Advances in Colloid and Interface Science 108 – 109 (2004) 303–318

Formation and stability of nano-emulsions

Tharwat Tadrosa,*, P. Izquierdob, J. Esquenab, C. Solansb
a
89 Nash Grove Lane, Wokingham, Berkshire RG40 4HE, UK
b
CSIC, Jordi Jirona 18-26, Barcelona 08034, Spain

Abstract

This review describes the principles of formation and stability of nano-emulsions. It starts with an introduction highlighting the
main advantages of nano-emulsions over macroemulsions for personal care and cosmetic formulations. It also describes the main
problems with lack of progress on nano-emulsions. The second section deals with the mechanism of emulsification and the
dynamic light scattering technique for measurement of the droplet size of nano-emulsions. This is followed by a section on
methods of emulsification and the role of surfactants. Three methods are described for nano-emulsion preparation, namely high
energy emulsification (using homogenisers), low energy emulsification whereby water is added to an oil solution of the surfactant
and the principle of the phase inversion temperature (PIT). A section is devoted to steric stabilisation and the role of the adsorbed
layer thickness. The problem of Ostwald ripening (which is the main instability process of nano-emulsions) is described in some
detail. The methods that can be applied to reduce Ostwald ripening are briefly described. This involves the addition of a second
less soluble oil phase such as squalene andyor addition of a strongly adsorbed and water insoluble polymeric surfactant. The last
part of the review gives some examples of nano-emulsions that are prepared by the PIT method as well as using high pressure
homogeniser. A comparison of the two methods is given and the rate of Ostwald ripening is measured in both cases. The effect
of changing the alkyl chain length and branching of the oil was investigated using decane, dodecane, tertadecane, hexadecane
and isohexadecane. The branched oil isohexadcecane showed higher Ostwald ripening rate when compared with a linear chain
oil with the same carbon number.
䊚 2003 Elsevier B.V. All rights reserved.

Keywords: Nano-emulsions; Phase inversion temperature (PIT); Emulsification

1. Introduction Unless adequately prepared (to control the droplet

Nano-emulsions are transparent or translucent systems
mostly covering the size range 50–200 nm w1,2x. Nano-
emulsions were also referred to as mini-emulsions w3,4x.
Unlike microemulsions (which are also transparent or
translucent and thermodynamically stable) nano-emul-
sions are only kinetically stable. However, the long-term
physical stability of nano-emulsions (with no apparent
flocculation or coalescence) make them unique and they
are sometimes referred to as ‘Approaching Thermody-
namic Stability’.
The inherently high colloid stability of nano-emul-
sions can be well understood from a consideration of
their steric stabilisation (when using non-ionic surfac-
tants andyor polymers) and how this is affected by the
ratio of the adsorbed layer thickness to droplet radius as
will be discussed below.
*Corresponding author. Tel.: q44-1189-732621.
E-mail address: tharwat@tadros.fsnet.co.uk (T. Tadros).
size distribution) and stabilised against Ostwald ripening
(that occur when the oil has some finite solubility in
the continuous medium), nano-emulsions may loose
their transparency with time as a result of increase in
droplet size.
The attraction of nano-emulsions for application in
personal care and cosmetics as well as in health care is
due to the following advantages:
(i) The very small droplet size causes a large reduc-
tion in the gravity force and the Brownian motion may
be sufficient for overcoming gravity. This means that no
creaming or sedimentation occurs on storage. (ii) The
small droplet size also prevents any flocculation of the
droplets. Weak flocculation is prevented and this enables
the system to remain dispersed with no separation. (iii)
The small droplets also prevent their coalescence, since
these droplets are non-deformable and hence surface
fluctuations are prevented. In addition, the significant
surfactant film thickness (relative to droplet radius)

0001-8686/04/$ - see front matter 䊚 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2003.10.023
304 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
prevents any thinning or disruption of the liquid film
between the droplets. (iv) Nano-emulsions are suitable
for efficient delivery of active ingredients through the
skin. The large surface area of the emulsion system
allows rapid penetration of actives. (v) Due to their
small size, nano-emulsions can penetrate through the
‘rough’ skin surface and this enhances penetration of
actives. (vi) The transparent nature of the system, their
fluidity (at reasonable oil concentrations) as well as the
absence of any thickeners may give them a pleasant
aesthetic character and skin feel. (vii) Unlike microe-
mulsions (which require a high surfactant concentration,
usually in the region of 20% and higher), nano-emul-
sions can be prepared using reasonable surfactant con-
centration. For a 20% OyW nano-emulsion, a surfactant
concentration in the region of 5–10% may be sufficient.
(viii) The small size of the droplets allows them to
deposit uniformly on substrates. Wetting, spreading and
penetration may be also enhanced as a result of the low
surface tension of the whole system and the low inter-
facial tension of the OyW droplets. (ix) Nano-emulsions
can be applied for delivery of fragrants, which may be
incorporated in many personal care products. This could
also be applied in perfumes, which are desirable to be
formulated alcohol free. (x) Nano-emulsions may be
applied as a substitute for liposomes and vesicles (which
are much less stable) and it is possible in some cases
to build lamellar liquid crystalline phases around the
nano-emulsion droplets.
Inspite of the above advantages, nano-emulsions have
only attracted interest in recent years for the following
reasons: (i) Preparation of nano-emulsions requires in
many cases special application techniques, such as the
use of high pressure homogenisers as well as ultrasonics.
Such equipments (such as the Microfluidiser) became
available only in recent years. (ii) There is a perception
in the personal care and cosmetic industry that nano-
emulsions are expensive to produce. Expensive equip-
ments are required as well as the use of high
concentrations of emulsifiers. (iii) Lack of understand-
ing of the mechanism of production of submicron
droplets and the role of surfactants and cosurfactants.
(iv) Lack of demonstration of the benefits that can be
obtained from using nano-emulsions when compared
with the classical macroemulsion systems. (v) Lack of
understanding of the interfacial chemistry that is
involved in production of nano-emulsions. For example,
few formulations chemists are aware of the use of the
phase inversion temperature (PIT) Concept and how
this can be usefully applied for the production of small
emulsion droplets. (vi) Lack of knowledge on the
mechanism of Ostwald ripening, which is perhaps the
most serious instability problem with nano-emulsions.
(vii) Lack of knowledge of the ingredients that may be
incorporated to overcome Ostwald ripening. For exam-
ple, addition of a second oil phase with very low
solubility andyor incorporation of polymeric surfactants
that strongly adsorb at the OyW interface (which are
also insoluble in the aqueous medium). (viii) Fear of
introduction of new systems without full evaluation of
the cost and benefits.
Inspite of the above difficulties, several companies
have introduced nano-emulsions in the market and
within the next few years, the benefits will be evaluated.
Nano-emulsions were used in the pharmaceutical field
as drug delivery systems w7x.
Acceptance of nano-emulsions as a new type of
formulation depends on customer perception and accept-
ability. With the advent of new instruments for high
pressure homogenizers and the competition between
various manufacturers, the cost of production of nano-
emulsions will decrease and that may approach that of
classical macroemulsions.
Fundamental research in investigation of the role of
surfactants in the process w5,6x will lead to optimized
emulsifier systems and more economic use of surfactants
will emerge. The importance of phase behaviour in the
preparation of nano-emulsions is also very crucial. As
we will see later the method of mixing of oil, water and
surfactant is very important.
In this review, I will discuss the following topics: (i)
Fundamental principles of emulsification and the role of
surfactants. (ii) Production of nano-emulsions using:
high pressure homogenizers. The phase inversion tem-
perature (PIT) principle. (iii) Theory of steric stabili-
zation of emulsions. The role of the relative ratio of
adsorbed layer thickness to the droplet radius. (iv)
Theory of Ostwald ripening and methods of reduction
of the process: incorporation of a second oil phase with
very low solubility. Use of strongly adsorbed polymeric
surfactants. (iv) Examples of recently prepared nano-
emulsions and investigation of the above effects.
2. Mechanism of emulsification
To prepare an emulsions oil, water, surfactant and
energy are needed. This can be considered from a
consideration of the energy required to expand the
interface, DAg (where DA is the increase in interfacial
area when the bulk oil with area A1 produces a large
number of droplets with area A2; A24A1, g is the
interfacial tension). Since g is positive, the energy to
expand the interface is large and positive. This energy
term cannot be compensated by the small entropy of
dispersion TDS (which is also positive) and the total
free energy of formation of an emulsion, DG is positive,
DGsDAg y TDS (1)
Thus, emulsion formation is non-spontaneous and
energy is required to produce the droplets. The formation
of large droplets (few micrometers) as is the case for
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
macroemulsions is fairly easy and hence high speed
stirrers such as the Ultraturrax or Silverson Mixer is
sufficient to produce the emulsion. In contrast the
formation of small drops (submicron as is the case with
nano-emulsions) is difficult and this requires a large
amount of surfactant andyor energy.
The high energy required for formation of nano-
emulsions can be understood from a consideration of
the Laplace pressure p (the difference in pressure
between inside and outside the droplet,
B 1 1E
psgC q F
D R1 R2 G
where R1 and R2 are the principal radii of curvature of
the drop.
For a spherical drop, R1sR2sR and,
2g
ps
R
To break up a drop into smaller ones, it must be
strongly deformed and this deformation increases p.
This can be shown when a spherical drop deforms into
a prolate ellipsoid. For a spherical drop, there is only
one radius of curvature Ra, whereas for a prolate
ellipsoid there are two radii of curvature Rb,1 and Rb,2.
Consequently, the stress needed to deform the drop is
higher for a smaller drop. Since the stress is generally
transmitted by the surrounding liquid via agitation,
higher stresses need more vigorous agitation, hence more
energy is needed to produce smaller drops w8x.
Surfactants play major roles in the formation of nano-
emulsions: By lowering the interfacial tension, p is
reduced and hence the stress needed to break up a drop
is reduced. Surfactants prevent coalescence of newly
formed drops.
Various processes occurring during emulsification,
namely break up of droplets, adsorption of surfactants
and droplet collision (which may or may not lead to
coalescence occur w8x. Each of these processes occurs
numerous times during emulsification and the time scale
of each process is very short, typically a microsecond.
This shows that the emulsification process is a dynamic
process and events that occur in a microsecond range
could be very important. To describe emulsion formation
one has to consider two main factors: Hydrodynamics
and interfacial science.
To assess nano-emulsion formation, one usually meas-
ures the droplet size distribution using dynamic light
scattering techniques (photon correlation spectroscopy,
PCS). In this technique, one measures the intensity
fluctuation of scattered light by the droplets as they
undergo Brownian motion w9x. When a light beam passes
through a nano-emulsion, an oscillating dipole moment
305
is induced in the droplets, thereby reradiating the light.
Due to the random position of the droplets, the intensity
of scattered light will, at any instant appears as a random
diffraction or ‘speckle’ pattern. As the droplets undergo
Brownian motion, the random configuration of the
pattern will, therefore, fluctuate such that the time taken
for an intensity maximum to become a minimum, i.e.
the coherence time corresponds exactly to the time
required for the droplet to move one wavelength. Using
a photomultiplier of active area about the diffraction
maximum, i.e. one coherence area, this intensity fluctu-
ation can be measured. The analogue output is digitised
(2) using a digital correlator that measures the photocount
(or intensity) correlation function of the scattered light.
The photocount correlation function G (2)(t) is given by
the equation,
2
GŽ2.Žt.sB 1 q g2 wygŽ1.Žt.z~
Ž x |
. (4)
(3) where t is the correlation delay time. The correlator
compares G (2)(t) for many values of t. B is the
background value to which G (2)(t) decays at long delay
times. g (1)(t) is the normalised correlation function of
the scattered electric field and g is a constant (approx.
1).
For monodisperse non-interacting droplets,
gŽ1.sexpŽy Gt. (5)
where G is the decay rate or inverse coherence time,
that is related to the translational diffusion coefficient
D by the equation,
GsDK2 (6)
where K is the scattering vector,
4pn BuE
Ks sinC F (7)
lo D2G
l is the wavelength of light in vacuo, n is the refractive
index of the solution and u is the scattering angle.
The droplet radius R can be calculated from D using
the Stokes–Einstein equation,
kT
Ds (8)
6p ho R
ho is the viscosity of the medium.
The above analysis is valid for dilute monodisperse
droplets. With many nano-emulsions, the droplets are
not perfectly mono-disperse (usually with a narrow size
distribution) and the light scattering results are analysed
for polydispersity (the data are expressed as an average
306 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
size and a polydispersity index that gives information
on the deviation from the average size.
3. Methods of emulsification and the role of
surfactants
With macroemulsions, several procedures may be
applied for emulsion preparation, these range from
simple pipe flow (low agitation energy L), static mixers
and general stirrers (low to medium energy, L–M), high
speed mixers such as the Ultraturrex (M), colloid mills
and high pressure homogenizers (high energy, H), ultra-
sound generators (M–H). The method of preparation
can be continuous (C) or batch-wise (B). With nano-
emulsions, however, a higher power density is required
and this restricts the preparation of nano-emulsions to
the use of high pressure homogenisers and ultrasonics.
An important parameter that describes droplet defor-
mation is the Weber number, We, which gives the ratio
of the external stress Gh (where G is the velocity
gradient and h is the viscosity) over the Laplace
pressure w10x,
Ghr
Wes
2g
The droplet deformation increases with increase in
the Weber number, which means that for producing
small droplets one requires high stresses (high shear
rates). In other words, the production of nano-emulsions
costs more energy than that required to produce macroe-
mulsions w4x.
Surfactants lower the interfacial tension g and this
causes a reduction in droplet size. The latter decrease
with decrease in g. For Turbulent Inertial regime, the
droplet diameter is proportional to g3y5.
The amount of surfactant required to produce the
smallest drop size will depend on its activity a (concen-
tration) in the bulk which determines the reduction in
g, as given by the Gibbs adsorption equation,
ydgsRTGdln a
where R is the gas constant, T is the absolute temperature
and G is the surface excess (number of moles adsorbed
per unit area of the interface).
G increases with increase in surfactant concentration
and eventually it reaches a plateau value (saturation
adsorption). The value of g obtained depends on the
nature of the oil and surfactant used. Small molecules
such as non-ionic surfactants lower g more than poly-
meric surfactants such as poly(vinyl alcohol).
Another important role of the surfactant is its effect
on the interfacial dilational modulus ´ w11–14x,
dg
´s
dln A
During emulsification an increase in the interfacial
area A takes place and this causes a reduction in G. The
equilibrium is restored by adsorption of surfactant from
the bulk, but this takes time (shorter times occur at
higher surfactant activity). Thus, ´ is small at small a
and also at large a. Because of the lack or slowness of
equilibrium with polymeric surfactants, ´ will not be
the same for expansion and compression of the interface.
In practice, surfactant mixtures are used and these have
pronounced effects on g and ´: Some specific surfactant
mixtures give lower g values than either of the two
individual components. The presence of more than one
surfactant molecule at the interface tends to increase ´
at high surfactant concentrations. The various compo-
nents vary in surface activity. Those with the lowest g
tend to predominate at the interface, but if present at
low concentrations, it may take long time before reach-
ing the lowest value. Polymer-surfactant mixtures may
show some synergetic surface activity.
Apart for their effect on reducing g, surfactants play
major roles in deformation and break-up of droplets.
Surfactants allow the existence of interfacial tension
gradients, which is crucial for formation of stable drop-
(9) lets. In the absence of surfactants (clean interface), the
interface cannot withstand a tangential stress; the liquid
motion will be continuous. If a liquid flows along the
interface with surfactants, the latter will be swept down-
stream causing an interfacial tension gradient. A balance
of forces will be established,
B dV E dy
hC F
x
sy (12)
D dy Gys0 dx
If the g-gradient can become large enough, it will
arrest the interface. If the surfactant is applied at one
site of the interface, a g-gradient is formed that will
cause the interface to move roughly at a velocity given
by,
Vs1.2 Žhrz.y1y3 )Dg)2y3 (13)
(10)
The interface will then drag some of the bordering
liquid with it. Interfacial tension gradients are very
important in stabilising the thin liquid film between the
droplets, which is very important during the beginning
of emulsification (films of the continuous phase may be
drawn through the disperse phase and collision is very
large).
The magnitude of the g-gradients and of the Maran-
goni effect depends on the surface dilational modulus
´, which for a plane interface with one surfactant-
containing phase, is given by the expression,
B dg E
´sC y F Ž1 q 2zq2z2.1y2 (14)
(11) D dln G G
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
B dm E B DE
1y
2 Closely related to the above mechanism, is the Gibbs–
´sC FC F
C
D dg G D 2v G
dln A
vs
dt
where D is the diffusion coefficient of the surfactant
and v represents a time scale (time needed for doubling
the surface area) that is roughly equal to tdef.
During emulsification, ´ is dominated by the magni-
tude of the denominator in Eq. (14) because z remains
small. The value of dmydG tends to go to very high
values when G reaches its plateau value. ´ goes to a
maximum when mC is increased.
For conditions that prevail during emulsification, ´
increases with mC and it is given by the relationship,
dp
´s
dln G
where p is the surface pressure (psgo yg). ´ is given
by the slope of the line of plots of p vs. ln G. Such
plots show that a surfactant such as sodium dodecyl
sulfate (SDS) gives a much higher ´ value when
compared with a protein such as b-casein or lysozome
w15x. This is because the value of G is higher for SDS.
The two proteins show difference in their ´ values,
which may be attributed to the conformational change
that occur upon adsorption.
The presence of a surfactant means that during emul-
sification the interfacial tension need not to be the same
every where. This has two consequences: (i) the equi-
librium shape of the drop is affected; (ii) any g-gradient
formed will slow down the motion of the liquid inside
the drop (this diminish the amount of energy needed to
deform and break-up the drop).
Another important role of the emulsifier is to prevent
coalescence during emulsification. This is certainly not
due to the strong repulsion between the droplets, since
the pressure at which two drops are pressed together is
much greater than the repulsive stresses. The counter-
acting stress must be due to the formation of g-gradients.
When two drops are pushed together, liquid will flow
out from the thin layer between them, and the flow will
induce a g-gradient. This produces a counteracting stress
given by,
2 )Dg)
tDgf
Ž1y2.d
The factor 2 follows from the fact that two interfaces
are involved. Taking a value of Dgs10 mØNmy1, the
stress amounts to 40 kPa (which is of the same order
of magnitude as the external stress.
307
(15) Marangoni effect. The depletion of surfactant in the thin
film between approaching drops results in g-gradient
without liquid flow being involved. This results in an
(16) inward flow of liquid that tends to drive the drops apart.
The Gibbs–Marangoni effect also explains the Bancroft
rule, which states that the phase in which the surfactant
is most soluble form the continuous phase. If the
surfactant is in the droplets, a g-gradient cannot develop
and the drops would be prone to coalescence. Thus,
surfactants with HLB)7 tend to form OyW emulsions
and HLB-7 tend to form WyO emulsions. The Gibbs–
Marangoni effect also explains the difference between
surfactants and polymers for emulsification. Polymers
give larger drops when compared with surfactants. Pol-
ymers give a smaller value of ´ at small concentrations
when compared to surfactants.
Various other factors should also be considered for
emulsification, the most important is the disperse phase
(17)
volume fraction w. Increase in w leads to increase in
droplet collision and hence coalescence during emulsi-
fication. With increase in w, the viscosity of the emul-
sion increases and could change the flow from being
turbulent to being laminar (LV regime). The presence
of many particles results in a local increase in velocity
gradients. This means that G increases. In turbulent
flow, increase in w will induce turbulence depression.
This will result in larger droplets. Turbulence depression
by added polymers tend to remove the small eddies,
resulting in the formation of larger droplets. If the mass
ratio of surfactant to continuous phase is kept constant,
increase in w results in decrease in surfactant concentra-
tion and hence an increase in geq. This results in larger
droplets. If the mass ratio of surfactant to disperse phase
is kept constant, these changes are reversed.
General conclusions cannot be drawn since several of
the above mentioned mechanism may come into play.
Experiments using a high pressure homogenizer at var-
ious w values at constant initial mC (regime TI changing
to TV at higher w showed that with increasing w ()
0.1) the resulting droplet diameter increased and the
dependence on energy consumption became weaker. A
comparison of the average droplet diameter vs. power
consumption using different emulsifying machines,
showed that the smallest droplet diameters were obtained
when using the high pressure homogenizers.
4. Preparation of nano-emulsions
(18) Three methods may be applied for the preparation of
nano-emulsions (covering the droplet radius size range
50–200 nm). Use of high pressure homogenisers (aided
by appropriate choice of surfactants and cosurfactants),
use of low energy emulsification method at constant
temperature or application of the phase inversion tem-
perature (PIT) concept.
308 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 1. Schematic representation of the experimental path in two emul-
sification methods: Method A, addition of decane to waterysurfactant
mixture; method B, addition of water to decaneyBrij 30 solutions.
(Reproduced with permission from Ref. w15bx).
4.1. Use of high pressure homogenizers
The production of small droplets (submicron) requires
application of high energy. The process of emulsification
is generally inefficient as illustrated below.
Simple calculations show that the mechanical energy
required for emulsification exceeds the interfacial energy
by several orders of magnitude. For example, to produce
an emulsion at ws0.1 with a d32s0.6 mm, using a
surfactant that gives an interfacial tension gs10
mØNmy1, the net increase in surface free energy is Ags
6wg yd32s104 Jmy3. The mechanical energy required
in a homogenizer is 107 Jmy3, i.e. an efficiency of
0.1%. The rest of the energy (99.9%) is dissipated as
heat w10x.
The intensity of the process or the effectiveness in
making small droplets is often governed by the net
power density (´(t)).
ps´Žt. dt
where t is the time during which emulsification occurs.
Break up of droplets will only occur at high ´ values,
which means that the energy dissipated at low ´ levels
is wasted. Batch processes are generally less efficient
than continuous processes. This shows why with a stirrer
in a large vessel, most of the energy applies at low
intensity is dissipated as heat. In a homogenizer, p is
simply equal to the homogenizer pressure.
Several procedures may be applied to enhance the
efficiency of emulsification when producing nano-emul-
sions: One should optimise the efficiency of agitation
by increasing ´ and decreasing dissipation time. The
emulsion is preferably prepared at high volume faction
of the disperse phase and diluted afterwards. However,
very high w values may result in coalescence during
emulsification. Add more surfactant, whereby creating a
smaller geff and possibly diminishing recoalescence. Use
surfactant mixture that shows more reduction in g the
individual components. If possible dissolve the surfac-
Fig. 2. Emulsion droplet diameters (circles) and rate constant for
attaining steady size (squares) as function of HLB-Cyclohex-
aneyNonylphenol Ethoxylate. (Reproduced with permission from Ref.
w15cx).
tant in the disperse phase rather than the continuous
phase; this often leads to smaller droplets.
It may be useful to emulsify in steps of increasing
intensity, particularly with emulsions having highly vis-
cous disperse phase.
4.2. Low energy emulsification methods
A study of the phase behaviour of wateryoilysurfac-
tant systems demonstrated that emulsification can be
achieved by three different low energy emulsification
methods w5x, as schematically shown in Fig. 1 (a)
stepwise addition of oil to a water surfactant mixture;
(b) stepwise addition of water to a solution of the
surfactant in oil; and (c) mixing all the components in
(19) the final composition, pre-equilibrating the samples prior
to emulsification. In these studies, the system watery
Brij 30 (polyoxyethlene lauryl ether with an average of
4 mol of ethylene oxideydecane was chosen as a model
to obtain OyW emulsions.
The results showed that nano-emulsions with droplet
sizes of the order of 50 nm were formed only when
water was added to mixtures of surfactant and oil
(method b).
4.3. Phase inversion temperature (PIT) principle
Phase inversion in emulsions can be one of two types:
Transitional inversion induced by changing factors
which affect the HLB of the system, e.g. temperature
andyor electrolyte concentration. Catastrophic Inversion,
which is induced by increasing the volume fraction of
the disperse phase.
Transitional Inversion can also be induced by chang-
ing the HLB number of the surfactant at constant
temperature using surfactant mixtures. This is illustrated
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 3. The PIT concept. (Reproduced with permission from Ref. w15dx).
in Fig. 2, which shows the average droplet diameter and
rate constant for attaining constant droplet size as a
function of the HLB number.
It can be seen that the diameter decreases and the
rate constant increases as inversion is approached. For
application of the phase inversion principle one uses the
transitional inversion method which has been demon-
strated by Shinoda and coworkers w16,17x when using
non-ionic surfactants of the ethoxylate type. These
surfactants are highly dependent on temperature, becom-
ing lipophilic with increasing temperature due to the
dehydration of the polyethyleneoxide chain. When an
OyW emulsion is prepared using a non-ionic surfactant
of the ethoxylate type is heated, then at a critical
temperature (the PIT), the emulsion inverts to a WyO
emulsion. At the PIT the droplet size reaches a minimum
and the interfacial tension also reaches a minimum.
However, the small droplets are unstable and they
coalesce very rapidly. By rapid cooling of the emulsion
that is prepared at a temperature near the PIT, very
stable and small emulsion droplets could be produced.
A clear demonstration of the phase inversion that
occurs on heating an emulsion is illustrated from a study
of the phase behaviour of emulsions as a function of
309
temperature. This is illustrated in Fig. 3, which shows
schematically what happens when the temperature is
increased w18,19x.
At low temperature, over the Winsor I region, OyW
macroemulsions can be formed and are quite stable. On
increasing the temperature, the OyW emulsion stability
decreases and the macroemulsion finally resolves when
the system reaches the Winsor III phase region (both
OyW and WyO emulsions are unstable). At higher
temperature, over the Winsor II region, WyO emulsions
become stable.
Fig. 4 shows the most clear-cut image of the macroe-
mulsion inversion as a function of temperature. Equal
volumes of oil and water are emulsified at various
temperatures. Five hours after preparation, macroemul-
sions completely sediment. Below the balanced temper-
ature (HLB temperature), a stable OyW macroemulsion
is formed, whereas above the balanced temperature a
stable WyO emulsion is formed.
Close to the balanced point (60–68 8C), a three phase
equilibrium is observed and neither OyW or WyO
emulsions are stable.
Near the HLB temperature, the interfacial tension
reaches a minimum. This is illustrated in Fig. 5. Thus
310 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318

consider the interaction forces between droplets contain-

ing adsorbed layers (Steric stabilization). This was
described in detail in several reviews and textbooks only
a summary is given here w20,21x.
When two droplets each containing an adsorbed layer
of thickness d approach to a distance of separation h,
whereby h becomes -2d, repulsion occurs as a result
of two main effects: (i) Unfavourable mixing of the
stabilizing chains A of the adsorbed layers, when these
are in good solvent conditions. This is referred to as the
mixing (osmotic interaction, Gmix and is given by the
following expression,

Gmix 4p 2 B 1 E B hE
Fig. 4. Macroemulsion stability diagram of cyclohexane-water- s f2 C yxF C3aq2dq F (20)
kT 3V1 D2 G D 2G
polyoxyethylene (9.7) nonyl phenol ether system. (Reproduced with
permission from Ref. w16x).
where k is the Boltzmann constant, T is the absolute
temperature, V1 is the molar volume of the solvent, w2
by preparing the emulsion at a temperature 2–4 8C
is the volume fraction of the polymer (the A chains) in
below the PIT (near the minimum in g) followed by
the adsorbed layer and x is the Flory–Huggins (poly-
rapid cooling of the system, nano-emulsions may be
mer–solvent interaction) parameter.
produced.
It can be seen that Gmix depends on three main
The minimum in g can be explained in terms of the
parameters: The volume fraction of the A chains in the
change in curvature H of the interfacial region, as the
adsorbed layer (the more dense the layer is the higher
system changes from OyW to WyO.
the value of Gmix). The Flory–Huggins interaction
For OyW system and normal micelles, the monolayer
parameter x (for Gmix to remain positive, i.e. repulsive,
curves towards the oil and H is given a positive value.
x should be lower than 1y2). The adsorbed layer
For a WyO emulsions and inverse micelles, the mono-
thickness d .
layer curves towards the water and H is assigned a
(ii) Reduction in configurational entropy of the chains
negative value. At the inversion point (HLB tempera-
on significant overlap. This referred to as elastic (entrop-
ture) H becomes zero and g reaches a minimum.
ic) interaction and is given by the expression,
5. Steric stabilization and the role of the adsorbed w z
VŽh.
Gels2n2lnx |
layer thickness
(21)
y VŽ`. ~
Since most nano-emulsions are prepared using non-
ionic andyor polymeric surfactants, it is necessary to where n2 is the number of chains per unit area, V(h) is

Fig. 5. Interfacial tensions of n-octane against water in the presence of various CnEm surfactants above the cmc as a function of temperature.
(Reproduced with permission from Ref. w19x).
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318 311

6. Ostwald ripening

One of the main problems with nano-emulsions is

Ostwald ripening which results from the difference in
solubility between small and large droplets. The differ-
ence in chemical potential of dispersed phase droplets
between different sized droplets as given by Lord Kelvin
w22x,

B 2gV E
cŽr.scŽ`. expC F
m
(23)
D rRT G

where c(r) is the solubility surrounding a particle of

Fig. 6. Variation of Gmix, Gel, GA and GT with h.
the configurational entropy of the chains at a separation
distance h and V(`) is the configurational entropy at
infinite distance of separation.
Combination of Gmix, Gel with the van der Waals
attraction GA gives the total energy of interaction GT,
radius r, c(`) is the bulk phase solubility and Vm is
the molar volume of the dispersed phase.
The quantity (2gVm yrRT) is termed the characteristic
length. It has an order of ;1 nm or less, indicating that
the difference in solubility of a 1 mm droplet is of the
order of 0.1% or less.
Theoretically, Ostwald ripening should lead to con-
densation of all droplets into a single drop (i.e. phase
separation). This does not occur in practice since the
rate of growth decreases with increase of droplet size.
For two droplets of radii r1 and r2 (where r1-r2),

GTsGmixqGelqGA (22) w
B RT E cŽr1. z B 1E
C
D Vm G
F lnx | s 2g CD r1
cŽr2. ~
y F
r2 G
(24)
y
Fig. 6 gives a schematic representation of the variation 1

of Gmix, Gel, GA and GT with h. As can be seen form

Fig. 5, Gmix increases very rapidly with decrease of h Eq. (24) shows that the larger the difference between
as soon as h-2d, Gel increase very rapidly with decrease r1 and r2, the higher the rate of Ostwald ripening.
of h when h-d. GT shows one minimum, Gmin, and it Ostwald ripening can be quantitatively assessed from
increases very rapidly with decrease of h when h-2d. plots of the cube of the radius vs. time t (the Lifshitz–
The magnitude of Gmin depends on the following Slesov–Wagner, LSW, Theory) w23,24x,
parameters: The particle radius R. The Hamaker constant
A. The adsorbed layer thickness d. w z
8 cŽ`.gVmD
As an illustration, Fig. 7 shows the variation of GT rs x
3 |t (25)
with h at various ratios of d yR. It can be seen from Fig. 9 y rRT ~

7 that the depth of the minimum decreases with increas-

ing d yR. This is the basis of the high kinetic stability
of nano-emulsions. With nano-emulsions having a radius
in the region of 50 nm and an adsorbed layer thickness
of say 10 nm, the value of d yR is 0.2. This high value
(when compared with the situation with macroemulsions
where d yR is at least an order of magnitude lower)
results in a very shallow minimum (which could be less
than kT).
The above situation results in very high stability with
no flocculation (weak or strong). In addition, the very
small size of the droplets and the dense adsorbed layers
ensures lack of deformation of the interface, lack of
thinning and disruption of the liquid film between the
droplets and hence coalescence is also prevented.
The only instability problem with nano-emulsions is
Ostwald ripening which is discussed below. Fig. 7. Variation of GT with h with increasing dyR.
312 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 8. Pseudoternary phase diagram at 258 of the system water-C12EO4-hexadecane. (Reproduced with permission from Ref. w29bx).
where D is the diffusion coefficient of the disperse
phase in the continuous phase and r is the density of
the disperse phase.
Several methods may be applied to reduce Ostwald
ripening w25–27x:
(i) Addition of a second disperse phase component,
which is insoluble in the continuous phase (e.g. squa-
lene). In this case, significant partitioning between
different droplets occurs, with the component having
low solubility in the continuous phase expected to be
concentrated in the smaller droplets. During Ostwald
ripening in two component disperse phase system, equi-
librium is established when the difference in chemical
potential between different size droplets (which results
from curvature effects) is balanced by the difference in
chemical potential resulting from partioning of the two
components. If the secondary component has zero sol-
ubility in the continuous phase, the size distribution will
not deviate from the initial one (the growth rate is equal
to zero). In the case of limited solubility of the second-
ary component, the distribution is the same as governed
by Eq. (16), i.e. a mixture growth rate is obtained which
is still lower than that of the more soluble component.
The above method is of limited application since one
requires a highly insoluble oil as the second phase,
which is miscible with the primary phase.
(ii) Modification of the interfacial film at the OyW
interface: According to Eq. (24) reduction in g results
in reduction of Ostwald ripening. However, this alone
is not sufficient since one has to reduce g by several
orders of magnitude. Walstra w28x suggested that by
using surfactants, which are strongly adsorbed at the Oy
W interface (i.e. polymeric surfactants) and which do
not desorb during ripening, the rate could be signifi-
cantly reduced. An increase in the surface dilational
modulus and decrease in g would be observed for the
shrinking drops. The difference in g between the drop-
lets would balance the difference in capillary pressure
(i.e. curvature effects).
To achieve the above effect it is useful to use A-B-A
block copolymers that are soluble in the oil phase and
insoluble in the continuous phase. The polymeric sur-
factant should enhance the lowering of g by the emul-
sifier. In other words, the emulsifier and the polymeric
surfactant should show synergy in lowering g.
7. Practical examples of nano-emulsions
Several experiments were recently carried to investi-
gate the methods of preparation of nano-emulsions and
their stability w29x. The first method applied the PIT
principle for preparation of nano-emulsions. Experi-
ments were carried out using hexadecane and isohex-
adecane (Arlamol HD) as the oil phase and Brij 30
(C12EO4) as the non-ionic emulsifier. The phase dia-
grams of the ternary system water-C12EO4-hexadecane
and water-C12EO4-isohexadecane are shown in Figs. 8
and 9. The main features of the pseudoternary system
are as follows: (i) Om isotropic liquid transparent phase,
which extends along the hexadecane-C12EO4 or isohex-
adecane-C12EO4 axis, corresponding to inverse micelles
or WyO microemulsions; (ii) La lamellar liquid crystal-
line phase extending from the W-C12EO4 axis toward
the oil vertex; (iii) The rest of the phase diagram
consists of two- or three-phase regions: (WmqO) two-
liquid-phase region, which appears along the water–oil
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 9. Pseudoternary phase diagram at 258 of the system water-C12EO4-isohexadecane. (Reproduced with permission from Ref. w29ax).
axis; (WmqLaqO) three-phase region, which consists
of a bluish liquid phase (OyW microemulsion), a
lamellar liquid crystalline phase (La) and a transparent
oil phase; (LaqOm) two-phase region consisting of an
oil and liquid crystalline region; MLC a multiphase
region containing a lamellar liquid crystalline phase
(La).
The HLB temperature was determined using conduc-
tivity measurements, whereby 10y2 mol dmy3 NaCl
was added to the aqueous phase (to increase the sensi-
tivity of the conductibility measurements). The concen-
tration of NaCl was low and hence it had little effect
on the phase behaviour.
Fig. 10 shows the variation of conductivity vs. tem-
perature for 20% OyW emulsions at different surfactant
concentrations. It can be seen that there is a sharp
decrease in conductivity at the PIT or HLB temperature
of the system.
The HLB temperature decreases with increase in
surfactant concentration. This could be due to the excess
non-ionic surfactant remaining in the continuous phase.
However, at a concentration of surfactant higher than
5%, the conductivity plots showed a second maximum
(Fig. 10). This was attributed to the presence of La
phase and bicontinuous L3 or D9 phases w30x.
Nano-emulsions were prepared by rapid cooling of
the system to 25 8C. The droplet diameter was deter-
mined using photon correlation spectroscopy (PCS).
The results are summarised in Table 1, which shows the
exact composition of the emulsions, HLB temperature,
z-average radius and polydispersity index.
OyW nano-emulsions with droplet radii in the range
26–66 nm could be obtained at surfactant concentrations
between 4 and 8%. The nano-emulsion droplet size and
313
polydispersity index decreases with increase in surfac-
tant concentration. The decrease in droplet size with
increase in surfactant concentration is due to the increase
in surfactant interfacial area and decrease in interfacial
tension, g. As mentioned above, g reaches a minimum
at the HLB temperature. Therefore, the minimum in
interfacial tension occurs at lower temperature as the
surfactant concentration increases. This temperature
becomes closer to the cooling temperature as the surfac-
tant concentration increases and this results in smaller
droplet sizes.
All nano-emulsions showed an increase in droplet
size with time, as a result of Ostwald ripening. Fig. 11
shows plots of r 3 vs. time for all the nano-emulsions
studied. The slope of the lines gives the rate of Ostwald
ripening v (m3 sy1) and this showed an increase from
2=10y27 to 39.7=10y27 m3 sy1 as the surfactant
concentration is increased from 4 to 8 wt.%. This
increase could be due to a number of factors: (i)
Decrease in droplet size increases the Brownian diffu-
sion and this enhances the rate; (ii) Presence of micelles,
which increases with increase in surfactant concentra-
tion. This has the effect of increasing the solublisation
of the oil into the core of the micelles. This results in
an increase of the flux J of diffusion of oil molecules
from different size droplets. Although the diffusion of
micelles is slower than the diffusion of oil molecules,
the concentration gradient (dCy dX) can be increased
by orders of magnitude as a result of solubilisation. The
overall effect will be an increase in J and this may
enhance Ostwald ripening; (iii) Partition of surfactant
molecules between the oil and aqueous phases. With
higher surfactant concentrations, the molecules with
shorter EO chains (lower HLB number) may preferen-
314 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318

Fig. 10. Conductivity vs. temperature for a 20:80 hexadecane: water emulsions at various C12EO4 concentrations. (Reproduced with permission
from Ref. w29cx).

Table 1 Table 2
Composition, HLB temperature (THLB ), droplet radius r and polydis- Composition, HLB temperature (THLB ), droplet radius r and polydis-
persity index (pol.) for the system water-C12 EO4 -hexadecane at 25 8C persity index (pol.) at 258 for emulsions in the system water-
C12EO4-isohexadecane
Surfactant Water OilyWater THLB(8C) rynm pol.
(wt.%) (wt.%) Surfactant Water OyW THLBy oC rynm pol.
2.0 78.0 20.4y79.6 – 320 1.00 (wt.%) (wt.%)
3.0 77.0 20.6y79.4 57.0 82 0.41
3.5 76.5 20.7y79.3 54.0 69 0.30 2.0 78.0 20.4y79.6 – 97 0.50
4.0 76.0 20.8y79.2 49.0 66 0.17 3.0 77.0 20.6y79.4 51.3 80 0.13
5.0 75.0 21.2y78.9 46.8 48 0.09 4.0 76.0 20.8y79.2 43.0 65 0.06
6.0 74.0 21.3y78.7 45.6 34 0.12 5.0 75.0 21.1y78.9 38.8 43 0.07
7.0 73.0 21.5y78.5 40.9 30 0.07 6.0 74.0 21.3y78.7 36.7 33 0.05
8.0 72.0 21.7y78.3 40.8 26 0.08 7.0 73.0 21.3y78.7 33.4 29 0.06
8.0 72.0 21.7y78.3 32.7 27 0.12

tially accumulate at the OyW interface and this may

result in reduction of the Gibbs elasticity, which in turn As with the hexadecane system, the droplet size and
results in an increase in the Ostwald ripening rate. polydispersity index decreased with increase in surfac-
The results with isohexadecane are summarised in tant concentration. Nano-emulsions with droplet radii of
Table 2. 25–80 nm were obtained at 3–8% surfactant concentra-

Fig. 11. r 3 vs. time at 25 8C for nano-emulsions prepared using the system water-C12 EO4 -hexadecane. (Reproduced with permission from Ref.
w29cx).
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318 315

tion. It should be noted, however, that nano-emulsions

could be produced at lower surfactant concentration
when using isohexadecane, when compared with the
results obtained with hexadecane. This could be attrib-
uted to the higher solubility of the isohexadecane (a
branched hydrocarbon), the lower HLB temperature and
the lower interfacial tension.
The stability of the nano-emulsions prepared using
isohexadecane was assessed by following the droplet
size as a function of time. Plots of r 3 vs. time for four
surfactant concentrations (3, 4, 5 and 6 wt.%) are shown
in Fig. 12. The results show an increase in Ostwald
ripening rate as the surfactant concentration is increased
from 3 to 6% (the rate increased from 4.1=10y27 to
50.7=10y27 m3 sy1). The nano-emulsions prepared
using 7 wt.% surfactant were so unstable that they Fig. 13. r 3 vs. time at 25 8C for nano-emulsions (OyW ratio 20y80)
showed significant creaming after 8 h. However, when with hydrocarbons of various alkyl chain lengths. System water-
C12EO4-hydrocarbon (4 wt.% surfactant). (Reproduced with permis-
the surfactant concentration was increased to 8 wt.%, a
sion from Ref. w29cx).
very stable nano-emulsion could be produced with no
apparent increase in droplet size over several months.
This unexpected stability was attributed to the phase not sufficient to produce the nano-emulsion droplets
behaviour at such surfactant concentrations. The sample with high surface area. Similar results were obtained
containing 8 wt.% surfactant showed birifringence to with isohexadecane. However, nano-emulsions could be
shear when observed under polarised light. It seems that produced using 30y70 OyW ratio (droplet size being 81
the ratio between the phases (WmqLaqO) may play a nm), but with high polydispersity index (0.28). The
key factor in nano-emulsion stability. nano-emulsions showed significant Ostwald ripening.
Attempts were made to prepare nano-emulsions at The effect of changing the alkyl chain length and
higher OyW ratios (hexadecane being the oil phase), branching was investigated using decane, dodecane,
while keeping the surfactant concentration constant at 4 tetradecane, hexadecane and isohexadecane. Plots of r 3
wt.%. When the oil content was increased from 40% to vs. time are shown in Fig. 13 for 20y80 OyW ratio and
50%, the droplet radius increased from 188 nm to 297 surfactant concentration of 4 wt.%. As expected by
nm, respectively. In addition, the polydispersity index reducing the oil solubility from decane to hexadecane,
also increased to 0.95. These systems become so unsta- the rate of Ostwald ripening decreases. The branched
ble that they showed creaming within few hours. This oil isohexadecane also shows higher Ostwald ripening
is not surprising, since the surfactant concentration is rate when compared with hexadecane. A summary of

Fig. 12. r 3 vs. time at 25 8C for the system water-C12 EO4 -isohexadecane at various surfactant concentration; OyW ratio 20y80. (Reproduced with
permission from w29ax).
316 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318

Table 3 tions of a less soluble oil, namely squalene, was added.

HLB temperature (THLB), droplet radius r, Ostwald ripening rate v The results using hexadecane did significant decrease in
and oil solubility for nanao-emulsions prepared using hydrocarbons
with different alkyl chain length stability on addition of 10% squalane. This was thought
to be due to coalescence rather than increase in Ostwald
Oil THLBy8C rynm vØ1027 m3 sy1 C(`) mlØmly1 ripening rate. In some cases, addition of a hydrocarbon
Decane 38.5 59 20.9 710.0 with a long alkyl chain can induce instability as a result
Dodecane 45.5 62 9.3 52.0 of change in the adsorption and conformation of the
Tetradecane 49.5 64 4.0 3.7 surfactant at the OyW interface.
Heaxadecane 49.8 66 2.3 0.3 In contrast to the results obtained with hexadecane,
Isohexadecane 43.0 60 8.0 –
addition of squalene to the OyW nano-emulsion system
based on isohexadecane showed a systematic decrease
the results is shown in Table 3 which also shows the in Ostwald ripening rate as the squalene content was
solubility of the oil C(`). increased. The results are shown in Fig. 14, which
As expected from the Ostwald ripening theory (LSW shows plots of r 3 vs. time for nano-emulsions containing
theory, Eq. (25), the rate of Ostwald ripening decreases varying amounts of squalene. Addition of squalene up
as the oil solubility decreases. Isohexadecan has a rate to 20% based on the oil phase showed a systematic
of Ostwald ripening similar to that of dodecane. reduction in the rate (from 8.0=1027 to 4.1=1027 m3
As discussed before, one would expect that the sy1). It should be noted that when squalene alone was
Ostwald ripening of any given oil should decrease on used as the oil phase, the system was very unstable and
incorporation of a second oil with much lower solubility. it showed creaming within 1 h. This shows that the
To test this hypothesis, nano-emulsions were made using surfactant used is not suitable for emulsification of
hexadecane or isohexadecane to which various propor- squalane.

Fig. 14. r 3 vs. time at 25 8C for the system water-C12EO4-isohexadecane-squalane (20y80 OyW and 4 wt.% surfactant). (Reproduced with
permission from Ref. w29ax).

Fig. 15. r vs. HLB number at two different surfactant concentrations (OyW ratio 20y80). (Reproduced with permission from Ref. w29ax).
 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 16. v vs. HLB number in the systems water-C12EO4-C12 EO6 -
isohexadecane at two surfactant concentrations. (Reproduced with
permission from Ref. w29ax).
The effect of HLB number on nano-emulsion forma-
tion and stability was investigated by using mixtures of
C12EO4 (HLBs9.7) and C12EO4 (HLBs11.7) (Fig.
15). Two surfactant concentrations (4 and 8 wt.%) were
used and the OyW ratio was kept at 20y80. Fig. 15
shows the variation of droplet radius with HLB number.
This figure shows that the droplet radius remain virtually
constant in the HLB range 9.7–11.0, after which there
is a gradual increase in droplet radius with increase in
the HLB number of the surfactant mixture. All nano-
emulsions showed an increase in droplet radius with
time, except for the sample prepared at 8 wt.% surfactant
with an HLB number of 9.7 (100% C12EO4). Fig. 16
shows the variation of Ostwald ripening rate constant v
with HLB number of surfactant. The rate seems to
decrease with increase of surfactant HLB number and
when the latter is )10.5, the rate reaches a low value
(-4=10y27 m3 sy1).
As discussed above, the incorporation of an oil soluble
Fig. 17. r vs. R(OyS) at 25 8C for the system water-C12EO4-hexadecane. Wm smicellar solution or OyW microemulsion, Laslamellar liquid
crystalline phase; Osoil phase. (Reproduced with permission from Ref. w29ax).
317
polymeric surfactant that adsorbs strongly at the OyW
interface, one would expect reduction in the Ostwald
ripening rate. To test this hypothesis, an A-B-A block
copolymer of polyhroxystearic acid (PHS, the A chains)
and polyethylene oxide (PEO, the B chain) PHS-PEO-
PHS (Arlacel P135) was incorporated in the oil phase
at low concentrations (the ratio of surfactant to Arlacel
was varied between 99:1 and 92:8). For the hexadecane
system, the Ostwald ripening rate showed a decrease
with the addition of Arlacel P135 surfactant at ratios
lower than 94:6. Similar results were obtained using
isohexadecane. However, at higher polymeric surfactant
concentrations, the nano-emulsion became unstable.
As mentioned above, the nano-emulsions prepared
using the PIT method are relatively polydisperse and
they generally give higher Ostwald ripening rates when
compared to nano-emulsions prepared using high pres-
sure homogenisation techniques. To test this hypothesis,
several nano-emulsions were prepared using a Micro-
fluidiser (that can apply pressures in the range 5000–
15 000 psi or 350–1000 bar). Using an oil:surfactant
ratio of 4:8 and OyW ratios of 20:80 and 50:50,
emulsions were prepared first using the Ultturrax fol-
lowed by high pressure homogenisation (ranging from
1500 to 15 000 psi). The best results were obtained
using a pressure of 15 000 psi (one cycle of homogen-
isation). The droplet radius was plotted vs. the
oil:surfactant ratio, R(OyS) as shown in Fig. 17.
For comparison, the theoretical radii values calculated
by assuming that all surfactant molecules are at the
interface was calculated using Nakajima equation w1,2x,
B 3Mb E B 3aM E
rsC FRqC Fqd
b
(26)
D ANra G D ANrb G
where Mb is the molecular weight of the surfactant, A
is the area occupied by a single molecule, N is the
Avogadro’s number, ra is the oil density, rb is the
318 T. Tadros et al. / Advances in Colloid and Interface Science 108 – 109 (2004) 303–318
Fig. 18. r 3 vs. time for nano-emulsion systems prepared using the PIT and Microfluidiser. 20:80 OyW and 4 wt.% surfactant. (Reproduced with
permission from Ref. w31x).
density of the surfactant alkyl chain, a is the alkyl chain
weight fraction and d is the thickness of the hydrated
layer of PEO.
In all cases, there is an increase in nano-emulsion
radius with increase in the R(OyS). However, when
using the high pressure homogeniser, the droplet size
can be maintained to values below 100 nm at high
R(OyS) values. With the PIT method, there is a rapid
increase in r with increase in R(OyS) when the latter
exceeds 7.
As expected, the nano-emulsions prepared using high
pressure homogenisation showed a lower Ostwald rip-
ening rate when compared to the systems prepared using
the PIT method. This is illustrated in Fig. 18, which
shows plots of r 3 vs. time for the two systems.
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