Emulsifiers: Types and Uses

R Miller, Kansas State University, Manhattan, KS, USA

ã 2016 Elsevier Ltd. All rights reserved.

Introduction (3) hydrophilic/lipophilic balance (HLB), and (4) functional

groups that compose them.
Surfactants, also called surface-active agents, are molecules that
migrate to the interface between two phases (solid, liquid, or
gas). The three most common two-phase systems in food prod- Charge in Aqueous Systems
ucts are emulsions, foams, and dispersions (Table 1). Emulsions
There are four classifications of emulsifiers based on the charge
are composed of two immiscible liquids. One liquid is dispersed
of the hydrophilic group when it solubilizes in water. They
within the other as individual droplets and is called the discon-
may be anionic, cationic, nonionic, or amphoteric. Anionic
tinuous phase, while the other liquid surrounds the droplets and
emulsifiers form negatively charged ions. They are effective in
is called the continuous phase. The emulsion behaves like the
the neutral to alkaline pH range and are also sensitive to ionic
continuous phase. The typical food emulsions are oil-in-water
strength and so do not function well in high salt-containing
(o/w), which consists of discontinuous droplets of oil dispersed
systems. The salt shields the negative charges so the anionic
in a continuous water matrix, and water-in-oil (w/o), which is
emulsifiers become ineffective and the emulsion breaks down
composed of discontinuous droplets of water dispersed in a
rapidly. Sodium stearoyl-2-lactylate (SSL) is an example of
continuous oil matrix. When describing emulsions, the ‘oil’
an anionic emulsifier. Cationic emulsifiers form positively
component may be actual oil or some other ingredient that is
charged ions in water and are functional in the acidic pH
not soluble in water. Examples of o/w emulsions are homoge-
range. They are somewhat toxic and so are not used as food
nized milk and ice cream, while common w/o emulsions include
additives. Nonionic emulsifiers have no net charge and form
margarine, salad dressing, and mayonnaise. Emulsions can be
no ions. They are highly effective and are compatible with all
formed mechanically by shaking or stirring; however, they are
other types of emulsifiers. They are relatively insensitive to pH
not stable for long periods of time and will separate into the two
and salt concentrations. Mono- and diglycerides (MDGs) are
separate components relatively quickly. Emulsifiers are a type of
nonionic. Amphoteric emulsifiers form both positively and
surfactant that is used to stabilize emulsions.
negatively charged ions when dissolved in water. They are not
affected by pH values except some are not effective near the
isoelectric point (pH at which protein is uncharged). Lecithin
Types of Emulsifiers is an amphoteric emulsifier.

There are many types of emulsifiers. They are classified

according to (1) charge in aqueous systems, (2) solubility,
Solubility
The solubility of an emulsifier governs the type of emulsion
Table 1 Interfaces in food systems that will be formed. The phase in which the emulsifier is least
soluble becomes the continuous phase. A key attribute of
Food system Continuous phase Discontinuous phase emulsifiers is that they are amphiphilic. This means one end
of the molecule is lipophilic and the other end is hydrophilic
Emulsion Liquid Liquid
(Figure 1(a)). The lipophilic end, referred to as the tail, is
Foam Liquid Gas
Dispersion Liquid Solid
usually a long-chain fatty acid taken from a food grade fat or
oil. It is not soluble in water but is soluble in oil and is called

oil water
“tail”
lipophilic
nonpolar
oil soluble
water oil

“head”
hydrophilic
polar group
water soluble
(a) (b) (c)

Figure 1 Emulsifier molecules contain a lipophilic ‘tail’ and a hydrophilic ‘head’ (a). Orientation of the emulsifier molecules in water-in-oil (b) and
oil-in-water (c) emulsions.

498 Encyclopedia of Food and Health http://dx.doi.org/10.1016/B978-0-12-384947-2.00249-X

 Emulsifiers: Types and Uses 499

oil-loving. The hydrophilic end is often referred to as the head serves as a useful guide for classifying and selecting emulsifier
and is polar. Thus, it easily dissolves in water and is termed systems. Selecting the ideal emulsifier or combination of emul-
water-loving. Emulsifiers that are easily soluble in water (more sifiers often requires experimental work.
hydrophilic) produce o/w emulsions. The emulsifier interacts
strongly with the water, thus reducing the surface tension of
the water so that it approaches zero. The water no longer forms Functional Groups
droplets and becomes the outer (continuous) phase of the emul-
Food emulsifiers are created by alcoholysis or direct esterifica-
sion, leaving the oil dispersed as discrete droplets (inner or
tion of edible fatty acids taken from animal or vegetable sources
discontinuous phase) to form an o/w emulsion (Figure 1(b)).
with polyols (i.e., glycerol, propylene glycol, and sorbitol).
Lipophilic emulsifiers are not water-soluble and interact with the
Further processing by reaction with ethylene oxide or esterifi-
oil phase. As a result, the surface tension of the water is not
cation with organic acids produces a wide range of emulsifiers
significantly reduced so it remains as discrete droplets in the
with differing properties. The most commonly used food emul-
oil, producing a w/o emulsion (Figure 1(c)).
sifiers include MDGs, stearoyl lactylates, sorbitan esters, poly-
glycerol esters, sucrose esters, and lecithin. They find use in a
wide array of food products (Table 3).
Hydrophilic/Lipophilic Balance MDGs are the most commonly used food emulsifiers,
Several methods of classifying emulsifiers are available. The composing about 75% of total emulsifier production. The
most commonly used is HLB. HLB is an index of the solubiliz- largest use is in yeast-raised baked goods to increase shelf
ing properties of emulsifiers and indicates the type of emulsion life, followed by cake and cake icings. Another major use is
(o/w or w/o) that the emulsifier is best suited for (Table 2). in margarine manufacture. MDGs are produced by heating
HLB values can be calculated based on the molecular structure triglycerides and glycerol with an alkaline catalyst. The
of the emulsifier or determined empirically. The values range
from 0 to 20, but some emulsifiers have been shown experi-
Table 3 Common food emulsifiers and uses
mentally to have higher values. Emulsifiers with low HLB
values are more oil-soluble (lipophilic), while those with Emulsifier Food products
higher values are more water-soluble (hydrophilic). In general,
emulsifiers with HLB values of 3–6 are lipophilic and best Mono- and diglycerides Bread, cake, pasta, frozen dessert, icing,
suited for w/o emulsions. Emulsifiers in this range include topping, peanut butter, margarine,
dehydrated potatoes, shortening, coffee
MDGs and propylene glycol monostearate (PGMS). Hydro-
whitener, and pasta
philic emulsifiers with HLB values of 10–18 are best suited
Glycerol monolaurate Bread, whipped topping, frosting, glaze,
for o/w emulsions. Examples include diacetyl tartaric acid and cheese products
esters of monoglyceride (DATEMs) and lecithin. The effective- Ethoxylated Bread, whipped topping, icing, frozen
ness of emulsifiers is affected by processing conditions and monoglyceride dessert, and coffee whitener
ingredients such as sugar, salt, and protein. It has been reported Diacetyl tartaric acid Bread, extruded products, icing,
that the strength of the interaction is more important than the esters of monoglyceride margarine, and salad dressing
number of reactive groups in determining the hydrophilic Succinylated Bread
properties of emulsifiers. However, HLB can provide an esti- monoglyceride
mate of the hydrophilic nature of various emulsifiers and Calcium stearoyl-2- Bread, egg whites, and dehydrated
lactylate potatoes
Sodium stearoyl-2- Bread, pasta, dehydrated potatoes, and
Table 2 Hydrophilic/lipophilic balance (HLB) values of common food lactylate coffee whitener
emulsifiers Propylene glycol esters Cake, whipped topping, dehydrated
potatoes, and shortening
HLB Sorbitan esters Whipped topping, cake, cake mix, cocoa,
Emulsifier Abbreviation value icing, filling, and coffee whitener
Polysorbate 60 Whipped topping, cake, cake mix, cocoa,
Mono- and diglycerides MDGs 4 icing, filling, coffee whitener,
Glycerol monolaurate 7 shortening, salad dressing, and
Ethoxylated monoglyceride EMG 13 edible oil
Diacetyl tartaric acid esters of DATEMs 9 Polysorbate 65 Ice cream, frozen custard, ice milk,
monoglyceride sherbet, frozen dessert, icing, cake, cake
Succinylated monoglyceride SMG 5 mix, whipped topping, filling, and coffee
Lactylated monoglyceride LMG 3 whitener
Sodium stearoyl-2-lactylate SSL 22 Polysorbate 80 Ice cream, frozen custard, ice milk,
Propylene glycol monostearate PGMS 3 sherbet, frozen dessert, gelatin mix,
Sorbitan monostearate 6 shortening, baked goods, bakery mixes,
Sodium stearoyl-2-lactylate SSL 15 filling, icing, topping, and frying oil
Polysorbate 65 11 Sucrose esters Bread, bakery mixes, frozen dessert,
Polysorbate 80 15 whipped milk products, and ice cream
Sucrose monostearate 5 Lecithin Baked goods, chocolate, cooking spray,
Calcium stearoyl-2-lactylate CSL 8 instant foods, and margarine
500 Emulsifiers: Types and Uses

resulting product is a mixture of about 45% monoglycerides, (discontinuous phase) within the continuous oil phase. Emul-
45% diglycerides, and 10% triglycerides. The monoglyceride sifiers are added to promote emulsion formation and
concentration can be increased to about 90% using molecular stabilization.
distillation to produce distilled monoglycerides. MDGs can Emulsifiers do not create emulsions. An emulsion is typi-
also be processed to produce emulsifiers with various func- cally created using mechanical means such as mixing or stirring.
tionalities. Ethoxylated monoglycerides (EMGs) are formed However, one of the roles of emulsifiers is promoting the
by treating monoglycerides with ethylene oxide gas. DATEMs formation of smaller oil droplets during emulsion creation,
are produced from the reaction of monoglyceride with diacetyl which slows the rate of coalescence. When the appropriate
tartaric acid anhydride. Succinylated monoglycerides (SMGs) emulsifier is added into the oil and water mixture, the mole-
result from the reaction of distilled monoglycerides with suc- cules orient at the interface between the water and the oil
cinic anhydride. Stearoyl lactylates are the reaction products droplets. The hydrophilic heads are attracted to the water,
of stearic acid and lactic acid, which are further converted whereas the lipophilic tails are repelled by the water and
into the calcium or sodium salts and become calcium attracted to the oil. As a result, the lipophilic tail will react
stearoyl-2-lactylate and SSL. SSL is one of the most common with the oil droplet, while the hydrophilic head will react
anionic emulsifiers used in the food industry. Sorbitan mono- with the water at the surface of the oil droplet; thus, it reacts at
stearate, a sorbitan ester, is produced by reacting sorbitol and the interface between the two immiscible phases. When this
stearic acid. It can then be reacted with ethylene oxide to happens, the surface tension of the oil droplet decreases
produce polyoxyethylene sorbitan monostearate (polysorbate considerably, which decreases the surface tension and allows
60), polyoxyethylene sorbitan tristearate (polysorbate 65), the droplets to be subdivided into smaller droplets during mix-
and polyoxyethylene sorbitan monooleate (polysorbate 80). ing. The effectiveness of lowering surface tension varies
Polysorbate 60 is the most widely used in the group. Polygly- between different emulsifiers.
cerol esters result from reacting fatty acids with polymerized The second role of emulsifiers is stabilizing the emulsion
glycerol of three to ten molecules. Sucrose esters are derived once it has formed. This is the main reason that emulsifiers are
from sucrose and edible tallow and consist of the mono-, used in food systems. Even though smaller droplets are more
di-, and triesters of sucrose with fatty acids. Emulsifiers stable, emulsion stabilization by emulsifiers is not directly the
that solidify into the stable alpha crystalline form are called result of their ability to lower interfacial tension and allow for
alpha-tending and include acetylated monoglycerides (AMGs), the creation of smaller droplets. Rather, emulsifiers stabilize
lactylated monoglycerides (LMGs), and propylene glycerol emulsions by accumulating at the interface of the two phases
monoesters (PGMEs). Lecithin is a mixture of phosphatides where they form a barrier that prevents the droplets of the
including phosphatidylcholine, phosphatidylethanolamine, discontinuous phase from coalescing. The mechanism by
and inositol phosphatide. It is a natural component found in which the barrier forms is determined by the properties of
animal and vegetable products. Egg yolk, which contains about the emulsifier. One mechanism of stabilization is due to like-
20% phospholipid, is well known for its emulsifying ability. It is charged particles repelling each other. Anionic emulsifiers
too expensive to isolate lecithin from egg yolk; therefore, most carry negative charges that repel each other to keep the droplets
commercial lecithin is derived from soybeans, which contain apart. SSL, SMG, and DATEM are anionic emulsifiers. They are
about 2% lecithin. Many other emulsifiers and emulsifier blends not highly effective in systems with high salt levels because the
are available for specific applications. salt shields the charge, which suppresses the repulsive forces
and leads to rapid coalescence and breakdown of the emul-
sion. Although not used in food systems, cationic emulsifiers
carry positive charges that also repel each other to stabilize the
Mechanism of Action in Food Products emulsion. In nonfood systems, anionic and cationic emulsi-
fiers should not be used in combination as the opposite
An o/w emulsion will be used as an example of how an charges would interact, thus rendering the emulsifiers inactive.
emulsion is formed. When water and oil are mixed vigorously Another form of stabilization is employed by emulsifiers that
(i.e., whipped, stirred, and shaken), the oil will form into contain a large hydrophilic portion such as EMG. The large
individual droplets dispersed within the water. The oil droplets hydrophilic head holds a large amount of water and creates a
are the discontinuous phase because they are separated by the layer of ‘bound’ water around the droplet, which prevents
water. The water (also referred to as the aqueous phase) is the coalescence. These emulsifiers are not sensitive to salt. Simple
continuous phase where each water molecule is touching steric hindrance is a third type of stabilization. The emulsifier
another water molecule. Although an emulsion was formed, forms a solid layer at the interface, which physically prevents
it is not stable. Within a short period of time, the oil droplets coalescence even if the droplets touch each other. This occurs
will bump into each other, and the two droplets will merge in alpha-tending emulsifiers such as PGME.
into a single, larger droplet. This is called coalescence. These
larger oil droplets have less surface area and higher surface
tension. Ultimately, all of the oil droplets will coalesce and Food Uses of Emulsifiers
rise out of the water to form into a separate layer floating on
top of the water. The rate at which the oil droplets rise out of In the food industry, the term ‘emulsifier’ is used generically and
the emulsion is inversely proportional to their size; thus, larger includes surfactants that are not technically classified as emulsi-
droplets rise faster than smaller droplets. In the case of a w/o fiers. Additives categorized as emulsifiers in the food industry
emulsion, the water is present as individual droplets provide a broad range of functions in a wide range of food
 Emulsifiers: Types and Uses 501

products including emulsification, stabilization, antistaling, where the levels of sugar and liquid are present at higher levels
crumb softening, foaming, fat crystal modification, mouthfeel, than the flour, contain several emulsifiers including distilled
agglomeration, defoaming, wetting, solubilizing, and stickiness monoglycerides, LMG, and PGME. These shortenings allow
control. Many food products contain emulsifiers that perform better air incorporation during mixing and bind more sugar
many different functions (Table 3). A few are discussed here. and water.

Dairy Products Pasta

Emulsifiers are added to ice cream to shorten the freezing time, SSL and distilled monoglycerides are added into pasta products
improve whipping, and produce a dry, stiff texture that melts to aid in extrusion. They are also used in pasta for soups or
slowly. The ice cream mix is an o/w emulsion. Emulsifiers stabi- canned products to reduce stickiness and improve the texture
lize the emulsion and prevent the fat globules from agglomerat- of the cooked product.
ing in the mix. When the mix is churned into ice cream, the
emulsifiers function to destabilize the natural milk protein film
Baked Products
that surrounds the milk fat globules so they can surround the air
bubbles and stabilize into a frozen foam. MDGs, sucrose esters, In the baking industry, the term ‘emulsifier’ is used to describe
and polysorbates are commonly used in ice cream. a broader group of surfactants, which includes those that are
Nondairy whipped toppings are whipped cream replacers active in foams (air-in-water) and dispersions (liquid-in-solid)
made using vegetable fats. They may be frozen or in pressur- and in emulsions (liquid-in-liquid). Thus, the term emulsifiers
ized cans. In these products, emulsifiers are added as destabi- will be used in this section to encompass the common surfac-
lizers to promote aeration. In this role, the emulsifier causes tants used in baked products.
the fat globules to agglomerate during whipping. This is done Doughs and batters are complex systems that contain mul-
to create a fat network in the continuous aqueous phase, which tiple interfacial interactions that occur simultaneously, some of
stabilizes the air bubbles and imparts stiffness to the foam. which change forms as the products are heated. Emulsifiers
Polysorbate 60 and alpha-tending emulsifiers such as LMG and play many different roles in these products. Most batters and
propylene glycol monoesters are commonly used in the pro- doughs contain a polar, continuous phase that consists of an
duction of commercial nondairy whipped toppings. aqueous (water) solution of salts, sugars, water-soluble pro-
Coffee whiteners are liquid or powdered cream replacers. teins, and other solubilized formula ingredients, which can be
Emulsifiers are added to improve their dispersion in hot coffee. a component of an emulsion, a foam, and a dispersion simul-
Typical emulsifiers used include distilled monoglycerides, taneously in a single batter or dough. For example, the contin-
DATEM, polysorbate 60, and sorbitan monostearate. uous aqueous phase may form an emulsion in which a lipid in
some form (oil or solid fat) constitutes the nonpolar, discon-
tinuous phase. It may be the continuous phase in an emulsion
Salad Dressings
with a nonpolar, discontinuous polar discontinuous phase of
Mayonnaise is an o/w emulsion that contains at least 65% lipid in some form (oil or solid fat). Almost all batters and
vegetable oil. The emulsion is stabilized by the high level of doughs contain a foam of the continuous aqueous phase with
lecithin in the egg yolk. FDA standards of identity do not allow a discontinuous phase of air bubbles, which are incorporated
the addition of other emulsifiers. during mixing. Furthermore, the continuous aqueous phase
Pourable salad dressings are w/o emulsions that contain at makes a dispersion with the insoluble formula ingredients,
least 30% vegetable oil. Typically, consumers shake the bottle to which include the starch and gluten in the flour.
form the emulsion before pouring the dressing over their salad. In cake batters, distilled monoglycerides and alpha-tending
Polysorbates and DATEMs are commonly used to enhance emul- emulsifiers such as AMG and PGMS function as aerating agents
sification when the bottle is shaken. to speed up the whipping rate and facilitate the incorporation
of many small air cells. This leads to a more stable emulsion
and results in a cake with a larger volume and fine, uniform
Margarine
crumb grain. Alpha-tending emulsifiers are critical in cakes
Margarine is a w/o emulsion containing about 80% fat. It is made using a one-stage mixing procedure or prepared from
usually made with MDGs of long-chain fatty acids and lecithin. boxed cake mixes where liquid shortening or oil is used
The MDGs promote the formation of the emulsion, while the because they form a solid film at the oil–water interface,
lecithin is added to increase the solubility of the MDGs in the which stabilizes the emulsion and also keeps the liquid oil
oil blend. Distilled monoglycerides with a high concentration from breaking the emulsion or foam that is prepared during
of unsaturated fatty acids and lecithin are used in low-calorie mixing.
spreads, which are also w/o emulsions that contain at least Emulsifiers used in yeast-leavened bread products are also
50% water and 40% fat. active in the solid–liquid interface (dispersion) where they
function as crumb softeners and dough strengtheners. As
crumb softeners, they interact with starch granules and gluten
Shortening
protein polymers to impart a softening effect on the crumb
Shortening consists of a fat blend that contains emulsifiers. grain and extend the shelf life of the product. Monoglycerides
All-purpose shortenings contain about 1% distilled monoglyc- are the primary crumb softener used in bread. Other common
erides. High-ratio or emulsified shortenings, for use in cakes crumb softeners include DATEM, sucrose esters, and PGMS.
502 Emulsifiers: Types and Uses

Dough strengtheners interact with the gluten protein and alter Further Reading
the rheology of the dough to produce a stronger gluten struc-
ture. Anionic emulsifiers such as DATEM, SSL, SMG, EMG, and Norm V (2015) Emulsifiers in food technology, 2nd ed. Oxford: Blackwell.
Pomeranz Y (1991) Additives. In: Pomeranz Y (ed.) Functional properties of food
polysorbates are good dough strengtheners. Some of the emul-
components, 2nd ed., pp. 339–367. San Diego, CA: Academic Press.
sifiers used in baking have only one or the other of the Schuster G and Adams WF (1984) Emulsifiers as additives in bread and fine baked
functionalities, while others have both. For example, SSL func- products. In: Pomeranz Y (ed.) Advances in cereal science and technology, vol. VI,
tions mainly as a dough strengthener, but it also plays a minor pp. 139–287. St. Paul, MN: AACC.
role promoting the emulsification, incorporation, and subdi- Stauffer CE (1990) Emulsifiers and dough strengtheners. In: Stauffer CE (ed.)
Functional additives for bakery foods, pp. 69–124. New York: AVI.
vision of air cells during mixing and crumb softening. Stauffer CE (1999) Emulsifiers. St. Paul, MN: AACC International, Inc.

See also: Aeromonas; Bread: Chemistry of Baking; Food Additives:

Classification, Uses and Regulation; Rheological Properties of Food Relevant Websites
Materials; Stabilizers: Types and Function; Triacylglycerols: Structures
www.emulsifiers.org – European Food Emulsifiers Manufacturers Association (EFEMA).
and Properties. www.faia.org.uk – Food Additives and Ingredients Association (FAIA).