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Emulsion Formulation Engineering for the Practitioner

Jean-Louis Salagera; Johnny Bullna; Aldo Pizzinoa; Marianna Rondn-Gonzlezab; Laura Tolosaa
a
Laboratory of Formulations, Interfaces, Rheology and Processes, University of the Andes, Merida,
Venezuela b Total Petrochemicals, Lacq, France

Online publication date: 13 October 2010

To cite this Section Salager, Jean-Louis , Bulln, Johnny , Pizzino, Aldo , Rondn-Gonzlez, Marianna and Tolosa,
Laura(2010) 'Emulsion Formulation Engineering for the Practitioner', Encyclopedia of Surface and Colloid Science, 1: 1, 1
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 Emulsion Formulation Engineering for the Practitioner

Absorbance
Antibiotics
Jean-Louis Salager
Johnny Bulln
Aldo Pizzino
Marianna Rondn-Gonzlez*
Laura Tolosa
Laboratory of Formulations, Interfaces, Rheology and Processes, University of the Andes, Merida, Venezuela
*Now with Total Petrochemicals, Lacq, France

Abstract
The formulation and formation of emulsions imply a very large number of variables; hence, attaining the
sought properties is usually long and tedious because of the large number of experiments to be carried out.
The current state-of-the-art of physicochemical formulation may be thoroughly used to considerably reduce
the number of required experiments and to indicate to the formulator the relation between the kind of proper-
ties to expect and the generalized formulation expression. After these first-order formulation factors are dealt
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with, several second-order factors are shown to be available to adjust the emulsion properties upward or
downward in order to satisfy the specifications, either directly or by means of a multistep process.

INTRODUCTION can change considerably) and in a lesser measure on the

Emulsions are systems in which two immiscible liquids
(referred to as oil and water) are temporarily mixed in
some homogeneous way at some microscale to macroscale
to produce the dispersion of one phase in the other. In gen-
eral, it is called an emulsion only if the coalescence of the
drops is inhibited during some time by some process in-
volving surfactants or particles. This entry only deals with
surfactant-stabilized emulsions.
The emulsion desirable properties (type, drop size, and
distribution, rheology, and persistence, often called stabil-
ity) depend on the application. In most cases, the formula-
tor challenge is to attain the sought-after product through
1) selecting the right substances (surfactant, oil, aqueous
phase) and their right proportions, then 2) mixing them
and making an emulsion through a process which could
be quite complex. The optimization of the formulation and
emulsification procedure may be made relatively simpler if
the different aspects are segregated and treated separately,
as shown in the following.
FORMULATION CONCEPTS APPLIED
TO EMULSIONS
Early Concepts: HLB, PIT, Winsors R
A surfactant has a dual affinity for the aqueous (polar) and
oil (nonpolar) phases, and the emulsion properties depend
on that, i.e., strongly on the surfactant nature (because it
Encyclopedia of Surface and Colloid Science DOI: 10.1081/E-ESCS-120045970
Copyright 2010 by Taylor & Francis. All rights reserved.
oil and aqueous phase nature, and other variable such as
temperature. The characteristics of the components, par-
ticularly, the surfactant, have been represented by various
parameters introduced over the years.
About 50 years ago, the hydrophiliclipophilic balance
(HLB) number[1] was introduced as an empirical estima-
tion of the dual tendency of the surfactant, essentially re-
lated to the proportions of its hydrophilic and lipophilic
parts and, to some extent, to the oil type. This approach
is rather inaccurate, but it is extremely simple and is still
useful as a first approximation and to compare similar
cases. However, it may be completely erroneous in some
instances like comparing cases with different surfactant or
oil families. Davies[2] intent to separate the HLB number
into group contributions made it easier to use in practice,
but it did not really improve the accuracy, which is some-
times worse than 2 units.
Winsors R ratio approach is based on the interac-
tions of the surfactant molecule adsorbed at interface with
neighboring oil and water molecules (labeled Aco and
Acw, respectively, in Fig. 1).[3] It allows to carry out some
qualitative reasoning and to relate the R ratio of interac-
tions at interface with the phase behavior at equilibrium
as indicated in Fig. 1. There are only four different cases,
hence much less than the number of actual variables in
practice. R<1 and R>1 correspond to the so-called Winsor
I and Winsor II biphasic systems, respectively, which ex-
hibit an aqueous and an oil phase microemulsion in equi-
librium with an excess oil and aqueous phase, respectively.
R=1 is associated with the three-phase behavior so-called


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Absorbance
Antibiotics
Fig. 1 Winsors R ratio and its relation with the phase behavior
of surfactantoilwater systems.
Winsor III, in which a bicontinuous microemulsion, con-
taining essentially all the surfactant, is in equilibrium with
two (oil and aqueous) excess phases. [4] If the amount of
surfactant is high enough, the microemulsion embodies the
whole system volume and a so-called Winsor IV single-
phase behavior is observed.
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Hence, when a variable like the aqueous phase salinity
or the length of surfactant tail changes (in some monoto-
nous way), a so-called formulation scan results in a contin-
uous change in the ratio of interactions. When R changes
from R<1 to R>1, a phase behavior transition takes place
and is noted WIWIIIWII or vice versa. Fig. 2 illus-
trates the evolution of the systems during a phase behavior
transition versus some formulation changes.[4]
As far as emulsions are concerned, the Winsor R ra-
tio allows to accurately interpret rules of thumb such as
Bancroft rule and Langmuir wedge theory. However, the
R ratio cannot be translated into numbers to be handled
quantitatively.
Shinodas phase inversion temperature (PIT)[5] ap-
proach is based on an experimentally attainable informa-
tion, i.e., the temperature at which the emulsion made with
a polyethoxylated surfactant inverts from oil/water (O/W)
to water/oil (W/O). This temperature essentially corre-
sponds to the swapping of the dominant affinity of the sur-
factant from water to oil phase, which is essentially related
to the phase behavior. In other words, the PIT corresponds
to Winsor R=1 case, with R<1 at temperature below the
PIT and R>1 above it. Because it is an experimental ap-
proach, the PIT takes into account all variables, which is
quite an improvement with respect to earlier concepts like
the HLB number. However, there are serious limitations to
its general use, e.g., the liquid water temperature range and
its applicability mostly limited to polyethoxylated surfac-
tants whose hydrophilic group is dehydrated as tempera-
ture increases.
Generalized Formulation Expression
In the 1970s, the enhanced oil recovery research promoted
many experimental studies, which may be said to have
numerically quantified Winsors R concept in terms of all
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Emulsion Formulation Engineering for the Practitioner
formulation variables for many systems, and thus extended
the PIT approach.
The balance of affinity was written as a formula that
is a generalized expression of the surfactant affinity dif-
ference (SAD), i.e., the variation of chemical potential
of a surfactant molecule when it transfers from water to
oil (D).[6] This expression was related to thermodynamic
concepts, such as the surfactant partition coefficient be-
tween excess phases in three-phase systems, which can be
experimentally measured. It is generally expressed in a di-
mensionless way with respect to a reference in a situation
in which the surfactant exhibits exactly the same standard
chemical potential in the oil and aqueous phases, at ambient
temperature and pressure. The generalized formulation
expression is a linear summation of energetic contribu-
tions that involves all variables describing the nature of
the components as well as temperature and pressure. In
the simplest cases, the expression is similar to the correla-
tion for three-phase behavior and minimum tension,[7,8]
and may be written as the dimensionless hydrophilic
lipophilic deviation from the optimum formulation for
three-phase behavior, which is taken as the reference state
[9]. This deviation, so called HLD, may be expressed as
follows (see Eqs. 1 and 2)
HLD=(SAD-SADref)/RT=lnS-kACN-f(A)+s-aTDT
(1)
for ionic surfactant
HLD=(SAD-SADref)/RT=bS-kACN-f(A)+b+cTDT
(2)
for nonionic surfactant
where S is the salinity of the aqueous phase in wt.% NaCl;
ACN is the alkane carbon number, i.e., the number of carbon
atoms in an n-alkane oil; s or b are the ionic and nonionic
characteristic parameters of the surfactant. These param-
eters increase linearly with the surfactant tail length[10]
and decrease with the number of ethylene oxide groups
for polyethoxylated nonionics.[8] f(A) is a function that
renders both the type (through mA) and the concentra-
tion (CA) of the (alcohol) cosurfactant in f(A)=mACA. DT
is the temperature difference with respect to a reference,
usually ambient temperature. These expressions apply to
simple surfactantoilbrine systems but may be extended
Fig. 2 Phase behavior transition along some formulation changes.
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 Emulsion Formulation Engineering for the Practitioner 
to different oils and aqueous phase electrolytes, change in
pH, mixtures of surfactants, and oils as in most real world
cases.[1118]
In the past 20 years, the characteristic parameters for
surfactants, oil and water phases, as well as the tempera-
ture and pressure effects were determined in a large num-
ber of different systems. They may be predicted in many
instances, in practice, and may also be experimentally de-
termined when no estimate is available.[19]
Mixing rules for surfactants and oils were found to be
simple (e.g., linear), in some cases, and depart from ideal
behavior in others. The non-ideality of the mixing rules
was also quantified and interpreted through the partition-
ing and segregation of species, hence showing that mix-
tures could be either a problem or a solution.[19,20]
The generality of HLD formulation expression results in
a direct relationship with the phase behavior, i.e., HLD<0
and HLD>0 correspond to R<1 and Winsor I and R>1 and
Winsor II, respectively. HLD=0 is associated with Winsor
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III three-phase behavior transition.[9] This corresponds to
R=1, and it is an extremely important circumstance because
it is a reference and a boundary, as far as the properties of
equilibrated and non-equilibrated systems are concerned,
independent of the actual variable values such as salinity,
oil nature, temperature, etc.
HLD determines the physicochemical balance (if
HLD=0) or unbalance (if HLD 0), whatever the actual
values of the formulation variables. This is noteworthy
because it means that two systems may be considered
to be in equivalent physicochemical states if they have
the same HLD value, even though they do not exhibit
necessarily the same salinity, same surfactant type, same
temperature, etc. Actually, none of the variables may
coincide, although the two systems are in similar physi-
cochemical states and may be compared as far as perfor-
mance is concerned.
QUALITATIVE GENERAL PHENOMENOLOGY:
EMULSION PROPERTIES VERSUS
FORMULATION AND COMPOSITION
(FIRST-ORDER FACTORS)
Early systematic studies to relate the formulation with the
emulsion properties[21] indicated that reproducible results
were attained when the system were equilibrated prior to
emulsification, so that no mass transfer was taking place
at the time of interfacial area generation during emulsifi-
cation. A few studies with non-equilibrated systems indi-
cated that the time-scale of equilibration could change the
results, with a shorter pseudo-equilibration time-scale, as
HLD is close to zero.[22] When the systems are not pre-
equilibrated prior to emulsification, a reproducible result
is usually attained when the surfactant and co-surfactant
species are introduced in the phase where they will parti-
tion at equilibrium.
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Emulsion Properties
Absorbance
Antibiotics
The type of emulsion is essentially related to the natural inter-
facial curvature that results in O/W or W/O simple morphol-
ogy and is related to formulation according to the century old
Bancrofts rule. Drop size and distribution depend on physi-
cal properties like the interfacial tension and surfactant ad-
sorption.[23] Emulsions are not stable systems, and sooner or
later, they will separate into their phases. However, they may
be quite persistent, and the expression kinetics stability (or
often just stability) is used to describe their lifetime scale,
which is frequently expressed as the time required for some
fraction, e.g., 50% or 75%, of one of the phases, usually the
originally dispersed one, to separate.
Rheological properties of emulsions are essentially
dues to physical factors and effects like the external phase
viscosity, the internal phase volume, drop interactions,
and eventual deformation under shear.[21] Emulsions with
drop in the 150 m range with internal phase content
over 60% exhibits non-Newtonian behavior of the shear-
thinning type and are often viscoelastic when they contain
a large proportion of submicron droplets. Monodispersed
distributions tend to exhibit a high viscosity, while very
polydispersed, particularly bimodal distributions, re-
sult in a reduced viscosity which is quite useful for some
applications.[24]
Turbidity or opacity have to do with the drop proportion,
drop size, and refractive indexes of the liquid, as well as the
radiation wavelength.[21] The higher reflectivity with day-
light takes place for a drop size around the micrometer.[25]
Emulsion Properties versus Generalized
Formulation (Unidimensional Scan)
The variation of formulation variables for systems con-
taining similar amounts (i.e., from 30% to 70%) of oil and
water results in systematic patterns when the formulation
is expressed as HLD. These studies were carried out more
than 20 years ago according to the so-called unidimen-
sional formulation scan method, in which a single formu-
lation variable is monotonously changed so that a phase
behavior transition takes place in the WIWIIIWII di-
rection or vice versa as in Fig. 2.[8]
The general qualitative property trends along a unidi-
mensional formulation scan are essentially determined
by what happens at the formulation that corresponds to
HLD=0 in the scan. Whatever the formulation variable
used to change the balance of affinity, in particular, the
temperature for polyethoxylated nonionics, the surfactant
oil-water equilibrated system exhibits at HLD=0 the fol-
lowing two characteristics (see Fig. 3a graph):
1. a minimum of interfacial tension, sometimes ultra
low, which is why it was originally referred to as
optimum formulation by researchers on enhanced
oil recovery.[2628]
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Absorbance
Antibiotics
Fig. 3 a) Interfacial tension, phase behavior, and emulsion morphology; b) stability; c) drop size 9; d) viscosity and light scattering
(reflectance) versus generalized formulation HLD.
2. a three-phase behavior (bicontinuous microemul-
sion in equilibrium with both oil and aqueous excess
phases) and eventually a single-phase behavior if the
surfactant concentration is high enough.[29]
As far as the emulsified system is concerned, HLD=0 is
associated with a crucial feature in each of the five proper-
ties as shown in Fig. 3 as follows.
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First is a change in emulsion type from O/W to W/O
or vice versa (Fig. 3a), which is referred to as morphology
inversion. This is generally determined by a drastic change
in conductivity as well as other properties like viscosity
and optical reflectance, whose variations might be more
difficult to interpret.[2934]
Second, a very deep minimum in the emulsion stability
exactly at HLD=0 (Fig. 3b).[29,30,35,36] The actual value of
the phase separation time at HLD=0 is similar to the case
of a system containing equal oil and water phases without
surfactant.[37] This clearly shows that at optimum formula-
tion the surfactant is trapped in the microemulsion and that
it is not available to adsorb at the interface formed during
the stirring process. Other more complex explanations have
been proposed.[38,39] When the formulation departs consid-
erably from HLD=0, then it may be said that the surfactant
is either too hydrophilic or too lipophilic. In such case, it is
not likely to adsorb at interface but rather to partition into
one of the bulk phases, and thus it does not protect the emul-
sion drops against coalescence. As a consequence, the emul-
sion stability curve versus formulation typically exhibits two
maxima first noted a long time ago,[40] one on the negative
HLD side and one on the positive side, typically somewhere
in the HLD=24 range in absolute value (see Fig. 3.b). The
exact position of the maxima and the extension of the high-
stability range essentially depend on second-order factors to
be discussed later.
Third, the drop size attained along a formulation scan,
when a constant emulsification procedure (i.e., same stirring
equipment, energy, and duration) is applied, results from the
competition of two opposite phenomena: the drop breakup,
which depends on the tension and is quicker and easier close
to HLD=0 formulation, and the coalescence of formed drops
before the surfactant can adsorb efficiently, which is much
faster at HLD=0 formulation since the surfactant does not
migrate to the created interface. The two opposite effects
generate a minimum of drop size at some distance of HLD=0
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Emulsion Formulation Engineering for the Practitioner
and on both sides of it (see Fig. 3c plot), where the tension
is low enough to result in small droplets, which are not too
likely to coalesce instantly.[41] The minima in drop size are
much closer to HLD=0 than the stability maxima, typically
at about 1 HLD unit or less. However, their occurrence and
characteristics depend on second-order factors susceptible
to alter the tension and stability curves, as well as on the stir-
ring energy.[42] The increasing drop-size tendency, indicated
in Fig. 3c region to be close to HLD=0, is the consequence of
the very low stability that quickly increases coalesce and in-
creases the size if it could be measured. However, this could
not result in larger droplets available, in practice, because
the emulsion vanishes in seconds.
Fourth, the viscosity of an emulsion submitted to shear
is in local minimum at HLD=0 formulation, where the ten-
sion is ultra low and the drops are easy to elongate in the
direction of flow (Fig. 3d, lower plot). The effect is similar
in laminar flow through porous media and in turbulent flow
cases. Since there are two drop-size minima on both sides
of HLD=0, hence, there are often two concomitant viscosity
maxima (see Fig. 3d, lower plot) because of the general as-
sociation between smaller drops and higher viscosity.[43]
Fifth, optical effects are associated with the morphol-
ogy as well as some physical properties such as refractive
index, light wavelength, and drop proportion and size.[21]
The transmittance obscuration and diffusion, particularly,
the backscattering, increase with the drop proportion, but
does not vary monotonously with the size. A maximum
backscattering (reflectance) is attained for droplets about
0.51 m in size.[25] As a consequence, and for the case of
drops larger than 1 m, the variation of size associated with
the formulation, i.e., the presence of a drop-size minima on
both sides of HLD=0 induces a complex variation of the
backscattering (Fig. 3d, upper plot).[44]
Combined Effects of Formulation and
Composition (FC Map)
Up to now, only the effect of the nature of the components,
temperature, and pressure, i.e., intensive formulation vari-
ables, have been considered. Since the chemical potential
driving force also depends on concentrations, extensive
variables, labeled here as composition variables, such as
surfactant concentration and water-to-oil ratio (WOR),
should be taken into account somehow.
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 Emulsion Formulation Engineering for the Practitioner 
Fig. 4 Generalized FC maps with typical emulsion properties: a) type; b) stability; c) drop size; and d) viscosity.
The previous results are quite general and valid when-
ever the WOR is close to unity, say from 30% to 70% of
one of the phases. When one of the phase proportions is
too low, e.g., less than 20%, it turns out that it may be dif-
ficult to disperse the high-volume phase into the smaller-
volume phase, and the phase in higher volume tends to be
the external phase.
The way the phases are mixed becomes crucial to fa-
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vor one or the other type of dispersion independently of
the formulation,[45] and the global or local WOR value is
the key to establish the emulsion morphology in some pro-
cesses and with particular devices.[46]
When the formulation and composition effects are in
conflict, e.g., the formulation would favor an O/W emul-
sion but there is only 10% of W which cannot be made
the external phase, then double or multiple emulsions are
formed with droplets in drops. The droplets in drops in-
ner emulsion is usually the one favored by the formula-
tion, while the outer emulsion, i.e., drops in continuous
phase, is the one imposed by the W/O composition. The
resulting multiple emulsion morphologies are indicated as
w/O/W and o/W/O in Fig. 4a.
These results may be summed up in a bidimensional
formulationcomposition (FC) map, first introduced with
the PIT,[47] then systematized,[48] in which the formulation
refers to any variable modification able to change HLD
or any combination of them, and the composition to the
water/oil proportions, generally the water fraction as in Fig 4
plots. Six regions are found in this map (Fig. 4a), depend-
ing on the formulation and composition.[48,49] A is in the
center part, where oil and water proportions are similar,
and B and C are located on the left and right, respectively,
where there is much more oil than water in the former and
more water than oil in the latter. In the upper and lower
parts, HLD is positive and negative and the letter indi-
cating the region is associated with (+) and () sign, re-
spectively. The so-called standard inversion line is the
frontier that separates the two regions with different
kinds of morphology, i.e., water external or oil external
emulsions. In the central A region, the morphology only
depends on the formulation, i.e., on the HLD sign, and the
emulsions are referred to as normal ones because their
interface curvature corresponds to the formulation require-
ment. In the B region the external phase is oil, whatever
the formulation, and there is a simple W/O emulsion in
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Absorbance
Antibiotics
the B+ region (as in A+), where HLD>0. In the so-called
abnormal B- region, a multiple emulsion of the o/W/O
type is often found, where o represent oil droplets in-
side W drops which are dispersed in the O oil external
phase. In the C region where there is a large excess of wa-
ter, the emulsions are water external, with an O/W normal
morphology in the C- zone, and an abnormal one of the
multiple w/O/W type in the C+ zone.
This mapping is quite general and qualitatively the
same whatever the formulation variable used to produce
the scan.[48,5056] The central horizontal branch of the in-
version frontier closely follows the HLD=0 line in the
formulation scale and the three-phase behavior region in
the map. Departure from a completely horizontal central
segment is due to phenomena that alter the actual interfa-
cial formulation when the WOR changes such as the parti-
tioning of the species present in a surfactant mixture,[57,58]
which is out of the present scope. In most practical cases,
the inversion line crosses the three-phase behavior zone as
indicated in Fig. 4a plot, i.e., slightly slanted even when an
isomerically pure surfactant is used.[59]
The lateral almost vertical branches of the standard in-
version frontier may be shifted with the change of some
other variables. An increase in oil and aqueous phase vis-
cosities tend to shift the A+/C+ and the B/A frontiers to
the left and right sides, respectively.[46,48,60] An increase in
surfactant concentration tends to widen the A zone, i.e., to
shift both vertical branches outward.[61] Conversely, the A
region tends to shrink as the stirring rate used to emulsify the
systems is increased.[62] Since the bidimensional FC map
has always the same aspect, with the width of the A region
as the only change, this later may be associated to any other
variable effect to produce a very general phenomenology
which accounts for the effect of score of variables in a three-
dimensional space, which is described elsewhere.[63,64]
The previously discussed relationship between formula-
tion and emulsion properties is valid in the central A region
and may be extended to the normal C and B+ regions, pro-
vided that the property changes due to a variation in WOR
are taken into account, for instance, an increase in viscos-
ity with an internal phase content rise. In the abnormal
regions, the presence of multiple emulsions implies that the
same surfactant has to stabilize two opposite curvatures,
which is not possible since the curvature is associated with
HLD.[65,66] Hence, in such regions, the most outer emulsion
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is unstable (because of the unfavorable formulation),
Absorbance
whereas the most inner one is as stable as the one with a
Antibiotics
more balanced WOR in the corresponding A region.
The change in properties with the WOR has a conse-
quence on the drop-size map, because in the high-viscosity
normal region close to the vertical branch of the inversion
line, a particularly efficient emulsification takes place at
low-velocity stirring, with a pseudo-plastic or viscoelastic
behavior able to concentrate the shear on the droplets.[6769]
This very favorable situation is not only a flow mechanics
curiosity but also a way to make small drop emulsions with
high-viscosity oils, sometimes at a very large scale.[70]
The four maps displayed in Fig. 4 are very general[49]
and qualitatively express the variations of the emulsion
properties according to the first-order effects of HLD gen-
eralized formulation and WOR composition. These maps
extend the results shown in Fig. 3 to the regions containing
a large excess of one of the phases. The position of the
horizontal branch in the central part is essentially matching
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the HLD=0 line when the proper formulation scale is used,
i.e., when an eventual correction to substitute the overall
formulation by the interfacial one is carried out.[58] As
mentioned previously, the lateral vertical branches of the
standard inversion line may be shifted outward or inward
by a change in any of the other variables, e.g., the surfac-
tant concentration, emulsification energy, or phase viscos-
ity ratio. Since each A/B/C + and - regions is associated
with specific emulsion characteristics as indicated in Fig. 4,
e.g., high stability or small drop size, once the inversion
frontier is known, it is quite easy to know where some
emulsion property is likely to happen. In Fig 4c, there is no
indication of large drop size close to HLD=0 since this is
not really a general size property because of very unstable
emulsions. In practice, the change in a variable susceptible
to laterally shift the vertical branches is the best way to in-
crease or limit the area where some property occurs. There
is another way to shift the vertical branches of the inver-
sion line, which is the use of a dynamic process and the
associated memory features to be discussed next.
Dynamic Emulsion Inversion
The emulsion inversion frontier which has been discussed
in the previous section is the limit between the regions
where one morphology or another is attained upon stirring
a pre-equilibrated system. This is the best condition to cor-
relate the formulation with resulting properties. However,
sometimes, the stirred system is not at equilibrium and a
mass transfer could take place during the emulsification
or after it as time elapses. This is the case in complex phe-
nomena that take place in the so-called apparent equilibra-
tion process and spontaneous emulsification,[22,7174] which
are out of the scope of this entry.
In other instances, the formulation is continuously mod-
ified by changing an appropriate variable, particularly, the
temperature. In such case, the system representative point
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Emulsion Formulation Engineering for the Practitioner
on the bidimensional map is moving vertically upward or
downward, as indicated in Fig. 5 HLDWOR map, and at
some time, it can hit and cross the horizontal branch of the
standard inversion frontier. This event is called a dynamic
inversion process, since it is due to a variation of condi-
tions with time.[60]
When such a change in formulation of the emulsion
under constant stirring produces an emulsion morphology
inversion, it is called a transitional inversion. This label
comes from the fact that in such change the underlying phe-
nomenon is a WIWIIIWII phase-behavior transition
(or vice versa) in which the microemulsion middle phase
present at HLD=0 becomes the water or the oil phase in the
two-phase systems found in the WI and WII extremes of
the scan in Fig. 2.[32,60,7578]
As a consequence, this is not really an emulsion inversion
in which the curvature of the interface swaps, but rather the
disappearance of one of the excess phase by solubilization
in the microemulsion surfactant-rich phase, which always
constitutes the external phase of the emulsion.[78]
Another way to produce a dynamic inversion is to
change the WOR of the emulsion along the arrows in Fig. 6,
while keeping it stirred, until its morphology swaps.[78,79]
This second type is referred to as catastrophic inversion
because it exhibits some features such as hysteresis and
irreversibility, which may be modeled by catastrophe the-
ory.[80, 81] In this case, the curvature of the interface is able
to suddenly reverse when the change is from a simple O/W
to a simple W/O morphology or vice versa.[78,79]
Such a change takes place usually with some delay in
both directions, thus generating hysteresis zones (located
around the standard inversion vertical branches) in which
the emulsion type depends on the previous history.[78]
In some cases, the inversion does not take place directly
from one to the other simple morphologies (O/W or W/O)
but undergoes through a multiple emulsion o/W/O or w/
O/W.[8284] A multiple emulsion is actually a structure in
which both morphologies coexist; hence, the change may
Fig. 5 Phase behavior at equilibrium and emulsion transitional
inversion process induced by a change in formulation or
temperature in a nonionic system.
11/06/2010 05:10AM
 Emulsion Formulation Engineering for the Practitioner 
Fig. 6 Catastrophic inversion process induced by a change
in WOR.
be considered as being not sudden but progressive with one
of the emulsions prevailing in one direction while the other
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in the opposite direction. When the direction of change is
from normal to abnormal morphology, the occurrence of a
multiple emulsion is not likely to happen. On the contrary,
it is almost always the case when the change is from abnor-
mal to normal morphology. In such a process with an inter-
mediate multiple morphology, the inner normal emulsion,
i.e., the droplets in drops, tends to prevail by the formation
of more and more droplets which do not coalesce but swell
the external drops and make them enter in contact and co-
alesce. These processes are difficult to control because the
actual mechanism and results are quite dependent on the
operational conditions.[82,8588]
By the way, a long-time stirring of an abnormal emulsion
produce the same effect, because the inner emulsion is gen-
erally much more stable than the outer one and thus tend to
prevail when the system is submitted to perturbations.[86, 89,90]
Emulsion inversion processes may be even more complex
in the presence of mixtures of surfactants or surfactants and
cosurfactants that are able to migrate as time elapses and
produce changes in interfacial formulation. This is the case
of the so-called emulsification along a dilution path, e.g., by
the addition of water to an oil phase containing a high con-
centration of surfactant(s) and cosurfactant(s).[91,92] These
transfers result in a spontaneous emulsification,[73,74,93]
a generic label to describe several different out-of-equilib-
rium phenomena, used in practice because they lead to very
small droplet emulsions at a very low expense of energy,
although they are not very well understood yet.
Final Comment on First-Order Factors
Before moving to the second category of factors, it is worth
remarking that the trends, indicated as the effect of a for-
mulation unidimensional scan or of an FC bidimensional
scan, are general in a qualitative way. For example, they
indicate that there is a zone with a specific property, e.g.,
maximum stability on both sides of HLD=0, as indicated
120045970  Manila Typesetting Company
in Fig. 7, left plot. However, the actual exact location (in
Absorbance
formulation terms) and the actual value of the property
Antibiotics
(i.e., the persistence time), whose position could change as
indicated by arrows in Fig. 7, depend on other issues which
will next be referred to as second-order factors.
Nevertheless, it is worth remarking that a clear discrim-
ination of the first-order factors as the formulator priority
and the use of a generalized formulation framework is de-
terminant, in practice, to decide where to look for a solu-
tion, and how to make comparisons and optimize a process
by modifying second-order factors. The paramount impor-
tance of such an approach is illustrated in Fig. 8, left plot,
which shows the stability of two different emulsions as a
function of salinity. The formulator first thinking may be
to carry out the comparison at the same salinity so that the
conditions are equal or similar. If so, if the fixed salinity is
taken as indicated by dashed lines, for instance, it is clear
that depending on the salinity, emulsion (A) is going to ap-
pear to be more or less stable than emulsion (B), and this
is a wrong conclusion. On the contrary, if the two stability
curves are represented versus a HLD scale (graduated in
lnS as in Fig. 8, right plot), it is clear that emulsion A is
more stable than emulsion B in the regions where it mat-
ters, i.e., at some distance from HLD=0 where both are
stable. This representation also allows making compari-
sons and further discussing some precise differences. For
instance, it may be said that both kinds of emulsions are
more stable in the high HLD case, but that the range of
stability of the B case is quite wider for the O/W type than
for the O/W one, particularly, farther from HLD=0, i.e., at
low salinity.
QUANTITATIVE TRENDS AND FEATURES
EMULSION PROPERTY ADJUSTMENT
(SECOND-ORDER FACTORS)
On top of the general phenomenology dealing with first-
order factors, there are some additional effects that would
alter some phenomena and mechanisms and would produce
a quantitative change in some property in one direction or
the other. Sometimes two opposite effects would compete,
hence with the attainment of a minimum or maximum in
some property.
Fig. 7 General trend on a qualitative basis (left) and specific
quantitative changes in stability (center and right) according to
particular second-order effects.
11/06/2010 05:10AM
 
Absorbance
Antibiotics
Fig. 8 Emulsion stability comparison according to a formulation
variable and to the generalized formulation HLD.
Basic Phenomena Related to
Emulsion Properties
The emulsion persistence is related to different phenom-
ena which are influencing the rate of coalescence of drops
and depend on the presence of adsorbed surfactant mole-
cules at interface. This adsorption inhibits the coalescence
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in different ways through various mechanisms, namely:
1) the physical strength and elastic behavior of the interfa-
cial film with respect to dropdrop collision; 2) the repul-
sion forces that prevent the drops to approach under the
effect of attractive forces; 3) the fluid properties of the in-
terdrop film of continuous phase, particularly, its rheology;
4) some geometric considerations such as the drop size and
distribution, and the internal phase ratio; 5) the tempera-
ture, which has an effect on a large number of phenomena
and, on top of it, may have a strong formulation influence
one way or the other depending on the type of surfactant.
These phenomena are related to intensive properties that
mostly depend on the nature of the components, not on
the size of the system or the concentrations. Hence they
may be altered by changing the conditions or adding some
products as discussed in the next section.
On the other side there are phenomena which depends
on extensive properties like the WOR or the species con-
centrations, particularly, of surfactant, with a direct effect
on the emulsion morphology and drop size, and hence on
other properties.
Surfactant concentration affects properties in different
ways. Below the critical micelle concentration (CMC),
an increase in surfactant concentration decreases the in-
terfacial tension and thus tends to decrease the drop size.
Above the CMC, the equilibrium interfacial tension does
not change, but the increase in surfactant concentration
could rise the adsorption rate of surfactant molecules from
the bulk phase to the interface, thus reducing the dynamic
tension and consequently the drop size, and finally increas-
ing the emulsion stability. In general, an increase of surfac-
tant concentration decreases rapidly the drop size of the
emulsion until a minimal size is reached, which becomes
independent of the surfactant concentration.[94]
The electrolyte concentration is also an extensive vari-
able to be taken into account. It will be seen later that an
increase in salinity tends to reduce the repulsion of head
120045970  Manila Typesetting Company
Emulsion Formulation Engineering for the Practitioner
group between adjacent ionic surfactant molecules, e.g.,
dodecyl sulfate, hence it will allow for more adsorption
density, and a more compact interfacial film tends to in-
crease the stability. However, it will also decrease the
electrical repulsion between approaching drops, with the
opposite effect.
Finally the Laplaces law about the difference in pres-
sure between the sides of a curved interface results in the
so-called Oswald ripening decay, particularly, in very
small droplet emulsions. This effect is an osmotic drive
transfer of matter between a small drop and a neighboring
large one, because of the gradient of internal pressure.[95]
It is particularly significant with nanoemulsions, since the
Laplace pressure is inversely proportional to the drop size.
Of course the first way to reduce this effect is to have an
almost monodispersed drop-size distribution, but this is of
course associated to a higher viscosity. Since the transfer
takes place through a film of external phase located be-
tween neighboring drops, a low solubility of the internal
phase in the external one would reduce the effect. A clas-
sical trick to offset the osmotic pressure transfer is to use
a mixture of substances in the internal phase, one which is
much less soluble in the external phase that the other. As a
consequence of a difference in transfer velocity, a gradient
in the concentration of one specie is quickly established
and results in a counter effect that cancels out the osmotic
pressure driving force.[96]
Effects of Second-Order Factors Which May Be
Manipulated by the Formulator to Adjust the
Emulsion Properties
Surfactant film at interface
The presence of an adsorbed surfactant film at interface
results in some barrier that prevents the approaching drops
to coalesce instantly as it happens when two pure liquids
are used. To be effective in stabilizing the emulsion, the
surfactant layer should exhibit a good coverage of the
surface, forming a rigid elastic layer that resists collision
and stretching. The interfacial coverage depends on the
equilibrium concentration in the bulk, but in all cases it is
attained at or below the CMC. Since the surfactant con-
centration should be larger than CMC, lowering the CMC
by changing the surfactant or altering the formulation
(e.g., by increasing salinity for ionics or temperature for
nonionics) may help. A better condensed adsorbed layer
may be attained by increasing the density, e.g., with linear
tails instead of branched ones, with no or less electrical
charge between adjacent hydrophilic heads. A higher den-
sity is also attained by selecting a surfactant with strong
lateral interactions, either between the head or tail groups,
eventually with interaction through overlapping to induce
elasticity and to boost the Gibbs-Marangoni effect. If the
surfactant is able to produce a mesophase, this is also a way
to generate some wrapping around the drops and protect
11/06/2010 05:10AM
 Emulsion Formulation Engineering for the Practitioner 
them against collision effectiveness. These molecular ar-
rangements may be extremely well organized like in liquid
crystals, or more or less isotropic as in asphaltene gel pre-
cipitation close to the interface.
Generally, an increase in the surfactant molecular size
on both sides of the interface results in a thicker interfacial
layer, which also results in a gain in the resistance of the
film through a repulsion of some kind. Larger surfactants,
surfactant mixtures with hydrophilic and lipophilic com-
ponents, polyethoxylated surfactant mixture of oligomers,
lipophilic linker additives and extended surfactants are all
candidates to contribute this way.[97,98]
The size of the surfactant influences also the emulsion
properties. A low molecular weight surfactant migrates
quickly to the interface, allowing a rapid stabilization of
interfaces during the emulsification process. However,
short surfactant molecules adsorb in a low-energy way at
interface, producing less stable emulsions than long chains
and polymeric surfactants. It was reported that in some
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cases the droplet size of an O/W emulsion is inversely re-
lated to the length of the alkyl tail of the surfactant.[99]
When a mixture of surfactants is used, a change in sur-
factant concentration can alter the formulation at interface
because of the partitioning of different species, and this
could directly influence the drop size, stability, and vis-
cosity of emulsions. Similarly, a change in purity, from
isomerically pure to commercial mixture could result in
a change of the PIT with surfactant concentration.[100,101]
Amphiphilic polymers could have a complementary role
when they are used combined with surfactants. Short chain
surfactants adsorb rapidly at the interface during emulsifi-
cation, hence avoiding instant coalescence and favoring a
small drop size. On the other hand, polymers adsorb later
providing a long-term stability. In some cases, some syn-
ergy occurs, and surfactants and polymers which do not
stabilize emulsion on their own, could do it if they are used
together.[102]
The presence of very short amphiphiles at interface like
alcohols, tends to pull apart surfactant molecules and tend
to reduce their adsorption density, even at relatively high
concentration in the bulk. As a consequence, the surfactant
stabilizing effects are weakened. For instance, the addi-
tion of a few percents of sec-butanol, an alcohol which has
some intermediate hydrophiliclipophilic tendency hence
no significant formulation shift, produces a considerable
decrease in stability of any kind of emulsion. It is often
used as an additive to speed up stability experimentation,
to test some formulation effects at a much shorter time
scale, i.e., a few days instead of a few months.
Repulsions
The approach of neighboring drops is driven by different
kinds of mechanisms like gravity settling or other body
forces (electrical field) as well as Brownian motion. Then,
when the drops are at some distance the issue is a matter of
120045970  Manila Typesetting Company
balance between the attractive Van der Waals forces which
Absorbance
depends on the drop nature and size, and the repulsive ones
Antibiotics
which depend on the adsorbed surfactant at their surface.
The increase in repulsive force is a direct and very ef-
ficient way to boost the emulsion stability, in particular, if
it prevents the drops to be close enough for the interdrop
film to break.
This may be produced by an electrostatic repulsion due
to the adsorption of ions at or close to the interface, e.g.,
the use of ionic surfactants. This result in a diffuse layer
more or less extended, which produces a repulsion at a
large or a short distance whenever in the absence or in the
presence of electrolyte. This has an important effect when
the continuous phase is water, i.e., for the stabilization of
O/W emulsions.
A stronger surface charge and a lower electrolyte
concentration tend to increase stability. Things are not
straightforward anyway, because in presence of an ionic
surfactant the adsorbed molecules repeal each other and
the interface density is not that good. A small concentra-
tion of electrolyte produces a screen between the head
groups and the adsorbed density tends to increase, hence
resulting in a higher charge density at interface. But, if a
high electrolyte concentration is added, then the electri-
cal double layer becomes thinner and the interdrop repul-
sion decreases.[103] This means that there is an optimum
electrolyte content to boost the ionic emulsion stability; in
general, it is quite low, but non-zero. It is worth noting
too that the surface charge may be attained with nonionic
adsorbed surfactants, typically a negative 60 mV zeta po-
tential because of the preferential adsorption of OH- ions
in the polyethylenoxide chains.
The effect of the surface potential is clearly illustrated
in the so-called DLVO theory, which has been developed
for colloid particles, but is qualitatively valid for macro-
emulsions,[22] whose stability also depends on the resulting
balance of attractive and repulsive forces. In some cases,
there is a so-called secondary minimum in the potential
and the drops may flocculate, i.e., stick together with a
weak attraction that does not promote coalescence. This
flocculation results in transient emulsion properties like
thyxotropy and may be reversed by some shearing, thus it
is not considered as an instability.
Steric repulsion forces become quite effective when
there is a physical contact between the adsorbed layers at
the interface of approaching drops. Thick layers are partic-
ularly efficient if they prevent the interfaces to come close
enough for the attractive forces to be significant.[104] Such
thick layers may be attained with large size surfactants,
e.g., extended surfactants or mixture of hydrophilic and
lipophilic kinds, or gemini or polymeric types, or floccu-
lated species as asphaltenes that stabilize W/O emulsions.
It is worth remarking that the concept of thickness of the
adsorbed layer is relative, and that the same 40 layer
may be thick or thin depending on the size of the drop.
For O/W emulsions, highly ethoxylated nonionics would
11/06/2010 05:10AM
 10
produce hydrophilic chains that overlap one another and
Absorbance
result in a gel like thick layer on the water side of the inter-
Antibiotics
face. With W/O emulsions, it is the surfactant hydropho-
bic tail that should exhibit a strong steric repulsion, i.e.,
it should be bulky, branched, or exhibit multiple chains.
Mixing effects generally improve stability because of en-
tropic considerations, not only bulky hindrance.
Nature tends to make use of polymeric surfactants that
lay flat on the interface, rather than perpendicular to it.
Such species often overlap and pile up on top of each other,
thus producing a very high interfacial viscosity effect that
is quite similar to an encapsulation with a plastic wrap.
This often considerably increases the stability against co-
alescence, although it does not prevent flocculation to take
place.
Film drainage
Before two droplets coalesce, they must first approach
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each other, hence the interdrop film has to drain. Anything
that reduces this drainage rate would slow down the co-
alescence rate. The increase in the external phase viscos-
ity does that and tends to improve the emulsion stability.
However, when a liquid-liquid system is stirred, the general
tendency, independently of the formulation and composi-
tion effects, is that the internal phase is the more viscous
one.[105] This has some consequence on the formulator
clever strategy. If the external phase is going to be made
more viscous to increase the stability of the emulsion, the
more effective way to do it is to first produce the emulsion
with the original phases, and to add later the polymer to the
external phase. The film drainage rate can also be reduced
by some dynamic phenomena like the streaming potential
and the interfacial rheology, which are quite complex to
handle in practice.
Geometric factors
One of the principal stabilization mechanism has to do
with the repulsion forces which are due to the presence
of adsorbed surfactant at interface, and as a consequence
depend on the drop surface area, i.e., they are proportional
to the square of the drop size. On the other hand the drop
drop attractive forces vary with the volume of the drop,
hence as the third power of its size. This means that when
the drop size is decreased by 10 times, the repulsive forces
decrease 100 times and the attractive forces 1000 times.
This size reduction tends to favor the repulsive forces over
the attractive forces, and accordingly it is likely to reduce
the coalescence rate.
This is not the only reason why a smaller drop size tends
to increase the emulsion kinetic stability, since it also re-
sults in a slower Stokes law settling velocity and increases
the entropic disorder. The internal phase volume propor-
tion is also an important geometric parameter. The hex-
agonal compact packing is attained at 74% of occupation
120045970 10 Manila Typesetting Company
Emulsion Formulation Engineering for the Practitioner
of the space. It means that monodispersed drops are often
in contact at about 6570% of internal phase or less, hence
they coalesce instantly unless there is a barrier. In most
cases the coalescence of unstable abnormal emulsions
starts when the internal phase ratio approaches 3040%.
On the contrary, in normal emulsions exhibiting a high sta-
bility of the interdrop film, the drops may be deformed in
a foam-like morphology containing, in some cases, more
than 90% of internal phase such as in mayonnaise. As far
as the emulsification process is concerned the WOR has
an importance, and the general trends are complex (see
Fig. 4c map).[69]
Temperature complex influence
As seen previously, the temperature is a primordial vari-
able in formulation. Its increase turns ionic surfactants
more hydrophilic and nonionics more lipophilic. But tem-
perature is also influencing second-order effects, because
it alters many physical properties.
An increase in temperature generally decreases the inter-
facial tension and the phase viscosity, which both result in
an easier emulsification, hence often a smaller drop size and
related properties. An increase in temperature could, when
approaching the cloud point from below (HLD<0) make the
polyethoxylated surfactant less hydrophilic, and drive it to
interfaces hence increasing its adsorption and even precipi-
tating it as a coacervate. The same phenomena can take place
on the other side (HLD>0) when the temperature decreases.
This is what happens in water-in-crude oil emulsions stabi-
lized by asphaltenes that aggregate close to interface when
temperature is lowered during production.
On the other hand a temperature rise tends to decrease the
emulsion stability, because it alters some phenomena and
mechanisms. First, it increases the molecular motion and
thus decreases the adsorption at interface, independently
of the fact that the HLD is also linked to adsorption. Since
the temperature also decreases the viscosity of the interdrop
film, the drainage turns out to be quicker. Aside, an increase
in temperature that moves the formulation far away from
HLD=0 would result in a surfactant which is more soluble in
a bulk phase (i.e., more unbalanced) hence it would decrease
its adsorption, and thus its stabilization performance.
This alteration could happens at HLD>2 units (or
HLD<-2) or 6 or 8 units, depending on the case.
Temperature variations produce opposite formulation
effects on ionic and nonionic surfactants; hence, they may
be opposed and cancel out. Indeed, the combination of
ionic and nonionic surfactants has been found to offset the
temperature dependence and to allow the formulation of
systems insensitive to temperature.[106,107]
Process variables
A stirring energy increase is highly efficient to reduce drop
size in poor yield conditions (low surfactant concentration,
11/06/2010 05:10AM
 Emulsion Formulation Engineering for the Practitioner 11
low stirring energy),[108,109] but it is not very likely to
produce significant changes at high surfactant concentra-
tion or for already very efficient conditions, particularly,
at high internal phase ratio or close to HLD=0.[109] When
inversion processes are used, the stirring speed determines
the internal droplet inclusion/escape process and may be
a critical issue on the performance. Dynamic changes in
formulation and interfacial properties during the emulsifi-
cation process can be used to produce emulsions with very
low drop sizes.[110] Finally, the emulsion drop size depends
on both the location in the map and the generalized for-
mulation of the final system[69] as well as the process of
emulsification.[111,112]
Combination or Programming of Effects
(Using Memory Feature)
The principle of using a programming strategy of the F
C conditions is to take advantage of delayed changes or
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memory features, thanks to which some property may be
changed without altering another. This opens the possibil-
ity of attaining a set of properties which is not reachable in
a single step emulsification process. For instance, the drop
size is likely to stay the same provided that the emulsion is
fairly stable during a few minutes, while the formulation or
composition is modified to alter the stability or viscosity.
In many instances, the emulsification is carried out
where small drops are easy to generate, particularly, at the
point where the drop size is minimum, which is, at some
distance (typically 1 unit), from HLD=0, e.g., point 1 in
Fig. 9, left plots. However, since the emulsion is not very
stable at this point, its formulation has to be rapidly moved
away, to point 2, where the emulsion stability is much
higher, say at 34 HLD units.
Such a rapid 12 change in formulation to enhance
stability may be provided by a quick decrease in tempera-
ture, i.e., a quench (case of an O/W emulsion with a non-
ionic surfactant), or by adding a second surfactant in a
small amount of the external phase immediately after the
emulsification is carried out. This is, in particular, the case
Fig. 9 a) Stability and b) drop-size variations with formulation, and bidimensional FC map at c) low- and d) high-viscosity water
phases.
120045970 11 Manila Typesetting Company
when adding a polymeric amphiphile, such as carboxy-
Absorbance
methyl cellulose, which also increases the viscosity of the
Antibiotics
aqueous phase. If such an additive were added prior to
emulsification, it would displace the B/A vertical branch
to the right, i.e., to a higher amount of water, as from
Fig. 9-c to Fig. 9-d. This could prevent the O/W emulsion
morphology to be generated in the first place with the car-
boxymethyl cellulose in water before emulsification, as
shown in Fig. 9cd plots. Therefore, the polymer should
be added, somehow quickly after the emulsification
process.
A classical programming consists in moving the repre-
sentative point in the map slowly enough for the emulsion
properties to change according to the phenomenology. In
some cases, the programming keeps the emulsion on the
same side of the inversion line, whereas in other cases,
it passes on the other side with or without the intermedi-
ate formation of a double emulsion.[63] The programming
may be applied sequentially, for instance, in the making
of a multiple emulsion of the w/O/W type. Because the
same surfactant cannot stabilize the two morphologies at
the same time, an overall stability implies that the two
kinds of interfaces have to be covered by different ad-
sorbed species. The usual technique illustrated in Fig. 10
consists in starting with a W1/O emulsion with a lipo-
philic surfactant S1 mostly in the oil phase, then adding
this EM1 emulsion to a W2 water phase in which a hy
drophilic surfactant is present to favor a W2 external mor-
phology. This may be done by slowly pouring the W1/O
emulsion into a W2 phase under constant stirring or by
using a dual mixing device that promotes an appropri-
ate local WOR.[46] Provided that the hydrophilic surfac-
tant S2 is somehow inhibited to migrate through the oil
layer to reach the inner droplets interface, for instance,
by selecting a polymeric species with an extremely low
solubility in oil, the two morphologies are stabilized and
the overall multiple emulsion is persistent enough for the
applications, because both representative points of the in-
ner and outer emulsions are located in stable zones as
seen in Fig. 10 map.
11/06/2010 05:10AM
 12
Absorbance
Antibiotics
Fig. 10 Making a multiple emulsion by a two-step procedure.
CONCLUDING WRAP-UP: PRACTITIONER
STRATEGY TO FORMULATE AND PREPARE
AN EMULSION
The first thing the practitioner must do is to use the gen-
eral phenomenology to select the proper formulation and
composition conditions to attain the sought properties, i.e.,
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emulsion type, internal phase content, stability, drop size,
and viscosity. Once this first-order factor conditions are
chosen, it is possible to use second-order factor effects to
fine-tune the properties after the emulsion has been made
according to the first-order FC conditions or in combina-
tion with them.
If no location in the FC map offers the desired set of
properties, there might be two alternative reasons. The first
one is because there is a conflict between two properties
which are generally antagonistic, e.g., the concomitant re-
quirements of a high internal phase content and a low vis-
cosity. In such case, some compromise should be found to
reduce the conflict between opposite first-order factors, and
some second-order factor should be used to enhance the
compromise. For instance, a feature like a polydispersed
distribution could very significantly reduce the emulsion
viscosity and resolve the antagonism.
In the second case, it is because the conditions for
the two requirements are not met at the same location
in the map although they are not in conflict, e.g., very
small droplets of a viscous oil and a low internal phase
content. An FC programming to catch several character-
istics along the path should be designed, as indicated in
Fig. 11a map. In the case of very small droplets and low
internal phase ratio, the emulsification may be started in
Fig. 11 Examples of complex programming processes.
120045970 12 Manila Typesetting Company
Emulsion Formulation Engineering for the Practitioner
the best conditions close to HLD=0 formulation, then it
can be made a high internal phase ratio emulsion to take
advantage of the efficient shear to produce small drops
even with a viscous oil, that is by shifting the inversion
line to less than 20% of water external phase before fi-
nally diluting it.
Complex processes are generally handled in such a
way, for instance, the inversion of a lubricating emulsion
for laminating purpose, a product which is added on top of
a hot aluminum slab when it is passed between two rollers
at a very high pressure. As indicated in Fig. 11b map, the
original O/W emulsion typically contains 5% of lubricat-
ing oil, and when it is in contact with the hot slab, water
evaporates and the representative point moves to the left,
i.e., from C to A regions and then to B. Because a poly
ethoxylated surfactant is used, the increase in temperature
shifts the formulation from HLD<0 to HLD>0, and as a
consequence, the representative point moves upward and
passes into the A+ and B+ region. In the B+ region the
emulsion has a low internal phase content W/O morphol-
ogy which is quite stable. When the emulsion enters the
gap between the rollers, the extreme pressure convert the
water drop in very rigid spheres, which cannot elongate
and penetrate in the gap, and thus stay outside. Accord-
ingly, only the oil wets the roller and insures the proper
lubrication and slippage. The residual products are mixed
with cold water to return to low stability conditions close
to HLD=0 where the phases separate and may be filtered
or otherwise treated.
In these cases and in almost any other, the second-order
factors must be adjusted to quantitatively boost or inhibit
some phenomena likely to shift the properties in the proper
direction. It may be a matter of fine-tuning the conditions,
such as changing the ethoxylation degree of the surfactant
to shift the location of the inversion line. It could be also a
change in the value of some properties, such as the stabil-
ity, viscosity, or drop size, by introducing a new surfactant
or an additive (surfactant, cosurfactant, lipophilic linker,
polymer) or by changing the temperature or electrolyte
content. There are so many possibilities that the formula-
tor performance and efficiency directly depends on his ac-
cumulated know-how, i.e., the combination of knowledge
and experience to produce expertise.
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 Emulsion Formulation Engineering for the Practitioner 13
This might also require to check the literature which
is quite extended. A lot of information is available to find
general and specific data concerning emulsion character-
istics, properties, and applications: books on emulsion
basic science by specialists[113116] or books on advanced
properties with high-technology entries by well-known
researchers.[117123] Other sources of information, with a
large diversity from easy to understand applications for
nonexpert readers[124,125] to highly technological and sci-
entific researchers, are presented as talks and published
papers associated to international congresses, in particu-
lar, the one on World Congress on Emulsions organized
every 4 years in France by European industrial companies
and universities since 1993.[126]
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