Current Opinion in Colloid & Interface Science 12 (2007) 196 – 205

www.elsevier.com/locate/cocis

Emulsion drops in external flow fields — The role of liquid interfaces

Peter Fischer a,⁎, Philipp Erni b
a
Institute of Food Science & Nutrition and Materials Research Center, ETH Zurich, 8092 Zurich, Switzerland
b
Hatsopoulos Microfluids Laboratory, Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA

Received 15 July 2007; received in revised form 30 July 2007; accepted 31 July 2007
Available online 10 August 2007

Abstract

We review the flow of emulsion drops, focusing on recent work involving complex interfaces, which may include the presence of surfactants,
particles, surface-active polymers, or solid-like membrane layers. En route, important phenomena in multiphase flow associated with emulsion
rheology are considered, including drop coalescence and breakup, surfactant transport, or the mechanics of composite interfaces.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Interfacial tension; Interfacial rheology; Dilatational rheology; Marangoni stresses; Microfluidics; Emulsifiers; Colloidosomes; Soft glasses; Globular
proteins; Boundary Integral Method; Volume of Fluid Method; Finite Element Method

1. The role of single drop dynamics en route to emulsion
rheology
An emulsion is a dispersion of drops of one liquid in another
one with which it is incompletely miscible [1]. This same
definition applies for polymeric blends of two immiscible
polymer solutions or melts [2] and for mixtures of two
thermodynamically segregated biopolymers [3]. The physico-
chemical properties and, in particular, the rheological responses
of emulsions may vary from Newtonian behavior of a dilute
suspension undeformed, surfactant-free drops, described well
by Taylor's classical extension [4] of Einstein's theory on
suspension viscosity, to the case of highly concentrated
multidrop systems, where the drops are only separated by thin
liquid films and yield a solid-like rheological response [5,6].
Macroscopically measurable properties such as the interfacial
tension and the fluid stresses are commonly used to characterize
single and multidrop systems. However, a variety of additional
material and flow properties, including viscoelasticity of the
fluids [7–9] or the complex mechanical properties of an
interfacial adsorption layer (for example, formed by adsorbed
proteins [10–12]) are still a subject of active research.
⁎ Corresponding author.
E-mail address: peter.fischer@ilw.agrl.ethz.ch (P. Fischer).
1359-0294/$ - see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2007.07.014
In this review, we focus on fluid mechanical aspects and
interfacial rheology for the case of isolated emulsion drops and
dilute emulsions, as these continue to play an important role for
fundamental on interfacial properties, investigations on the
process of emulsification, and the flow and stability of
concentrated emulsions. For a comprehensive discussion of
rheology and stability of emulsion in particular in the broad
context of pasty and soft glassy materials, colloidal interactions
(depletion interaction, Ostwald ripening, aggregation and floccu-
lation), miscibility, and engineering aspect such as emulsification,
must be considered, all of which are discussed in a number of
excellent monographs and overview articles [13–28].
2. Single drop rheology
The study of single emulsion drops, bubbles, or capsules in
simple flow fields is an important element to understand
multiphase flow phenomena. In contrast to suspensions of solid
particles, emulsions leave us with the additional feature that the
dispersed drops have mobile surfaces and their ability to
deform. The small deformation behavior provides information
about the interplay between interfacial stresses and hydrody-
namic stresses, whereas the critical breakup behavior [29] is
relevant for the analysis of emulsification and foaming
processes, which are often still designed by trial and error.
Recent advances in the controlled generation of emulsions using
 P. Fischer, P. Erni / Current Opinion in Colloid & Interface Science 12 (2007) 196–205
microfluidic methods [30,31–33] further underscore the need
for a detailed description of the physics governing the formation
of drops from liquid jets [34,35] or the dripping from a capillary
[36–38].
We will group the research on single drop dynamics in
simple homogeneous flow fields, both experimental and
theoretical, into three classes: (i) Studies of surfactant-free
drops, starting with Taylor's pioneering work [39] which
includes both theoretical analysis and experimental observa-
tions and focuses on the deformation of single drops suspended
in a second liquid on which either a simple shear or a
elongational flow is applied. (ii) Studies on compatibilized or
surfactant-covered drops; due to the manifold possibilities of
surfactant physical chemistry, this area is very diverse. As we
will discuss in more detail below, the case of interfacially active
proteins or polypeptides is of particular interest due to their
adsorption behavior, which is effectively irreversible on
practical laboratory time scales: once adsorbed, many surface-
active proteins are therefore reminiscent of insoluble surfactant
layers. These quasi-insoluble characteristics make protein layers
an attractive choice for comparisons with numerical studies on
deformation and breakup of surfactant-covered drops, which
often rely on the assumption of an insoluble layer. However, this
comes at the expense of a much more complex interfacial
equation of state σ(Γ) (relating the interfacial tension σ to the
interfacial concentration Γ), which in the case of proteins and
other polyampholytes is itself is a field of active research [40].
Additionally, protein layers not only influence the interfacial
tension and charge, but may also constitute a complex, solid-
like membrane to stabilizing the drops, which leaves us with the
third case: (iii) Investigations on liquid capsules surrounded by
a viscous, elastic or viscoelastic membrane with predominantly
solid mechanical properties. This field has been strongly
influenced and motivated by the biomedical sciences where
the deformation behavior of erythrocytes (red blood cells) is of
interest. Motivated by recent observations of the effect of a
globular protein layer on the deformation response of emulsion
drops [10] we will include a brief discussion of the subject of
liquid capsules in external flow fields in this review.
3. Clean drops
3.1. Classical drop deformation theories
Taylor [39] was among the first to analyze the problem of a
neutrally buoyant drop deforming in simple base flows,
providing solutions for the internal and external velocity fields
at low capillary numbers and infinite viscosity ratios, and giving
first order expressions for the drop deformation and orientation
angle. When a drop is subjected to a local straining rate, the
steady state deformation is the result of an equilibrium between
viscous forces, which tend to deform the drop and even break it,
and interfacial forces, which attempt to recover the initial state.
This relationship is expressed by the Capillary number Ca =
τmR / σ, where τm is the shear stress in the matrix phase, R the
drop radius in the absence of flow, σ the interfacial tension,
and λ =ηd /ηm is the ratio of the drop and matrix phase viscosities.
197
Assuming a spheroid drop morphology, the shape is characterized
by a deformation parameter D = (a − b) / (a + b), involving
the lengths of the major and minor axes a and b of an ellipsoid
projected into the velocity-shear rate plane, and the orientation
angle α between the major drop axis and the perpendicular to the
flow direction. Boundary conditions for Taylor's creeping flow
analysis are (i) steady flow, (ii) incompressible Newtonian liquids,
(iii) negligible inertia and buoyancy, (iv) the velocity and
tangential stresses are continuous at the interface, (v) the
interfacial stress boundary condition is comprised only of the
interfacial tension balancing the normal stresses. Taylor's famous
limiting case results in shear flow for Ca → 0 (flow dominated by
interfacial tension) are D = Ca(19λ + 16) / (16λ + 16) and α = π / 4.
For λ → ∞ (flow dominated by viscous stresses), the Taylor
theory predicts D = 5 / (4λ) and α = π / 2, i.e. the major axis of the
spheroid is oriented in the flow direction.
Extensions of Taylor's small deformation theory cover wider
ranges of capillary numbers, deformations, and viscosity ratios
[41,42], refined description of the drop shape [43], transient
behavior [41,44–46], critical conditions for drop breakup
[29,47–49], and include a series of constitutive models [50–
52]. For highly extended drops, Taylor proposed a slender body
theory [53], which has subsequently been taken up by a number
of authors [42,54–58].
On the experimental side, drop deformation experiments are
performed in optical flow cells, such as: (a) the four roll mill that
creates all flow fields from pure elongational to pure shear flow
[45,59–62], (b) the parallel band shear cell for simple shear
flow [10,39,63], (c) Couette geometries consisting of concen-
trically rotating or counterrotating transparent cylinders
[47,64,65], (d) rotating parallel disks [66], cone/plate [67,68]
and sliding glass plate devices in combination with a movable
microscope [69], and more recently (e) miniaturized and
microfluidic flow cells [30,32,70], and micropipettes [71].
In order to describe the detailed transient drop deformation
behavior arising from a given external flow field, more recently
numerical approaches such as Volume of Fluid (VoF) method
[72–74] or the Boundary Integral Method (BIM) [48,75–79])
have been used. Both methods have been applied successfully
for the simulation of concentrated emulsion flows [80], for the
coarsening from a single drop to concentrated emulsions [81],
and their consistency has been demonstrated by comparison of
numerical and experimental results [48,49].
3.2. Drop breakup
Drop breakup occurs if Ca exceeds a so-called critical
Capillary number Cacrit, i.e. a drop no longer reaches a steady
shape, but continues to deform until it eventually breaks up.
Values for Cacrit as a function of the viscosity ratio λ = ηd / ηm in
both shear and extensional flow fields have been collected for
various flow types and materials [48,58,60] leading to the
famous representation by Grace [29]. Critical capillary numbers
in shear flows consistently exceed those in elongational flows,
e.g. at λ = 1 breakup occurs around Ca = 0.43 in simple shear
flow and around Ca = 0.12 in elongation. In shear flow, the
critical capillary number also becomes infinite as the viscosity
198 P. Fischer, P. Erni / Current Opinion in Colloid & Interface Science 12 (2007) 196–205
ratio becomes small or exceeds a value of three, which makes
elongational contributions, where breakup occurs at lower
Capillary numbers and only weakly depends on the viscosity
ratio, an important element of dispersing flows.
4. Drops with complex interfaces
4.1. Surfactant-covered drops
Surface-active species such as surfactants (emulsifiers),
compatibilizers, and proteins influence the drop dynamics by
reducing the interfacial tension upon adsorption and in many
cases by forming an adsorption layer exhibiting distinct local
fluid mechanical and rheological properties. The interfacial
stress boundary condition necessary to describe the drop is now
no longer governed by the static interfacial tension alone, as for
clean drops, but depends on a variety of additional stresses that
can be both ‘intrinsic’ surface properties (such as shear and
dilatation interface stresses, i.e. the scalar interfacial tension is
upgraded with deformation-dependent, tensorial components),
or induced by the flow field (e.g. the local distribution of
surfactant on the interface, which produces coupled temporal
and spatial gradients in interfacial tension). Surface active
components may diffuse, adsorb, and desorb from the bulk
liquids to the interface and vice versa, which leaves us with a
local net change of the surfactant concentration when drops are
deformed and fragmented. It is no surprise that the description
of such free-surface problems with generalized interfacial stress
boundary conditions quickly becomes a formidable task.
To facilitate fluid mechanical analyses, many studies in a
first approximation only consider insoluble surfactants, i.e.
constant total surfactant coverage and no net adsorption and
desorption processes. Under flow then two competing process-
es, surfactant dilution and surfactant convection within the
interface, are considered for drop deformation. Dilution is due
to the increase of interfacial area as the drop deforms, which
tends to decrease surfactant concentration and results in
increased interfacial tension and hence smaller drop deforma-
tion. Surfactant convection along the interface will increase
surfactant concentration at the tips of the drop, which decreases
interfacial tension there and results in increased drop deforma-
tion. Dilution and convection effects depend on several factors,
such as the magnitude of Marangoni stresses (i. e., stresses due
to local gradients in surface tension), curvature effects, the
initial interfacial tension and coverage, the ratio of the fluid
viscosities, and the capillary number (e.g., [79,82–84]). It is
also important to note the assumption of an insoluble surfactant
layer introduces some complications that would be less critical
in the case of a soluble surfactant. For example, simulated
fragmentation of a drop with an uneven distribution of
surfactant at the time of breakup leads to daughter drops with
individually varying interfacial tensions and surface coverages
that are different from those of the mother drop [84]. This will
ultimately be reflected in increased polydispersity in the
resulting emulsion.
If interfacial rheological properties, such as the interfacial
shear and dilatational moduli and viscosities [85–87], are
ignored, Marangoni stresses may be sufficient to describe the
surface tension driven redistribution towards a homogeneous
surfactant distribution on the deforming drop interface. In this
case, such additional stresses enter into the tangential
component of the interfacial stress balance, meaning that the
pressure jump across the liquid interface is no longer balanced
by the static interfacial tension alone. Note that even if
interfacial rheology is not considered, the Marangoni stresses
may be included in an effective dilatational/compressional
interfacial viscosity [59,85]. While using such a combined
parameter may seem inappropriate at first because it blurs the
border between two distinct effects (dilatational viscosity and
surface tension gradients), it also has the advantage that an
effective dilatational viscosity is an experimentally measurable
parameter that can be used to directly compare experimental
data with analytical or simulated results [85,88].
Besides a number of analytical approaches [58,82] which are
usually only applicable to minor deviations from the spherical
drop shape at rest, numerical methods are vital to describe the
motion of drops in the presence of surfactants. Drop
morphologies and, in some cases, breakup criteria of surfac-
tant-covered drops can be obtained using the Boundary Integral
(BIM) [83,89–94], the Volume of Fluid (VOF) [74,95], or
Finite Element (FEM) [84] methods, always in combination
with a suitable interface description containing an interfacial
equation of state and, in the case of soluble surfactants, an
adsorption isotherm. Feiglet al. [79] studied the effects of
surfactants on the drop deformation at different viscosity ratios
and discussed them in the context of previous findings
[90,96,97]. Calculations differ with regard to the interfacial
equation of state used, ranging from linear relationships
between the interfacial tension σ and the interfacial surfactant
concentration Γ, to the Frumkin equation of state [89].
Furthermore, the results strongly depend on how fast or slow
the surfactant transport processes are with regard to the flow
timescale, expressed in the Péclet number [82,83,90,96,98],
with the extreme cases being those of insoluble surfactants
[84,99] and of fully soluble, small molecular weight surfactants
where diffusion-controlled transport dominates [96,99]. Com-
plex interfacial properties, which might include non-Newtonian
constitutive laws for the interface in shear and dilatation have
received comparatively less attention and will be discussed in
the following.
4.2. Drops with interfacial viscosities
Flumerfelt [59] extended Cox' earlier small-deformation
theory, formulated for clean drops, to a more general expression
for the interfacial stress boundary condition, accounting for
dynamic interfacial effects by replacing the thermodynamic
interfacial tension by the Boussinesq–Scriven interfacial stress
law [100], including both shear and dilatational stresses at the
interface. In his model, spacial variations in concentrations are
assumed to be small, therefore gradients in interfacial tension
(Marangoni stresses) are accounted for as an apparent
dilatational interfacial viscosity. The interfacial viscosities in
the Flumerfelt model lead to additional interfacial viscosity
 P. Fischer, P. Erni / Current Opinion in Colloid & Interface Science 12 (2007) 196–205
ratios, and the expression for the drop deformation is then given
by D = f(Ca,λ,λη,λκ), where the additional ratios λη, and λκ are
dimensionless groups relating the interfacial shear viscosity and
the effective dilatational viscosity (which is a combined
quantity, containing both the actual dilatational viscosity as
well as the Marangoni stresses due to surface concentration
gradients) to the viscosity of the matrix liquid. An experimental
study of the model for various soluble surfactants was
performed by Phillips et al. [88]. Their results show that
interfacial shear viscosity and apparent dilatational viscosity
can be obtained from drop deformation experiments, and that
these quantities play a significant role in the behavior of drops
in shear fields. The authors claim that only for very highly
viscous systems the theories of Cox and Taylor are applicable to
their experiments, whereas in all other cases the interfacial
stress boundary condition contains interfacial rheological
stresses to some extent. Consequently, just as the thermody-
namic interfacial tension can be obtained for surfactant-free
systems from Taylor's theory, the Flumerfelt theory can be used
to calculate interfacial shear viscosity and apparent dilatational
viscosity from drop deformation data if one of the properties is
independently measured. In a later publication, Pozrikidis [75]
showed how those effects can be obtained using the numerical
Boundary Integral Method (BIM).
4.3. Deformation and breakup of protein-covered drops
Proteins adsorbed at liquid interfaces are important for a number
of phenomena in colloidal systems, such as the stability and flow
behavior of food foams and emulsions [101,102,40]. Unlike usual
surfactants, proteins do not only decrease the interfacial tension
upon adsorption, but they strongly modify the rheological
properties of the interface, both under shear and dilatational/
compressional interface deformations [85,103,101,104]. Fur-
thermore, adsorption of surface-active proteins is effectively
irreversible, as was recently shown in subphase exchange exper-
iments [105,103]: only minor desorption and negligible changes in
interfacial tension are observed after a protein solution is replaced
with protein-free buffer surrounding a protein-covered pendant
drop. These effects have been described for a number of surface-
active proteins of both biological and technical relevance, such as
β-casein [106–108], β-lactoglobulin [101,104,107,109,110],
bovine serum albumin [111,112], or lysozyme [103,111].
Several authors have studied protein-covered drops in
external flow fields [10,11,64,97,113,114]. Williams [11]
studied the effect of two structurally diverse protein emulsifiers,
β-lactoglobulin and β-casein on the breakup behavior of a
single drops in shear flow. They found that β-casein and low
concentrations of β-lactoglobulin increase the stability of drops
and attributed this effect to interfacial elasticity; they discussed
a concept of an ‘effective interfacial tension’ which contains
interfacial rheological effects and is higher than the static
interfacial tension. On the other hand, in the case of high
concentrations of β-lactoglobulin the found the drops to be less
stable than expected, and discussed the role of interfacial
rigidity, which makes the drop more susceptible to tangential
stresses, as a possible reason. This latter case with a rigid protein
199
layer results in Ca and the entire breakup behavior being
practically independent of the viscosity ratio, with the layer
properties completely dominating the behavior. In a similar
study, [12] confirmed these findings with emulsions drops
produced in a Couette flow cell, and suggested that the
deformation response of protein-covered drops might be similar
to capsules surrounded by a stress-transmitting network.
4.4. Liquid capsules, composite membranes and particle-
stabilized interfaces
Deformable capsules surrounded by a membrane have been
the subject of numerous fluid mechanical and rheological studies
[115–124], mostly motivated by the relevance of the mechanical
response in the flow behavior of cells [125,126], for example
erythrocytes [127] moving in blood capillaries. Related work has
been published about deformation of vesicles in flow fields
[65,128]. Effects such as tank-treading and swinging of capsules
in shear flows have been observed, and much progress has been
made in the theoretical description of various transient
phenomena [125,126]. A fundamental difference to drop
deformation theories is the absence of a static interfacial tension:
the membrane is seen as a thin layer of a (visco-)elastic solid,
expressed in terms of constitutive laws borrowed from solid
material mechanics. For example, [117] compared the influence
of various membrane constitutive laws (Hooke, Skalak, and
Moonry–Rivlin law) on the deformation behavior of capsules.
Literature is available on a number of experimental [122–124]
and theoretical [116,118–121] aspects of the field. Recently,
liquid interfaces covered with colloidal particles have received
renewed attention [129–131]. Solid-stabilized emulsions, often
called ‘Pickering’ emulsions [132], have been known since
thousand of years — mustard, milk-based emulsions or fluids
used in oil recovery are only a few examples. In the context of
interfacial rheology, Lucassen has first pointed out the
importance of non-homogeneous interfaces in a 1992 paper
about the dilatational modulus of ‘composite’ interfaces [133].
Recent developments include the development of microfluidic
methods for the generation of particle-stabilized drops and
bubbles [130,134] or the study of particle monolayers in defined
surface flows [135]. A possible analogy between layers of
globular proteins and those formed by colloidal particles has
been pointed out by Cicuta and coworkers [104]. It appears that
for the behavior of such ‘armored’ drops or bubbles the relevant
physicochemical parameters are far more diverse than the
‘simple’ static interfacial tension of a clean emulsion drop [131].
Whereas a first step towards a better description can be made by
using interfacial rheological quantities in both shear and
dilatational interface deformations [87], a full characterization
of composite interfaces will not only include the linear and non-
linear interfacial rheology, but also further quantities such as the
Young's modulus [117,136] and the bending stiffness [121].
5. From drops to dilute emulsions
Linear viscoelastic data of emulsions are often analyzed in
terms of the Palierne model [137,138] for the complex shear
200 P. Fischer, P. Erni / Current Opinion in Colloid & Interface Science 12 (2007) 196–205
modulus GE⁎(ω) of an emulsion, GE⁎ being a function of the
complex moduli of the matrix and drop phases, the interfacial
tension, and the drop size distribution. Modifications of the
Palierne model use average drop diameters rather than the entire
distribution [139] or the relaxation time spectrum of the emulsion
to obtain information about relaxation processes of the drops
[140]. The latter method is based on the Choi and Schowalter
theory [141], showed that the relaxation time spectrum of the
emulsion is a combination of the spectra of the individual phases,
and an additional peak in the spectrum (relaxation shoulder) can
then be attributed to the shape relaxation (due to the constant
interfacial tension) of the drops. Their expression for the emulsion
modulus contains a characteristic time scale, t0 = ηmR /σd f(γ)
1
where f ¼ 40 ð19k þ 16Þð2k þ 3Þ=ðk þ 1Þ which is adopted from Old-
royd's 1953 emulsion model [142] and often used in the analysis
of drop relaxation experiments [20,143]. f is only a function of the
viscosity ratio λ; if emulsions are considered rather than single
drops [144], f additionally contains a term with the drop phase
volume fraction ϕ. The drop size distribution in an emulsion
under flow may vary, i.e. the morphology of the emulsion is
transient, with the processes of coalescence and drop breakup
competing during the measurements. Such processes are
summarized in diameter versus shear rate diagrams (‘Elmendorp
plot’) [2,145]. Therefore, in emulsion rheology it is important to
configure the sample before experiments are performed. For
uncompatibilized (surfactant-free) immiscible polymer blends,
measurements should be performed according to pre-shear
protocols similar to the one described by [146]; in principle,
this is also true for compatibilized blends or for surfactant-
stabilized emulsions — however, in those cases, it is often
possible to produce a stable emulsion in which drops do not
significantly recoalesce. Flow-induced morphologies of emulsion
drops are associated with characteristic light scattering patterns
reflecting the shape anisotropy and orientation, and therefore can
be studied by combined rheological and small angle light
scattering (Rheo-SALS) experiments [146–149] or microscopy
[150]. Most experimental work focuses on the steady and
transient microstructure and shows that it is possible to study the
different stages of drop breakup after a shear rate step, such as
drop deformation and rotation, extension of drops to fibrils, and
development of interfacial instabilities accompanied by very
characteristic light-scattering patterns [2,151].
6. Emulsions and the role of interfacial rheology
The fields of interfacial rheology, single drop dynamics, and
the physics of foams and emulsions have been studied in detail
for decades now; significantly less work is published about
connections between these fields — note that the Introduction
section of many publications about interfacial rheology contains
hints at the relevance of the field to flow behavior and stability
of foams and emulsions. However, the actual number of
investigations establishing such links is still surprisingly small.
Some examples are coalescence studies at the oil/water interface
[152] where a positive correlation of coalescence stability with
the interfacial shear viscosity was established, a discussion of
the influence on the dilatational modulus on Ostwald ripening
[153], experiments on the breakup behavior of emulsion drops
covered with a protein emulsifier [11,12], or investigations on
foam lamellae or liquid films [154–156]. Moldenaer's group
[157] performed measurements on compatibilized immiscible
polymer blends and attributed a slow relaxation process found
in small amplitude oscillatory shear to in-plane interfacial
relaxation; they interpreted their results in terms of a modified
Palierne model described earlier by Jacobs et al. [158]; an early
ancestor of this model, including interfacial rheological effects,
was already proposed by Oldroyd as early as 1955 [159], and
various other treatments for dilute emulsions [160,161] are
published. Stone [162] reviewed aspects of interfacial rheology
in foam drainage; overviews are also given in the monograph by
[85] and in two articles by Lucassen-Reynders [163,164].
In a recent study, we have investigated the small-deformation
behavior of single Newtonian oil drops covered by an adsorbed
layer [10] formed by lysozyme, a surface-active globular
protein. While uncovered drops deform to the expected steady
ellipsoidal shape, drops covered with the globular protein resist
the bulk shear stress to a much higher degree, leading to a
smaller average deformation and to temporal fluctuations of the
drop shape, very similar to observations made with red blood
cells [125], solid capsules [122], or vesicles [128]. Those results
illustrate the important role of in-plane interfacial stresses of a
viscoelastic protein network on the macroscopic drop deforma-
tion, as opposed to the static interfacial tension. However,
proteins with different secondary and tertiary structure have
been shown to impart very different properties on emulsion
drops [11,114,165]. The effect of two structurally different
proteins, β-lactoglobulin (globular) and β-casein (flexible) on
the flow-induced morphology of emulsion drops in shear flow
has been investigated by interfacial rheology and by flow
experiments of dilute emulsions in an optical flow cell
[114,165]. The globular protein strongly restricts the extent to
which the drops are deformed in shear flow, whereas the flexible
protein does not show this effect. Those effects can be explained
terms of the interfacial mechanical properties of the proteins.
Therefore, emulsion drops covered with an adsorption layer of a
globular protein, such as β-lactoglobulin, behave as ‘capsules’
rather than surfactant-covered drops if the deformations are
small. Note that in case of large deformations and under critical
breakup conditions, these effects can be reversed and a solid,
shell-like interfacial layer formed by a globular protein can
enhance drop breakup [11]. In this latter case, which essentially
is a breakup process of a capsule with a rigid protein shell, the
breakup event and, consequently, the size distribution of the
resulting drops appears to be less regular than for clean drops, or
for drops with a small molecular weight surfactant.
7. Summary and perspectives
Coarsening the rheological response function from interfacial
physics, single drop dynamics via dilute emulsions to concen-
trated emulsion remains a considerable challenge. Besides
physicochemical aspects, which in this overview have been
discussed only in the context of modified interfaces, in particular
for protein-stabilized emulsions, the influence of viscoelastic
 P. Fischer, P. Erni / Current Opinion in Colloid & Interface Science 12 (2007) 196–205
matrix phases and the dynamics of surface-active species during
transport processes to and along the deformable interfaces are still
far from being fully understood. Whereas research on systems
involving non-Newtonian matrix and drop fluids originally had
started in parallel to studies of Newtonian phases, it has only
recently received increased attention, both from experimental,
analytical and numerical perspectives [7–9,166–169]. A major
challenge in ongoing research is the proper incorporation of
viscoelastic constitutive equations into drop models or computer
simulations. As discussed in Section 4, interfacial layers with
complex local mechanics and structure also need some future
attention.
The rheology and stability of emulsions is not only ruled by
drop deformation and breakup, but also by drop coalescence.
While these aspects have also been studied for several decades
now [170–172], many questions are still to be answered in the
areas of drop collision and coalescence [173,174] as well as
their link to the behavior of concentrated emulsions. Another lot
of challenging problems can be expected from the fact that the
external flow fields in most examples discussed above are linear
and relatively simple, whereas actual dispersing devices
generally create highly complex flows. An example is the
study of transient deformation behavior of single drops
undergoing a complex laminar 2D flow along a particle track,
which was analyzed both experimentally and numerically in a
simplified rotor-stator device and in counterrotating cylinders
with teethed walls capable of producing a mixed shear and
elongational planar flow [48,79,175].
Recent years have also seen increased interest in emulsion
flows in confined geometries and near solid walls. For example,
these effects were studied in contraction flow [176], in confined
shear flow [66,177,178], more recently in real microfluidic
devices (MFDs) [30,32,179,180], and in BIM studies
[181,182]. MFDs are miniaturized fluid–fluid dispersing
devices and paved the way not only to the well-known lab-
on-a-chip applications or fundamental research on low
Reynolds number flows, but also into potential industrial
emulsification and encapsulation processes. Recently, consid-
erable efforts in engineering of new flow cell designs has been
made to achieve monodisperse drops, double emulsions, and
microcapsules. Comparably less attention has been paid yet to
the influence of surfactants and polymers present in the fluids.
In contrast to macroscopic, unconfined flows, fluid/wall
interactions of the dispersed drops in MFDs must be
emphasized, and three-phase wetting phenomena strongly
influence the practical relevance for such devices, in particular
for fluids with different chemistry. From an industrial
perspective with the goal of delivering high quality, monodis-
perse emulsions in economically meaningful amounts, a clear
distinction must be made between high-value/low-volume
products (such as in the fields of medical diagnostics and
drop-based lab-on-a-chip applications), and low-value/high-
volume products, including those found the food and consumer
product industries. Even with advances in highly parallel
microfluidic architectures, drop-based MFDs are still far from
replacing the traditional industrial dispersing technologies.
However, a number of important aspects of microfluidics-based
201
research has already been integrated into yet another class of
emulsification processes which has become popular during the
last years: membrane emulsification [183,184] can in many
respects be seen as the first successful implementation of drop-
based MFDs on the industrial scale, with the pores of the
emulsification membrane taking over the role of the micro-
fluidic channels. For the time being, a look at dedicated journals
reveals that these interesting and challenging questions have
created a vast amount of loosely connected publications on
observed dispersing effects, flow and wetting phenomena, and
possible applications under numerous flow and material
conditions. Recent reviews on microfluidics written by Stone
et al. [32], Squires and Quake [31] and Whitesides [33] provide
coherent overviews of the field.
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