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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.
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.
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d ln A
dA
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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].
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].
M. Karbaschi et al. / Current Opinion in Colloid & Interface Science 19 (2014) 514519
00
00
Gi Gi iGi Gi ii
Xi
lX v
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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.
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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