Emulsions and Foams

Oil-in-water and water-in-oil emulsions

An emulsion is a dispersed system in which the phases are immiscible or partially miscible liquids. The
globules of the dispersed liquid in the usual type of emulsion (sometimes now called a macroemulsion)
are usually between 0.1 m and 10 m in diameter, and so tend to be larger than the particles found in
sols

The practical application of emulsions and emulsion technology is considerable and includes foodstuffs
(especially dairy produce), pharmaceutical preparations, cosmetics, agricultural sprays, and
bituminous products.

Emulsions enable the dilution of an expensive or concentrated ingredient with an inexpensive, but
immiscible, diluent. For example, water-insoluble agrochemicals are generally marketed in the form of oil
in water emulsions which can be diluted with water by the user to permit even, low-level application.

Emulsions also allow enhanced control over other factors, such as rheology and the various
manifestations of chemical reactivity (including taste, odor, and toxicity).
Microemulsions, with droplet diameters of 0.01-0.1 m, can also be prepared and these are currently the
subject of much fundamental investigation and new applications (e.g. oil recovery from porous rocks). Whether
microemulsions should be regarded as true emulsions or as swollen micelles is a matter of controversy.

The visual appearance of an emulsion reflects the influence of droplet size on light scattering. It varies from
milky-white-opaque, with large droplets, through blue-white, then gray-translucent, to transparent, with small
microemulsion droplets.

If the oil is the dispersed phase, the emulsion is termed an oil-in-water (O/W) emulsion; if the aqueous medium
is the dispersed phase, the emulsion is termed a water-in-oil (W/O) emulsion. There are several methods by
which the emulsion type may be identified.

1. Generally, an O/W emulsion has a creamy texture and a W/O emulsion feels greasy.

2. The emulsion mixes readily with a liquid that is miscible with its dispersion medium.

3. The emulsion is readily colored by dyes soluble in the dispersion medium.

4. O/W emulsions usually have a much higher electrical conductivity than W/O emulsions.
Emulsifying agents and emulsion stability

The term 'emulsion stability' can be used about three essentially different phenomena - creaming (or
sedimentation), coagulation, and a breaking of the emulsion due to droplet coalescence.

Creaming results from a density difference between the two phases and is not necessarily accompanied by
droplet coagulation, although it facilitates this process.

Droplet collisions may result in coagulation, which, in turn, may lead to coalescence into larger globules.
Eventually, the dispersed phase may become a continuous phase, separated from the dispersion medium by a
single interface. The time taken for such a phase separation may be anything from seconds to years,
depending on the emulsion formulation and manufacturing conditions

Assessment of the stability of an emulsion against coalescence involves droplet counting.

The Coulter counter affords a convenient indirect technique for determining droplet size distributions in O/W
emulsions. In this method, a dilute dispersion is made to flow through a small orifice. The passage of a non-
conducting particle through the orifice causes a momentary increase in the electric resistance between
electrodes placed on either side of the orifice. The magnitude of this increase in resistance depends on the
size of the particle.
The electronic circuitry of the system is such that particles above a certain size are counted every time the
resistance rises above the corresponding preselected cut-off value.

By varying this cut-off value, a cumulative particle size distribution can be determined. The lower particle
diameter limit for this technique is about 0.7 microns, which makes it unsuitable for the study of most
colloidal dispersions, but suitable for studying the relatively large droplets in O/W emulsions.
To prepare reasonably stable emulsions, a third component - an emulsifying agent (or emulsifier) - must
be present.

The materials that are most effective as emulsifying (and foaming) agents can be broadly classified as:
1. Surface-active materials.
2. Naturally occurring materials.
3. Finely divided solids.

The functions of the emulsifying agent are to facilitate emulsification and promote emulsion stability. The
emulsifying agent forms an adsorbed film around the dispersed droplets which helps prevent coagulation
and coalescence.

The stabilizing mechanism is usually complex and may vary from system to system. In general, however,
the factors that control droplet coagulation are the same as those that control the stability of sols,
whereas stability against droplet coalescence depends mainly on the mechanical properties of the
interfacial film.

The following factors (which depend on the nature of the emulsifying agent and/or on a suitable choice
of formulation and manufacturing conditions) favor emulsion stability.
1. Low interfacial tension: The adsorption of surfactant at oil-water interfaces causes a lowering of
interfacial energy, thus facilitating the development and enhancing the stability of the large interfacial
areas associated with emulsions.

2. A mechanically strong and elastic interfacial film: This is particularly important when the volume fraction
of the dispersed phase is high.

The stability of emulsions stabilized by proteins arises from the mechanical protection given by the adsorbed
films around the droplets rather than from a reduction of interfacial tension.

Finely divided solids for which the contact angle is between 0° and 180° tend to collect at the oil-water
interface where they impart stability to the emulsion.

Surfactants can also stabilize in the mechanical sense. Coalescence involves droplet coagulation followed
by a squeezing of film material from the region of droplet contact, and the latter is more favored with an
expanded film than with a closed-packed film. For example, very stable hydrocarbon oil in water emulsions
can be prepared with sodium cetyl sulfate (dissolved in the water) plus cetyl alcohol (dissolved in the oil) as
an emulsifier (a condensed mixed film being formed at the interface), whereas hydrocarbon oil in water
emulsions prepared with sodium cetyl sulfate plus oleyl alcohol (which gives an expanded mixed film) are
much less stable
3. Electrical double layer repulsions: Interparticle repulsion due to the overlap of similarly charged electric double
layers is an important stabilizing mechanism in O/W emulsions.

When ionic emulsifying agents are used, lateral electric double-layer repulsion may prevent the formation of a
close-packed film. This film-expanding effect can be minimized by using a mixed ionic plus non-ionic film and/or
by increasing the electrolyte concentration in the aqueous phase.

4. A relatively small volume of dispersed phase (see below).

5. Narrow droplet size distribution Larger droplets are less unstable than smaller droplets on account of their
smaller area-to-volume ratio, and so will tend to grow at the expense of the smaller droplets. Emulsions with a
fairly uniform droplet size will be less prone to this effect.

6. High viscosity A high Newtonian viscosity simply retards the rates of creaming, coalescence, etc. If a weak gel
network is formed by, for example, dissolving sodium carboxymethyl cellulose in an O/W emulsion, genuine
stability might ensue.

Emulsifying agents and emulsion type

The type of emulsion that is formed when a given pair of immiscible liquids is homogenized depends on (1) the
relative volumes of the two phases, and (2) the nature of the emulsifying agent
1. Phase volume The higher its phase volume, the more likely a liquid is to become the dispersion medium.
However, the liquid with the greater phase volume need not necessarily be the dispersion medium.

If the emulsion consisted of an assembly of closely packed uniform spherical droplets, the dispersed phase
would occupy 0.74 of the total volume. Stable emulsions can, however, be prepared in which the volume
fraction of the dispersed phase exceeds 0.74, because (a) the droplets are not of uniform size and can,
therefore, be packed more densely, and (b) the droplets may be deformed into polyhedra, the interfacial
film preventing coalescence.

2. Nature of the emulsifying agent Alkali-metal soaps favor the formation of O/W emulsions, whereas
heavy-metal soaps favor the formation of W/O emulsions. O/W emulsions in the middle concentration
region stabilized by alkali-metal soaps can often be broken, and even inverted into W/O emulsions, by the
addition of heavy-metal ions.

The most satisfactory general theory

of emulsion type is that originally
proposed for emulsions stabilized
by finely divided solids
For example, bentonite clays (which are preferentially wetted by water) tend to give O/W emulsions, whereas
carbon black (which is preferentially oil-wetted) tends to give W/O emulsions.

This preferential wetting theory can be extended to cover other types of emulsifying agents. The type of
emulsion which tends to form depends on the balance between the hydrophilic and lipophilic properties of the
emulsifier – alkali metal soaps favor the formation of O/W emulsions because they are more hydrophilic than
lipophilic, whereas the reverse holds for heavy-metal soaps

The generalization that 'the phase in which the emulsifying agent is the more soluble tends to the dispersion
medium' is known as Bancroft's rule.

The amphiphilic nature of many emulsifying agents (particularly non-ionic surfactants) can be expressed in
terms of an empirical scale of so-called HLB (hydrophile-lipophile balance) numbers (see Table 10.1). The least
hydrophilic surfactants are assigned the lowest HLB values. Several formulae have been established for
calculating HLB numbers from composition data and they can also be determined experimentally.

The optimum HLB number for forming an emulsion depends to some extent on the nature of the particular
system. Suppose that 20 per cent sorbitan tristearate (HLB 2.1) plus 80 per cent polyoxyethylene sorbitan
monostearate (HLB 14.9) is the optimum composition of a mixture of these emulsifiers for preparing a
particular O/W emulsion. The HLB of the mixture is, therefore, (0.2 x 2.1) + (0.8 x 14.9) = 12.3.
The theory is that an HLB of 12.3 should be optimum for the formation of this particular O/W emulsion
by use of other emulsifier systems.
A major disadvantage of the HLB concept is that it makes no allowance for temperature effects. With
increasing temperature, the hydration of lyophilic (particularly poly(ethylene oxide)) groups decreases
and the emulsifying agent becomes less hydrophilic- i.e. its HLB decreases.

An alternative method for characterizing emulsifying agents is in terms of phase inversion temperature
(PIT). An emulsion containing equal weights of oil and water phases and 3-5 percent emulsifier is
heated and agitated, and the temperature at which the emulsion inverts is noted; i.e. the emulsion is
W/O above and O/W below the PIT.

Therefore, the PIT should be higher than the proposed storage temperature for an O/W emulsion and
lower than the proposed storage temperature for a W/O emulsion. O/W emulsions with a very small
droplet size can be obtained if prepared at only a few kelvins below the PIT.

At this temperature, the emulsion will be unstable to coalescence, but subsequent cooling to 20 K or
more below the PIT can enhance the stability of the emulsion while retaining the small average droplet
size
Microemulsions

Microemulsions are emulsions with droplet diameters in the range of about 0.01 to 0.1 m. They are,
consequently, of low turbidity. The formation of a microemulsion involves the creation of a situation in which
the oil-water interfacial tension approaches zero (or even becomes transiently negative). With all single ionic
surfactants and most single non-ionic surfactants, this is not possible, since ow is still sizeable when the c.m.c.
or the limit of solubility is reached.

To achieve the required lowering of ow a co-surfactant must be included. For example, O/W microemulsions
can be formed using a mixture of potassium oleate and pentanol as the emulsifying agent.

In general, less co-surfactant is required for O/W than for W/O microemulsions. Electrolytes promote the
formation of W/O microemulsions.

Given the high oil-water interfacial area that must be created, the fraction of emulsifying agents in
microemulsion formulations tends to be significantly higher than that in ordinary emulsions. A typical
microemulsion formulation would be 10-70 percent oil, 10-70 percent water and 5-40 percent emulsifying
agent.
With ow close to zero, microemulsions will form spontaneously and are thermodynamically stable. The
droplets of microemulsions tend to be monodispersed. A microemulsion may form as a separate phase in
equilibrium with excess oil (O/W) or water (W/O) (i.e. it is saturated with respect to droplets).
Microemulsions are usually of low viscosity.

Microemulsions represent an intermediate state between micelles and ordinary emulsions, and it is a
debatable issue whether or not they should be considered swollen micelles rather than small droplet
emulsions.

Droplet size, though small, is nonetheless large enough to justify classification as emulsions. On the other
hand, the observed thermodynamic stability and reproducibility is uncharacteristic of ordinary emulsions

Microemulsions are potentially exploitable in any situation where the mixing of oil and water is desired. The
possibility of using them to enhance tertiary oil recovery has recently attracted a great deal of attention.

The recovery of oil from natural reservoirs involves three stages. In the primary stage, oil is forced out of the
reservoir by the pressure of natural gases. When this pressure is no longer adequate, the secondary stage is
kicked in which water is pumped into the reservoir to force out further oil. This still usually leaves well over
half of the total oil is unrecovered, most of it being trapped in the pore structure of the reservoir by capillary
and viscous forces.
In the tertiary stage, some of this residual oil can be recovered by injection of oil-miscible fluids and/or
forced out by steam under high pressure.

The injection of appropriate micro-emulsifying surfactant mixtures offers the possibility of significantly
enhancing this final stage of oil recovery.

Foams

A foam is a coarse dispersion of gas in the liquid, and two extreme structural situations can be recognized.
The first type (dilute foams) consists of nearly spherical bubbles separated by rather thick films of
somewhat viscous liquid.

The other types (concentrated foams) are mostly gas phase and consist of polyhedral gas cells separated
by thin liquid films (which may develop from more dilute foams as a result of liquid drainage, or directly
from a liquid of relatively low viscosity)*.

The nature of thin liquid films (as found in these concentrated foams) has been the subject of a great deal
of fundamental research.
Foam stability

Only transitory foams can be formed with pure liquids and, as with emulsions, a third (surface-active)
component - a foaming agent – is necessary to achieve any reasonable degree of stability.

Good emulsifying agents are, in general, also good foaming agents, since the factors that influence emulsion
stability (against droplet coalescence) and foam stability (against bubble collapse) are somewhat similar.

The stability of a foam depends upon two principal factors – the tendency for the liquid films to drain and
become thinner, and their tendency to rupture as a result of random disturbances. Other factors which may
significantly influence foam stability include evaporation and gas diffusion through the liquid films.

Owing to their high interfacial area (and surface free energy), all foams are unstable in the thermodynamic
sense. Some distinction can be made, however, between unstable and metastable foam structures. Unstable
foams are typified by those formed from aqueous solutions of short-chain fatty acids or alcohols.

The presence of these mildly surface-active agents retards drainage and film rupture to some extent but does
not stop these processes from continuously taking place to the point of complete foam collapse.
Metastable foams are typified by those formed from solutions of soaps, synthetic detergents, proteins,
saponins, etc. The balance of forces is such that the drainage of liquid stops when a certain film
thickness is reached and, in the absence of disturbing influences (such as vibration, draughts,
evaporation, diffusion of gas from small bubbles to large bubbles, heat, temperature gradients, dust,
and other impurities), these foams would persist almost indefinitely.

Gibbs-Marangoni surface elasticity effect

This is an important stabilizing effect in foams which are formed from solutions of soaps, detergents, etc.
If a film is subjected to local stretching as a result of some external disturbance, the consequent increase
in surface area will be accompanied by a decrease in the surface excess concentration of the foaming
agent and, therefore, a local increase in surface tension (Gibbs effect).

Since a certain time is required for surfactant molecules to diffuse to this surface region and restore the
original surface tension (Marangoni effect), this increased surface tension may persist for long enough to
cause the disturbed film region to recover its original thickness.

An absence of the Gibbs-Marangoni effect is the main reason why pure liquids do not foam.
Antifoaming agents

The prevention of foaming and the destruction of existing foams is often a matter of practical importance; for
example, polyamides and silicones find use as foam inhibitors in water boilers.

Antifoaming agents act against the various factors that promote foam stability (described above) and,
therefore, a number of mechanisms may be operative.

Foam inhibitors are, in general, materials that tend to be adsorbed in preference to the foaming agent, yet do
not have the requisites to form a stable foam. They may be effective by virtue of rapid adsorption; for example,
the addition of tributyl phosphate to aqueous sodium oleate solutions significantly reduces the time
required to reach equilibrium surface tension, thus lessening the Marangoni surface elasticity effect and the
foam stability. They may also act, for example, by reducing electric double-layer repulsion or by facilitating
drainage by reducing hydrogen bonding between the surface films and the underlying solution.

Foams can often be broken by spraying with small quantities of substances such as ether and n-octanol. As a
result of their high surface activity, these foam breakers raise the surface pressure over small regions of the
liquid films and spread from these regions, displacing the foaming agent and carrying with them some of the
underlying liquid. Small regions of film are, therefore, thinned and left without the properties to resist rupture.