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i~LolDs
A
SURFACES
Colloids and Surfaces
ELSEVIER A: Physicochemical and Engineering Aspects 91(1994) 57-77

Some applications of emulsions

M. Chappat
COLAS, 7, Place Renk Clair, 92653 Boulogne Billancourt Cedex, France

Received 20 November 1993; accepted 5 July 1994

Abstract

This overview describes some applications of emulsions in industry. The first part deals with milk and the dairy
industry, which involve complex emulsion systems stabilized by natural surfactants. This is followed by a description
of emulsions in the food industry in which complex recipes are required and storage stability becomes an important
issue. The third application of emulsions is in pharmacy and is concerned with providing suitable systems for injecting
insoluble drugs. Other systems include blood substitutes and emulsions used in chemotherapy. Cosmetic emulsions
have been by far the most commonly used systems for many centuries. The interaction of emulsions with skin is briefly
described. Another application of emulsions is in agriculture, where active substances for treating plants and soils
have often been formulated as emulsions. The last part of this overview deals with the application of bitumen emulsions
in road construction techniques.

Keywords: Emulsions; Industrial applications

1. Introduction dispersion must remain perfectly stable and homo-

geneous over a certain period of time. In many
As defined in several papers in this conference, cases, the emulsion may be used as a concentrate
emulsions are formed from two immiscible liquids: and the required period of stability depends to a
one constitutes the droplets which are dispersed in large extent on the application. However, in many
the other liquid which is referred to as the con- other applications, dilution of the concentrate is
tinuous phase (Fig. 1). In some applications, this necessary. In other words, the concentrated emul-
sion is dispersed in another liquid and the system
may be further homogenised by mechanical means.
I I I I I I I I I
000000000 In some cases, dilution of the concentrated emul-
sion may be spontaneous. This dilution procedure
is used in many medical and pharmaceutical pre-
parations, cosmetics, petroleum products, road
construction and maintenance techniques, and
agriculture. Since the active ingredient is contained
in the emulsion droplets it is necessary in some
Water in Oil (W/O) Oil in Water (O/W)
applications to “break” the emulsion in order to
or “oil” 01 “aqueous”
release the active material. This is particularly the
Fig. 1. Schematic representation of both O/W and W/O case with many pharmaceutical emulsions which
emulsions. may require “breaking” at the site of action.

0927-7757/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

SSDI 0927-7757(94)02976-Y
58 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

Barnes [l] and Tadros [Z] showed the impor-

tance of the following factors on emulsion proper-
ties and stability: the relative volume of the
dispersed phase, i.e. the volume fraction, and the
average size of the droplets, the viscosity of each
phase, the nature and concentration of the emulsi-
fier. These parameters also control the rheology
of the emulsion, which is important in many
applications.
In this overview, I shall endeavour to examine
different classes of emulsions, highlighting the
importance of the above-mentioned factors accord-
ing to their application demands. The examples
that will be described demonstrate the wide appli-
cation of emulsions in many industrial products.

2. Milk and dairy products

Milk is perhaps one of the most stable emulsions

produced in nature. It is not well understood why
milk is produced in nature as an emulsion. The
exact mechanism of how the fat droplets in milk
are stabilised is also not sufficiently understood
although as we shall see later there are some
acceptable concepts of how these droplets remain
stable.
Milk is a low concentration natural oil-in-water
(O/W) emulsion (4-5%). Its viscosity at room
temperature is near that of water (1 mPa s). The
emulsifier content is in the region of l-3%. The
emulsifiers are phospholipids (lecithin), although
proteins also play the role of an emulsifier. The
properties of the milk depend on temperature.
Milk is not stable over a long period of time; this
is, however, due to fermentation rather than to the
fact that it is an emulsion. The milk properties
may be changed as a result of mechanical action.
It can cream, and phase changes may occur at
certain temperatures where phase inversion may
become more favourable.
Fig. 2 shows a schematic representation of milk,
which is an emulsion consisting of animal fat
dispersed in water. The proportion of water is
around 87.5%. The fatty substances are essentially
triglycerides. The fat droplets, whose size ranges
from 0.1 to 10 pm (average of 3-6 pm), are sur-
rounded by a complex double membrane. A study
CAPILLARY SYSTEM
Fig. 2. Schematic representation of milk emulsion: G; fat
globules; M, micelles; V, vacuoles.
of the interface shows that it is formed by an
assembly of molecules which become more and
more polar as one moves away from the lipid
centre. A schematic representation of the fat glob-
ule “membrane” in its initial state (“fresh milk”) is
shown in Fig. 3.
The composition of the membrane can be deter-
mined using centrifugation techniques. It consists
mainly of phospholipids and cholesterol, glyco-
proteins, enzymes (alkaline phosphatide, oxydide
xanthine or aldehyde reductide), various metals
and elements.
The membrane’s inner layer is made up of
globular proteins and phospholipids, as is the cell
membrane. This membrane has “solid-like” proper-
ties; it is essentially a viscoelastic membrane.
With a high level of enzyme activity, the outer
layer is quickly destroyed. It is separated from the
inner layer by a cytoplasmic layer which is several
nanometres thick. When the outer membrane has
been broken down, it is replaced by casein micelles
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77
FAT
CELLULAR
CYTOPLASMA
I ENDOPIASMIC GoLG’
RETICULUM
MEMBRANE UNIT
CASEIN
MICELL WITH LIPASE
Fig. 3. Diagram of the fat globule
which are naturally present in the aqueous phase.
These micelles increase the milk viscosity.
From the beginning of time, man has tried to
transform milk, essentially to extract and preserve
the fatty substances. Several dairy products are
produced from milk, of which cream, butter and
cheese are probably the most common examples.
A schematic representation of the essential compo-
nents in these products is given in Fig. 4. The main
differences between these products are the water
content and the nature of the emulsion. The water
content is 87.5% in milk; 54% in cream, 45% in
cheese, and 16% in butter (inverse emulsion).
Cream is the product which results from milk
separation into two layers by sedimentation; it is
the part which is rich in fatty substances. Butter is
an inverse emulsion obtained by churning. Firstly,
churning mixes in air bubbles and creates a foam.
With time, the air bubbles compress the fat drop-
lets, destroying their “protective” membrane. By
phase inversion, the fat then becomes a solution
59
\
RIBOSOMES
CASEIN MICELLS
LIPASE
e COFACTOR
membrane, initial state in fresh milk.
to form butter. This operation is most efficient
when carried out at low temperatures.
A summary of the main properties and composi-
tion of milk, butter and margarine is given in
Table 1. Fig. 5 shows an optical micrograph of the
water droplet size distribution in a margarine
emulsion (Fig. 5(a)) and the finished margarine
(Fig. 5(b)). This illustrates the reduction of the
water droplet size distribution obtained in the pro-
cessing of margarine.
3. Emulsions in the food industry
In addition to the above-mentioned milk pro-
ducts, many emulsions are present in our daily
diet, such as sauces, dressings and sausages, and
many ready-to-use products.
In all these emulsions, it is true that the emulsifi-
ers are quite easily identifiable and show very little
variation. They are mostly monoglycerides (or fatty
60 M. Chappat/CoNoids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

MlLK(COW)

CREAM

rdr$extract of n&+~ t
I fat milk 9

BUTTER

CHEESE water 45%

Fig. 4. Analysis of milk products.

Table 1
The properties and typical composition of milk, butter and margarine

Type Aspect Storage Components Emulsifiers Average Viscosity

stability size

Milk O/W White fluid Infinite at Fat Phospholipids 2-5 pm 1mPas

low (triglycerides glycoproteins +
temperature 3-4%) chlolesterol+
enzymes

Butter and margarine O/W Yellow mixture Infinite at Fat Phospholipids 2-5 pm 500 mPa s at
normal (triglycerides glycoproteins + 20°C;
temperature 1%) cholesterol + 100 mPa s at
enzymes 60°C
Lecithin
(several %o)

acid esters) produced from triglycerides, the fat
globules in milk, or their by-products such as
lactic, acetic or citric acid esters, obtained from
non-ionic animal fat (lard, tallow) or vegetable fat.
These emulsifiers are soluble in oil and insoluble
in water. They can also act as foaming agents,
rising agents for pastry, or agents ensuring oleophi-
lit quality in pasta. Generally a mixture of several
different emulsifiers is used as it has been proven
that this is more efficient than using one emulsi-
fier only.
As is the case with other emulsions, a sufficiently
high concentration of emulsifier is used to reduce
coalescence between the droplets. The diameters
of the latter increase with time until they reach a
stable level at 3-6 pm. This is illustrated in Fig. 6
which shows the variation of droplet size with
time. Fig. 7 shows a histogram of an olive oil in
 M. ChappatjColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77
II
100 urn
Fig. 5. Water droplet size distribution
water emulsion stabilized with lecithin and con-
taining 0.152 g dme3 hydroxyethyl cellulose (HEC)
after storage for 10 months at 10°C.
It has been observed that emulsion stability is
increased by adding sucrose or polymers (for exam-
ple HEC), or even salt. The concentration level of
these ingredients is usually of the order of several
per cent. Proteins also play an active role in this
emulsification process as well as in the long term
stability of many food emulsions.
Emulsions are easy to manufacture because they
can be obtained by simply mixing the ingredients
together using a high speed stirrer, as is usually
the case for making mayonnaise.
It should be mentioned, however, that the above
considerations are not sufficient since the products
which are to be sold must remain stable for many
months at different temperatures. Lowering the
temperature during emulsification helps in making
61
in (a) margarine (b) finished margarine.
the emulsion (it is well known that to make good
mayonnaise, one has to place the mixing bowl in
cold water).
Apart from stability considerations, food pro-
ducts which are to be ingested must be of “good”
quality. Besides the product’s physicochemical
qualities, food emulsions need to satisfy the cus-
tomers’ taste, which points to considering the
oleophilic qualities of sauces and dressings. Fat is
smooth and it gives the right consistency for appre-
ciating the taste of food. Finally, uncooked sauces
and dressings must be liquid at body temperature,
i.e. 37°C. These considerations necessitate the use
of more complex mixtures in which additives are
added to the emulsifiers. These additives such as
sugars, polymers, and salts will not only modify
the emulsifier properties but also produce addi-
tional modifications to the consistency of the final
food emulsion. It has been claimed that the taste
62 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77
-_ 0.108
I I
60
Fig. 6. Average volume diameter of oil droplets as a function
oil volume fractions.
of many food emulsions is determined by its rheol-
ogy which is controlled by the proper choice of
the emulsifiers and the thickeners.
Emulsified sauces and dressings are usually O/W
emulsions, the most typical of which is mayonnaise.
The oil content of these sauces may vary. Three
classes may be distinguished: category A, 80% oil
(mayonnaise); category B, 50-80% oil, sauces
derived from mayonnaise; category C, salad dress-
ings with 15-50% fat content (vinaigrette).
These emulsions are complex mixtures and the
continuous aqueous phase comprises a great
variety of components: proteins, polysaccharides,
sugars, acidifiers, minerals, etc. Generally speaking,
the presence of egg phospholipids and even hydro-
colloids in the aqueous phase is enough to stabilise
some of these emulsions, especially mayonnaise.
Synthetic emulsifiers are often incorporated for
economic or dietary reasons in order to limit
the amount of eggs used. The emulsifier is thus
I I I I
120 180
Time/ days
of time for lecithin-stabilized O/W emulsions stored at 10°C at various
adsorbed at the oil/water interface and its main
role is to stabilise the emulsion.
The above-mentioned emulsifiers produce a film
around the droplets, which prevents emulsion
coalescence as a result of its interfacial properties,
i.e. elasticity and viscosity [3]. Owing to the
complex nature of the emulsifiers, using the simple
hydrophilic lipophilic balance (HLB) is not suffi-
cient for emulsifier selection. In addition, emulsifier
mesomorphic characteristics (which produce a
liquid crystalline phase at the O/W interface) play
a large role in stabilizing the emulsion against
coalescence. The efficiency of liquid crytalline
phases in stabilising emulsions can be attributed
to their rheological characteristics (high interfacial
elasticity and viscosity) [a].
Certain sausages and cooked pork meat pro-
ducts (pates etc.) may be considered as emulsions
since they have an oil phase and an aqueous
continuous phase. The emulsifiers are mostly pro-
 M. ChappallColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77
25
20-i
(M, = 950 000) and stored at 10°C for 10 months.
teins with a concentration of l-2% to which caseins
1
; s
I
Fig. 7. Size distribution of an olive oil in water emulsion (0.1 volume fraction) stabilized by 2% soy lecithin with 0.152 g 1-l HEC
are also added.
The size of the droplets should be kept small. It
is well known that the smaller the size, the better
the resistance against microbiological attacks such
as moulding.
Another important emulsion in the food industry
is ice cream. This is partially frozen foam, 40-50%
of which is composed of air. The continuous phase
contains dissolved or dispersed materials: sugar,
proteins, stabilisers, and fatty substances in an
O/W emulsified form. Several of these milk pro-
teins are linked to the emulsion’s fat globules. Two
steps in the manufacturing process may be distin-
guished. The first step is the formation of the
“mixture”. The main aim of this process is to try
to split up the fat globules as much as possible
and disperse them with air bubbles to achieve
proper expansion. Homogenisation is usually car-
ried out at 80°C. The second step is freezing of
the “mixture” at - 5°C. During this process,
demulsification and crystallisation of the ice cream
and fatty substances occur. Crystallisation plays
an important role in the texture of the end product.
Lowering the temperature facilitates protein
63
D(3,2)=220pm
D(v,05)= 2.58pm
DistributionRange=1.12
Specific Surface = 2.725 m2/g
L
Diameter /pm
adsorption, in this case casein, at the surface of the
fat globules, thus stabilising the cream and limiting
demulsification. The emulsifiers are monoglycer-
ides and digylcerides of fatty acid at a concen-
tration of less than 3 g kg-‘.
A summary of the composition and properties
of some food emulsions is given in Table 2.
4. Emulsions in pharmacy
As carriers of active materials, emulsions are
especially useful in pharmaceutical applications.
An active substance can only be efficient if it is
able to reach its precise target in a proper condition
and in the appropriate form, without producing
any side effects. Another example can be cited
during a surgical operation in which nutritive
materials or blood substitutes are introduced into
the human body. Three main ways to introduce
active material may be considered: orally (absorp-
tion), parentally (intravenous or intramuscular)
and cutaneously (ointments). Here I shall mainly
concentrate on the parental means of application.
Many water-soluble drugs may be injected either
64 M. ChappatlCoNoids Surfaces A: Physicochem. Eng. Aspects 91 ( 1994) 57-77

Table 2
Summary of composition and properties of some food emulsions

Advantages Type Storage Components Emulsifiers Average Viscosity

of stability size
emulsions (months) (pm)

Sauces O/W 6 Fat (vegetable oil) Fatty acid esters 5-10 100 mPa s at
20°C
Practical
Mayonnaise dilution o/w 6 Fat (vegetable oil) 5-10 100 mPa s at
oleophilic 20°C

Meat o/w 6 Fat (animal fat) Phospholipids >lOO 400 mPa s

before
cooking

as aqueous solutions or as water-in-oil (W/O)
emulsions. However, experiments have shown that
transportation by fatty emulsions was much more
efficient. In fact, an aqueous dilution is digested in
the stomach whereas a fatty emulsion is not [4].
This is illustrated in Fig. 8 which shows the effect
of replacing an aqueous solution with a W/O
emulsion for ‘311-labelled ragweed emulsion.
The components that make up an emulsion must
be very carefully selected in order to avoid risks.
The oil must be either paraffinic or vegetable. Only
non-ionic emulsifiers are used and these are limited
to lecithin or other phospholipids and to fatty
alcohols. These emulsifiers usually have a low
IO
I I I
10 I
molecular weight. The size of the droplets must be
small for a number of reasons, one of the most
important being that the droplets must not clog
up the vessels during their transport, which could
otherwise lead to blockage. Large-size droplets
may also increase the risk of toxicity. The average
droplet size used in pharmaceutical applications is
much smaller than that in the food industry; an
average droplet size of the order of 1 urn or less is
usually the case (the largest droplet should always
be less than 5 urn).
O/W emulsions are sometimes used for intra-
muscular injections and W/O emulsions are fre-
quently used for intravenous injections. O/W
emulsions are often used for chemotherapy treat-
ments for cancer. The emulsions used must have a
low viscosity, usually in the region of 1 mPa s, i.e.
very close to the viscosity of water.
Pharmaceutical emulsions are stored for long
periods of time and they should remain stable for
a period of 1-2 years. They must also remain
sterile; they are normally kept at 3-4°C (i.e. in a
refrigerator). On application the emulsion may
have to break at its site of action under body
temperature conditions (37°C) in order to liberate
its active components. Investigations have shown
that many pharmaceutical emulsions may become
unstable at high temperatures (around 40°C) and

0 5 10 15 20 this may cause problems of toxicity as a result of

Time / days
Fig. 8. Adjuvant effect of emulsions on the rate of disappearance
of radioactivity from the site of application of ‘351-labelled
ragweed pollen extract: W, saline; 0, W/O emulsion.
the increase in the droplet size. The emulsifier
content in many of these pharmaceutical emul-
sions is usually a few per cent. High pressure
homogenisers are normally used to produce these
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77 65

fine emulsions. Table 3 gives the composition of
some examples of commercially available lipid
emulsions. The composition of the vegetable oils in
these lipid emulsions is given by the charts in Fig. 9.
Other examples of pharmaceutical emulsions are
those used as blood substitutes. For those the
droplet size is even smaller, being in the range
0.1-0.2 urn (perfluorocarbons). Other systems
include radioplaques, vaccinates, anaesthetics
(barbiturates).
The efficiency of pharmaceutical emulsions
depends on the properties of the emulsifier. The
latter should control the length of time needed to
dissolve the active ingredient in the organism. In
this respect, it may be necessary to modify the
properties of the emulsifier by incorporating an
additive. In some cases, using an emulsion enables
one to reduce the amount of active medicine
applied. Some examples of pharmaceutical emul-
sions that are used in parental use are given in
Table 4. Table 5 gives an example of an emulsion
used as a blood substitute.
A summary of the compositions and properties
of some pharmaceutical emulsions is given in
Table 6.
In some pharmaceutical applications, multiple
emulsions (an emulsion of an emulsion) have been
proposed as a means of sustained release. These
multiple emulsions are produced by emulsifying a
W/O emulsion in water (to produce W/O/W emul-
sion) or an O/W emulsion in oil (to produce
O/W/O emulsion).
These systems enable one to formulate more
than one active ingredient. For example, with a

Table 3
Some commercially available lipid emulsions

Trade name Oil phase Emulsifier Other

components

Intralipid Soybean 10% or 20% Egg lecithin 1.2% Glycerol 2.5%

(Kabi-Vitrum)
Lipofundin S Soybean 10% or 20% Soybean lecithin 0.75% or 1.2% Xylitol 5.0%
(Braun)
Lipofundin Cottonseed 10% Soybean lecithin 0.75% Sorbitol 5.0%
(Braun)
Liposyn Safflower 10% (and 20%) Egg lecithin 1.2% Glycerol 2.5%
(Abbott)
Travemulsion Soybean 10% or 20% Egg lecithin 1.2% Glycerol 2.5%
(Travenol)

Linoleic

Others
(2.7%)

\ OleicK’” /

Fig. 9. Composition of vegetable oils: a, safflower; b, soybean.

66 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

Table 4
Medical and pharmaceutical examples of emulsions

1. Hexobarbital 3.75 g
Soy oil 1Og
Ethanol 25 g
Egg phosphatide fg
Mryj 52 0.5 g
Water to 100 ml

2. Phenylbutazone 2g
Soy oil fOg
Monoglyceride acetyl 10 g
Glycerol 2.5 g
Pluronic F68 0.5 g
Water to 100 ml

3. Diazepam 0.5 g
Soy oil f5g
Monoglyceride acetyl 5.0 g
Egg phosphatide 1.2g
Glycerol 2.5 g
Water to 100 ml

Table 5
Composition of an emulsion used as a blood substitute

Substance Quantity

Perfluorocarbon 20 ml
Pluronic F68 2.2 g
Hydroxyethyl starch 3.0 g
Glucose 100 mg
Potassium chloride 32.0 mg
Magnesium chloride 7.0 mg
Monobasic sodium phosphate 9.6 mg
Sodium chloride 54.0 mg
Calcium chloride 18.0 mg
Sodium carbonate to pH 7.44
water to 100 ml

W/O/W multiple emulsion, two water-soluble

active ingredients may be formulated with one in
the internal water droplets and one in the external
aqueous continuous phase. When taken orally the
first active ingredient in the outside continuous
phase will be digested in the stomach. The oil
droplets that now makes a W/O emulsion will pass
to another location to release the second ingredient
in the water phase at the site of action.
Several other applications are common for
multiple emulsions, for example, in treatment of
toxic uraemia and intoxication. It should also be
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) S-77 61

mentioned that multiple emulsions are used in Table I

Example of a formula for a W/O/W multiple emulsion
other fields such as removal of phenol in residual
water (using O/W/O multiple emulsions) and to Primary emulsion W/O %
refine hydrocarbons (using W/O/W multiple emul-
sions). Multiple emulsions have also been used in Beeswax 10.0
cosmetic applications [ 51. Microcrystalline wax 10.0
Vaseline 15.0
The emulsifiers used for the preparation of
Lanolin 5.0
multiple emulsions are generally non-ionic in Perhydrosqualane 15.0
nature. With pharmaceutical systems, emulsifiers Olive oil 12.0
that are approved by the food and drug administra- Sorbitan monooleate 4.0
tion can only be used. This may impose a limit on Sorbitan monostearate 3.0
Sucrose 1.5
their stability. With cosmetic multiple emulsions
Scent 1.0
the choice of surfactants is also limited. This is not Water 23.5
the case with industrial applications for which
most surfactants can be used. The droplet size in Multiple emulsion W/O
the internal phase of the multiple emulsion droplet
Primary emulsion 78.0
is usually of the order of 1 pm. However, the size
Sucrose ester 2.0
of the multiple emulsion droplet can be in the Preservatives q.s.
region of 5-20 pm. A schematic representation of Water 2.0
a multiple emulsion is given in Fig. 10. An example
of a formula for a W/O/W multiple emulsion that
is used as a night cream is given in Table 7. and “Doctrina Decorationis” by Henri de
Mondeville and Guy de Chauliac. In the 17th and
18th century, people only used tallow, beeswax,
5. Cosmetic emulsions olive oil, lard and essential oils. Then factory-
manufactured soap, almond paste ointments, cocoa
Since antiquity, emulsions have been used in butter and vanilla cleansing creams made their
cosmetics. Galen (130-200 AD), mentioned appearance. Olive oil was replaced by
“ceratum refrigerans”, an ancester of O/W emul- sweet almond oil and borax and spermaceti were
sions. Then came the 13th and the 14th centuries discovered. To guarantee efficiency, safety and a
long-lasting product, natural or synthetic raw
materials that make up cosmetic emulsions must
be pure, stable and inoffensive.
A summary of the main components of cosmetic
emulsions is given in Tables 8 and 9.
Cosmetic emulsions are applied through skin

@C
contact. In contrast to a pharmaceutical ointment’s

@,O 0
0 “o” active ingredients, which must penetrate deep into
the skin either to diffuse throughout the body or

0
OO o
0
8ooo to act locally, the action of cosmetic emulsions is
limited to the immediate surface of the skin, i.e.
o

0
&I
0
0
c3
the epidermis. To understand the action of cosmetic
emulsions we must first consider the structure of

\@(& @
the skin. The latter is a complex living organism
0
that contains between 10% (at the surface) and
65% (deeper layers) water and is very plastic. Skin
is made up of three layers which are as follows
Fig. 10. Schematic representation of a multiple emulsion. from the outer layer inward: the epidermis
68 M. ChappatjCoNoids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77
Table 8
Main components of cosmetic emulsions
Origin Vegetable
Lipophilic components
Oils Almonds
Peanuts
Castor oil
Copra
Cotton
Waxes Carnauba
candelilla
Cocoa butter
Surfactants Lecithin
Hydrophilic components Arabic gum
Dragon gum
Guar gum
(0.1 mm), the dermis (0.5-2 mm), the hydrodermis
(5-40 mm); the skin’s main role is to protect the
internal organs. This is illustrated in Figs. 11 and
12. Penetration through this thick layer is still not
very well understood. It is thought to take place
by infiltration through the hair shafts, between the
intercellular spaces or by dissolution or emulsifica-
tion by cutaneous lipids (sebum). For these reasons,
O/W emulsions have been widely used since they
were thought to enhance penetration.
The skin’s characteristics determine the proper-
ties which a cosmetic emulsion should have. Firstly
the emulsion should remain stable for a long period
of time over a wide range of temperatures. The
emulsion should give a pleasant feeling of applica-
tion. The emulsion should have the right consis-
tency (rheology) to achieve this pleasant feeling. It
also should be suitable for various types of skin
(greasy or dry). Epidermic reactions and intoxic-
ations must be carefully avoided. In other words,
the emulsion should not cause any skin irritation.
For these reasons, selection of emulsifiers for cos-
metic applications should be carefully considered
and a compromise is sometimes reached between
adequate shelf-life and suitability of application.
The nature and the content of the emulsifiers must
also be carefully considered. Generally speaking,
O/W emulsions are preferable since they are easier
to manufacture and they have better oleophilic
Animal Mineral
Squalene Vaseline
Mink Paraffin
Lanolin Paraffin wax
Beeswax Microcrystalline wax
Spermaceti
Egg lecithin
Cholesterol
Colloid silicates (clay)
properties. Various other parameters must also be
controlled such as the water content, the final
consistency, the final pH and the nature of the
additives (perfume, colouring agents).
In most cosmetic emulsions, non-ionic surfac-
tants are commonly used. Sometimes, anionic and
amphoteric surfactants can be used but rarely
cationics are allowed owing to their skin irritation
properties. The oil content in cosmetic emulsions
varies between 20% and 40%. These oil droplets
usually contain the fragrances. Fluid or semifluid
emulsions only contain 5% oil and they are mostly
described as lotions. The pH is usually adjusted to
7 (i.e. neutral). The emulsifier content is rather
high, reaching a value of 10% in some cases.
A summary of the composition of some cosmetic
emulsions and some of their properties are given
in Table 10.
6. Emulsions in agriculture
Emulsions are used in agriculture to formulate
active substances for the treatment of plants and
soil. In this section, I shall only discuss plant
treatments through leaves, i.e. pesticides and herbi-
cides. As with the case of human or animal organ-
isms, the active ingredient must cross a material
barrier, i.e. the leaf, to penetrate into a living
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77 69

Table 9 up through the wood vessels to the leaves where

Main surfactants of cosmetic emulsions they are combined with carbon from carbon diox-
ide present in the air. Sugar (saccharose) is formed
Lipophilic components
Fatty acids Stearic, palmitic, lauric which is then transformed into cellulose, the build-
Fatty alcohols Myristyl, cetyl, stearyl, ing block of wood. Fig. 13 shows a schematic
isostearyl, isocetyl.. representation of the cross-section of the limb.
Fatty esters Glycerol The exchange of gases occurs on the inner side
Ethylene-di-ethylene, triethyne
glycol
of the leaf through orifices called stomatas. Located
Propylene glycol on the lower side of the leaf, these openings also
Isopropyl alcohol permit water exchange and transpiration. The
Ethylhexyl outer side of the leaf is covered by the cuticle, a
Silicones rather impervious material which prevents evapo-
Lanolin and wool grease
ration. These stomatas which are between 2 and
Emulsifiers 20 urn are located where they will encounter most
Anionic Alkyl sulphates, alkyl of the water. Under drought conditions, they are
sulphonates protected by hairs. The protective film of the cuticle
Alkyarylsulphonates
is also covered by a waxy layer consisting of
Soaps from alkali or amino
metals
paraffinic and fatty hydroxy acid polymers. This is
Non-ionic Ethoxylic fatty alcohol in contrast to the skin whose epidermis ends with
Ethoxylic fatty acid a layer of keratin cells. One may envisage an
Ethoxylic fatty esters analogy between the skin and the limb in terms of
Ethoxyhc alkylphenol
the action of an emulsion; however, this is definitely
Polyglycol fatty esters
Ethoxylic polyoxypropylene
not the case.
Sorbitan fatty acids As carriers of active ingredients, emulsions must
Saccharose esters be able to spread out upon contact with the leaf
Cationic Quaternary ammonium salts to liberate the active materials, and then penetrate
Amphoteric Betainic by-products
through the lower stomatas or through the upper
Hydrophilic components
intercellular zones after crossing the waxy cuticle.
Polyalcohols Glycerol, sorbitol, propylene In the middle areas, at the heart of the limb, they
glycol may enter the plant cells. The easiest pathway is
Polyglycerols through the lower epidermis or the hidden side of
Poly(ethylene glycol)
the leaves. Active ingredients may also serve as
Cellulose by-products
Alginates, carraghenates
external protection, in which case they will not
Polyvinyhc penetrate but will simply stay as deposits on the
Polyacrylates leaf surface. In either case, the active ingredient
will be diluted and care should be taken to ensure
that this emulsion is not toxic. In addition to quick
organism and carry out its function as a pesticide spreading, once in contact with the surface, the
or herbicide. In some cases, the active ingredient emulsion must break quickly to avoid dripping,
may remain on the leaf surface for protection as being washed off, or evaporating. It should be
in the case for skin treatment. The method of mentioned, however, that the interaction between
penetration through the leaf will be considered an emulsion and the hydrophobic leaf surface is
below. far from understood. In the complex situation of
Before describing the process of penetration of treating plants and soil, the mode of action of the
the chemical, it is necessary to say a few words chemicals and the role of the formulation are also
about photosynthesis. Photosynthesis takes place difficult to study particularly when one considers
in leaves, more precisely in the limb. Water and the complex atmospheric conditions under which
dissolved minerals absorbed by the roots are drawn the treatment is applied.
 M. ChappatjCoNoids Surfaces A: Physieochem. Eng. Aspects 91 (1994) 57-77

Comeus layer

Granulous layer
LO5 mm

Malplghi mucous

Basal layer

0,25 mm

\ \
Basal dermal membrane

Papilla dermis
I
E
d” I \,
Captllafy

CROSS SECllON OF SKIN

Fig. 11. Schematic cross-section of skin.

Comeus layer
Mucous layer
Dermis papllla
Z$
Melssner corpuscle -L ‘I
a- PaplIla loops vessels

Ruffini corpuscle _ L SubpapIlla network

Ascending vessels

Arterial networK

Fig. 12. Schematic cross-section of skin.

A schematic representation of the transfer of a lo-100 m from the point of impact may be used.
herbicide that is applied by spraying is shown Conditions such as humidity, temperature and
in Fig. 14. velocity of the impacting droplets are not easily
For application of emulsion to the leaves of a controlled. One can only apply the chemical within
plant or a tree, it must be sprayed either from the certain threshold limits. Under spraying condi-
ground or from an aeroplane. Thus a distance of tions, water evaporation will occur and this
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77 71

Table 10
Summary of the composition and properties of some cosmetic emulsions

Advantages of Type Aspect Storage Components Emulsifiers Average Viscosity PH

emulsions stability size

Spreading power, o/w Rich, white Long (2-3 Vegetable or Lecithin or 0.1-2 urn 100-200 mPa s 7
dilution, w/o years), hot animal oil alcohol or
psychology or cold (20-40%), fatty acid
fatty acids or esters (several
alcohol, %)
hydrocarbons

1. Culicle
UPPER EPIDERMIS
2. Epidmna
3. Paliis cells
4. Chlomptants
5. Paliasadr tissue
6. Vaeuok
7. Nuelwa
0. Nowe
9. Lacum parenetrqna
10. slorm

LOWER EPIDERMIS

Fig. 13. Leaf: cross-section of the limb.

enhances breaking of emulsions. This process is
further influenced by the wind speed. To avoid
these disturbances the size of the spread droplets
should be adequately controlled. The role of the
emulsion droplet size distribution may also play a
role in this process. To reduce the process of spray
drift, one usually uses large spray droplets.
For many practical applications, pesticides are
formulated as emulsifiable concentrates. In this
case, the active ingredient is dissolved in an oil to
which one or two surfactants are added. When this
concentrate is diluted in the spray tank it spontane-
ously emulsifies producing an O/W emulsion. The
stability of the emulsion produced is influenced by
the concentration and type of electrolyte in the
water as well as the temperature. This is illustrated
in Fig. 15 which shows the relative emulsion sta-
bility at various temperatures in the presence of
calcium carbonate [ 63.
Emulsifiers are selected to produce optimum
stability. These generally consist of a mixture of
an anionic surfactant such as calcium dodecyl
benzenesulphonate and a non-ionic surfactant such
as an alkyl phenol ethoxylate. In some cases,
phosphate surfactants are added to make the emul-
sion compatible with fertilizers used in agriculture.
The optimum emulsifier content in the final emul-
sion is between 0.5% and 1% and the droplets are
in the region of l-3 urn.
A summary of the composition of a typical
emulsifiable concentrate is given in Table 11.
7. Bitumen emulsion in road construction
techniques
Bitumen emulsions are used to carry an active
material, mainly bitumen, for road application
while avoiding solvents. Bitumen is used to bind
aggregates together to make up the layers of
12 M. ChappatlCoNoids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57~ 77

DUCT FOR SLIGHTLY

LIPOPHILIC SUBSTAINCES
(dalapon piclorame)
HERBICIDE ON THE LEAF

!_I

UTICLJLE

PALISADE
PARENCHYMA

P LEAF

(C.S.)

NERVE

LACUNA
PARENCHYMA

LOWER EPIDERMIS

1
STOMA DUCT
C.S. : Cross section
000 : Duct for slightly lipophilic substance:
000 : Duct for lipophilic substances

Fig. 14. Transfer of herbicide applied by spraying.

pavement. Emphasis is placed on emulsion sta- mix before the final compacted application under
bility from manufacturing to application on the traffic conditions. Adhesion takes place if the
aggregates and on quick separation from water bitumen properly wets the aggregate in dry or
after contact with the materials. This separation wet weather. Cationic emulsions have less wetting
can be either total or partial depending on power than do anionic emulsions as the emulsifi-
whether or not the aggregates will be stored as a ers are less hydrophilic.
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77 13

77°F
28°C

100°F
42°C

Water Hardness
I I I 1
1000 500 0 500 1000 1500
Na as ppm CaC03 ppm CaC03

Fig. 15. Stability of emulsions as a function of water hardness.

Table 11
Composition and properties of a typical emulsifiable concentrate used in agriculture

Advantages of Type Storage Components Emulsifiers Average Viscosity PH

emulsions stability size

Dilution, environment o/w Several days, Vegetable or Non-ionic, l-3 urn 1mPasat 7
from -5 to animal oil anionic 20°C
+30ac ( 120%) (0.25-l%),
esters, soya
amino,
calcium
sulphonate

Depending on whether the aggregates are calcar-
eous or basaltic (electropositive surface) or siliceous
(electronegative surface), proper adhesion is
obtained with cationic or anionic emulsions in the
first case and only with cationic solutions in the
second. This is why anionic emulsions have not
been commonly used. Siliceous aggregates are used
when possible and adhesion is better in the pH
range 3-5.
A schematic representation of the bitumen emul-
sion application is shown in Table 12.
The emulsions are applied simply by spraying
on aggregates under either low or high pressure
conditions. Under low pressure (0.05 MPa) a mixer
is used to ensure a proper liquid-aggregate distri-
bution. Under high pressure (0.1 MPa) a mobile
spreader that projects a fine film of emulsion on
the road surface to be covered is used. In both
cases, the variable weather conditions such as
humidity, temperature and wind velocity must be
taken into account. Clearly one should not work
in the rain. The breaking of the emulsion on the
chipping surface can be induced using another
agent.
The bitumen emulsion is manufactured from
the following ingredients: bitumen (modified or
unmodified) heated to a temperature of 130-150°C
to obtain an optimum viscosity of 200 mPa s -
emulsifying additives at room temperature (20” C)
for liquid amines or at a higher temperature (about
14 M. ChappatlCoNoids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

Table 12
Schematic representation of bitumen emulsion application

+++++
Material Anionic Emulsion

+
Cationic Emulsion

+
++++
++
+
Electropositive
(calcium

++
++
material
, basalt)
neutralizing

BREAKING
‘I
reaction attraction
V
BREAKING

0+++++
V V
forming of insoluble forming of insoluble
amine carbonate calcium soap
V V
ADHESION ADHESION

-_-
Electronegative
(silex, quartz,
materials
granite)
attraction

BRETKING
no neutralizing

0
1
V
forming of insoluble
amine silicate
_-
V
--
_-
ADHESION no attraction

60°C) for thick amines - acid at room temper-
ature (20°C) - cold water (lo-20°C) or hot
water (about 40°C).
Both temperature and water hardness play an
important role in the quality of the emulsion
produced. The bitumen emulsion must remain
stable during storage in insulated, heated tanks
which may be equipped with a mixing device. To
maintain stability, one should keep the pH low
(3-5).
For the cationic emulsions used, a bitumen with
a fixed degree of acidity is selected. The role of the
bitumen’s quality and composition on the emulsion
stability is far from well understood. Hard water
should be avoided, especially when preparing emul-
sions with polymers. The emulsifiers used are usu-
ally synthetic amine chlorhydrates which vary in
composition according to the final applications.
They have a very big effect on the droplet size
distribution of the emulsion. This is illustrated in
Fig. 16 which shows the droplet size distribution
of 60% cationic bitumen emulsion prepared using
three different emulsifiers. A typical histogram of
the bitumen emulsion is shown in Fig. 17. In some
cases, binders may be added and this will have an
effect on the viscosity of the emulsion as illustrated
in Fig. 18.
Generally speaking, the bitumen emulsion
concentration ranges from 60% to 70%, giving
the emulsion a viscosity range between 50 and
500 mPa s. A summary of the bitumen emulsion
composition is given in Table 13.
8. Other applications of emulsions
Several other examples where emulsions are used
may be listed: paints, photographic films, paper
coatings, lubrication, petroleum extraction, etc. In
most of these systems or processes, toxicity may
not be a problem, although in recent years several
environmental constraints (such as use of volatile
organic solvents) have been imposed. Paint emul-
sions have some common ground with bitumen
whereby the oil droplets should strongly adhere to
the substrate to be painted. In addition, storage
stability must be adequate since such paints may
not be used directly after preparation. The same
principles also apply to other emulsions such as
those used in photographic films and paper coat-
ings (where a latex emulsion is used to coat the
paper fibres).
9. Conclusions
In every application I have considered, emul-
sions are very environmentally friendly. They make
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

100 -

E
.m
P
.E 50 -

m
I:
x?

B
3
2
3
8

1 2 3 4 5 6 78910 20
D/pm

Fig. 16. Droplet size distribution of 60% bitumen cationic emulsions prepared using three different emulsifiers (A, B and mixture BE).

6’8
III 12 16 24 32 48
Diameter/pm

Fig. 17. Typical size histogram of a bitumen emulsion.

64
I
96
I

100
, I
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77

ing, very simple and in some cases the emulsion is

01 I I I I
40 50
Binder Content
Fig. 18. Effect of binder content on bitumen
it possible to avoid using solvents, and the emulsi-
fiers used, which are added in small quantities, are
generally harmless. In many cases an emulsion
form is selected because it is more fluid than the
active matter and thus it spreads more easily.
Moreover, homogeneity of an emulsion enables
smaller amounts of active elements to be more
evenly spread.
The production conditions are, generally speak-
obtained by chemical action with little demand for
mechanical energy to obtain shearing. However,
with many emulsions, such as bitumen, mechanical
energy is required to produce the system.
The storage conditions of emulsions must be
carefully controlled to maintain their stability. For
example, with pharmaceutical emulsions the sys-
tems must be stored at low temperature (4°C) to
avoid bacterial growth and to give the emulsion a
shelf-life of l-2 years. Often emulsions such as
bitumen have to be stored at much higher temper-
atures (80’ C) but only for much shorter periods
(l-2 months).
In many cases, such as cosmetic or agrochemical
emulsions, the storage temperatures could vary
over a wide range (- 5 to + 50’ C) and the formula-
tions need to remain stable over a period of l-2
years. In addition, the consistency (rheology) of
cosmetic and food emulsions needs to be controlled
for aesthetic reasons (e.g. taste with food emul-
sions). Breaking of an emulsion upon application
is essential in many cases. With bitumen emulsions
I I
the droplets need to coalesce at the chippings to
60
provide good coating. This is also the case with
many agrochemical emulsions which need to break
emulsion viscosity. on the leaf surface to allow spreading and adhesion
to occur. The same applies to many cosmetic
emulsion creams where the oil droplets need to
spread on the skin to form a protective film. With
many medical emulsions the droplets have to break
at the site of action to release the active ingredient.
O/W emulsions are most common in industrial
applications than W/O emulsions and in most
cases non-ionic emulsifiers are preferred. This is
not the case with bitumen emulsions where cationic
emulsifiers are required.

Table 13
Summary of road bitumen emulsion characteristics

Advantages of Type Storage Components Emulsifiers Average Viscosity PH

emulsions stability size

Dilution, environment o/w From several Bitumen Amine chlorohydrates 4-6 urn 20-100 mPa s 3-5
hours at (60-70%) (2%) at 25°C
60°C to
several days
at 20°C
 M. ChappatlColloids Surfaces A: Physicochem. Eng. Aspects 91 (1994) 57-77 II

The average droplet size of most emulsions is exchange of ideas between manufacturers in vari-
usually of the order of a few microns and this is ous fields is far from being achieved and every
achieved in most cases by the use of high speed industry sets its own rules and concepts. A unified
stirrers. In some cases, such as in pharmaceutical approach to emulsion formation and stability is
emulsions, submicron emulsions need to be pre- required in the future.
pared and this required application of homog-
enisers and/or ultrasonics.
The emulsifier concentration is usually a few per
cent, except for cosmetic emulsions where higher References
concentrations may be used.
A number of technical problems still require a [l] H. Barnes, Colloids Surfaces A: Physicochem. Eng. Aspects,
great deal of research in the future. For example, 91 (1994) 89-95.
[2] Th.F. Tadros, Colloids Surfaces A: Physicochem. Eng.
the selection of emulsifiers (which at present is
Aspects, 91 (1994) 39-55.
carried out by trial and error) needs to be rational- [3] Th.F. Tadros and B. Vincent, in P. Becher (Ed.),
ised using basic concepts. Also, the problem of Encyclopedia of Emulsion Technology, Vol. 1, Marcel
emulsion breakdown (coalescence) needs to be Dekker, New York, 1983.
addressed at a fundamental level. Then breakdown [4] S.S. Davis, J. Hadgraft and K. Palin, in P. Becher (Ed.),
Encyclopedia of Emulsion Technology, Vol. 2, Marcel
of emulsions upon application needs to be con-
Dekker, New York, 1985.
trolled and this also requires fundamental under- [ 51 Th.F. Tadros, Int. J. Cosmet. Sci., 14 (1992) 93.
standing of the interactions between the droplets [6] D.Z. Becher, in P. Becher (Ed.), Encyclopedia of Emulsion
and the substrate. It should be stressed that Technology, Vol. 2, Marcel Dekker, New York, 1985.