Chapter 26

Liquid Crystals and

Emulsions:
A Wonderful Marriage
Ken Klein
Cosmetech Laboratories
Fairfield, New Jersey, USA

KEY WORDS:

emulsions, liquid crystals

ABSTRACT:

While liquid crystal stabilization of emulsions is certainly not a new

phenomenon, it is one that can be rediscovered by cosmetic chemists to
the benefit of consumers.

The science of emulsion formulation has, in recent years (15 years is still
considered recent to me!), taken great leaps forward as we have begun to
increase our understanding of the mechanisms, on the micro level, that are
responsible for producing stable emulsions.
We must remember, of course, that all emulsions we cosmetic chemists create (forgetting about spontaneously forming microemulsions) are
thermodynamically unstable and will, some day, exhibit signs of emulsion
instability. Hopefully, that day will be after the emulsion is sold and used
by the consumer.

Emulsions as a Dispersion
Early cosmetic chemists thought of emulsions as a dispersion of one liquid
in another (usually oil or oil-soluble materials in water or water-soluble
materials). This was called (and still is) an oil-in-water (O/W) emulsion.
In the United States, this type of emulsion predominates, with more than
90% of all emulsions being of this type.

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The dispersed phase was depicted, rather simplistically, as a sphere

with adsorbed emulsifier molecules on its surface. Figure 1 is a depiction
of this type for an oil-in-water emulsion. In this case, the emulsifier has a
net negative charge and is, thus, termed anionic. Typical of this category
are the soap emulsifiers (TEA Stearate).

Figure 1. Anionic O/W micelle (Ana Sayfa, Ziya Gokalp and Bilgi Merkezi)

In well-formulated emulsions, these droplets would typically be

between 1 and 5 microns in diameter with a narrow particle size distribution. We have since learned1 that a more accurate way to visualize the
relative size difference between the dispersed droplets and the adsorbed
emulsifier is to picture a large beach ball (20 feet in diameter) covered
with peach fuzz (the emulsifier).
While this explanation of emulsions sufficed for many years, it
failed to explain several observations regarding the behavior and stability of emulsions. Sometimes emulsions with rather large particles
(greater than 10 microns) exhibited good long-term stability. Additionally, when fatty alcohols were added to many oil-in-water emulsions,
researchers noticed a dramatic increase in viscosity along with an
improvement in product stability.
Who among us hasnt made an oil-in-water emulsion and then added
a small amount of fatty alcohol (cetyl or stearyl is most used, but behenyl
will also work) to modify the skin feel and watched the viscosity increase
from a thin lotion to a robust cream? This can be an increase from 10,000

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cps to 75,000 cps or more. Yet, we only added a few tenths of 1% fatty
alcohol to an internal (oil) phase that may have been 25%. Certainly
increasing the size of the internal phase from 25% to 25.5% cant explain
the viscosity increase! This was first understood by Suzuki, Tsutsumi and
Ishida, who correctly stated, The self bodying action of fatty alcohols is
caused by the formation of a network structure of liquid crystalline phase
in the emulsion system.2

Liquid Crystals
Now is a good time to define liquid crystals. Liquid crystals are highly
anisotropic fluids that exist as a result of long-range orientational ordering
among constituent molecules. They are also three-dimensional association
structures that stabilize emulsions.
This ordering is adequate to provide for increased viscosity in the
immediate vicinity of the emulsion droplets, but not strong enough to
prevent flow. Thus viscous liquids are typical.
This dualism between a solid (crystal) and a flowing liquid gives rise
to the term liquid crystal. Their structure (anisotropic) has the ability to
bend/refract and reflect polarized light and, as a result, they exhibit birefringence under the microscope.
These association structures are formed by the molecular attractions
that result from Van der Waals forces. These forces act as a consequence
of three components relating to the polarity of the molecules (emulsifiers):

Keesom: dipole-dipole (permanent dipoles)

Debye: dipole-induced dipole (depends on polarizibility of the
molecule)

London dispersive: In neutral molecules the positively charged

nucleus is surrounded by a negatively charged cloud (electrons).

At any given instant, this cloud is not symmetrical, thus a dipole
is formed.

More on this important topic is available from several publications.3-5

Liquid crystals can be formed via either of two principal mechanisms
and are referred to as thermotropic or lyotropic, depending on how they
are formed.
Thermotropic liquid crystals are formed by the action of heating and
controlled cooling. Liquid crystal thermometers strips that we place on the
foreheads of babies to take their temperature are typical of this class.
Lyotropic liquid crystals are formed by the solvent action/interaction of
three components usually water, oil and a surfactant. The relative ratios
of these three components are often described via a phase diagram where
the mixtures produce different forms of liquid crystals.

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In cosmetic emulsions, the most commonly found form of liquid

crystal is the lyotropic type. Further, these lyotropic liquid crystals take on
a structural arrangement that has been designated as lamellar. This lamellar phase is responsible for the emulsion stabilization we seek and for the
increase in viscosity seen when fatty alcohols are added to emulsions.
They stabilize emulsions via two related but different mechanisms.
In Figures 2, 3 and 4, we see barriers forming around the emulsion
droplets and strengthening the o/w interface, which acts as a barrier to
coalescence and eventual emulsion breakdown. When the lamellar liquid
crystals extend from the surface of the droplets (Figures 2, 3 and 4) out
into the bulk of the external phase, we see the classic dramatic increase in
viscosity, which is shown in Figure 5.

Figure 2. Lamellar gel networks surrounding emulsion droplets

More specifically, Figure 2 shows the formation of a gel network,

which extends from the surface of the droplets out into the bulk of the
external phase. This increases the viscosity and impedes droplet movement. This is the reason fatty alcohols thicken emulsions! Both Figures
2 and 3 show the emulsion droplets surrounded by a highly structured
lamellar liquid crystalline gel network acting to reduce the likelihood of
particle coalescence. Figure 4 is a photomicrograph, which clearly shows
the birefringence, which is the hallmark of liquid crystals surrounding
emulsion droplets.

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(photo by Uniqema)

Figure 3. Lamellar gel networks surrounding emulsion droplets

Figure 4. Phase contrast microscopy of liquid crystals

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