Microemulsions
MATTHIAS HLOUCHA, BASF Personal Care and Nutrition GmbH, D€
usseldorf-
Holthausen, Germany
1. Characterization of Microemulsions . . .
2. Rheology . . . . . . . . . . . . . . . . . . . . . .
3. Phase Behavior of Emulsions and
Microemulsions. . . . . . . . . . . . . . . . . .
The dispersion of two incompletely miscible
liquids is called an emulsion. Ordinary emul-
sions are thermodynamically unstable and their
average droplet size grows with time. Micro-
emulsions are defined as thermodynamically
stable emulsions their properties are time inde-
pendent and not influenced by the production
process, such as order of mixing or mechanical
energy. Their average structure sizes are below
100 nm. Microemulsions usually appear trans-
parent, although they often contain high
amounts of water and oil.
1. Characterization of
Microemulsions
Several experimental methods are used for the
characterization of microemulsions [1]. One
important goal is the characterization of the
structure of the microemulsions, which are
often very complex systems with regard to
changes in composition and temperature. It is
often an advantage to use different methods to
obtain a complete picture [2].
Freeze fracture electron microscopy
(FFEM) delivers images of the microemulsion
structure. The microemulsion is rapidly frozen,
followed by rapture and replication of the frac-
ture face. Depending on the composition, drop-
let-like structures as well as bicontinuous
structures are found in a simple three-compo-
nent system [3].
Light scattering methods are widely used
for particle size measurements. They require
# 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007
1 References . . . . . . . . . . . . . . . . . . . . . 4
2
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highly diluted emulsions for the measurement
of droplet sizes. However, in most cases the
addition of water to a microemulsion leads to a
phase separation, in which an oil-in-water
emulsion is formed. To overcome this limita-
tion, a model was proposed to correct scattering
data from undiluted microemulsions. With this
numerical approach, it is possible to estimate
particle sizes in undiluted microemulsions [4];
the calculated structure sizes are in the range of
8–20 nm.
Small angle X-ray scattering (SAXS) is a
technique for measuring the elastic scattering
of X rays by a sample at very low angles. SAXS
is capable of measuring structural sizes in the
nanometer range and gives information on
ordered systems, such as liquid crystalline
phases. It has been applied to evaluate the
structure size of microemulsions. Microemul-
sions based on a sulfonate-type surfactant and
octane have been investigated [5]; the structure
size is nearly constant (10–12 nm) over a large
range of oil-to-water ratios.
Small angle neutron scattering (SANS)
uses elastic neutron scattering to investigate
the structure of liquid systems in the range of
1–1 000 nm. It is used to study the size,
polydispersity, and the fluctuation in micro-
emulsions. It covers a larger range of wave
vectors than SAXS. It is therefore suited to
investigate short and long-range structures
for liquid systems. Scattering data are fitted
to models for the microemulsion structure.
Examples are studies on microemulsions consist-
ing of sodium bis(2-ethylhexyl) sulfosuccinate
2 Microemulsions
(AOT), alkane, and water [6, 7]. These studies
provide detailed information on the critical
behavior and structures of a microemulsion,
where oil-in-water, water-in-oil, or bicontinuous
structures are present depending on the compo-
sition of the microemulsion.
Nuclear Magnetic Resonance (NMR) Spec-
troscopy. For microemulsion characterization,
NMR spectroscopy is used to measure the self-
diffusion coefficients of surfactants, cosurfac-
tants, oil, and water. The results give a clear
indication of the microemulsion structure. Oil-
in-water, water-in-oil, and bicontinuous type
microemulsions can be distinguished by the
self-diffusion coefficients of the oil- and
water-phase molecules [8, 9].
2. Rheology
The flow behavior of microemulsions is impor-
tant for their technical application profile. Pro-
cesses, such as pumping, spraying, or spreading
require each a different flow behavior. One
example is gels for skin treatment. On the
one hand, they should be spread on easily, on
the other hand, not run off the skin. The require-
ment for this application is a low viscosity at
high shear rates and a significantly higher
viscosity at low shear rates. The flow behavior
can be optimized by varying the microemulsion
composition [10].
3. Phase Behavior of Emulsions and
Microemulsions
The systematic investigation and understanding
of the phase behavior of microemulsions and
Figure 1. Winsor types classification of equilibrated emulsions with oil (O), water (W) and surfactants (S) [11]. A) Winsor
type I; B) Winsor type II; C) Winsor type III; D) Winsor type IV
related systems, such as emulsions or liquid
crystalline phases is of fundamental importance
for the practical development of all microemul-
sions. A classification scheme for liquid formu-
lations with oil, water, and surfactants was
proposed by Winsor [11]. An important pre-
condition for this classification is that the for-
mulations are in their equilibrium state, which
means that macroemulsions are demixed.
The four different classification types
are shown in Figure 1. Winsor type I systems
(Fig. 1A) are two separated phases consisting of
an oil phase and a water phase containing the
dissolved surfactants. Winsor type II systems
(Fig. 1B) consist of an oil phase with dissolved
surfactants and a water phase. Winsor type III
systems (Fig. 1C) consist of three phases: 1) A
middle phase with oil, surfactants, and water;
2) water excess phase; 3) oil excess phase.
Winsor type IV systems (Fig. 1D) consist of
one phase of oil, water, and surfactants.
Because microemulsions are defined as ther-
modynamic stable systems with oil, water, and
surfactants, the middle phase in Winsor type III
systems and the Winsor type IV systems are
microemulsions. In practice, it is often not easy
to characterize emulsions based on this classi-
fication scheme. After homogenization, macro-
emulsions are formed, which are kinetically
stabilized. Two examples are given in
Figure 2. It is not possible to directly make a
classification according to Winsor, when the
system is not demixed. Centrifugation can help
to speed up the equilibration, which is needed
for the Winsor classification.
The fundamental phase behavior of micro-
emulsions based on ethoxylated surfactants has
been discussed in detail [12]. An important
general pattern in many microemulsions is

Figure 2. Dispersed state of Winsor type I (A) and Winsor
type II (B) emulsions after creaming and sedimentation
the so-called fish diagram. A generalized ver-
sion is shown in Figure 3. Depending on the
total surfactant concentration g and a tuning
parameter X, which can be either temperature,
surfactant mixture, or salt concentration, the
four different Winsor type systems can be
obtained.
One-phase microemulsions are formed with
high total surfactant concentrations and often a
narrow range for a tuning parameter X (Winsor
type IV). This area is also called a fishtail.
Below the minimum surfactant concentra-
tion for one-phase microemulsions only multi-
phase systems are formed, where the tuning
parameter X can be used to switch between
Winsor type I, II, and III systems. This general
pattern is important for the targeted develop-
ment of microemulsions and interpretation of
experimental data.
Technical microemulsions usually have four
or more components, which makes the
Figure 3. Generalized fish diagram for microemulsions
Microemulsions 3
visualization and discussion of the results chal-
lenging. To overcome this drawback, it is often
helpful to use parameters to describe the for-
mulations in a simplified way to make the
planning of experiments and interpretation of
data easier.
All components are assumed to be added in
a) oil phase, b) water phase, c) surfactant
(water-soluble), d) cosurfactant (oil-soluble).
Based on this simplification the following
parameters are useful for the description of
microemulsions:
mðoilÞ
a ¼
mðwaterÞ þ mðoilÞ
mðcosurfactantÞ
d ¼
mðsurfactantÞ þ mðcosurfactantÞ
mðsurfactantÞ þ mðcosurfactantÞ
g ¼
mðtotalÞ
a is the ratio of the mass fractions of oil and
water phases; d represents the mixing ratio of
surfactant and cosurfactant; g gives the overall
surfactant and cosurfactant fraction in the
formulation.
In practice, a is often set by the application
and the required amount of oil. g is often related
to formulation costs and is to be minimized in
order to use a minimum amount of surfactant
for a given amount of oil. Therefore, the sur-
factant mixture d is often the main degree of
freedom for a microemulsion product devel-
oper. In this case, the fish diagram can be
represented by a vertical axis d and a horizontal
axis g (see Fig. 3). For one-phase microemul-
sions, it is important to know the point with a
minimum overall surfactant plus cosurfactant
fraction gmin, where the surfactant mixture is at
its optimum efficiency dopt. Below this point
at g < gmin a typical sequence of phase behav-
ior is obtained for a variation of d at constant
g: 1) Winsor type I, 2) Winsor type III, 3)
Winsor type II (see Fig. 3).
An example for this representation of phase
behavior studies is given in Figure 4. The
formulations consist of an alkyl polyglucoside
(surfactant), glycerol monooleate (cosurfac-
tant), dioctyl ether (oil) and a fixed oil-to-water
ratio of a ¼ 0.30 [13].
4 Microemulsions
Figure 4. Phase behavior of emulsions with alkyl polyglucoside, glycerol monooleate and dioctyl ether at a ¼ 0.30. The
variation of the total surfactant amount g and surfactant mixture d leads to different dispersion types: One-phase micro-
emulsion (ME), o/w emulsion, w/o emulsion, and liquid crystalline phases (Lc) [13].
The results are shown as a function of g and
d. The phases were characterized by polarized
light microscopy and conductivity measure-
ments. Oil-in-water emulsions have a high
conductivity and, under the microscope, show
spherical oil droplets with a typical diameter of
5–20 mm. Microemulsions are transparent and
isotropic. Water-in-oil emulsions usually have
finer structures than o/w emulsions and a low
conductivity. At higher surfactant amounts liq-
uid crystalline phases are formed, which show
typical patterns in polarized light microscopy.
In this example, the region for one-phase
microemulsions extends over a large range for
total surfactant concentration g, but it is small
with regard to a change of surfactant mixture d.
With an increase in g, smaller d values are
required to form a microemulsion. Oil-in-water
emulsions are located below the microemulsion
region, above w/o emulsions are formed.
An interpretation of this can be made based
on the solubility of the surfactant mixture. With
large amounts of alkyl polyglucoside (a low d
value), the surfactant mixture is water-soluble
and tends to form a water continuous phase
(o/w). With high amounts of glycerol
monooleate the surfactant mixture is oil-solu-
ble, and the formation of an oil continuous
phase is favored (w/o). Figure 4 shows also
that one-phase microemulsions are not formed
below a minimum total surfactant concentra-
tion gmin.
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