578

Surface rheology of adsorbed surfactants and proteins

Reinhard Miller", Valentin B Fainermant, Jurqen Kraqel" and Guiseppe
Loglio+
Interfacial rheological methods have been developed to a
level which allow the quantification of the shear and dilational
behaviour of mixed protein/surfactants systems. First attempts
are published to provide an insight into the complex interfacial
layer properties. The type of interaction between the
components controls the changes in rheological parameters
as compared to the pure protein. The understanding of the
rheological behaviour, in particular the compressibility, of lung
surfactant monolayers as one of the highly practical, relevant
systems is in the focus of interest.

Addresses
'Max Planck Institute of Colloids and Interfaces, BerlinAdlershof,
0,12489, Germany
tlnstitute of Technical Ecology, 25 Bulv. Shevchenko, Oonetsk,
340017, Ukraine
University of Florence, Institute of Organic Chemistry, Via G.
Capponi 9, Florence, Italy
Correspondance: Reinhard Miller

Current Opinion in Colloid & Interface Science 1997,2:578-583

Electronic identifier: 1359-0294'002-00578

processes, there are not many studies of such properties.

The reason is that there are different surface rheological
parameters which reflect the different aspects of a complex
behaviour. It is not trivial to predict which of the
parameters provide an understanding and control of a
technological problem. In two recent reviews, various
classic and newly developed techniques of interfacial
shear and dilarional studies have been compared and
some selected experimental examples given [3,12]. In this
review, emphasis is made on the latest developments in
interfacial rheology and new progress in the understanding
of protein/surfactant adsorption layers.

Interfacial shear rheology

Interfacial shear rheological studies of adsorbed layers,
along with other interfacial investigations, are useful for
the discussion of the layer structure at liquid interfaces.
Numerous experimental techniques have been employed
for the measurement of interfacial shear viscosity all
of which have to avoid the creation of surface tension
gradients.

Current Chemistry Ltd ISSN 1359-0294

Progress in methodology

Abbreviations
CTAB
cetyl trimethyl ammoniom bromide
SOS
sodium dodecyl sulphate

The effect of adsorbed layers on the formation and stabilisation of liquid dispersions, like foams and emulsions, can
be understood on the basis of elementary processes, such
as stability of thin liquid films, coalescence of two drops or
bubbles, break-up process of drops in flow fields, motion of
bubbles and drops in solutions, and so on. The relevance
of dilational properties, exchange of matter mechanisms as
well as shear rheological parameters to phenomena such as
foaming and emulsification has already been emphasised,
and is explained by the rapid expansion of surfaces during
the generation of foams or emulsions [9-11].

An oscillating disk rheometer for measurements at low

frequencies (0.4 mHz-l Hz) has been reported by Muller
et 0/. [13]. The shear torque is applied by forcing a small
circular disk placed on the liquid surface to oscillate.
The oscillation is caused by a magnetic system, which
allows the application of very low forces. A newly designed
canal surface viscometer, which measures the steady shear
viscosity of monolayers at the air/water interface, has
been described by Sacchetti et 0/. [14]. The viscometer
is based on a constant surface pressure gradient along
the canal and measures the monolayer flow rate. An
interfacial rheometer, for measuring the dynamic response
of a liquid/liquid interface subjected to a small amplitude
oscillatory shear stress, was proposed by Nagarajan and
\Vasan [15]. The experiments were conducted in a
deep channel rheometer fitted with an oscillatory floor.
The middle liquid/liquid interface and upper gas/liquid
interface are both plane horizontal layers sandwiched
between the adjacent bulk phases. The walls are stationary
whereas the base moves. The rheological parameters were
calculated from a hydrodynamic analysis incorporating
interfacial rheological models. Ghaskadvi et al. [16] built an
apparatus to study the viscoelastic response of Langmuir
monolayers as a function of the frequency and amplitude
of the applied sinusoidal shear strain. A low-frequency
external magnetic field is used to drive the rotor into
forced oscillations at the desired frequency (1 mHz-l Hz).

Although it is usually accepted that knowledge of surface

rheology is essential for the tailoring of many technological

Another newly designed instrument, based on a ring

with a sharp edge hanging at a torsion wire, allows

Introduction
The dilational and shear mechanical behaviour of adsorbed
layers of surfactants and polymers and their mixtures
is of fundamental importance to many technologies
and natural phenomena, for example, coating processes
of photographic emulsions containing gelatine and surfactants [1,2], the process of enhanced oil recovery,
food industry technology [3-5], flotation processes [6],
pharmaceutical industry [7], or processes occurring at the
atmosphere/ocean interface [8].

Surface rheology of adsorbed surfactants and proteins Miller et el;

experiments with very small mechanical deformations

of the adsorbed layer. When applying an impulsive
torque by an instantaneous movement of the torsion
head, the performance of the pendulum is damped. This
kind of experiment provides simultaneous information
of the surface shear viscosity and elasticity from one
single experiment. The computer-driven rheometer (commercially available as ISR1 from Gamma-Lab, Berlin,
Germany) has the disadvantage that the frequency range
is rather narrow [17]. The measuring principle, however,
is suitable for investigations at liquid/liquid interfaces
[18,19]. Another commercial apparatus, built by Carnrel
Ltd (Royston, UK) is based on forced oscillations and
allows measurements to be taken in a broad frequency
interval [20]. So far, there are no data available which
would allow a direct comparison with other instruments.

579

Figure 1
350
300
250

]'
til

200

Z
2: 150

r:

100
50
0
0

100

50
t

150

[min]

Surface shear experiments

Proteins, the most frequently studied polymers at liquid

interfaces, have been more and more quantitatively characterised by all available techniques. The adsorption kinetics
have been determined from dynamic surface tensions
and ellipsometry, and correlated to mechanical properties
such as shear and dilational elasticity and viscosity. For
example, Dickinson et 0/. [18,19] studied extensively the
shear rheological behaviour of protein adsorption layers of
gelatine, ~-casein, x-casein, a-lactalbumin, ~.Iactoglobu
lin, and lysozyme at water/oil interfaces. The surface shear
viscosity of the protein layers and their mixtures depends
strongly upon the age and the protein .composition.
Displacement of one protein by another, for example,
a-lactalbumin by ~.casein is indicated by a sudden drop in
surface viscosity immediately after addition of the second
protein.
The effect of different samples has been discussed by
Clark et 0/. [21] using shear rheology and surface tension
measurements. Different Lot numbers and differences
in the preparation of the samples solutions result in
tremendous changes in the surface properties. As an
example, the surface shear viscosity of four ~-Iactoglobulin
samples is shown in Figure 1. It turns Out that the
purification procedure has a significant influence on the
structure of the protein in the solution bulk. Surface
rheological measurements seem to be suitable for the
detection of contaminating surface active substances.
Mixed protein/surfactant adsorption layers

As a general picture for globular proteins, the surface shear

viscosity increases with adsorption time and then levels
off at sufficiently low bulk concentration. At higher concentrations, it runs through a maximum. This maximum
appears earlier and becomes lower with increasing protein
bulk concentration. The explanation given by Fainerman
et 0/. [22] and Wtlstneck el 0/. [23] is that at small protein
concentrations, the area per molecule is large when the
adsorption process starts. This area decreases due to the
increasing surface pressure. At high protein concentration,

Surface shear viscosity as a function of time for different

~-Iactoglobulin samples, Sigma Lot 51 H7210 (<), Sigma Lot
91 H7005 (Ia), charcoal-treated Sigma Lot 91 H7005 and used as
solution (*) and charcoal-treated Sigma Lot 91 H7005 following
freeze drying and resolubilisation (e), according to Clark et a/. [211

unfolding and rearrangement processes are hindered by

further adsorbing protein molecules.
The same systems have been further investigated by
comparing the adsorption kinetics with shear rheology
as a function of time and bulk concentration [24,25].
Although mixtures with nonionics adsorb essentially in
the framework of a competitive adsorption, the interaction
of ionics with the protein molecules yields to the
formation of complexes which may have completely
different properties at the interface than the original
proteins. Possibly, these interactions can lead to a partial
protein denaturation and hence to strong changes in the
shear rheology. At higher concentrations of ionics, the
competitive effects again become dominant. The surface
tension and shear viscosity as a function of surfactant
concentration are shown in Figure 2.
As an example of practical relevance, the results for natural
mixed systems, fulvic acids extracted from seawater
sampled in Leghorn, Italy (Tyrrhenian Sea) during a
period from May to July after the spring algae bloom,
were studied recently [18] as shown in Figure 3. The
adsorption kinetics and shear rheological behaviour could
be correlated to the differences in origin of the fulvic acids
samples.

Interfacial dilation rheology

The dilational rheology is based on area changes and
stress relaxation experiments. The exchange of matter
functions are generally applicable to both harmonic and
transient types of relaxations as pointed out by Loglio et
0/. [26], whereas stress relaxation experiments may yield
results deviating from the small disturbance measurements

580

Food colloids, emulsions, gels and foams

due to harmonic disturbances is the oscillating bubble

method. The technique involves the generation of radial
oscillations of a gas. The theory of pulsating bubbles in
surfactant solutions has been further developed [31-33].
According to the most recent results, the determination
of the frequency-dependence of the phase lag between
oscillation generation and pressure response allows the
differentiation between the exchange of surfactant as
one contribution to the dilational viscosity and additional
surface relaxation processes being part of the dilational
viscosity.

Figure 2

120
100

E
z'"

80

2:- 60

r:

40
20

25

50

75
t [min]

100

125

150

Adsorption time-dependence of the surface shear viscosity of

10-7 mol/l ~Iacloglobulin (u), CTAB/~-Iactog'obulinmixtures with
10-7 mol/l CTAB (11), 10-5 molll CTAB (~or lO-3 mol/l CTAB (0),
and SOS/~-lacloglobulin mixtures with 10-5 mol/l SOS 0, lO-4 mol/l
SOS (tJ or 10-3 molll SOS (e) according to Wilstneck et at. [25]

The drop shape oscillation technique, as developed by

Apfel and co-workers [37,38], is suitable to close the gap
in the experimental techniques for liquid/liquid interfaces.
This method is based on the analysis of drop shape
oscillation modes and yields again the matter exchange
mechanism and the dilational interfacial elasticity.

Figure 3

500
400

--Z'" 300
~

r:

Another group of measurements suitable for studying the

dilational rheology of interfacial layers are stress relaxation
experiments performed by 100s and co-workers [34-36].
Special experiments based on a linear area expansion
of the interface were called 'peak tensiometry', as the
experimental result is a dynamic surface tension running
through a maximum [35]. The localisation and height
of this peak is characteristic to the matter exchange
mechanism and yields the dilational elasticity.

200
100
0

100

10
t

1000

[min]

Another group of measurements is the transient relaxation

study based on different instruments which allow for
a small short-time disturbance of the interfacial layer
[39-41]. The elastic ring is one of these methods which
can also be used for harmonic, sinusoidal area changes. For
a surfactant model system, it has been demonstrated that
one and the same exchange of matter theory can be used
to describe both transient and harmonic relaxations with
the same system parameters [41].
Progress in the understanding of mixed protein/surfactant
layers

Interfacial relaxation experiments and theories

The dynamics of mixtures of surfactants with proteins is

of great importance for the coating process of photographic
films, where mixtures of gelatine with surfactants and
surface active dyes adsorb at the interface simultaneously.
Adsorbed gelatine alone does not show a measurable
frequency-dependence of surface elasticity. The presence
of a surfactant changes the elastic and relaxation behaviours dramatically, as shown in Figure 4 for gelatine
mixed with a perfluorinated surfactant [33].

The damping of capillary waves at interfaces is the

classic version of all relaxation methods at interfaces.
The response of the system is measured in terms of a
relative damping of the propagated wave. Recent work
has been focused on theoretical modifications for this
technique as well as on experimental improvements
[28-30]. One of the more recently developed methods
used to investigate surface relaxations of adsorption layers

The surface tension amplitudes obtained for the mixture

are caused by surface concentration changes and by an
additional part which is proportional to the deformation
rate. This linear increase in !!.y is not in line with a
diffusional exchange of matter mechanism, but rather
characterises another relaxation mechanism possibly the
exchange of surfactant bound to the protein.

Time-dependence of surface shear viscosity of different fulvic acid

samples FA4CA (u), FA5AC (0), FA5CA (~, FA3CA (e) according
to Kragel et at. [17].

as discussed by Lucassen-Reynders and Lucassen [27].

A discussion of experimental and theoretical aspects of
dilational rheology has been also given by Dukhin et 01. [6].

Surface rheology of adsorbed surfactants and proteins Miller et el.

581

and Tween 20 as a model system [46]. The addition of

the trivalent cations resulted in a noticable improvement
in the foamability and foam stability. The appearance of
aggregates in the foam films, nonuniformity of the films,
and an increase in the dilational viscosity/elasticity of
the surface, associated with the addition of aluminium
cations, have contributed to the development of a
phenomenological model which explains the observed
increase in foam stability.

Figure 4

2,5
2

~
... 1,5
~
0,5

Conclusions and future perspectives

f[Hz]
Dynamic surface tension amplitudes 6.yas a function of frequency
f at a relative area change of 10.2%; (el 0.7 wt% gelatine, ..,
8.10-7 mol/em sodium dioctyl sulfosuccinate, (l.) mixture of 0.7 wt%
gelatine and 8'10-7 mol/cm sodium dioctyl sulfosuccinate; according
to Fruhner and Wantke [331.

Recently, a number of experimental studies have been

published on lung surfactanrs or model systems simulating
them. These biological systems consist of lipids and
proteins in a definite composition. Part of the proteins
are water-soluble, whereas other parts are water-insoluble
[42,43]. Interfacial layers formed in different ways show
extremely high compressibility. Different mechanisms
have been discussed, but the very complex systems and
the role of the various components are far from being
understood.

Correlation between interfacial rheology and

parameters relevant for application
Progress has been made in finding a direct correlation
between interfacial rheology and parameters relevant,
for instance, in the stabilisation or destabilisation of
disperse systems such as foams and emulsions [44-48].
Another area of research where the properties of mixed
protein/surfactant layers are of significant importance is
the support of medical diagnosis. Here, blood and urine
are used as indicators [49]. Correlation has been found
between selected dynamic adsorption layer properties and
the diagnosis of some diseases, such as cancer or kidney
diseases.
There are examples in the literature which suggest a
better understanding of the overall behaviour of foams
or emulsions. The influence of interfacial rheology on
the macroscopic foam visco-elasticity has been discussed
in [45]. The dilational viscosity is not linear with the
macroscopic foam elasticity modulus, whereas the interfacial shear viscosity is linear. The potential for cations to
crosslink protein molecules through electrostatic interaction, and thereby enhancing foaming properties has been
investigated using aluminium chloride, beta-lactoglobulin

Interfacial shear experiments are useful to learn about

interactions of molecules in adsorption layers or rnonolayers. In particular, in mixed layers the various interactions
change drastically with the composition. For example,
mixed polymer/polymer or polymer/surfactant systems
form adsorption layers with complex natures, and the
time-dependence of the interfacial rheology can give
access to an understanding of structure formation and
molecular exchange processes.
Although new developments have been made, such as
oscillating bubbles and drops, there is a lack of sufficient
systematic experimental studies on protein/surfactant
mixed adsorption layers. So far, however, there is a
deficiency in respect to relaxation theories for polymers
and mixed polymer/surfactant systems. The first ideas
about dilational properties of composite adsorption layers
were published by Lucassen [50] and Fainerman et 0/.
[22]. These ideas will help to understand the rheological
behaviour of layers formed by mixtures of surfactants and
proteins, for example, lung surfactant layers and their
extreme compressibility, or the nontypical high frequency
relaxation behaviour of some mixed gelatine/surfactant
layers.

Acknowledgements
The work was financially supported by projects of the European Community
(lNTAS 93-2-163-ext and INCa ERB-ICI5-CT96-0809) and the DFG (Mi
418/5-1, Mi 41817-1).This review is dedicated to the 70th birthdav of Gunter

Krctzcharnar,

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