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Current Opinion in Colloid & Interface Science 19 (2014) 514519

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Current Opinion in Colloid & Interface Science


journal homepage: www.elsevier.com/locate/cocis

Rheology of interfacial layers


M. Karbaschi a,, M. Lot a,b, J. Krgel a, A. Javadi a,c, D. Bastani b, R. Miller a
a
b
c

Max-Planck Institute of Colloids & Interfaces, Potsdam/Golm, Germany


Sharif University of Technology, Tehran, Iran
Chemical Engineering Department, University of Tehran, Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 3 June 2014
Accepted 25 August 2014
Available online 2 September 2014
Keywords:
Interfacial dilational rheology
Interfacial shear rheology
Dynamic interfacial properties
Bulk rheology of emulsion and foams

a b s t r a c t
Dilational and shear viscoelasticities are important properties of interfacial layers. These quantities are particularly relevant in all systems which contain a huge internal interfacial area such as foams and emulsions. Therefore,
also the 3D rheological behavior of foams or emulsions studied by respective methods is superimposed by the 2D
interfacial rheology.
We report on recent developments in dilational and shear rheology from an experimental point of view as well as
discuss the state of the art of the underlying theories. Examples of most relevant experiments are also presented
and discussed. Although not yet extensively investigated, the links between bulk rheology of foams and
emulsions and the rheology of the corresponding interfacial layers are discussed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Understanding the mechanism of surfactant adsorption at uid
interfaces is a main item in the knowledge of their functionality and applications. Nowadays, there are many fundamental and applied dynamic processes for which the characterization of adsorbed interfacial layers
of surfactant and polymer molecules is very essential. These include
foaming and emulsication widely used in production of cosmetics,
pharmaceuticals and food, mining, oil industry, etc. In addition to the
large interest on industrial applications, studying dynamics of interfacial
layers is still also very important from a fundamental point of view,
such as understanding the interaction between molecules, change of
molecular conformations or molecular aggregations.
In literature there are many publications on surfactant equilibrium
adsorption properties, i.e. adsorption isotherms [1]. However, for
many modern technologies studies of dynamic interfacial properties
are even more essential. These investigations are dedicated to the adsorption kinetics, the interfacial viscoelastic behavior, changes of the interfacial electric charge.
The easiest accessible dynamic quantity of a liquid surface or interface representing the dynamics of adsorption of surfactant or polymer
molecules at the interface is the interfacial tension. This methodology
is based on a quick formation of a fresh surface and subsequent measurement of the surface tension as a function of time. However, for a
comprehensive study of the dynamic interfacial behavior more efforts
are required, such as interfacial shear and dilational rheology, surface
potential, interfacial ellipsometry, non-linear optical methods, neutron
reectivity or small angle neutron scattering.
Corresponding author. Tel.: +49 331 567 9259; fax: +49 331 567 9202.
E-mail address: Mohsen.karbaschi@mpikg.mpg.de (M. Karbaschi).

http://dx.doi.org/10.1016/j.cocis.2014.08.003
1359-0294/ 2014 Elsevier Ltd. All rights reserved.

This paper starts with a brief overview of the most recent advances
in dynamic interfacial tensiometry. Then, the progress in interfacial
dilational and shear rheology is discussed. This includes rigorous
attempts to understand the rheological behavior of single and mixed interfacial layers. Furthermore, some rst ndings made on the description of emulsion and foam stability linked with interfacial rheological
properties of different systems are discussed.

2. Dynamic interfacial properties


The afnity of surface active molecules to be adsorbed at liquid interfaces is well known from their special amphiphilic structure. As a result
of this process, adsorbed layer is formed. These adsorbed layers, in the
equilibrium state, can be characterized by surface pressure isotherms.
The surface pressure corresponds to the change in surface free energy
per unit area. As mentioned above, adsorption is a dynamic process,
and the properties of the adsorbed layers are signicantly inuenced
by the adsorption mechanism. In addition, for many industrial processes
like emulsication and foaming, the interfaces are subject to different
types of external perturbations, like expansion and compression or
shear, caused by changes in size and shape of the interface. Therefore,
also knowledge on the relaxation behavior of adsorbed layer after
such external perturbations is very essential.
There are different experimental protocols applied to measure, for
example the dynamic interfacial tension or the dilational viscoelasticity
by using the optimum experimental tools [2,3]. There are quite a
number of publications where both aspects of liquid interfacial layers
have been considered and interfaces of different complexity investigated, in particular mixed polymer/surfactant solutions at various liquid/
uid interfaces [411]. Each dynamic process is characterized by a

M. Karbaschi et al. / Current Opinion in Colloid & Interface Science 19 (2014) 514519

characteristic time, and many or even all of them are required for the
understanding the complexity of such systems.

515

experimental techniques please refer to [13]. An extensive overview


on relaxation mechanisms in interfacial layers was recently published
in [14].

3. Rheology of interfacial layers


3.1. Dilational rheology properties
The analysis of surface coverage and rate of change of surface pressure as functions of time give access to information on the mechanism
involved. However, much more sensitive to changes in the adsorption
layer structures and compositions are the mechanical properties like
the viscoelasticity of the interfaces after dilation/compression or shear.
Dilational elasticity which describes the term of elastic energy stored
in interfacial layers mostly referred to as the variation of interfacial tension with the relative surface coverage due to a change in surface area,
ignoring any dissipation. The dissipative of the viscoelasticity, i.e.
dilational viscosity refers to the relaxation processes within interfacial
layer in their interactions with the adjacent bulk phase [12]. While the
interactions with the adjacent phase is mainly controlled by a diffusional
transport, the relaxation processes happening in the interface are molecular re-orientation, conformational changes and aggregation processes.
All these phenomena are inuencing the frequency dependence of the
dilational viscoelasticity.
The dilational interfacial rheology can be studied with different
types of deformations, such as transient or harmonic area changes.
The interfacial dilational viscoelasticity can be presented with complex
quantities

d
d
A
d ln A
dA

This complex modulus consists of a real part, a storage modulus or


elastic component d, and an imaginary part known as the loss modulus
or viscosity component ():
d id

A more detailed description of available theoretical formulations on


dilational rheology was summarized in a recent monograph [13]. Fig. 1
shows the typical frequency dependence of a viscoelastic lm [12]. For
a more detailed theoretical background and recently developed

Fig. 1. Typical frequency dependence of viscoelastic properties, according to [12].

There are various studies published in the literature on the dilational


viscoelastic properties of single and mixed surface active components.
Here, a short overview of some well-selected systems recently studied
for a better understanding about interfacial phenomena is given and
the main results are briey discussed.
In the literature there are several publications performed on the effect of surfactant molecular structure on the rheological properties of
corresponding adsorbed interfacial layers. For example, the effect of hydrophobic chains on the interfacial properties of a mixture of the cationic
polyelectrolyte polyallylamine hydrochloride and anionic homologues of
sodium alkyl sulfates was studied by Sharipova et al. [15]. A similar study
was published by Cao et al. [16] on imidazolium surfactants solutions at
the decane/water interface. The dilational rheology measurements
showed large elasticity values for longer hydrophobic chains at low surfactant concentrations as compared to those with shorter hydrophobic
chains. The opposite was observed for higher concentrations, when surfactants with longer hydrophobic chain could easier desorb from the
interface.
Ramrez et al. [17] worked on the effect of the hydrophilic group on
the rheological properties of polyoxyethylene surfactants. The results
showed that the adsorbed surfactant molecules underwent a reorientation with increasing bulk concentration and hence surface coverage. The
rheological properties of some block copolymers as biocompatible molecules were studied recently in [4].
These polymer systems are interesting due to their special use for
the design of stabilized nanoemulsions and in biomedicine for a better
understanding of their interactions with physiological media. An important overview on the dilational interfacial rheology of mixed polymer/
surfactant surface layers was presented by Noskov [18]. In particular
systems including polyelectrolytes were discussed, which alone did
not adsorb, but in combination with added countercharged surfactants
the formed complexes exhibited pronounced surface activity. In Fig. 2
the dependence of the dilational viscoelastic properties on SDS concentration and perturbation frequency for PAH/SDS mixtures are shown as
taken from [19]. The results show high dynamic surface elasticities for
the mixture at low surfactant concentrations which indicates complexes formed via electrostatic interaction between polyelectrolyte segments and the surfactant molecules. These interactions can lead to twodimensional heterogeneities in the adsorption layer. It is obvious that
the dilational viscosity of PAH/SDS mixtures at lower frequencies is
much higher than that at higher frequencies. With increasing SDS concentration the observed dilational viscosity of PAH/SDS mixture became
identical to that of pure SDS which indicates the depletion of PAH/SDS
complexes from the surface layer. This phenomena was dominated
then by single SDS molecules [19].
Several studies have also been dedicated to the rheological behavior
of monolayers formed by particles and their mixtures with surfactants
[20,21]. Mendoza et al. [12] reviewed the works on this topic recently.
Due to the growing importance quite a number of new investigations
were performed on the interfacial viscoelastic properties of so-called
green interfaces [22]. Studies were dedicated to systems containing
bio-surfactants [6,7], and protein solutions [23,24]. In contrast to classical surfactant molecules, proteins follow a kind of kinetically irreversible adsorption process. In his review Noskov summarized the most
popular interfacial experimental techniques and critically discussed
experimental results for various protein solution systems [25]. Also a
summary is given of the available theoretical models to be applied to
liquid protein adsorption layers.
The interaction of proteins and surfactants and the special effects on
the rheological properties of liquid interfaces is the subject of many

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M. Karbaschi et al. / Current Opinion in Colloid & Interface Science 19 (2014) 514519

Fig. 2. a) Dependence of the dilational elasticity of PAH/SDS complexes on SDS concentration at a xed PAH concentration of 102 M and different frequencies [Hz]: () 0.005; ( ) 0.01;
( ) 0.02; ( ) 0.04; ( ) 0.05; ( ) 0.1; b) dependence of dilational viscosity properties of SDS () and mixture PAH/SDS ( ) on frequency at the xed PAH concentration of 102 M and SDS
7 105 M; data taken from [19].

publications. For example in [26] various data on such systems were


reviewed. In this article also studies on the interfacial rheology of surfactantprotein mixtures were discussed. In another study Noskov et al.
[27] reported on the dynamic and dilational rheological properties of
mixed adsorption layers of -casein and surfactant as well as nonionic homopolymers, as measured by the oscillating ring method. The
dependencies of the dynamic surface elasticity modulus on surface
pressure (-casein mixed with PNIPAM, see Fig. 3) for different bulk
compositions show that the hydrophobic interaction between the polymer and protein molecules leads to different structures. With a transfer
to mica plates and investigation by scanning probe microscopy the
different structures were visualized.
Also the effect of denaturants on the surface structure of protein containing interfacial layers has recently been studied. The effect of urea, for
instance, on the dilational properties of BLG solutions was discussed in
[28] and it was shown that in the surface layer the protein molecules
unfold at lower urea concentrations than in the bulk solution. Moreover,
it was shown that guanidine hydrochloride as denaturant was about

one order of magnitude stronger than urea. This demonstrated the


high sensibility of the viscoelasticity to the conformation of protein
molecules.
The effect of the ionic strength, i.e. the concentration of added electrolyte, on the rheological properties of interfacial layers is subject of
several publications. Sharipova et al. showed that the interaction between polyelectrolytes and oppositely charged surfactant molecules is
a challenging topic in the eld of surface rheology [29]. She demonstrated in these papers that similar features were observed at different
water/alkane interfaces and at the water/air interface [30]; however,
particular effects of the hydrophobic phase on the adsorption layer formation kinetics have been observed. Also the formation of heterogeneities in protein adsorption layers and multilayer structures has been
detected via interfacial rheology studies. Experimental results and techniques for the detection of interfacial inhomogeneities were reviewed
[25,31].
For performing optimum measurements of the dilational interfacial
viscoelasticity, the frequency range available by the chosen instrument
should correspond to the characteristic frequency range of the dominating relaxation processes occurring at the interface. Although there are
various experimental techniques the most modern are based on forced
oscillations of drop and bubble surfaces. Besides the small amount of required sample solution also a quite broad frequency range for the experiments is available [32]. Nevertheless, due to gravity smallest deviations
from sphericity lead to unwanted overtones in oscillating drop/bubble
experiments setting limits for these methods. Further improvements
with respect to the limitation of the existing instruments for their applicability at higher dynamic surface deformation rates, without challenging the physical limits by using microgravity conditions, appear to be
possible by performing additional numerical simulations and taking
into account deviations from an ideal shape of drops. The attempt
made in [33,34] shows that for example the Laplace equation, originally
derived via an equilibrium balance of forces, can be modied such that it
applies also to menisci under the conditions of drop growth and oscillations. Also the solution of the Navier Stokes equations for free liquid
menisci under the conditions of growing drops leads to drop proles
valid for non-equilibrium conditions [33,34].
3.2. Shear rheological properties

Fig. 3. Dynamic surface elasticity modulus on surface pressure for -casein (0.004 mg/ml)/
PNIPAM solutions at the molar ratios (black squares), 50:1 (pink diamonds), 20:1 (bluegreen snowakes), 10:1 (orange diamonds), 5:1 (red circles), 2:1 (blue triangles down), 1:1
(green triangles up), and 1:5 (blue asterisks); data taken from [27].

In shear deformation experiments the area of an interfacial layer is


only changed in shape while its area size remains constant. Therefore,
the compressibility can be neglected and only the lateral forces are
probed. Interfacial shear rheology gives access to information about

M. Karbaschi et al. / Current Opinion in Colloid & Interface Science 19 (2014) 514519

network formation or interaction forces lateral to the interfacial layer.


Such layers can be formed by adsorption of soluble interfacial active
compounds (Gibbs layers) or by spreading insoluble substances
(Langmuir layers).
In the xy-plane an interfacial shear elasticity modulus Gi can be dened as the proportionality factor between the applied deformation
uxy and the shear stress txy. For a solid like interfacial layer an elastic
behavior (Hookian) is observed txy = Gi/uxy. In the opposite case pure
viscous behavior (Newtonian) is obtained for ideal liquid like layers
txy = iduxy/dt. Here the shear stress is proportional to the rate of
shear and the proportionality factor is the interfacial shear viscosity.
Due to attractive interactions between the adsorbed or spread molecules the interfacial shear moduli Gi and hi can increase. To overcome
the interaction forces energy must be applied so that the interfacial elements are able to ow. Due to the complexity of composition and interactions within the interfacial layer, most of them have viscous and
elastic properties. They behave viscoelastic and the complex interfacial
shear modulus Gi* consists of a real (storage) Gi and an imaginary
(loss) component Gi.
00

00

00

Gi Gi iGi Gi ii

where is the angular frequency. The dynamics of interfacial layers are


inuenced not only by the equilibrium interfacial properties, like interfacial tension but also by the rate of deformation. In any case the interfacial layer is connected with the bulk phase. For a linear relationship
between interfacial shear stress and strain under certain boundary conditions a ratio, the dimensionless Boussinesq number Bo, between the
interfacial (Xi) and subphase drag (Xv) can be dened.
Bo

Xi
lX v

where l is a characteristic length. In classical shear rheometers this


length is the contact line of the measuring body in the interface. High
values of Bo 1 indicate that the measured quantities are mainly
governed by the interfacial properties. The interfacial ow is almost
not coupled with the adjacent subphase ow, while for very small
Bo 1 the instrument is not suitable for interfacial studies. Hence, for
all applied measuring techniques a careful hydrodynamic analysis is
required to discriminate the interfacial contribution from the overall
measuring effect [35]. Typically, the producers of good commercial
instruments provide such necessary analysis.
The variety of existing measuring techniques can be classied into
indirect and direct methods. The indirect techniques measure the velocity proles using inert particles. An interesting option of this idea has
been used for the development of particle tracking techniques. At
present very large unexplained discrepancies still exist between the
measured quantities obtained with this method and other ones [36]. Direct measuring techniques determine the displacement or torque of a
measuring probe located within the interface. A variety of sophisticated
geometries have been proposed so far using different measuring bodies
or techniques to detect the resulting motion. For the design of such instruments it is important to provide an adequate sensitivity to detect
stresses in the interfacial layer in the presence of stresses in the adjacent
subphase. Many modern instruments use bicones or special shaped
rings which can be mounted on commercial rheometer allowing the determination of rheological properties in a large range of frequencies and
shear strains.
The shear rheological properties can be studied for a lot of interfacial
systems, containing for example surfactants, proteins, polymers, and
lipids. Such studies are often performed to relate the interfacial rheological quantities to the stability of foams and emulsions, for which especially the performance of foaming agents and emulsiers is of interest. Often
the stabilizers or destabilizers of foams and emulsions are complex mixtures. For soluble adsorption layers formed by low molecular weight

517

surfactants, the rheological properties are very low and difcult to measure. For example, the analysis of published data for sodium dodecyl sulfate (SDS) obtained with different measuring techniques shows that it
spans over two orders of magnitude and it seems to be impossible to
identify the source for such a large scattering [37]. The rheological properties of insoluble monolayers at interfaces like lipids or polymers show
a much more complex behavior. Monolayers can exist in a variety of different phases which depend on the lateral pressure in the interface. In
general the measured moduli increase with increasing lateral pressure
starting from a gas-analogue state over liquid expanded, liquid condensed up to a solid-like state. Due to the presence of coexisting phases
the number of different phases can be much larger. In denser states nonlinear effects are frequently observed.
The structure formation at the interface of polymers depends on
their polarity. Polymers with polar groups are assembled in an extended
conformation which corresponds to good solvent conditions. In case the
polymer chains come in contact, they can interpenetrate and form gellike networks. More hydrophobic polymers adopt in a more condensed
conformation which correspond to poor solvent conditions. The
polymer chains cannot interpenetrate and behave like individual particles. Above a certain surface concentration such monolayers are in a
glassy state. Systematic investigations with polymethylmethacrylate
(PMMA) which correspond to poor solvent conditions have been performed by Maestro et al. [3840]. Hermans and Vermant [41] described
a systematic study of phospholipid dipalmitoyl phosphatidyl choline
(DPPC) under physiologically relevant conditions.
There are several shear rheological investigations of nanoparticle
monolayers on liquid supports [12]. Vandebril et al. [42] studied hematite nanoparticles at the interface between two immiscible polymer
blends. The hematite nanoparticles formed a strong gel-like layer at
the polymer/polymer interface and stabilized the two liquid phases
against coalescence.
The majority of published studies have been performed with pure
proteins or mixtures with surfactants or other proteins, as these systems
are often used as stabilizers in food foams or emulsions. The shear rheological properties of interfacial layers are an important contribution for
the long term stability of these liquid disperse systems [43].
In recent years various publications reported on the very promising
properties of hydrophobins as stabilizers for foams and emulsions.
Hydrophobins are small proteins in which several disulde bridges
stabilize their structure. This compact structure does not even change
after adsorption at interfaces. Hydrophobin adsorption layers exhibit
very high shear elasticities. To modify the stabilizing effect for different
applications the hydrophobin can be used in mixtures with surfactants
or with other proteins. To compare and quantify such mixtures
different shear rheological investigations have been published in
literature [11,44,45].
The pH dependence of adsorption of -lactoglobulin brils at the
water/oil interface was investigated by Rhs et al. [46]. For this study a
shear rheometer with a bicone geometry measuring body has been modied for the exchange of subphase in the measuring cell. Such a setup enables experiments of the interfacial rheology with in situ changes of pH,
ionic strength, or composition of subphase. The -lactoglobulin brils
adsorbed rst at a pH of 2 at the water/oil interface. During the increase
of pH up to 6 the interfacial storage and loss moduli increased. The
maximum of both moduli has been observed at the isoelectric point.
Yang et al. [8] studied the adsorption behavior of silk broin at the
water/air interface. Gel-like structures were formed in the interfacial
layer which showed a non-monotonic concentration dependence
which passed through a maximum. It has been observed that the
changes in viscoelastic behavior corresponded to three states of a soft
glassy system which were related to different protein conformations
in the adsorption layer. Wang et al. [47] studied the interfacial viscoelastic properties of silk broin at the air/water and water/oil interfaces
with different oil polarity. The aqueous protein solutions have been
spread on a phosphate buffered saline subphase. The silk broin

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M. Karbaschi et al. / Current Opinion in Colloid & Interface Science 19 (2014) 514519

molecules formed stable viscoelastic layers at both interfaces. It was assumed that the gel-like layer was formed by ordered -sheet structures.
A similar behavior was reported by Nisal et al. [48] for regenerated silk
broin solutions.

4. Emulsion/foam stability characterization via interfacial


rheological studies
One of the main objects in the study of dynamic interfacial properties
is to understand basic principles of foaming and emulsication due to
their wide applications. For many studies dedicated to rheological properties of interfacial layers, there are attempts to correlate stability issues of
foams and emulsions with measured rheological quantities. We shall
present here a short summary of most recent studies conducted on this
topic.
Wang et al. studied the process of breakage of dispersed droplets
[49]. In another study presented by Rosenfeld and Fuller [50], consequences of interfacial viscoelasticity on the stability of thin liquid lms
were discussed. Additional work was dedicated to correlations between
adsorption layers and liquid lm properties, however, without a clear
link to foam/emulsion rheology and stability [5156]. In conclusion,
there is still no direct approach for a link between parameters on a molecular scale and those on a macro scale of lms and foams/emulsions.
Only a rst relationship between the surface dilational visco-elasticity
and the bulk viscoelasticity of a corresponding foam was presented
and discussed [57] a rst relationship between the surface dilational viscoelasticity and the bulk viscoelasticity of the corresponding foam was
presented and discussed. This seems to be a promising direction in
which general correlations between surface layers, liquid lms and
foam/emulsion properties can be expected.

5. Conclusions and outlook


Presently we can summarize that the viscoelasticity for shear and
dilational perturbations of liquid interfacial layers is quite well understood. Theoretical models and experimental tools do exist and allow
for most systems to nd quantitative explanations for the rheological
behavior for adsorption layers at liquid interfaces. This is denitely
true for water/air interfaces modied by surfactants. For layers formed
by polymers (proteins) and mixed adsorption layers, there are still
open questions and not all peculiarities can be explained in a quantitative way yet. For the interfaces between water and a second immiscible
liquid the situation is less clear; however, all observed phenomena are
essentially clear from a qualitative point of view.
In respect to rheological properties of free liquid foams and emulsion
lms (building blocks of foams and emulsions) much less is done so far,
and even reliable experimental methods do not exist for routine investigations. In contrast, the viscoelasticity of real foams and emulsions can
be studied with techniques available since a long time. Supposed the
foam/emulsion under study is stable enough, its viscoelastic behavior
can easily be studied by classical bulk rheology and discussed in terms
of classical rheological models. However, as these materials are composites, a clear physical explanation cannot always be given as the contributions coming from the interfaces are difcult to be separated from those
belonging to the bulk phases. Here, only rst attempts let us hope for a
more general understanding rather than operate with the so far existing
empirical knowledge.

Acknowledgments
The work was supported by projects of the EU (project CoWet), the
DFG (Mi418/18-2), the DLR (50WM1129), and the COST actions
CM1101 and MP1106.

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