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Emulsions: making oil and water mix

By Laura Cassiday

April 2014
After reading this article, you will understand:

the basic science of emulsions;

how formulators choose which emulsi er to use for a particular emulsion;
how emulsi ers are used in foods, nutraceuticals, personal and home care products,
industrial lubricants, environmental technologies, biofuels, and other applications.

The immiscibility of oil and water has inspired the proverb “Oil and water don’t mix” and
other expressions that re ect the general incompatibility of two entities, such as “My
coworker and I are like oil and water.” Yet within our homes are numerous examples of
products in which oil and water do mix: mayonnaise, milk, salad dressings, hand lotion, and
hair conditioner, to name but a few. These examples represent emulsions, which are stable
mixtures of tiny droplets of one immiscible uid within another, made possible by chemicals
called emulsi ers.

How emulsions and emulsi ers work

Simple emulsions are either oil suspended in an aqueous phase (o/w), or water suspended
in oil (w/o). Milk is an example of an o/w emulsion, in which the fat phase or cream forms
tiny droplets within the skim milk, or water phase. In contrast, margarine is a w/o emulsion
containing droplets of water or skim milk in a blend of vegetable oils and fat. In both cases,
emulsi ers are needed to prevent the suspended droplets from coalescing and breaking
the emulsion.

Anybody who has made a simple oil-and-vinegar salad dressing knows that, with enough
shaking or whisking, one can make a temporary emulsion. However, in the absence of
emulsi ers, this unstable emulsion breaks down within minutes, and the oil forms a layer on
top of the vinegar. For centuries, cooks have added natural emulsi ers, such as egg yolk,
mustard, or honey, to help prevent this separation. Today, a wide variety of nature-based
and synthetic emulsi ers are available for the diverse elds that bene t from them,
including food, nutraceuticals, home and personal care, biofuel, environmental cleanup,
and industrial lubricant applications.

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Emulsi ers work by forming physical barriers that keep droplets from coalescing. A type of
surfactant (see Sidebar), emulsi ers contain both a hydrophilic (water-loving, or polar) head
group and a hydrophobic (oil-loving, or nonpolar) tail. Therefore, emulsi ers are attracted to
both polar and nonpolar compounds. When added to an o/w emulsion, emulsi ers
surround the oil droplet with their nonpolar tails extending into the oil, and their polar head
groups facing the water (Fig. 1). For a w/o emulsion, the emulsi er’s orientation is reversed:
nonpolar tails extend outward into the oil phase, while polar head groups point into the
water droplet. In this way, emulsi ers lower the interfacial tension between the oil and water
phases, stabilizing the droplets and preventing them from coalescing.

Emulsi ers can be cationic (positively charged polar head group), anionic (negatively
charged head group), or non-ionic (uncharged head group). When charged emulsi ers coat
droplets in an o/w emulsion, the positive or negative charges on the outside of the oil
droplets electrostatically repel each other, helping to keep the droplets separated. Non-
ionic emulsi ers tend to have large, bulky head groups that point away from the oil droplet.
These polar head groups clash and tangle with head groups on other water droplets,
sterically hindering the droplets from coming together. The type of emulsi er used
depends on the application, with cationic emulsi ers typically used in low-to-neutral pH
solutions and anionic emulsi ers in alkaline solutions. Non-ionic emulsi ers can be used
alone or in combination with charged emulsi ers to increase emulsion stability.

How to choose the right emulsi er

How do product formulators choose which emulsi er to use for a particular emulsion?
Calculating the hydrophilic-lipophilic balance (HLB) of an emulsi er or combination of
emulsi ers can help. In an ideal emulsion, the emulsi er is equally attracted to the water
phase and the oil phase. If the balance is tipped in either direction, the emulsi er may lose
contact with the phase to which it is less attracted, causing the emulsion to break down.

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Di erent emulsi ers have di erent HLB values, which can predict their ability to stabilize
various kinds of emulsions (Fig. 2). The HLB scale ranges from 0 to 20, with 10
corresponding to an emulsi er that is equally attracted to water and oil. Emulsi ers with
HLB values greater than 10 are more hydrophilic and thus better at stabilizing o/w
emulsions. In contrast, emulsi ers with HLB values less than 10 are more hydrophobic and
therefore better suited for w/o emulsions.

Furthermore, di erent oils have di erent HLB requirements. For example, vegetable oil
emulsions need an emulsi er with an HLB of 7–8, whereas the required HLB value to form a
stable castor oil emulsion is 14. By matching the HLB value of the emulsi er with that of the
oil, formulators can greatly increase their chances of producing a stable emulsion.

According to George Smith, technical director for the Americas at Huntsman Performance
Products in The Woodlands, Texas, USA, a combination of emulsi ers usually works better
than any single emulsi er. “If you’re trying to make a mineral oil emulsion, for example, the
HLB for mineral oil is 10,” he says. “So you’ll pick a pair of emulsi ers, one with an HLB higher
than 10 and another with an HLB lower than 10. When you combine them, the average
comes out around 10.”

The HLB system, which works primarily for non-ionic emulsi ers, has been around since
1954. In the 1970s, the hydrophilic-lipophilic di erence (HLD) system was introduced. The
HLD system works for ionic as well as non-ionic surfactants, and it is better able to take into
account detailed characteristics of a particular emulsion such as salinity, oil type, surfactant
concentration, and temperature.

The HLD equation includes terms for the salt concentration, “oiliness” of the oil (the e ective
alkane carbon number), and the characteristic curvature (Cc) of the emulsi er. The Cc value
of an emulsi er re ects whether the emulsi er prefers to curve around an oil droplet in
water (negative Cc) or to curve around a water droplet in a w/o emulsion (positive Cc). For
example, a very hydrophilic emulsi er, sodium laurel sulfate, has a Cc of –2.3, whereas a
very hydrophobic emulsi er, dioctyl sodium sulfosuccinate, has a Cc of 2.6. The Cc for
combinations of emulsi ers is the weighted average for each emulsi er. The HLD scale
centers on 0, which corresponds to the optimal emulsion. Online calculators exist to
optimize the HLD for a particular emulsion (e.g., www.stevenabbott.co.uk/HLD-NAC.html).
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Macro- and microemulsions

Increasingly, formulators are interested in making microemulsions, which o er greater
stability than conventional macroemulsions. As the name suggests, microemulsions have
smaller droplet sizes than regular emulsions, making them appear transparent rather than
opaque. Unlike macroemulsions, microemulsions are thermodynamically stable. “Given
enough time, a macroemulsion will break down into water and oil phases,” says David
Sabatini, associate director of the Institute for Applied Surfactant Research at the University
of Oklahoma, Norman, USA. “But time is not a factor in how long a microemulsion will
remain in its current state.” In addition, if a temperature change causes an emulsion to break
down, a microemulsion will spontaneously reform when the temperature changes back to
its original value. In contrast, a macroemulsion requires an energy input to reappear.

Microemulsions are made di erently from macroemulsions. Macroemulsions require high-

intensity mixing. Because microemulsions are a thermodynamically stable end point that a
system naturally migrates toward, they generally do not require vigorous mixing. However,
formulators often use gentle agitation to evenly spread the components and speed up the
process of microemulsion formation.

Compared to macroemulsions, microemulsions require more surfactant. “Time stability

points in the direction of microemulsions, but surfactant requirement may point in favor of
macroemulsions,” says Sabatini. “It may be that 3 or 6 months is plenty long enough for your
application and time may not be a factor in that situation.” For example, food products will
often go bad before a macroemulsion breaks down, he says.

Because of their remarkable stability, microemulsions are nding applications in diverse

elds such as personal care products, oil eld chemicals, and medicine. “Macroemulsion
concepts have been around for centuries, but advanced microemulsion concepts are only
about two to three decades old,” says Sabatini. “There’s growing interest in microemulsions
because we’re just beginning to understand their capabilities.”

Foods
Many popular food items are emulsions, including mayonnaise, salad dressings, sauces
such as Hollandaise, chocolate, and ice cream. Lecithin, a blend of naturally occurring
phospholipids, is widely used in the food industry to promote o/w emulsions. Worldwide,
most commercial lecithin comes from soybean oil. Egg yolk, the traditional emulsi er for
mayonnaise and sauces, also contains lecithin. Other common emulsi ers in foods are
proteins, fatty acid esters, sodium stearoyl lactylate, and mono- and diglycerides.

Making food emulsions can be challenging because “foods are complex systems with many
di erent ingredients interacting,” says John Neddersen, senior application scientist in fats,
oils, and emulsi ers at DuPont Nutrition and Health, based in New Century, Kansas, USA.
“Although guidelines like the HLB scale can help, most of the time experience and
experimentation are needed to nd the optimal choice of emulsi ers and usage rates.”
Neddersen notes that processing can be another challenge when working with food
emulsions. “A company might have a single formula run at multiple locations and see
di erent results at the di erent plants,” he says. These di erences may arise from seemingly
subtle variations in plant conditions.

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DuPont sells a broad range of emulsi ers, including the Panodan® DATEM (diacetyl tartaric
acid ester of monoglycerides) line especially for bakery products and the Cremodan® line
for ice creams and other frozen desserts. As an alternative to lecithin in chocolates and
other confectionary, DuPont o ers Grindsted® CITREM, a citric acid ester. This emulsi er
can substitute for soy lecithin, which has recently come under re, particularly in Europe,
because most soy crops grown for export (especially the United States, Brazil, and
Argentina) are genetically modi ed. Non-genetically modi ed soy is expensive and in short
supply. Therefore, CITREM may prove an attractive alternative for confectioners who want
to avoid ingredients made from genetically modi ed soy.

Sustainable sourcing of palm oil has also become a customer concern, as reports have
surfaced that the development of palm oil plantations harms the environment and
threatens endangered wildlife in Malaysia and Indonesia, where most palm oil originates. As
a result, DuPont introduced a portfolio of emulsi ers based on sustainably sourced palm
and non-palm oils. By 2015, DuPont has pledged to source 100% of its palm oil from
plantations certi ed by the Roundtable on Sustainable Palm Oil (RSPO).

Reduced-fat emulsions are another hot topic for the food industry. When fat is removed
from a food to make a reduced-fat or fat-free version, the taste, appearance, and texture
often su er. D. Julian McClements, professor of physico-chemistry at the University of
Massachusetts Amherst, USA, says that there are several ways that emulsions or emulsi ers
could help reduce the fat content of foods. For instance, researchers could structure water-
in-oil-in-water (w/o/w) emulsions. “You could take some of the fat out of the droplets and
replace it with water,” he says.

Another approach, called heteroaggregation, is to mix oil droplets coated with emulsi ers of
opposite charge. “We mix a positive droplet and a negative droplet together, and they form
a gel network,” says McClements. “The resulting emulsion has a very high viscosity and low
fat content and mimics some of the characteristics of a high-fat product.”

Nutraceuticals
Researchers are exploring emulsions as delivery vehicles for vitamins, supplements, and
other nutraceuticals. McClements’ lab has used emulsions to encapsulate vitamin E,
carotenoids, omega-3 fatty acids, curcumin, coenzyme Q10, and other bioactive
compounds. Eventually, he would like to incorporate nutraceuticals such as these into
functional foods.

“One of our goals is to increase the stability of active compounds that are encapsulated in
emulsions in food particles,” says McClements. “We’d also like to control their fate in the
gastrointestinal tract once they’ve been digested.”

In addition to conventional emulsions, McClements’ lab makes more complex emulsions

such as nanoemulsions, solid-lipid nanoparticles, lled hydrogel particles (Fig. 3), and
multilayer emulsions. Di erent types of emulsions could have di erent applications. “Some
of them can protect components from chemical degradation, some can deliver compounds
to the colon, and some can control avor release,” says McClements. “So you have to have a
di erent kind of delivery system for each application.”

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Multilayer emulsions consist of oil droplets coated with an emulsi er plus one or more
biopolymer layers, dispersed in an aqueous solution. The emulsi er is typically electrically
charged, and the polymer layer(s) have opposite charges that attract them to the surface of
the oil droplet.

According to McClements, multilayer emulsions tend to have better physical stability than
single-layer emulsions through uctuations in pH, ionic strength, temperature, freezing and
thawing, and dehydration. In addition, researchers can design multilayer emulsions to
control their breakdown in the gastrointestinal tract. “You can make them so they’re
digested very quickly, like a normal emulsion, or you can make them so they go further
down the gastrointestinal tract,” he says. “The latter might be useful if you want to deliver
something to the colon or you’re trying to control satiety by getting undigested compounds
further down in the gastrointestinal tract.”

Personal care
Most personal care products, including lotions, creams, shampoos, and conditioners, are
emulsions. Common emulsi ers for personal care products include ethoxylated alcohols,
carboxylates, sodium isethionate, glycerol monostearate, cetyl alcohol, stearyl alcohol, and
silicone emulsi ers such as dimethicones.

“The trend right now is most people would like to use an emulsi er that’s based on plant
raw materials rather than petrochemicals,” says Smith. Synthetic emulsi ers such as
ethoxylated alcohols and their naturally derived counterparts have identical structures,
performance, and biodegradation. “The price swings back and forth depending on the price
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of palm kernel oil in Malaysia and the price of ethylene in North America,” says Smith. “At the
moment, I think petrochemicals have the advantage, but it switches every two to three
years.”

Juan Mateu, technical director at JEEN International in Fair eld, New Jersey, USA, says that
there has been a move away from synthetic ethoxylated alcohols in recent years due to
worries about residual 1,4-dioxane, a suspected carcinogen that is a by-product in their
manufacture. Naturally derived glucosides have been suggested as replacements for some
applications. However, “It’s too early to say that ethoxylated alcohols can be replaced,” says
Mateu. “There are some emulsions you can make with glucosides, but for the most part the
whole world is still using ethoxylates.”

In 2009, JEEN International launched its Jeesperse line of cold-process emulsi ers, which
allows formulators to make emulsions containing waxy substances at ambient
temperatures (25–30°C). Many common emulsi ers in personal care products, such as cetyl
alcohol and glycerol monostearate, are waxes with relatively high melting points (up to
165°C). Prior to Jeesperse, manufacturers had to heat emulsi ers in the oil phase to melt
them, and then add the melted emulsi er to the aqueous phase and cool the emulsion at a
controlled rate down to room temperature. In contrast, Jeesperse allows the emulsion to be
made in a single kettle at room temperature, resulting in signi cant savings of money and
time.

The secret ingredients in Jeesperse products are polyelectrolytes, such as sodium

polyacrylate. The polyelectrolytes are polar molecules that can induce polarity in nonpolar
waxes, enabling them to dissolve in cold water (a polar solvent). Mateu says that in the lab,
he can make an emulsion with the cold process in about 20 minutes, as opposed to several
hours of mixing, heating, and cooling with the conventional process. “Aesthetically, the
product is the same thing—it feels the same and looks the same—so why not?” he says.

A short video demonstrating the cold-process formulation of a lotion with a Jeesperse

emulsi er.

Home care
Many household cleaners and laundry detergents contain surfactants that emulsify oily dirt
particles so that they can be diluted and washed away. Ethoxylated alcohols are a common
ingredient of laundry detergents. Many detergents contain a blend of nonionic and anionic
emulsi ers to lift stains out of textiles.

According to Sabatini, removing triglycerides such as fats, bacon grease, and vegetable oils
from fabrics is particularly challenging. His lab has shown that extended surfactants, which
are surfactants with intermediate polarity groups (e.g., polypropylene oxide and
polyethylene oxide) inserted between the hydrophilic head and hydrophobic tail, are
e ective in removing these types of oily stains.

Industrial lubricants
Metalworking uids and other industrial lubricants are typically o/w emulsions. Emulsi ers
allow metalworkers to make use of both the lubricating properties of oils and the cooling
capabilities of water. Anionic and nonionic emulsi ers are often used together in

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metalworking uids. Cationic emulsi ers are rarely used because they are unstable in the
alkaline solutions (pH 8–9.5) required for metalworking uids.

Environmental technologies
Emulsions and microemulsions have been applied to environmental technologies such as
subsurface remediation and biofuel production. For example, when oil or gas is spilled, the
oil becomes trapped in pores in the soil and rock. Sabatini’s lab has developed alcohol-free
microemulsions that help remove oil contaminants from the subsurface in an
environmentally friendly manner. “The oil is trapped in the pores because of the interfacial
tension between water and oil,” says Sabatini. “If we can lower that interfacial tension with
emulsi ers, we can increase our rate of cleaning up contamination.”

In 1997, Sabatini and several colleagues founded a company called Surbec Environmental,
LLC, to implement this technology. Since then, Surbec has assisted with the environmental
cleanup of multiple sites in the United States and abroad. Examples include a gas station
with a leaky underground tank and a military site contaminated with jet fuel.

Sabatini has also applied his emulsions research to the more e cient production of biofuel.
Biodiesel is a vegetable oil, such as soybean oil, that has been chemically modi ed through
a transesteri cation reaction to reduce its viscosity. “In terms of combustion, you don’t need
to modify the vegetable oil. You can use vegetable oil in a diesel engine, and it’ll work
pretty well without modi cation,” says Sabatini. “It’s just that vegetable oil has viscosity
problems, especially at lower temperatures.”

As it turns out, microemulsi cation of vegetable oils can reduce viscosity without the need
for the transesteri cation reaction. This would save time and allow more of the raw material
to be used as fuel. However, Sabatini notes that the research is still in its early stages.

Although humans have been making emulsions for hundreds, if not thousands, of years, we
are only now beginning to appreciate their diverse applications in many elds. Complex
emulsions, such as microemulsions and multilayer emulsions, promise to further expand
the repertoire of applications, particularly in emerging areas such as functional foods and
biodiesel production. Now if only we could nd an emulsi er for that di cult coworker.

Laura Cassiday is a freelance science writer and editor based in Hudson, Colorado, USA.
She has a Ph.D. in biochemistry from the Mayo Graduate School and can be contacted at
[email protected].

Sidebar
What’s the di erence?
The terms surfactant, emulsi er, and detergent are often used interchangeably, but there
are distinctions.

Surfactant is the broadest term: Both emulsi ers and detergents are surfactants.
Surfactants, or surface-active agents, are compounds that lower the surface tension
between two liquids or between a liquid and a solid. Surfactants are amphiphilic, meaning
that they contain hydrophilic (water-loving) head groups and hydrophobic (water-hating, or
oil-loving) tails. Surfactants adsorb at the interface between oil and water, thereby
decreasing the surface tension.

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An emulsi er is a surfactant that stabilizes emulsions. Emulsi ers coat droplets within an
emulsion and prevent them from coming together, or coalescing.

A detergent is a surfactant that has cleaning properties in dilute solutions.

Likewise, the terms emulsion, suspension, and foam are sometimes confused.

An emulsion is a mixture of two or more liquids, with or without an emulsi er, that are
normally immiscible. One of the liquids, the “dispersed phase,” forms droplets in the other
liquid, the “continuous phase.”

A suspension is a solid dispersed in a liquid. The particles are large enough for
sedimentation.

A foam is a substance in which gas bubbles are suspended in a liquid.

Sidebar
Technical session highlights suspensions, emulsions, and foams
You can learn about the latest developments in suspensions, emulsions, and foams by
attending a joint technical session on these topics at the upcoming 2014 AOCS Annual
Meeting & Expo in San Antonio, Texas, USA. The session, which will be held on Wednesday,
May 7, from 1:55–5 p.m., will feature a wide range of technical topics—from the fabrication of
reduced-fat products by controlled aggregation of lipid droplets to the formulation of
lipopeptide biosurfactant mixtures for dispersing oil spills in seawater.

The session is jointly sponsored by AOCS’ Edible Applications Technology (EAT) and
Surfactant & Detergent (S&D) divisions, and is cross listed in the program as EAT 5.0 and
S&D 5.1. A complete list of presentations.

© 2020 The American Oil Chemists' Society

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