics of these systems concern the
conformational changes or phase transitions occurring at the air/solution interface during the adsorption kinetics which can be effectively
investigated by dilational rheology. Like for common surfactants the
dilational viscoelasticity versus frequency, adopting suitable theoretical models, can be related to the microscopic state of the monolayer
(molecular conformations etc.) and to the characteristic time of their
evolution. In Refs. [41,55,56,7880] the oscillating drops and bubbles methods are utilized to investigate the viscoelastic behavior of
adsorbed and spread polymer lms in association with other
surfactants at the airsolution interface. In some of these studies the
drop/bubble techniques are combined with other methods to enlarge
the frequency range, such as electrocapillary waves which work
between 100 Hz and 400 Hz [55,78].
Oscillating drop experiments utilising drop shape tensiometers are
also used to investigate the evolution of the viscoelasticity during the
equilibration of the adsorbed layer at xed frequency of the area
perturbation. This kind of studies have been utilised especially to
investigate polyelectrolyte/surfactant mixed interfacial layers and
aggregation processes at the water/air interfaces [56,79].
For protein and proteinsurfactant systems several studies are
available in recent literature where oscillating drop/bubbles are
utilized to investigate the time evolution of the adsorbed layers, the
protein unfolding and the rearrangement within the interfacial layer
[81]. Among them, several investigations concern proteins important
for food science and technology, both for liquidair and liquidliquid
interfaces [52,82,83], where the viscoelasticity change is acquired
during the adsorption by an oscillating drop technique. In other
studies [84,85] proteinsurfactant mixtures have been investigated,
allowing for a better comprehension of the phenomenon of the
competitive adsorption with ionic and non-ionic surfactants and for
the development of theoretical models suitable for this kind of
systems. Other similar experimental works are applied in the eld of
biological processes like, for example the rheological study on phospholipids at water/air interfaces in association with natural pulmonary surfactant [86].
Nanoparticles associated to ionic surfactants are other interest
systems which are increasingly investigated from the dilational rheology point of view using oscillating bubble/drop techniques. Examples of these experimental studies are reported in Refs. [58,87,88]
where mixed silica nanoparticlecationic surfactant layers have been
investigated at the dispersion/air and dispersion/oil interfaces
measuring the dilational viscoelasticity versus frequency under
different degree of hydrophobicity obtained varying the surfactant
concentrations.
In particular in Ref. [58] interpreting the measured E() data with
an appropriate mixed kinetics theoretical model, further information
on the transport processes and on the dynamics of the interfacial layer
were obtained, that is the onset of a reorganisation process of the
interfacial composite layer increasing the surfactant concentration.
Moreover a shift from diffusion-controlled to kinetic-controlled regime during the ageing of the layer calls for an irreversible aspect of
the nanoparticle transfer into the uid interface, appearing above a
certain degree of hydrophobicity.
Another important aspect which is the subject of many recent
works concerns the relationship between dilational rheology and the
properties of liquid lms and disperse systems like foams and
emulsions. The response of the interfacial layer to dilational stresses
expresses the capability of an adsorbed layer of damping the external
area disturbances. For this reason the E() feature can be relevant for

the stability conditions of liquid lms subjected to dynamic

perturbations and consequently for the drop or bubble coalescence
[8992] in emulsions and foams.
As an example in Ref. [93], the dilational viscoelasticity for nonionic surfactants was measured by oscillating bubble techniques from
0.005 to 100 Hz, to interpret the observed stability properties of the
corresponding liquid lms whose the behaviour was not completely
explicable in terms of surface forces. A correlation was evidenced
between the stability of these lms and the elasticity of the single
interface at high frequency.
Correlations between emulsion stability and dilational rheology of
the single liquidliquid interfaces are discussed on the bases of
viscoelasticity data, again obtained by oscillating drop measurements,
concerning water in oil and oil in water emulsions stabilized by an oil
soluble surfactant [94] and a non-ionic water soluble surfactant [95],
respectively. One of the conclusions drawn from all these studies is
that higher values of high frequency limit of the elasticity of the
water/oil interface corresponds to more stable emulsions.
Moreover also the dilational properties of particle laden interfacial
layers were put in relationship with the stability of particle stabilized
emulsion. In fact, solid nanoparticles, often in association with
surfactants, are increasingly employed to control the drop/bubble
coalescence in emulsion technology. Examples of these studies are
found in the above cited refs. [58,88].
6. Conclusions
Dilational rheology represents a powerful tool to investigate
equilibrium and dynamic properties of simple and more complex
interfacial layers containing surfactants, proteins, polymers or micronano sized particles.
The development of oscillating bubble and drop techniques during
the last years responded to the need of obtaining increasingly
accurate measurements of the parameters charactering dilational
rheology.
The oscillating drop/bubble methods provide today the possibility
to obtain accurate data of dilational viscoelasticity as a function of the
frequency in a quite broad frequency range. This is especially true
when the two kinds of tensiometers available, DPT and CPT, are
coupled to investigate the same system.
Many improvements of the efciency of these techniques have
been obtained during the last ten years due, from one side, to the
implementation of advanced instrumentations which make faster the
drop/bubble control and the data acquisition and, on the other side, to
the application of new theoretical approaches for data acquisition and
interpretation.
Further improvements of these techniques are however expected
especially concerning the enlargement of the frequency range and the
eld of applicability. In this way systematic and accurate rheological
investigations should be undertaken aimed at deepening the
understanding of the relationship expected between the interfacial
rheology and the stability conditions and the behaviour of liquid lms,
emulsions and foams.
Acknowledgements
The work was nancially supported by projects of the European
Space Agency (FASES, ESA AO-99-052) and the ESF-COST Actions P21
and D43.
References
[1] Kruglyakov PM, Exerowa DR. Foams and foam lms. In: Mbius D, Miller R, editors.
Studies of interface science, vol. 5. Amsterdam: Elsevier; 1997.
[2] Thin liquid lms: fundamentals and applications. In: Ivanov IB, editor. Surfactant
science series, vol. 29. New York: Marcel Dekker Inc; 1988.
[3] Sjoblom AJ, editor. Emulsion and emulsion stability, vol. 61. Marcel Dekker; 1996.

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228
[4] Ivanov IB, Kralchevsky PA. Stability of emulsions under equilibrium and dynamic
conditions. Colloids Surf A 1997;128:155.
[5] Edwards DA, Brenner H, Wasan DT. Interfacial transport process and rheology.
Boston: Butterworth-Heinemann; 1991.
[6] Ivanov IB, Danov KD, Ananthapadmanabhan KP, Lips A. Interfacial rheology of
adsorbed layers with surface reaction: on the origin of the dilatational surface
viscosity. Adv Colloid Interface Sci 2005;114:6192.
[7]
Miller R, Liggieri L, editors. Interfacial rheology. Prog Colloid Interface SciBrill

Academic Pub; 2009.Important book where all the modern aspects of dilational
and shear rheology are analyzed.
[8]
Hoorfar M, Neumann AW. Recent progress in Axisymmetric Drop Shape Analysis

(ADSA). Adv Colloid Interface Sci 2006;121:2549.Important contribution for the

improvement of the drop prole tensiometry especially for the application to
nearly spherical shape.
[9] Kotsmar C, Grigoriev DO, Makievski AV, Ferri J, Krgel J, Miller R, et al. Drop prole
analysis tensiometry with drop bulk exchange to study the sequential and
simultaneous adsorption of a mixed beta-casein/C12DMPO system. Colloid
Polymer Sci 2008;286:10717.
[10] Loglio G, Pandolni P, Makievski AV, Miller R. Calibration parameters of the
pendant drop tensiometer: assessment of accuracy. J Colloid Interface Sci
2003;265:1615.
[11] Kovalchuk VI, Krgel J, Makievski AV, Loglio G, Ravera F, Liggieri L, et al. Frequency
characteristics of amplitude and phase of oscillating bubble systems in a closed
measuring cell. J Colloid Interface Sci 2002;252:433.
[12] Liggieri L, Ferrari M, Mondelli D, Ravera F. Surface rheology as a tool for the
investigation of processes internal to surfactant adsorption layers. Faraday Discuss
2005;129:125.
[13]
Kovalchuk VI, Krgel J, Makievski AV, Ravera F, Liggieri L, Loglio G, et al.

Rheological surface properties of C12DMPO solution as obtained from amplitudeand phase-frequency characteristics of an oscillating bubble system. J Colloid
Interface Sci 2004;280:498.Example of experimental study on dilational rheology
using CPT where dilational viscoelastivity is calculated from the experimental
acquired data assuming a cell model taking into account viscous and inertial
contributions and compressibility of the system.
[14]
Loglio G, Pandolni P, Miller R, Makieski AV, Ravera F, Ferrari M, et al. In: Moebius

D, Miller R, editors. Novel methods to study interfacial layers. Studies in interface

science seriesElsevier-Amsterdam; 2001. p. 43983.
[15]
Kovalchuk VI, Krgel J, Aksenenko EV, Loglio G, Liggieri L. In: Mbius D, Miller R,

editors. Novel methods to study interfacial layers. Studies in interface science

seriesAmsterdam: Elsevier; 2001. p. 485516.
[16] Del Gaudio L, Pandolni P, Ravera F, Krgel J, Santini E, Makievski AV, et al.
Dynamic interfacial properties of drops relevant to W/O-emulsion-forming
systems: a rened measurement apparatus. Colloids Surf A 2008;323:38.
[17] Javadi A, Bastani D, Krgel J, Miller R. Interfacial instability of growing drop:
experimental study and conceptual analysis. Colloids Surf A 2009;347:16774.
[18] Liggieri L, Ravera F. In: Mbius D, Miller R, editors. Drops and bubbles in interfacial
research, Vol. 6. Amsterdam: Elsevier; 1998. p. 23978.
[19] F. Monroy, F. Ortega, R.G. Rubio, M.G. Velarde, Surface rheology, equilibrium and
dynamic features at interfaces, with emphasis on efcient tools for probing
polymer dynamics at interfaces, Advances in Colloid and Interface Sci., 134135
(2007), 175189
[20] Rusanov AI, Prokhorov VA. Interfacial tensiometry. In: Moebius D, Miller R, editors.
Studies in interface science series, vol. 3. Amsterdam: Elsevier; 1996.
[21] Bashforth F, Adams C. An attempt to test the theories of capillary action.
Cambridge Univ. Press; 1883.
[22] Lahooti S, Del Rio OI, Neumann AW, Cheng P. Axisymmetric Drop Shape Analysis
(ADSA). In: Neumann AW, Spelt JK, editors. Applied surface thermodynamics.
Surfactant science seriesNew York: Marcel Dekker Inc; 1996. p. 4867.
[23] Maze C, Burnet G. A non-linear regression method for calculating surface tension
and contact angle from the shape of a sessile drop. Surf Sci 1969;13:45170.
[24]
Rotenberg Y, Boruvka L, Neumann AW. Determination of surface tension and

contact angle from the shapes of axisymmetric uid interfaces. J Colloid Interface
Sci 1983;93:16973.
[25] Ricci E, Giuranno D, Grosso I, Lanata T, Amore S, Novakovic R, et al. Surface tension
of molten CuSn alloys under different oxygen containing atmospheres. J Chem
Eng Data 2009;54(6):16605.
[26] Pallas NR, Harrison Y. An automated drop shape apparatus and the surface tension
of pure water. Colloids Surf 1990;43:16994.
[27] Liggieri L, Passerone A. An automatic technique for measuring the surface tension
of liquid metals. High Temp Tech 1989;7:826.
[28] Zhou YZ, Gaydos J. Criteria for evaluating the accuracy of surface tension values
from digital vision systems. J Adhes 2004;80:101753.
[29] Hernndez-Baltazar E, Gracia-Fadrique J. Elliptic solution to the YoungLaplace
differential equation. J Colloid Interface Sci 2005;287:2136.
[30] Dingle NM, Tjiptowidjojo K, Basaran OA, Harris MT. A nite element based
algorithm for determining interfacial tension () from pendant drop proles. J
Colloid Interface Sci 2005;286:64760.
[31]
Zholob SA, Makievski AV, Miller R, Fainerman VB. Optimisation of calculation

methods for determination of surface tensions by drop prole analysis

tensiometry. Adv Colloid Interface Sci 2007;134(135):3229.Important contribution for the improvement of the accuracy of both numerical solution and edge
detection.
[32] Zuo YY, Ding M, Bateni A, Hoorfar M, Neumann AW. Improvement of interfacial
tension measurement using a captive bubble in conjunction with axisymmetric
drop shape analysis (ADSA). Colloid Surf A 2004;250:23346.

227

[33]
Cabezas MG, Bateni A, Montanero JM, Neumann AW. A new method of image

processing in the analysis of axisymmetric drop shapes. Colloid Surf A 2005;255:

193200.
[34] Liggieri L, Attolini V, Ferrari M, Ravera F. Measurement of the surface dilational
viscoelasticity of adsorbed layers with a capillary pressure tensiometer. J Colloid
Interface Sci 2002;252:22535.
[35] Ferrari M, Liggieri L, Ravera F. Adsorption properties of C10E8 at the waterhexane
interface. J Phys Chem B 1998;102:105217.
[36] Krgel J, Kovalchuk VI, Makievski AV, Simoncini M, Ravera F, Liggieri L, et al.
Analysis of amplitude- and phase-frequency characteristics of oscillating bubble
system with closed measuring cell. Microgravity Sci Tech J 2005;16:18690.
[37] Liggieri L, Ravera F, Ferrari M, Passerone A. Adsorption properties of C10E8 at
waterhexane interface investigated onboard STS-107 by the FAST facility.
Microgravity Sci Tech 2005;16:2014.
[38] Passerone A, Liggieri L, Rando N, Ravera F, Ricci E. A new experimental method for
the measurement of the interfacial tension between immiscible uids at zero
bond number. J Colloid Interface Sci 1991;146:15262.
[39] MacLeod CA, Radke CJ. A growing drop technique for measuring dynamic
interfacial tension. Colloid Interface Sci 1993;160:43548.
[40] Loglio G, Miller R, Stortini A, Tesei U, Degli Innocenti N, Cini R. Non-equilibrium
properties of uid interfaces aperiodic diffusion controlled regime. 1 theory.
Colloid Surf A 1994;90:2519.
[41]
Hansen FK. Surface dilatational elasticity of poly(oxy ethylene)-based surfactants

by oscillation and relaxation measurements of sessile bubbles. Langmuir 2008;24:

18997.Example of experimental dilational rheology study where low frequency
measurements are performed by DPT coupling oscillating bubble and transient
experiments.
[42] Loglio G, Tesei U, Cini R. Spectral data of surface viscoelastic modulus acquired via
digital Fourier transformation. J Colloid Interface Sci 1979;71:31620.
[43] Marze S. Relaxation processes of PGPR at the water/oil interface inferred by
oscillatory or transient viscoelasticity measurements. Langmuir 2009;25:
1206672.
[44] Lucassen J, van den Tempel M. Dynamic measurements of dilational properties of
a liquid interface. Chem Eng Sci 1972;27:128391.
[45] Fainerman VB, Miller R, Kovalchuk VI. Inuence of the compressibility of adsorbed
layers on the surface dilational elasticity. Langmuir 2002;18:774852.
[46] Fainerman VB, Kovalchuk VI, Aksenenko EV, Michel M, Leser E, Miller R. Models of
two-dimensional solution assuming the internal compressibility of adsorbed
molecules: a comparative analysis. J Phys Chem B 2004;108:13700.
[47] V.I. Kovalchuk, R. Miller, V.B. Fainerman, G. Loglio, Dilational rheology of adsorbed
surfactant layers role of the intrinsic two-dimensional compressibility,
Advances in Colloid and Interface Science 114115 (2005) 303 312.
[48] Kovalchuk VI, Loglio G, Fainerman VB, Miller R. Interpretation of surface dilational
elasticity data based on an intrinsic two-dimensional interfacial compressibility
model. J Colloid Interface Sci 2004;270:47582.
[49] Wantke KD, Fruhner H, Fang J, Lunkenheimer K. Measurements of the surface
elasticity in medium frequency range using the oscillating bubble method. J
Colloid Interface Sci 1998;208:3448.
[50] Wantke KD, Fruhner H. Determination of surface dilational viscosity using the
oscillating bubble method. J Colloid Interface Sci 2001;237:18599.
[51] Aksenenko EV, Kovalchuk VI, Fainerman VB, Miller R. Surface dilational rheology
of mixed adsorption layers at liquid interfaces. Adv Colloid Interface Sci 2006;122:
5766.
[52] Lucassen-Reynders EH, Fainerman VB, Miller R. Surface dilational modulus or
Gibbs' elasticity of protein adsorption layers. J Phys Chem B 2004;108:91736.
[53] Palazzolo R, Ravera F, Ferrari M, Liggieri L. Dynamic surface elasticity of adsorption
layers in the presence of a surface phase transition from monomers to large
aggregates. Langmuir 2002;18:35929.
[54] Ravera F, Ferrari M, Santini E, Liggieri L. Inuence of surface processes on the
dilational visco-elasticity of surfactant solutions. Adv Colloid Interface Sci
2005;117:75.
[55]
Dez-Pascual AM, Monroy F, Ortega F, Rubio RG, Miller R, Noskov BA. Adsorption of

water-soluble polymers with surfactant character. Dilational viscoelasticity.

Langmuir 2007;23:38028.This contribution is important because proves the
efciency of the combination of several techniques, oscillating drops, barrier
experiments and electrocapillary wave, to investigate the dynamics of an
interfacial layer in a broad frequency range.
[56] Noskov BA, Bilibin AY, Lezov AV, Loglio G, Filippov SK, Zorin IM, et al. Dynamic
surface elasticity of polyelectrolyte solutions. Colloids Surf A 2007;298:11522.
[57] F. Ravera, M. Ferrari, L. Liggieri, Modelling of dilational visco-elasticity of adsorbed layers
with multiple kinetic processes, Colloids and Surfaces A, 282283 (2006) 210 216.
[58]
Ravera F, Ferrari M, Liggieri L, Loglio G, Santini E, Zanobini A. Liquidliquid

interfacial properties of mixed nanoparticlesurfactant systems. Colloids Surf A

2008;323:99108.The dilational rheological data obtained by using DPT and CPT
and the application of mixed kinetic rheological model allows, in this work, the
dynamic characteristics of a composite layers to be investigated.
[59] Fruhner H, Wantke KD. A new oscillating bubble technique for measuring surface
dilational properties. Colloids Surf A 1996;114:539.
[60] Kim YH, Koczo K, Wasan DT. Dynamic lm and interfacial tensions in emulsion
and foam systems. J Colloid Interface Sci 1997;187:29.
[61] Chang CH, Coltharp KA, Park SY, Franses EI. Surface tension measurements with
the pulsating bubble method. Colloids Surf A 1996;114:18597.
[62] Ravera F, Liggieri L, Loglio G. Interfacial rheology. In: Miller R, Liggieri L,
editors. Progress in colloid and interface science, vol. 1. Leiden: Brill Publ;
2009. p. 137.

228

F. Ravera et al. / Current Opinion in Colloid & Interface Science 15 (2010) 217228

[63] Russev SC, Alexandrov N, Marinova KG, Danov KD, Denkov ND, Lyutov L, et al.
Instrument and methods for surface dilatational rheology measurements. Rev Sci
Instrum 2008;79:104102.
[64]
F. Ravera G. Loglio, P. Pandolni, E. Santini, L. Liggieri, Determination of the

dilational viscoelasticity by the oscillating drop/bubble method in a capillary

pressure tensiometer, Colloids and Surfaces A, in press, DOI: 10.1016/j.
colsurfa.2010.01.040.This work presents a systematic analysis of the effects of
experimental parameters on the accuracy of the CPT measurements and provides a
simplied and effective method to obtain the dilational viscoelasticity by the
acquired data.
[65] Loglio G, Pandolni P, Miller R, Makievski AV, Krgel J, Ravera F, et al.
Perturbationresponse relationship in liquid interfacial systems: non-linearity
assessment by frequency-domain analysis. Colloids Surf A 2005;261:5763.
[66] Loglio G, Pandolni P, Miller R, Makievski AV, Kragel J, Ravera F. Oscillation of
interfacial properties in liquid systems: assessment of harmonic distortion. Phys
Chem Chem Phys 2004;6:13759.
[67]
Liao YC, Basaran OA, Franses EI. Hydrodynamic effects on the oscillations of sup
ported bubbles: implications for accurate measurements of surface properties.
Colloids Surf A 2004;250:36784.Theoretical analysis of a CPT experimental
system under dynamic conditions. Important contribution for understanding the
frequency limits of CPT measurements.
[68]
Freer EM, Wong H, Radke CJ. Oscillating drop/bubble tensiometry: effect of viscous

forces on the measurement of interfacial tension. J Colloid Interface Sci 2005;282:

12832.Study on the possible effects of viscous forces on the accuracy of the
interfacial tension and dilational response measurement. Important contribution
for both DPT and CPT.
[69]
Leser ME, Acquistapace S, Cagna A, Makievski AV, Miller R. Limits of oscillation

frequencies in drop and bubble shape tensiometry. Colloids Surf A 2005;261:258.

Important contribution for the evaluation of the limits of the allowed frequency
range for DPT.
[70] Kovalchuk VI, Ravera F, Liggieri L, Loglio G, Pandolni P, Makievski AV, VincentBonnieu S, Krgel J, Javadi J, Miller R. Capillary pressure studies under low gravity
conditions. Adv Colloid Interface Sci 2010. [Electronic publication ahead of print]
[71]
Alexandrov N, Marinova KG, Danov KD, Ivanov IB. Surface dilatational rheology

measurements for oil/water systems with viscous oils. J Colloid Interface Sci
2009;339:54550.Theoretical analysis of a CPT system. It is important because
provides also a method to obtain the dilational viscoelasticity from the
experimental acquired pressure data.
[72] Kovalchuk VI, Krgel J, Miller R, Fainerman VB, Kovalchuk NM, Zholkovskij EK,
et al. Effect of the nonstationary viscous ow in the capillary on oscillating bubble
and oscillating drop measurements. J Colloid Interface Sci 2000;232:2532.
[73] Liggieri L, Ravera F, Passerone A. Drop formation instabilities induced by
entrapped gas bubbles. J Colloid Interface Sci 1990;140:43643.
[74] Kovalchuk VI, Zholkovskij EK, Krgel J, Miller R, Fainerman VB, Wstneck R, et al.
Bubble oscillations in a closed cell. J Colloid Interface Sci 2000;224:24554.
[75]
Y. C. Liao, O. A. Basaran, E. I. Franses, Effects of dynamic surface tension and uid

ow on the oscillations of a supported bubble Colloids and Surfaces A, 282283

(2006) 183202.
[76]
Loglio G, Pandolni P, Miller R, Ravera F. Optical observation of high-frequency

drop oscillations by a spectrum compression technique applied to the capillary

pressure tensiometry. Langmuir 2009;25:127806.A technique is here proposed
allowing for the determination of the drop/bubble geometrical characteristics at
high frequency. This is a very promising techniques especially for the high
frequency measurements in CPT.
[77] Fainerman VB, Aksenenko EV, Lylyk SV, Makievski AV, Ravera F, Petkov JT, et al.
Adsorption layer characteristics of Tritons surfactants 3. Dilational visco-elasticity.
Colloids Surf A: Physicochem Eng Aspects 2009;334:1621.

[78] Noskov BA, Loglio G, Miller R. Dilational viscoelasticity of polyelectolyte/surfactant

adsorption lms at the air/water interface: dodecyltrimethylammonium bromide
and sodium poly(styrenesulfonate). J Phys Chem B 2004;108:1861522.
[79] Noskov BA, Grigoriev DO, Lin S-Y, Loglio G, Miller R. Dynamic surface properties of
polyelectrolyte/surfactant adsorption lms at the air/water interface: poly
(dially1dimethylammonium chloride) and sodium dodecylsulfate. Langmuir
2007;23:964151.
[80] Babak VG, Desbrieres J, Tikhonov VE. Dynamic surface tension and dilational
viscoelasticity of adsorption layers of a hydrophobically modied chitosan.
Colloids Surf A 2005;255:11930.
[81] Freer EM, Sub Yim K, Fuller GG, Radke CJ. Shear and dilatational relaxation
mechanisms of globular and exible proteins at the hexadecane/water interface.
Langmuir 2004;20:1015967.
[82] Benjamins J, Lyklema J, Lucassen-Reynders EH. Compression/expansion rheology
of oil/water interfaces with adsorbed proteins. Comparison with the air/water
surface. Langmuir 2006;22:6181.
[83] Miller R, Leser ME, Michel M, Fainerman VB. Surface dilational rheology of mixed
beta-lactoglobulin/surfactant layers at the air/water interface. J Phys Chem B
2005;109:1332731.
[84] Miller R, Alahverdjievaa VS, Fainerman VB. Thermodynamics and rheology of
mixed protein-surfactant adsorption layers. Soft Matter 2008;4:11416.
[85] Alahverdjieva VS, Grigoriev DO, Fainerman VB, Aksenenko EV, Miller R, Molhwald
H. Competitive adsorption from mixed hen egg-white lysozyme/surfactant
solutions at the airwater interface studied by tensiometry, ellipsometry, and
surface dilational rheology. J Phys Chem B 2008;112:213643.
[86] Wustneck N, Wustneck R, Fainerman VB, Miller R, Pison U. Interfacial behaviour
and mechanical properties of spread lung surfactant protein/lipid layers. Colloids
Surf B 2001;21:191205.
[87] Ravera F, Santini E, Loglio G, Ferrari M, Liggieri L. Effect of nanoparticles on the
interfacial properties of liquid/liquid and liquid/air surface layers. J Phys Chem B
2006;110:19543.
[88]
Stocco A, Drenckhan W, Rio E, Langevin D, Binks BP. Particle-stabilised foams: an

interfacial study. Soft Matter 2009;5:221522.Interesting experimental study on a

composite interfacial layer providing results on the relationship between
dilational rheology and foam stability.
[89] Lucassen J. In: Lucassen-Reynders EH, editor. Anionic surfactants. Physical
chemistry of surfactant action. Surf. Sci. SeriesNY: Dekker; 1981. p. 21765.
[90] Georgieva D, Cagna A, Langevin D. Link between surface elasticity and foam
stability. Soft Matter 2009;5:206371.
[91] Valkovska DS, Danov KD, Ivanov IB. Stability of draining plane-parallel lms
containing surfactants. Adv Colloid Interface Sci 2002;96:101.
[92] Kovalchuk VI, Krgel J, Pandolni P, Loglio G, Liggieri L, Ravera F, et al. Dilatational
rheology of thin liquid lms. In: Miller R, Liggieri L, editors. Interfacial rheology,
progress in colloid and interface science, vol. 1. Leiden-Boston: Brill; 2009.
p. 476518.
[93] Santini E, Ravera F, Ferrari M, Stubenrauch C, Makievski A, Krgel J. A surface
rheological study of non-ionic surfactants at the waterair interface and the
stability of the corresponding thin foam lms. Colloids Surf A 2007;298:12.
[94] Santini E, Liggieri L, Sacca L, Clausse D, Ravera F. Interfacial rheology of Span 80
adsorbed layers at parafn oilwater interface and correlation with the
corresponding emulsion properties. Colloids Surf A 2007;309:270.
[95] Kalogianni EP, Varkaa EM, Karapantsios TD, Kostoglou M, Santini E, Liggieri L, et al.
A multi-probe non-intrusive electrical technique for monitoring emulsication of
hexane-in-water with the emulsier C10E5 soluble in both phases. Colloids Surf A
2010;354:35363.