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Factors & HLB Calculation

Selecting and Evaluating Emulsifiers for

Cosmetics

It takes a lot to develop complex cosmetic formulations that come

up to our expectations. Today, we are lucky to have a wide range of
different ‘drop-in-and-go’ technologies. They help us balance
creativity with emulsifiers under tight deadlines.

Get detailed information about:

the role of emulsifiers in cosmetic formulations, and the end-

consumer benefits they provide
the emulsifier types used to create emulsions and which one to
choose from
the selection & evaluation factors to consider while using them

After reading this guide, resume your emulsifier selection.

We would like to acknowledge Amanda Foxon-Hill and Nick Morante for providing
technical information needed to develop this guide.

Overview

How do emulsifiers stabilize mixtures?

Emulsions are systems composed of two or more immiscible materials. Here, one material suspends
or disperses throughout another material in separate droplets. The immiscible phases can be water,
oil, or silicone.

While making emulsions, surfactants called emulsifiers slower the separation of the immiscible
phases. All emulsions are unstable with the exception of some spontaneously forming
microemulsions.
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Simply put, any combination of unlike phases that are put together can be considered a type of
emulsion. Emulsions are classified by:

The continuous phase (external)

The discontinuous phase (internal)

The use of homogenizers and other equipment to minimize droplet size will improve the stability of
an emulsion.

When naming the emulsion type, the first letter is the discontinuous phase.

O/W stands for oil-in-water and is classified as an emulsion.

W/O stands for water-in-oil and is classified as an invert emulsion.
These types of emulsions are much more difficult to stabilize than oil-in-water systems.
They also must have much smaller droplets to help them stay together longer.

Making emulsions can sometimes be fun, and sometimes not. When things go well, it certainly is a
lot of fun. In all cases, emulsions vary in the size and type of each of the phases. This phase ratio is
critical in determining the characteristics and performance of the resulting product.

Changing the phase ratio alters the physical properties of the emulsion. It is the emulsifiers that help
keep emulsions together.

Benefits and Limitations

Creating cosmetic formulations could be a task without having comprehensive knowledge about the
ingredients involved in it. Before adding any ingredient, it becomes necessary for you to know about
the strengths and weaknesses it imparts.

Considering these aspects beforehand, you could decide if the additive is actually required or not. If
added, would it give an extra edge to the end product? Also, it could help you to engineer his
formulation to achieve desired end-use requirements.

Similarly, it is wise to look upon emulsifier benefits and limitations to stumble upon the right
emulsifier. The table below discusses emulsifier benefits in cosmetics and some limitations
associated with them.

Emulsifiers

Benefits Limitations

Correct use of emulsifiers creates

homogenous mixtures, dispersions or Being physically unstable they get separated
emulsions of oily or waxy substances with into distinctive phases.
water.

Addition of emulsifiers helps solids to be The dispersed oil droplets can fuse together
dispersed in liquids or insoluble liquids with and rise in o/w emulsion or may get settled
other liquids. down in w/o emulsions.

Greasy anhydrous creams can be modified to Permanently irreversible separation and

washable ones. fusion of the dispersed phase may occur.
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 Conversion of w/o to o/w (or vice versa) can
be observed.

Which emulsifiers are based on ingredient's chemistry?

Anionic Emulsifiers

Anionic emulsifiers are, in some ways, the old-fashioned cousins when it comes to emulsifier
technology. Soap-based emulsifiers can be extremely useful in cleansing formulations. But they can
also form part of a very elegant high-end anti-aging formulation as long as your selection of actives
is carefully chosen.

Anionic emulsifiers carry a net negative charge in solution. Thus, they are sensitive to
electrolytes like cations.
Anionics benefit from the presence of a little monovalent salt or acid up to a point. It increases
the saltiness/acidity up to critical micelle concentration and activity of the water phase).

Above that, the formula can critically fail in a similar way like over-salted surfactant blends. Salt
content can creep up in an active formula containing ingredients such as:

Aloe
Sodium PCA
Seaweed Extracts
Sodium Hyaluronate, and
even some herbal actives can push the limits

As such, freeze/ thaw stability is an essential part of early anionic emulsion stability testing

The old pharmacopeia-driven Sodium Lauryl Sulfate has been replaced. This is because of its ‘harsh-
on-skin’ reputation. Anionics, especially elegant phosphate esters are known for their skin
compatibility. Gentle surfactants such as lactylates or glutamates make it possible to make an
anionic emulsion that is kind and gentle on the skin. Anionic emulsifiers are the most commonly
used in emulsions. For example, Sodium Laureth Sulfate.

The PEG-100 part of the emulsifier is a function of adding Polyethylene Glycol, or PEG. This process
is called ethoxylation which is a common attribute of anionic emulsifiers. They are also compounds
that have been ethoxylated. This process creates ingredients that have varied amounts of water
solubility.

The higher the amount of ethylene oxide (or EtO for short), the more water solubility the emulsifier
has.

The one major issue with ethoxylates is that they can be irritating at high levels. The molecular
formula for Polyethylene Glycol is given below, where "n" is the number of moles of ethylene oxide in
the molecule.

OH–(CH2–CH2–O)n–H

Structure of Polyethylene Glycol

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Cationic Emulsifiers

Cationic technology for skin care arose from the wool industry. It then transferred to hair care. Hair
care and skin care are both keratin-derived. Hence, it didn’t take long for the benefits of cationics to
harness. These advantages took place in moisturizer technology.

Cationics function very well in formulations that are desired to stay on the skin for a long time such
as:

sunscreens,
long-wear make-up, and
barrier creams

This is because, they have a positive charge. The cationic charge adheres these products strongly to
the surface of the skin. This thereby resists wash-off and wear. An example of cationic emulsifiers is
in preventing sand from sticking to a freshly-sun-screened body. Thanks to its anti-static capacity.

Like anionics, cationics are also sensitive to what is going on in the water phase. They can cope best
with a relatively quiet external phase rather than one loaded with additives. Due to their natural
capacity for skin adhesion, they can be more likely to irritate than other chemical families. Having
said that, in many cases, the formulator can work around this – formulating to an acidic pH is
advisable.

The new generation of cationic emulsifiers tends to favor long hydrophobic tail(s). These tails have
the effect of reducing the charge density of the head group. This thus minimizes the irritation
potential. This, of course, must be balanced by the ingredients' capacity to form and hold an
emulsion.

As with anionic emulsifiers, cationics do benefit from a little monovalent salt. This can boost the
CMC and as a consequence, the viscosity. But beyond a certain point, the salt becomes detrimental
to stability.

Note: While using a cationic emulsifier system the formulator does rule out the use of pretty much all
grades of Carbomer, and even anionic thickening agents such as xanthan, unmodified guar and
tragacanth.

Cationic emulsifiers are those that are mostly used in hair care products. These are commonly called
quaternium ammonium compounds or "quats". An example is Distearyldimonium Chloride.

Apart from having excellent emulsification capabilities, they act as hair conditioners. This is
because of their natural electrical charge in association with that of the hair.
They also have very good preservative activity such as Quaternium-15 (Hexamethylenetetramine
Chloroallyl Chloride or Dowicil™ 200). These ingredients are very substantive and quite
functional.

One disadvantage of cationics is that they can be somewhat irritating at high levels. The irritancy is
more so than the anionic emulsifiers with higher levels of ethoxylation.

Cationic emulsifiers exhibit a charge on the molecule with the use of a halogen ion, such as a
chloride or bromide. Below is an example of Quaternium-70 (Stearamidopropyl Dimethyl Myristyl
Acetate Ammonium Chloride). An ingredient that can act as a cationic emulsifier and anti-static
conditioning agent in hair care. Select Emulsifier with Anti-static activity »

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 Structure of Quaternium-70

Notice the ammonium groups [-NH-] and the chloride ion, which gives the molecule its negative
charge.

View Several Emulsifiers Chemistry with Non-Irritant Benefit »

Non-ionic Emulsifiers

Non-ionics emulsifiers remain the first choice go-to emulsifiers for most applications. This is due to
their flexibility and low potential for chemical interaction. Non-ionic emulsifiers are those that are free
from any external electrical charge caused by free ions. Examples of these are:

Polysorbate 80
Polysorbate 20

These are familiarly known as Tweens™, a common trade name for emulsifiers offered by Croda.

It is often a non-ionic emulsifier blend that is chosen first when creating creams with high activity
levels or hard-to-stabilize ingredients such as:

Salicylic acid
AHA’s
Zinc Oxide or high strength vitamin C

There were ingredients such as Seppic’s MONTANOV™ 68 MB that first got us hooked on the self-
emulsifying blend of non-ionic and freed us from the trials of calculating HLB in a complex oil-phase
world.

The key benefit of a non-ionic emulsifier is its robust salt tolerance.

In fact, the addition of a little non-ionic is recommended in ionic emulsions as the mixed micelles
that will form tend to display a dramatically enhanced salt tolerance over the ionic alone.

While the presence of self-emulsifying blends has made things easier, it doesn’t for a moment mean
we shouldn’t consider what is going on inside of our product.

The HLB system is alive and well in the non-ionic world and gives us a great insight into where the
emulsifier will orient itself and whether it is able to bring any other features to the product. That said,
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it is also important to mention the existence of more than one HLB system so that one can compare
like with like.

Liquid Crystal Emulsifiers

Liquid Crystal Emulsifiers work on the principle of forming a lamella network in the cream. This most
closely mimics the skin barrier. This facilitates the effective delivery of actives. Lecithin naturally
works this way, as does Olivem 1000 and various other combinations available to purchase today.

Because of their skin-like structure, liquid crystal emulsifiers are often desired for their beautiful
aesthetics.

While it is possible to create a range of textures using almost any emulsifier, depending on what goes
into the rest of the formula, it would be reasonable to say that the liquid crystal generating emulsifier
is the most foolproof way of creating a beautiful texture without too much additional work.

Polymeric Emulsifiers

Polymeric emulsifiers are a good option for those looking for elegant and quick cold-process
solutions. They are often sold as liquid polymer suspensions. These emulsifiers can create anything
from lightweight sprayable milk to thicker, richer creams. This depends on what they are paired with.

Related Read: Formulating with Polymeric Emulsifiers for Sensory Benefits

While not for the natural market, these can be quite a sustainable option, due to:

Their low addition rate

The speed with which they can form an emulsion, and
Their cold processing capabilities

Polymeric emulsifiers won’t work in every situation. Often these emulsifiers are acrylic acid polymers
that tend to form complexes with cationic species.

In addition, the general salt tolerance of acrylates is low. This reflects the overall intolerance of
ionic substances).

They have one big advantage over ionic and non-ionic emulsifiers. It is their ability to form highly
stable emulsions with a very low level of polymer (with a non-polar or very slightly polar oil phase).
This makes them the perfect emulsifier for a silicone-based emulsion, even those containing
cyclomethicone.

Why is the stability of emulsions important?

As we have learnt so far, it is clear that emulsions are dispersed multiple-phase systems. They are
made out of at least two nearly immiscible fluids; one being dispersed in the other. The dispersed
phase forms droplets, which are surrounded by the continuous phase. Multiple emulsions are very
complex systems.

Compared with simple emulsions consisting of only two phases, much more destabilization Back to Top
processes need to be taken into consideration for complex emulsions. In cosmetics and personal
care products, complex emulsions are useful to prepare: :

sustained release aerosol fragrances,

prolonged skin moisturizers and protection of sensitive biologicals,
personal care formulations for perfumes, skin lipids, vitamins, and free radical scavengers, and
much more.

Thus, guaranteeing long-term stability of cosmetic emulsions is necessary. But it can be difficult &
costly. As many factors trigger instability, you may lose too much time finding the right causes &
appropriate solutions. Join our exclusive course to solve cosmetic emulsion stability issues faster.

Moreover, we are going to discuss a few destabilizing and stabilizing factors in the sections below. Let's
understand how critical it is to study the phases before making the right selection of emulsifier(s)
beginning with understanding of water phase.

What is the importance of chemistry of the water phase?

An emulsion is a combination of two immiscible phases held together. This looks and feels like
magic to many! What is really going on is a physical rearrangement of components, all trying to get
themselves into a position that means they are exerting the lowest possible amount of energy –
those dispersed phase droplets are lazy!

The dispersed and continuous phases are influenced by everything that comes into the formula.
Some things are more disruptive than others.

Impact of Surface Tension in Water Phase

The surface tension between oil and water is so high that they don’t mix unless you add a surfactant
(emulsifier in this situation). We understand that and have discussed the different types of
emulsifiers that we could add. But do we understand what other ingredients do to the product’s
surface tension?

Preservatives and solvents can dramatically alter the surface tension between the oil and water
droplets. As we see with our emulsifier, some reduction in surface tension is required to facilitate the
development of an emulsion. But in other cases, the changes are catastrophic and can result in
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viscosity and emulsion collapse.
Glycerin, Propylene Glycol, and Ethanol are common additives in a cosmetic product. They can all
impact surface tension. All of these ingredients decrease the polarity of the water phase. This thus
decreases the changes depending on the quantity of additive present. Although the relationship
between dose and effect is not strictly linear.

Reducing water phase polarity loosens the grip the water has on the dispersed phase somewhat by
toning down the intramolecular forces that make water behave as it does – Van Der Waals, Dipole-
Dipole and hydrogen bonding.

All emulsifiers depend on these forces to some degree to stabilize the product. The Ionic emulsifiers
depend on them more strongly. Thus, they are most likely to be influenced by their presence.

Impact of Ions in Water Phase

We often talk about salt and saltiness in formulating, but what we really need to talk about is the
ionic strength of the continuous phase.

The swapping of demineralized water for seawater might cause formulary issues. We are less likely
to accept that the actives we carefully measure into our water phase are doing the same. Be they
acids, bases, or salts, an ion-rich water phase, can cause havoc, for the stability of a product.

Ionic charge in the water phase can help increase intramolecular bonding. It can also help in the
formation of an electric double layer around the dispersed phase. This increases stability but things
can go too far, especially with:

Divalent salts such as zinc

Strong acids, and
Oxidizing agents such as glycolic and peroxide

In general, the cosmetic chemist is looking to minimize chemical reactions in their formula. So any
addition of ions should be thought of as fueling the fire of chemical rebellion. Every emulsion has its
limits, plus adding too many ions into the continuous phase will give the product a sticky/tacky/salty
feel when applied.

Can oil phases get tricky to handle?

When compared to vegetable oils, silicones demonstrate practically no polarity. They also have very
different chemical structures – flexible chains vs bulky triglycerides. Because of these differences,
silicone fluids tend to mix poorly or not at all with vegetable oils in the same formula. Some Back to Top
examples of silicone fluids include dimethicone and cyclomethicone.

If the formulator wishes to create a silicone-rich emulsion, he should consider the influence of this
low polarity.

Steps to reduce the polarity of the continuous phase would increase stability. It will take some of the
pressure off the emulsifier as the surface tension between the two phases decreases.

Related Read: Predictive Cosmetic Formulation via HLD - From Triphasic Emulsions to Single-phase
Emulsions

Silicone emulsifiers are available from the major silicone manufacturers. It should be the first port of
call for all those looking to create a silicone-dominant emulsion. Especially where the silicone phase
will be large or even dominant. Having said that, with careful consideration, it is also possible to
create a silicone-rich emulsion with non-silicone emulsifiers. This is possible if we consider the
chemistry of the whole product.

Solubility Parameter
(A difference of <2 indicates
Solvent Polarity mutual structural solubility)
Based on the theory of ‘like
dissolving like’

Water 23.40

Glycerin 16.26

Lactic Acid 14.81

Propylene Glycol 14.00

Ethanol 12.55

Isopropyl Alcohol 11.24

Cetyl Alcohol / Stearyl Alcohol 8.94 – 8.90

Castor Oil 8.90

Isopropyl Myristate 8.02

Olive Oil 7.87

Isopropyl Palmitate 7.78

White Mineral Oil 7.09

Squalene 6.03 - 6.19

Cyclomethicone D5 5.77

Dimethicone 5.92

Is your emulsion going to be salty, acidic, or basic? Or does it contain a high proportion of solvents
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that are less polar than water? Or does it contain Hydrogen Peroxide? If so, the best starting point is
non-ionic.

The regulation requires that any cosmetic product has guaranteed stability & integrity until shelf-life.
It takes lots of time to run stability tests. We all want to avoid as many stability issues in the final
development steps which would imply starting everything all over again!

Take this exclusive course to define reliable & efficient test plan to best combine predictive tests
(accelerated / long-term testing, micro testing...) depending on your formulation (highly viscous...).

What are the type of emulsifiers?

As water and oil do not mix, emulsifiers in cosmetics assist in forming homogenous mixtures of
both. Emulsifiers in cosmetics stabilize the emulsion and influence the consistency of the
formulation. Most of the cosmetic products make good use of emulsifiers in their formulations like:

Creams
Lotions
Sprays, and
Foams

Some common emulsifiers in cosmetics are:

Oil-in-water
Water-in-oil
Natural emulsifiers
Silicone emulsifiers, and
Co-emulsifiers

Key Features of Various Types of Emulsifiers

Oil-in-water (O/W) Water-in-oil (W/O) Natural Silicone

Derived from
Can be synthetic Can be synthetic Reduce the cost
natural resource
Keeps oil drops Keeps water of the overall
They are much
packed in water droplets packed formulation
into being due to
Used for in oil Water-in-silicone
a global
moisturizing Used for a fatty (W/S) emulsifiers
emphasis on
effects feel last longer
going green

Oil-in-water Emulsifiers

Oil-in-water emulsifiers create oil-in-water emulsions. In oil-in-water (o/w) emulsion systems, oil
droplets are dispersed in water.

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 Oil is the internal/ dispersed phase whereas water is the
external/continuous phase.
O/W emulsifiers are more soluble in water than in oil.
O/W emulsifiers have an HLB greater than 15.

The emulsions produced with the help of oil-in-water emulsifiers have

certain advantages, disadvantages and applications which are
discussed below.

Oil-in-water Emulsifiers

Advantages Applications Disadvantages

Oil-in-water emulsions
have a good spreadability
on skin.
They are economical and
can be easily Used in personal care
More vulnerable to
manufactured. products like:
microbial attack and
They have good physical Cleansing milks
bacterial contamination.
stability. Hair conditioning
Do not prove to be cost
Are stable at formulations
effective as addition of
temperatures even below Shaving creams
preservatives is required
0°C. Moisturizing lotions,
to prevent degradation of
Oil-in-water emulsions and
the formulation.
provide a cooling effect to Sprayable emulsions
the skin as water
constitutes the external
phase of these
emulsions.

Listed below are few oil-in-water emulsifiers along with their main properties and applications.

Product
INCI CAS Applications Main Properties
name

PEG-8
PROPYLENE Skin / Sun
Emulsynt™ GLYCOL 9007-48-1, care Acts as a water-in-oil, water-in-
1055 COCOATE 977061-81-6 Hair care silicone emulsifier as well as
and Fragrances auxiliary stabilizer for oil-in-
(Liquid) POLYGLYCERYL- 126645-98-5 Toiletries/ water preparations.
4 Make-up
OLEATE

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 Acts as a bodying agent, co-
emulsifying agent, emulsifying
Skin / Sun agent (o/w), emulsion
STEARAMIDE 111-60-4
HallStar® care stabilizing agent and viscosity
AMP and
EGAS Hair care stabilizer.
68951-62-2
Fragrances Is plant derived / vegetal-based
GLYCOL or
(Flakes) Toiletries/ and biodegradable.
STEARATE 36284-86-3
Make-up Provides good electrolyte
stability for both hair and skin
conditioning emulsions.

Acts as bodying agent, co

Skin / Sun
HallStar® emulsifying agent, emulsifying
11099-07-3 care
GMS SE GLYCERYL agent (o/w) and emulsion
and Hair care
STEARATE SE stabilizing agent.
593-29-3 Toiletries/
(Flakes) Is biodegradable, plant derived /
Make-up
vegetal-based.

Acts as a bodying agent, co-

emulsifying agent, emulsifying
agent (o/w), emulsion
PEG-100 Skin / Sun
HallStar® stabilizing agent and viscosity
STEARATE care
GMS SE/AS 123-94-4, stabilizer.
Hair care
9004-99-3 Is plant derived / vegetal-based
GLYCERYL Toiletries/
(Flakes) and biodegradable.
STEARATE Make-up
Provides good electrolyte
stability for both hair and skin
conditioning emulsions.

Water-in-oil Emulsifiers

Water-in-oil emulsifiers help in producing water-in-oil (w/o) emulsions.

In W/O emulsions, water droplets are dispersed in oil (oil encases
water).

The oil comes in contact with skin first providing more greasiness.
These emulsifiers are more soluble in oil than in water.
They have HLB between 2.5-6 are non-ionic or polymeric.

Emulsions produced by W/O emulsifiers aid in protecting and nurturing

dry and dehydrated skin (moisturizing effect). Thus, these are brought
to use in moisturizers, dry skin care, skin-nourishing lotions, etc.

The benefits of water-in-oil emulsifiers are given below along with their disadvantages and
applications.

Water-in-oil Emulsifiers

Benefits Applications Limitations

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 W/O emulsions are used in
Water resistant
manufacturing skin care
Lustrous and glossy
products like: When applied , these may
Opaque and
Lotions give a heavy and greasy
Great skin feel
Sunscreens feeling on the skin
Smooth application
Cold creams, as they Often difficult to obtain
Milder than o/w and do
are more water stable W/O systems,
not harm the lipid bilayers
resistant than O/W addition of stabilizers
in the skin
emulsions may be required
Less susceptible to
Make up products,
microbiological attack
with all types of oil

Some water-in-oil emulsifiers are listed below along with their properties and applications.

Product
INCI CAS Applications Main Properties
name

Glyceryl caprylate.
Capmul® Skin care
Acts as water / oil emulsifier.
MCM C10 GLYCERYL Fragrances
26402-22-2 Recommended for creams,
CAPRATE Toiletries/
lotions, ointments and
(Powder) Make-up
lipsticks.

Highly efficient emulsifier for

water-in-oil systems.
METHOXY
Elfacos® E Has a high water retention
PEG-
200 capacity that allows the
22/DODECYL 88507-00-0 Skin care
formulation of light creams
GLYCOL
(Paste) with a very high water content
COPOLYMER
that do not leave the skin
feeling greasy.

Used in W/O emulsions,

particularly suitable for liquid
and modern, soft preparations
Cremophor®
PEG-7 that are known as soft creams.
WO 7
HYDROGENATED 61788-85-0 Skin care Acts as a non-ionic emulsifier.
CASTOR OIL Does not leave a noticeable
(Liquid)
fatty sheen on the skin but
produce a visible cosmetic
effect.

Acts as a W/O emulsifier.

Dehymuls® POLYGLYCERYL-
Used in W/O creams containing
PGPH 2 144470-58-
Skin care greater fractions of high
DIPOLYHYDROXY 6
molecular oils, like vegetable
(Liquid) STEARATE
oils.

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Co-emulsifiers in Cosmetics

Co-emulsifiers are added to improve the viscosity and stability of the resultant emulsion. Borax, cetyl
alcohol, cetearyl alcohol, etc. are some examples of co-emulsifiers in cosmetics.

Product
INCI CAS Applications Main Properties
name

Cerasynt®
PROPYLENE Skin care
PA ester Acts as an opacifier, pearlizer
GLYCOL 1323-36-3 Hair care
and co-emulsifier.
STEARATE Toiletries
(Flakes)

Cetyl hydroxyethylcellulose, co-

Skin care
emulsifier, lubricant and
Hair care
Natrosol™ CETYL thickener.
Sun care
PLUS CS, HYDROXYETHYL 80455-45-4 Stabilizes O/W emulsions.
Decoratives/
Grade CELLULOSE Used in shampoos, cosmetics,
Make-up
shower gels, foam bath and
Toiletries
facial wash.

Skin care
Pluracare® Hair care
Acts as a non ionic surfactant.
F127 POLOXAMER Sun care
9003-11-6 Possesses solubilizing, bodying
407 Decoratives/
and gelling properties.
(Solid) Make-up
Toiletries

Acts as an EO free thickener

Hostacerin®
and co-emulsifier for O/W
DGMS POLYGLYCERYL-
61725-93-7 Skin care emulsions.
2 STEARATE
Used in liquid and creamy oil-in-
(Pellets)
water emulsions.

Silicone Emulsifiers in Cosmetics

Silicone-based emulsifiers are generally liquid at room temperature. There are two general structures
for this class of emulsifiers.

The first one is a rake silicone polyether in which the polyether segments are attached to a
silicone backbone. It allows the addition of alkyl chains to increase their compatibility with
organic oils.
The other structure is an (AB)n silicone polyether, where the polyether segments are added
within the silicone backbone.

These emulsifiers have an affinity for silicone and organic oils. This makes the oil phase flexible
enough for the addition of other specialty silicones. Silicone emulsifiers help to reduce the cost of
the overall formulation by emulsifying up to 80% water. Back to Top
Moreover, water in silicone (W/Si) emulsifiers last longer and are wash resistant when compared to
O/W emulsifiers. Silicone emulsifiers find uses in almost all skin care products.

Natural Emulsifiers in Cosmetics

Natural emulsifiers, as their name says, are naturally sourced. Since their introduction to the
cosmetic industry, they have received an overwhelming response. Thanks to the "global go-green"
emphasis.

Natural emulsifiers in cosmetics are more susceptible to microbial attack. Hence, the formulation
needs the addition of a preservative. They are not too effective as emulsifiers which call for their
addition in large quantities. Though a natural emulsifier-containing formulation has an extra edge
over others, it can have some serious repercussions on the skin of the end-user.

Being naturally sourced, natural emulsifiers in cosmetics can prove potential allergens to some
individuals.

Lanolin - sheep's water-free wool fat is a natural emulsifier that serves as a bond between water
and oil. It is added to skin care creams.
Lecithin is a natural emulsifier that can be used alone or in combination with other emulsifiers.
They are usually based on chemicals called phospholipids and can be both plant an animal
derived.
Depending upon the quantity of lecithin added, a formulator can achieve the desired
consistency in a lotion.
It is majorly used in skin care formulations due to its emollience/ moisturization effect.
For hair care applications, in addition to lecithin, pectin and glycerin is also used.
Beeswax, another natural emulsifier finds good use in lip balms, lipsticks, ointments, etc.

Product
INCI CAS Applications Main Properties
name

Acts as a thickener, foam

stabilizer, re-fatting agent,
Skin care detergent, emulsifier and
ALKOLAN®
PALM Hair care solubilizer for fragrances and
CD 80
KERNELAMIDE 68155-07-7 Sun care essential oils in the
DEA Fragrances formulation of personal care
(Liquid)
Toiletries products.
Exhibits emolliency and
neutralizing properties.

Used as extremely mild

SODIUM surfactants, especially in
Phoenotaine®
COCAMIDOPROPYL Skin care baby products such as
C-35
PG-DIMONIUM 83682-78-4 Hair care shampoos, bath and shower
CHLORIDE Toiletries gels, body wash, bath beads,
(Liquid)
PHOSPHATE and products used in
personal care.

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 Acts as a natural emulsifier.
GLYCINE SOJA
Phytocompo™ Enhances barrier properties,
STEROLS 92128-87-
-PP Skin care moisturizes skin and provides
5,
Hair care a unique skin feeling.
HYDROGENATED 68555-08-8
(Powder) It can be used in synthetic
LECITHIN
surfactant-free products.

Skin care
Hair care
Lecinol S- Used in cosmetics.
Sun care
PIE HYDROGENATED Possesses good heat and
92128-87-5 Fragrances
LECITHIN oxidation stability compared
Toiletries
(Powder) to natural lecithin.
Decorative/
Make-up

Which factors influence emulsifier selection?

There are four main factors that deserve consideration:

1. Marketing/ Product Positioning

2. Performance
3. Physical Character
4. Chemistry

As Cosmetic Chemistry is an applied science, it is appropriate to start with the marketing as this is
the main reason for us embarking on this formulation work.

Marketing

#1 Emulsifier-Free Claim

An emerging niche of ‘emulsifier-free’ creams designed around the

philosophy that the emulsifier, being a surface-active ingredient, may be a
source of irritation for very sensitive skin and that avoiding the use of an
emulsifier may make the product more suitable for this demographic.

Now, this may or may not work out to be true. But nevertheless, the
concept is of interest as there is some truth in the idea that surface-active
ingredients (of which emulsifiers are a part) can contribute to a product’s
irritation potential.

So, if you don’t use an emulsifier to hold the oil and water together, what
do you use?

Small amounts of oil can be held in suspension with the use of thickeners/
stabilizers such as Carbomer, and even xanthan and sclerotium gums to a
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lesser degree. These aren’t emulsifiers and neither are they forming an
emulsion, more of a suspension. But if the oil phase is light and dispersed well enough, these
products can be made stable through steric hindrance – the oil droplets are caught up, as if in a
fishing net!

Sometimes bentonite clays can also be used in this way. They bring opacity to the formula. They also
provide an electrical repulsion layer into the structure to help repel agglomeration of the dispersed
phase.

Another option in this space is a modified acrylate copolymer such as Acrylates/Beheneth-25

Methacrylate Copolymer.

Although this polymer is best suited to surfactant formulations, it does have a role to play in
leave-on skin care.
It is tolerant to relatively high levels of salt and other water-phase destabilizers. This makes it a
versatile choice for the ‘emulsifier-free’ concept developer.

The fact that the polymer can stabilize a reasonably sized oil phase while remaining ‘emulsifier-free’
paired with its low use levels adds to the cost efficiency of this solution. Another interesting feature
of these polymeric ‘emulsifier-free’ ingredients is their ability to be sprayed. This opens up new doors
for the formulator and marketing department.

What if you are looking to create something a bit richer and with an oil phase more typical of a
traditional moisturizer?

Modified lecithin chemistry has become the accepted technology in the ‘no emulsifier’ space.
This is especially because these lecithin fractions often have lipid-enhancing properties. It can
be sold on their ‘skin compatibility’ and moisture-binding powers. In addition, the phospholipid
structure also lends itself to active delivery given how similar in structure they are to human cell
membranes (well at least in terms of their chemical constituents).
Lecithin chemistry forms a liquid crystal network in the continuous phase. It traps and interacts
with the dispersed phase in an ultra-stable and skin-compatible 3D structure.

A number of companies are now offering a range of modified lecithins. They are suitable for
everything from light hypoallergenic milk formulations to super-rich balms which should please
marketing departments all over the world. But from a chemist's perspective, it is hard to see how
these ingredients have managed to escape the ‘emulsifier’ tag.

#2 Ingredient Origin and Ethics

Another important consideration for the general public and formulators alike is ingredient
sustainability and/or ethics. There is a steady yet growing interest in ‘palm oil-free or sustainable
palm’ concepts, the achieving of which is surprisingly difficult. That said, making an emulsion without
adding any palm derived ingredients used to be easy – just use petroleum derived chemicals – but
these days that is just as unacceptable for a growing number of brands.

The reality is, our enthusiasm for embracing the natural revolution has increased demand for
vegetable-based feedstock and those of us who have been in the industry for a while know that
means either palm (orang-u-tan habitat) or Rapeseed/ canola (pesticides and bees).

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So today while it is still not easy to create palm free emulsion it is not impossible too, given that our
previous ‘emulsifier free’ examples are predominantly palm free (lecithin phospholipids are frequently
made from Rapeseed, Egg, Soybean and/or Sunflower).

In fact, it would be fair to say that the hardest thing about making a palm free emulsion today is not
over which emulsifier to choose, but which supporting ingredients can be used to increase stability,
viscosity (without gumminess) and overall skin feel.

#3 INCI Name – It Has To Look Good On The Label!

Still, under the guise of marketing issues, the issue

of INCI names also comes up here. While ingredient
manufacturers do have to abide by a ‘truth in
marketing’ legislation when they apply for their INCI
names (they can’t just make them up). The reality is
that a natural sounding INCI will sell more and have
better shelf appeal than a more chemical sounding
ingredient.

This reality has really hit home and that can be both good and bad. In some cases, we have very
average ingredients (in terms of performance) becoming popular. This is because they have a nice
name while outstanding ingredients (that are still natural in many cases) are overlooked.

» Click Here to Get Information on Cosmetic Ingredients from SpecialChem's INCI Database
Directory!

#4 Show Me The Money!

Another important factor in the marketing basket is price. Emulsifiers can make quite a dent in the
formula budget. When comparing something natural to a stock-standard petroleum-based emulsifier
you can be looking at anything from three to five times the price which of course has to be justified.

In many ways this is the acid test – will customers put their money where their ethical mouths are or
do we have to sell them another benefit? Blending different technologies together can be a good way
to increase performance while managing price. This philosophy has kept many of the older
emulsifier’s options such as glyceryl stearate SE alive and selling well.

Performance

Performance benefits of different technology have been looked at more in the chemistry section. But
seeing from some of the claims related to emulsifier-free formulations, the ingredient that holds theBack to Top
oil and water together is, in many cases expected to do so much more besides.
When the Olive-derived Emulsifier Olivem 1000 first came onto the market there was a great deal of
interest in its ability to:

act as an active delivery system

make an emulsion possible

This contributed to the ‘emulsifier-free’ marketing tagline (it isn’t an emulsifier; it is an active delivery
system). It also helps the cosmetic chemists deliver oil-soluble actives deep into the skin
(theoretically).

This important dual functionality contributed to the immediate success of this technology. The
success continues today in spite of the ingredients' high price point compared with older
technologies. For example, cetearyl alcohol will form liquid crystal structures for a fraction of the
price!

In terms of integrating new emulsifier technology into the laboratory these days, the real question
isn’t the price. But it is how many benefits one gets for that price. The following benefits are possible
thanks to the combination of science and nature:

Water resistance
Barrier protection
Long-wear characteristics
Increased dispersion of actives
Viscosity boosting, and
Rheological benefits

Physical Character

Something that we may overlook when considering price is the emulsifier’s physical form. This is
because we often just think of emulsions as hot-process items and so the form of the emulsifier is
not really a talking point. But it doesn’t have to be that way.

Electricity prices are rising in many countries and even those with cheap power aren’t in the habit of
wasting it. So liquid emulsifiers that can be used in cold-process applications can help the formulator
to tick a few boxes from sustainability to the economic benefits of saving time and money.

The range of liquid emulsifiers is steadily growing and is worth a look, especially for markets that
demand an ultra-light touch finished product with little to no wax or butter content.

Chemistry

Of course, we couldn’t talk about emulsifier selection without talking about the chemistry. The
emulsifier is the heart of the formula and while it may often seem like, today the chemistry has all
been done for you, as mentioned in the beginning, there are some very challenging problems that
await the professional cosmetic chemist that only an appreciation of the underlying chemistry will
help solve!

Don't Let Complicated Emulsifiers Selection Rules Hinder Attainment of your Perfect Formulation!

Take our advanced course in emulsifiers selection to develop superior emulsions and other
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surfactant-based systems design by knowing the formulation constraints: how ingredients interact,
changing consumer tastes, call for restriction in use of certain higher-performing ingredients, etc.

How to select emulsifiers using HLB system?

While preparing an emulsion choosing an emulsifier can be cumbersome. HLB system was
introduced to save time and stumble upon the right emulsifier/ emulsifiers for an application. HLB
stands for Hydrophile-Lipophile Balance (balance between the hydrophilic portion to the lipophilic
portion of the non-ionic surfactant).

Between 1949-1954 Griffin developed a pretty robust yet simple HLB system and that is the
standard upon which the Span and Tween pairings from ICI were arranged.
The HLB system assist the formulator in making decisions about the types and amounts of
emulsifiers needed to create stable products.
The method produced a scale ranging from 0-20 indicating what percentage of the emulsifier
was hydrophilic. The number given was the percentage hydrophilicity / 5 (so the maximum
number 20 related to a molecule being 100% hydrophilic).

Every ingredient we use has a required HLB value assigned to it based on its physical properties.
Ingredients are either oil or water loving. Lower number being hydrophobic behavior - hating water (or
lipophilic - oil loving) and 20 being very hydrophilic - water loving (or lipophobic - hating oil). The
nominal HLB range is usually 2 to 14, with a midpoint of 7 (or HLB balanced).

Emulsifiers are rated by their affinity for oil or water. If an emulsifier has a low HLB number, there is a
low number of hydrophilic groups on the molecule and it will have more of a lipophilic character. The
higher HLB number would indicate that the emulsifier has a large number of hydrophilic groups on
the molecule and therefore should be more hydrophilic in character. Emulsifiers with low HLB values
are considered water-in-oil emulsifiers. Emulsifiers with high HLB values are considered oil-in-water
emulsifiers.

A cosmetic emulsion can be stabilized by using emulsifiers that match up with the ingredients in the
formula. Ingredients with low required HLB values need low HLB emulsifiers. Ingredients with high
required HLB values need high HLB emulsifiers. The HLB system assist the formulator in making
decisions about the types and amounts of emulsifiers needed to create stable products.

This simple system was expanded upon by Davie’s in 1957, who thought that some weight should be
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given to the functionality of the chemical groups on the molecule.

This makes sense given the variety of structures available to give a hydrophilic character.
This method is widely used today and is one of the reasons that ionic emulsifiers can be
assigned an HLB value.
It is also the reason that HLB numbers in 30’s is found (the maximum HLB in this system is 40).

While formulating both the emulsifier and the oils to be emulsified have an HLB attached to them.
The emulsifiers have a real HLB whereas the oils have a required HLB.

It is widely accepted that the best emulsifier pairings are formed when a high HLB emulsifier is
combined with an emulsifier with a low HLB rather than just selecting the emulsifier with the exact
HLB you want to achieve. This combination effect serves to best fill the interface surrounding the
continuous and dispersed phase, leaving less room for gaps and therefore increasing stability.

Calculating HLB Number of a System

In the HLB system, an ingredient or combinations of ingredients that need to be emulsified are
assigned a number and then an emulsifier having the same number is chosen to create an emulsion.

A lipophilic/oil-loving/non-polar emulsifier is assigned a low HLB number (below 9).

A hydrophilic/water-loving/polar emulsifier is assigned a high HLB (above 11.0).
The ones that fall in the range of 9-11 are intermediates.

Let's say for example we have a blend of emulsifiers to create an emulsion. To find out the HLB of the
blend the following calculations can be carried out:

Values: 70% Emulsifier 1 having an HLB number 15, 30% Emulsifier 2 having HLB number 4.3

HLB Calculation

Emulsifier 1 70% X 15 10.5

+ Emulsifier 2 30% X 4.3 1.3

HLB of Blend 11.8

Emulsifiers evaluation: What sets apart the best?

A very simple formula based on a common non-ionic

emulsifier – Cetearyl Alcohol and Cetearyl Glucoside has
been developed. This formula was then replicated with
different emulsifiers, one from each different class (except
silicone). The products were evaluated by an expert panel
of five people. They checked their viscosity before being
evaluated under the microscope.

The formula and feedback is not presented to help sway a

decision towards or away from a particular type of Back to Top
emulsifier. Merely it is to illustrate a point, that the emulsifier can impact everything from viscosity to
feel, efficacy to stability. It also demonstrates the importance of optimizing the whole formula so as
to get the most out of the emulsifier of choice. Plus there is always room for pairing up on
technologies or trying something new!

So the only difference between these formulations is the emulsifier except for the cationic version
which was incompatible with the thickener Acacia and Xanthan gum blend. In the cationic, a cationic
guar has been used at the same level. This could be seen from the table below:

Viscosity @ 3.0
Formula Skin Feel
Spindle

Cationic (Brassicyl Isoleucinate Thin, high spreading, slightly tacky to

Esylate (and) Brassica Glycerides touch at first drying to 19,380
(and) Brassica Alcohol) powdery

Silky, takes a while to absorb, feels

Anionic (Potassium Cetyl Phosphate) 90,630
substantive after drying.

Non-Ionic (Cetearyl Alcohol, Cetearyl

Easy to rub in 56,250
Glucoside)

Mixed Anionic/ Non-ionic. (Glyceryl

Stearate (and) Cetearyl Alcohol (and) Easily absorbed 74,690
Sodium Stearoyl Lactylate)

Non-Ionic Synthetic (Cetearyl Alcohol,

Very thick and creamy, light after feel 160,600
Ceteareth-20)

Polymeric (Acrylates/C10-30 Alkyl Ultra-light, quick break and high

15,310
Acrylate Crosspolymer) spreading. Tacky on drying.

Liquid Crystal Emulsifier (Cetearyl

Rich waxy texture, slow spreading 82,190
Olivate, Sorbitan Olivate)

HLB balance (Sorbitan Monooleate,

Very light and spreadable 13,440
PET-20 Sorbitan Monostearate)

Base formulation used could be observed from the table shown below:

Phase Ingredient % 200g Function

Water Phase Deionized Water 71.95 143.9 Solvent

Acacia and Thickener/

0.4 0.8
Xanthan Gum Stabilizer

Glycerin 3 6 Humectant

EDTA 0.1 0.2 Chelating Agent

Oil Phase Jojoba Oil 8 16 Emollient

Shea Butter 8 16 Back to Top

Barrier Protection
 Squalane 2.5 5 Emollient

Emulsifier of
3 6 Emulsifier
choice

Emulsion
Cetearyl Alcohol 1.25 1.25
Stabilizer

Finishing
Natural Vitamin E 0.5 1 Antioxidant
Touches

Perfume 0.3 0.6 Aroma

Preservative
Broad Spectrum
(Phenoxyethanol 1 2
Preservative
Ethylhexylglycerin)

TOTAL 100 200

Get Access to Emulsifiers Available Today!

View a wide range of emulsifiers (w/o, o/w, co-emulsifiers, etc.) available today, analyze technical
data of each product, get technical assistance or request samples

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ADEKA NOL F-108
ADEKA
Poloxamer 338. ADEKA NOL F-108 by ADEKA is an emulsifying agent in intravenous fat
emulsions, solubilizing agent, water gelling or wetting agent to maintain clarity. It is a mild
detergent & O/W... view more

ADEKA NOL L-44

ADEKA
Poloxamer 124. ADEKA NOL L-44 by ADEKA is a non-ionic, multifunctional, high-perfor‐
mance surfactant and cleansing agent with broad molecular weight & low toxicity. It is also
used as an emulsifier... view more

ADEKA NOL L-64

ADEKA
PEG/PPG-25/30 Copolymer (and) Poloxamer 184. ADEKA NOL L-64 by ADEKA is a non-
ionic, surfactant, solubilizer, stabilizer, co-emulsifier, foaming- and cleansing agent. It offer
good detergency and... view more

ADEKA NOL P-84

ADEKA
Poloxamer 234. ADEKA NOL P-84 by ADEKA is a non-ionic polymer surfactant, solubilizer
and dispersant. It functions as stabilizer, emulsifying, foaming and cleansing agent. It is
composed of... view more

DUROSOFT® PG10-O
Brenntag Specialties (EMEA)
Polyglyceryl-10 Oleate. DUROSOFT® PG10-O distributed by Brenntag Specialties (EMEA) is
a natural O/W emulsifier and emollient. It is ideal to make stable oil-in-water creams and lo‐
tions with a... view more

View All Products

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About Amanda Foxon-Hill

Amanda Foxon-Hill is a consultant Chemist and Science Communicator with over 14 years
of experience in the global cosmetics industry. She is a writer, after dinner speaker,
strategist and lecturer in all aspects of cosmetic science and runs a successful consultancy
practice under the name of Realize Beauty.

Amanda’s key skills are in networking and communicating ideas and opportunities both on a
business to business and business to market level. She is an advocate for green science
and through her team funds research into the development of more sustainable manufacturing practices.

About Nick Morante

Nick Morante is currently a Senior Chemist at IFC Solutions (formerly International

Foodcraft) in New Jersey where he works with many types of colors and additives for
both the food and cosmetics industries.

He has over 40 years of experience in the formulation of cosmetics, personal care

products and makeup products. Prior to joining IFC, Nick was a consultant to the
cosmetics industry for over 10 years providing custom formulations for clients as well as
giving presentations and seminars to various companies and organizations within the cosmetics industry
providing guidance in the practical use of color in consumer products.

He is current an adjunct faculty member at Fairleigh Dickinson University’s School of Natural Sciences in
Hackensack, NJ where he is an instructor in the Master of Science Program in Cosmetic Science.

Nick also spent over 30 years in Research and Development at The Estée Lauder Companies where he was
both a formulator and laboratory manager in the corporate makeup and hair care departments. He was also
in charge of the Color Science Laboratory where he was responsible for color measurement and
spectrophotometric analysis of finished products, ingredients and human skin as it relates to color that is
used in various cosmetic products, as well as developing testing protocols and methodologies for many
color applications.

Nick holds a Bachelor of Science degree from The New York Institute of Technology. He has taken numerous
continuing education courses in the area of cosmetic science. He is a long time member of U.S. The Society
of Cosmetic Chemists and has been active both on the local and national levels having served on the
executive committee for the Long Island Chapter and on the National Board, serving as Area Director and
National Secretary. He has been elected a Fellow of the Society and is an instructor for the Society’s
Continuing Education Program (CEP) Program in the area of color and makeup formulation problem solving
and troubleshooting.

He has given many seminars and presentations worldwide as well as to the SCC, CTFA and HBA. He has
been awarded numerous patents and has contributed many articles and papers and authored chapters in
numerous cosmetic, technical and beauty publications and texts.

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Rate this Content Publish

Nashay H Apr 25, 2023

This is thebest article I have found on explaining emulsifiers and emulsions in general.
Now I feel like I have a deeper understanding of how they work in products...thanks a
million for this information

Наталья М Jul 21, 2021

Нужная профессиональная информация. Спасибо.
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PAYAL A Jun 1, 2021
 Hi Vincent. Thank you for your feedback. We have made the correction.

Jorge R Apr 24, 2021

Excellent article. An optimal selection of theoretical and practical elements. This surely
is the best support that may be provided to help us for developing rational, focused,
balanced and succesful formulations with top profile . I can not wait for the next one.
Best regards from México.

Vincent O Jan 14, 2021

PEG-100 Stearate is not anionic, it is non-ionic.

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