Cover: FP90 dropping point apparatus courtesy of Mettler-Toledo,

Inc., Columbus, OH 43240; ice cream and cake, 1997 Artville LLC;
coffee, cream, and muffin courtesy of Virginia Dare; center photo
by DigitalVision.

Library of Congress Catalog Card Number: 99-61286

International Standard Book Number: 1-891127-02-0

1999 by the American Association of Cereal Chemists, Inc.

All rights reserved.

No part of this book may be reproduced in any form, including
photocopy, microfilm, information storage and retrieval system,
computer database or software, or by any means, including electronic
or mechanical, without written permission from the publisher.

Reference in this publication to a trademark, proprietary product,

or company name is intended for explicit description only and
does not imply approval or recommendation of the product to the
exclusion of others that may be suitable.

Printed in the United States of America on acid-free paper

American Association of Cereal Chemists

3340 Pilot Knob Road
St. Paul, Minnesota 55121-2097, USA
 Acknowledgments
Eagan Press thanks the following individuals for their contributions to
the preparation of this book:

Mario Colombo, Uniqema, Brantford, Ontario, Canada

Timothy Cottrell, Uniqema, Brantford, Ontario, Canada
Andre J. Eydt, Lonza Inc., Annandale, NJ
Dilip K. Nakhasi, Stepan Company, Maywood, NJ
Larry Skogerson, American Ingredients Company,
Kansas City, MO
Lawrence E. Werner, AC Humko Corp., Memphis, TN
Contents
1. Emulsions and Foams  1
Surface Activity: surfactants as amphiphiles • surface free energy and interfacial tension • surface excess
of emulsifier • measuring surface tension
Formation, Stabilization, and Wetting: formation of emulsions and foams • emulsion stabilization
• foam drainage and film breakage • wetting of solid particles
Microemulsions

2. Molecular Organization  15
Fat and Emulsifier Crystals: triglyceride crystals • emulsifier crystals • crystal modifiers
Mesophases: mesophase structures • surfactant phase diagrams
Significance for Food Applications

3. Food Emulsifiers  25
Emulsifier Types: monoglycerides • monoglyceride derivatives • sorbitan derivatives • polyhydric
emulsifiers • anionic emulsifiers • lecithin
Hydrophilic/Lipophilic Balance: basic principle of the concept • experimental determination of HLB
Proteins: foaming agents • emulsifying agents
Regulations

4. Bakery Products  47
Antistaling Agents: starch gelatinization • starch retrogradation • bread staling • emulsifier-starch
complexation
Dough Strengtheners
Aeration Agents
Troubleshooting

5. Dairy and Nondairy Products  67

Milk
Butter and Margarine: butter • margarine
Whipped Cream and Nondairy Whipped Toppings: whipped cream • nondairy whipped toppings
Ice Cream
Coffee Whiteners
Troubleshooting

v
6. Dressings and Sauces  77
Polysaccharides at Interfaces: gums • modified starch • cellulose derivatives
Salad Dressings: pourable salad dressings • spoonable salad dressings
Mayonnaise
Reduced-Fat Dressings and Sauces
Troubleshooting

7. Beverages  89
Flavor Emulsions: oil phase • emulsion stabilizers • emulsion preparation
Stability: creaming • flocculation • coalescence
Microemulsions
Troubleshooting

Glossary  95
Index  101

vi
 CHAPTER

Emulsions and Foams

Interfaces are ubiquitous features of foods. This is true during prepa-
ration of a cake batter or margarine blend, for example, as well as in In This Chapter:
finished products. Three specific kinds of interfaces are of particular Surface Activity
importance in foods: liquid-liquid, or emulsions; air-liquid, or foams; Surfactants as
and solid-liquid, or dispersions. Amphiphiles
Controlling the physical nature of the interfaces is often crucial to Surface Free Energy and
making a high-quality food product and is frequently achieved by in- Interfacial Tension
Surface Excess of
cluding emulsifiers (also called surfactants) among the ingredients. Emulsifier
Emulsifiers may be components of an ingredient (e.g., egg yolk) or Measuring Surface
additives (e.g., monoglyceride). Tension
From a technical point of view, the terms “emulsifier” and “surfac- Formation, Stabilization,
tant” are synonymous. In practice, however, an emulsifier is usually and Wetting
considered to be a food-related material, while a surfactant is gener- Formation of Emulsions
ally connected with other processes. For example, surfactants are and Foams
added to detergents for washing and are used to aid in flotation dur- Emulsion Stabilization
ing ore separation. Since this book is food-related, other uses of sur- Foam Drainage and Film
Breakage
factants will not be discussed.
Wetting of Solid Particles
Microemulsions
Surface Activity
SURFACTANTS AS AMPHIPHILES
“Surfactant” is a coined word (from “surface-active agent”) applied
to molecules that migrate to interfaces between two physical phases Interfaces—Boundaries be-
and thus are more concentrated in the interfacial region than in the tween two phases. Various
bulk solution phase. The key molecular characteristic of a surfactant types of interfaces occur in
is that it is amphiphilic. The lipophilic (or hydrophobic) part of the mol- foods: solid-liquid, gas-liquid,
ecule prefers to be in a lipid (nonpolar) environment, and the hy- gas-solid, and liquid-liquid (two
immiscible liquids).
drophilic part prefers to be in an aqueous (polar) environment. The
word “prefers” actually means that the thermodynamic free energy of Emulsifiers —Molecules that
the system is at a minimum when the lipophilic part is in an oil (or promote and/or stabilize emul-
air) phase and the hydrophilic part is in water. If a surfactant is dis- sification, i.e., dispersion of one
solved in one phase of an ordinary mixture of oil and water, some liquid in another (nonmiscible)
portion of the surfactant will concentrate at the oil-water interface; liquid.
and at equilibrium, the free energy of the interface, called interfacial
Amphiphilic —“Both loving.”
or surface tension (γ), will be lower than if the surfactant were absent. Pertains to molecules that
Putting mechanical energy into the system (e.g., by mixing) in a way possess both lipophilic (“fat-
that subdivides one phase will increase the total amount of interfacial loving”) and hydrophilic
area and energy. The lower the amount of interfacial free energy per (“water-loving”) regions.

1
2 / CHAPTER ONE

Lipophilic—”Lipid loving.”
Pertains to the nonpolar parts
of molecules that dissolve read-
ily in a nonpolar medium such
as vegetable oil. Generally syn-
onymous with “hydrophobic.”

Hydrophobic—”Water hat-
ing.” Pertains to the (nonpolar)
parts of molecules that do not
readily enter a polar medium
such as water.

Hydrophilic —”Water loving.”

Pertains to the (polar) parts of
molecules that readily dissolve
or disperse in a polar medium
such as water.

Free energy—The thermo-

dynamic energy of a closed
system. Absolute free energy
is not easily measured, but the
change in free energy when the
system is changed (e.g., when
oil is dispersed in water) is Fig. 1-1. Types of surfactants. The R group is a lipophilic hydrocarbon typified by
more easily established. stearic acid. CTAB = cetyltrimethylammonium bromide.

Discontinuous phase —The

dispersed (internal) phase in an unit area, the larger the amount of new interfacial area that can be
emulsion. In an oil-in-water created for a given amount of energy input. The subdivided phase is
emulsion, oil is the discontinu- called the discontinuous phase and the other the continuous phase.
ous phase. As shown in Figure 1-1, surfactants have a lipophilic (fat-loving)
and a hydrophilic (water-loving) part and thus are sometimes called
Continuous phase—The
amphiphilic (both-loving) compounds. The lipophilic part of emulsi-
undispersed phase of an emul-
sion. In an oil-in-water emul-
fiers (food surfactants) is usually a long-chain fatty acid obtained
sion, water is the continuous from a food-grade fat or oil. The hydrophilic portion is either non-
phase. ionic (e.g., glycerol), anionic (negatively charged; e.g., lactate), or am-
photeric (carrying both positive and negative charges; e.g., phos-
Ionic strength—Measure of phatidylcholine). Cationic (positively charged) surfactants such as
the ionic character of an aque- cetyltrimethylammonium bromide (CTAB) are usually bactericidal
ous solution of salts. Ionic
and somewhat toxic and are not used as food additives. Food surfac-
strength plays a role in numer-
ous physical phenomena such
tants include monoglyceride (nonionic), lauryl sulfate (anionic), and
as conductance of electrical phosphatidylcholine or lecithin (amphoteric). The nonionic surfac-
current, folding of protein mol- tants are relatively insensitive to pH and salt concentration in the
ecules, and degree of repulsion aqueous phase, while the functionality of the ionic types may be
of charged surfaces in water. markedly influenced by pH and ionic strength.
 EMULSIONS AND FOAMS \ 3

SURFACE FREE ENERGY AND INTERFACIAL TENSION

Increasing the amount of interface in a system re-
quires work (energy) input. In a practical sense, this
energy is supplied by shaking or mixing. If a stoppered
bottle containing oil and water is gently inverted, only
a small additional amount of interface (a few large oil
drops) is generated. More vigorous shaking subdivides
the oil droplets further; that is, it creates more interface.
The system has a higher energy content; or in physical
chemical terms, it has a higher total free energy. This l
concept is quantitated in the following manner.
Consider a soap film contained in a rectangular wire
frame (Fig. 1-2); the surface area of the film, A, equals
l × x. The right side of this frame, of length l, is moveable.
The work necessary to move this side to the right by a
distance dx is determined by the equation x dx
work = 2γldx = 2γdA (1) Fig. 1-2. Wire frame with one movable side (of
length l ) and containing an interior film. dx =
distance moved.
in which γ is the free energy of the water-air interface
(the factor 2 is used because both surfaces of the film
must be considered). The total surface free energy equals 2γlx. The
usual unit for γ is milli-Newtons per meter (mN/m), which is numer-
ically equal to the older (non-SI) unit of dyn/cm or erg/cm2. The con-
cept is general; the surface could be the interface between two con-
densed phases, e.g., water and oil, in which case γ is interfacial
tension. The terms surface free energy and surface tension are synony-
mous as are interfacial free energy and interfacial tension.
If the surface is curved (e.g., that of a droplet), the radius of curva-
ture plays a role. Given an air bubble of radius r, the total surface en-
ergy is 4πr2γ. Decreasing the radius by the amount dr decreases total
surface energy by 8πrγdr = 4πr2γdr. This change must be balanced by a
pressure increase (∆P), or the bubble would be compressed to noth-
ingness. This pressure difference times the change in surface area
equals the change in total surface energy:

∆P4πr2dr = 8πrγdr (2)

and

∆P = 2γ/r (3)

As indicated by equation 3, the internal pressure of a small bubble is

greater than that of a large bubble. This has practical consequences in
aerated food systems. In a cake batter, for example, time-lapse photog- Surface tension —The compo-
raphy shows that small bubbles (containing carbon dioxide) disappear nent of total free energy in a
and large bubbles increase in size. The carbon dioxide in the small closed system caused by the
bubbles dissolves into the aqueous phase because of the higher inter- presence of an interface.
4 / CHAPTER ONE

50

40

Interfacial tension
30

20

10

0
0.00001 0.0001 0.001 0.01 0.

Mole fraction PGMS in heptane

Fig. 1-3. Surface tension of laurylsulfonic acid Fig. 1-4. Tension at the interfaces of water and solutions of
solutions. propylene glycol monostearate (PGMS) in heptane.

nal pressure and then enters the large bubbles, which are regions of
lower internal pressure. Similar effects are expected in other foods in
which the continuous phase may act as a conduit for dissolved gases.
The surface tension of a solution of a surfactant is lower than that
of the pure solvent. Surface tension is roughly a linear function of
ln(surfactant concentration) up to the critical micelle concentration
(CMC) (Fig. 1-3). Above this concentration, the thermodynamic activ-
ity of the surfactant does not increase with the addition of more sur-
factant, and the surface tension remains constant. Interfacial tension
Critical micelle concentration also decreases with the concentration of an emulsifier dissolved in
(CMC) —Concentration of a one of the phases. As shown in Figure 1-4, the decrease in γ, or inter-
surfactant in aqueous solution facial tension, does not level off, because the emulsifier (propylene
at which colligative properties glycol monostearate) does not form micelles in the organic solvent
cease to change with increase phase (heptane). The changes in the slope of the plot are attributed to
in concentration.
changes in the orientation of emulsifier molecules at the interface.
Thermodynamic activity —
A factor accounting for the SURFACE EXCESS OF EMULSIFIER
fact that the concentration-
Surfactant molecules concentrate at the interface; the lipophilic
dependent properties of dis-
solved molecules often deviate portion is in the nonpolar phase (air, organic solvent), and the hy-
from a strictly linear depen- drophilic portion is in the polar (water) phase. This migration of sur-
dence. For surfactants below factant lowers the free energy of the total system, resulting in a
the critical micelle concentra- higher concentration of surfactant in the region that includes the in-
tion, this deviation is usually terface (Fig. 1-5). The difference between this concentration and the
negligible. bulk concentration is called the surface excess, Γ.
The surface excess is calculated from a plot of interfacial tension (γ)
Surface excess —The concen-
tration of a surfactant in the in- versus the thermodynamic activity (a) of the surfactant:
terfacial region compared with Γ = −(a/RT)(dγ/da) (4)
its concentration in the bulk
phase in which it is dissolved. in which R the universal gas constant and T is the temperature (°K).
 EMULSIONS AND FOAMS \ 5

For dilute solutions, surfactant thermody-

namic activity equals concentration, and γ is
Oil
calculated from the plot of γ versus molar con-
centration.
Interface
MEASURING SURFACE TENSION
Three things can be learned by measuring sur- Interfacial
face tension: 1) the minimum level of surface }Volume
tension achievable; 2) the corresponding mini-
mum CMC; and 3) the area covered by each sur-
face-active molecule (from the slope of γ versus Water
concentration curve) (Fig. 1-3).
Numerous ingenious methods have been de-
vised to measure surface and interfacial tension. Fig. 1-5. Excess concentration of an oil-soluble emulsifier
Space does not allow a full discussion of each at the water-oil interface.
method here, but selected methods will be de-
scribed briefly. For more details and some of
the tables of correction factors needed, see Chapter 1 of Physical
Chemistry of Surfaces (1).
Capillary rise. If a clean glass capillary tube is held vertically and
lowered to meet the surface of water or an aqueous solution, the liq-
uid will rise in the tube because of the concave meniscus formed
when the liquid wets the side of the tube. This curved meniscus re-
sults in a negative pressure (equation 3). The liquid rises until the
weight of the column balances the negative pressure force. If the ra-
dius of the tube is known, the surface tension of the liquid can be cal-
culated from the measured height of the column.
Drop weight. An ordinary laboratory burette with a tip of known di-
ameter can be used. Liquid from the burette is allowed to slowly form
a drop on the end of the tip. As the drop gradually increases in
weight, it reaches a point at which gravity overcomes the surface ten-
sion holding the droplet to the tip. A portion of the drop separates
and is caught in a tared container and weighed. By using a table of
correction factors, the diameter of the tip, and the density of the liq-
uid, surface tension is calculated.
Pendant drop. At some point before the drop separates, it has a bul-
bous shape with a somewhat narrow neck just below the tip of the
burette. Measurements of the diameter of this pendant drop taken
with an instrument such as a horizontal microscope at particular
points along the vertical axis and use of published correction factor
tables allow calculation of surface tension. This method is particu-
larly useful for measuring interfacial tension by placing a drop of
water into the oil being studied.
Ring tensiometer. A ring of known circumference, constructed of
wire of known diameter, is attached to a balance arm or similar in-
strument for measuring vertical force on the ring. It is lowered into
6 / CHAPTER ONE

the liquid and then gradually raised through the surface. (More con-
veniently, the beaker containing the liquid is supported on a labora-
tory jack, and the beaker is slowly lowered.) As the ring is raised
above the surface of the liquid, it carries a cylindrical film of liquid
with it, and the force on the ring increases. At some point, the film
ruptures. From the maximum force measured and with the aid of a
table of correction factors, the surface tension can be calculated.
This method is also convenient for measuring interfacial tensions.
The ring is immersed in the water, the oil is carefully layered on top,
and the ring is then raised through the interface.
Wilhelmy balance. The Wilhelmy balance method is similar to that
of the tensiometer in arrangement and operation, except that the
ring is replaced with a cleaned glass slide, which is wetted by the
water. Again, the maximum force is measured as the slide is slowly
raised relative to the water surface. Surface tension is directly propor-
tional to the total circumference (i.e., two sides plus two edges) of the
glass slide, and empirical correction factors are not needed.

More sophisticated methods are available for measur-

ing dynamic surface tension. As a practical recommen-
Shear dation, if surface or interfacial tension measurements
are contemplated, the ring tensiometer method is prob-
ably the easiest for obtaining reliable results with a min-
imum of investment and operational difficulty.

Formation, Stabilization,
and Wetting
FORMATION OF EMULSIONS AND FOAMS
Simply adding oil to water does not result in an emul-
sion, because oil is a nonpolar liquid and water is polar.
However, if the oil and water are shaken together, an
emulsion forms. For example, in an oil/water emulsion,
shaking causes the oil phase to separate into droplets
that are dispersed in the water phase. The oil is called
the dispersed phase, discontinuous phase, or internal
phase, and the water is called the continuous phase.
Division of internal phase. Input of mechanical energy
subdivides the droplets of the internal phase until a
final average droplet diameter of 1–100 µm is reached. A
cylinder of liquid whose length is more than 1.5 times
its circumference is unstable and tends to break up into
droplets. Mechanical stirring of an oil-water mixture
forms drops that are then distorted into cylinders (along
Fig. 1-6. Breakage of cylinders of liquid into the lines of flow), which break up into smaller droplets
small droplets caused by shear. (Fig. 1-6). The process is repeated until the droplets are
 EMULSIONS AND FOAMS \ 7

so small that they cannot be further distorted and further subdivision

ceases.
A suspended liquid drop forms a sphere, because this shape has
minimum surface area (hence, minimum interfacial free energy) for a
given volume. Distortion is a flow shear effect, depending on droplet
cross-section, which is related to the square of the radius. When
droplet diameters are large, shear forces are greater than interfacial
tension forces; droplets are distorted into cylinders; and subdivision
occurs. Droplet radius decreases until the interfacial tension forces
balance (or exceed) shear forces, and further division stops. In emul-
sification experiments in which the amount of mixing energy is
constant and γ is changed by adding emulsifier, the average oil droplet
diameter parallels γ; i.e., as more emulsifier is added, γ decreases and
so does average droplet size. If γ is unchanged but mixing energy is in-
creased, droplet size is also decreased. This is caused by the change in
the balance of shear and interfacial forces, allowing cylindrical distor-
tion of smaller droplets. Equipment design that enhances shear is
more effective at dividing droplets.
Oil/water versus water/oil emulsions. If oil and water are mixed
together and vigorously shaken, they form a dispersion of water
droplets in oil and oil droplets in water. When shaking is stopped, the
phases start to separate; small water drops fall toward the container
bottom and oil drops rise. When like drops come into contact with
each other, they coalesce and the emulsion quickly breaks down.
Adding an emulsifier to the system changes the outcome. After stand-
ing, one phase becomes continuous, while the other (the discontinu-
ous phase) remains dispersed. The nature of the emulsion is deter-
mined by the emulsifier. As a general rule, the continuous phase is
the one in which the emulsifier is soluble. Thus, sodium stearate pro-
motes an oil-in-water (O/W) emulsion in which the oil is dispersed in
the continuous water phase, and zinc distearate promotes a water-in-
oil (W/O) emulsion. Several qualitative theories have been advanced
to explain this empirical rule.

Box 1-1. Is It an O/W or a W/O Emulsion?

During early testing of systems, the question sometimes arises
about the nature of the emulsion formed. To easily determine
the answer, fill a beaker half way with the emulsion. Add half
that amount of water, stir gently, and let the beaker sit a few
minutes. If it is an oil-in-water emulsion, the water will dilute
the continuous phase and the contents of the beaker will ap-
pear uniform. If it is a water-in-oil emulsion, the added water
will collect on the bottom and the emulsion will float on top Coalesce —To combine; usually
of the water layer. refers to two liquid (e.g., oil)
drops combining into one
drop.
8 / CHAPTER ONE

The oriented wedge theory states that the emulsifier at the inter-
face is wedge shaped (Fig. 1-7). The ionized end of a sodium soap has
a wider (effective) radius than the hydrocarbon chain; hence, the oil-
water interface should be curved, with the convex side toward the
water phase. This favors formation of oil droplets and results in an
O/W emulsion. However, the polar end of zinc distearate is smaller
than the two hydrocarbon chains, the interface is convex toward the
water phase, and a W/O emulsion is formed.
A second theory considers
the relative ease with which
the two types of droplets can
coalesce. When a mixture is
shaken, drops of both phases
are formed. Sodium stearate
ionizes, and the electrical po-
tential hinders approach and
coalescence of oil droplets.
Water droplets, however, ex-
perience no such hindrance
and readily touch and coa-
lesce. Zinc distearate does not
ionize and therefore does not
interfere with the mutual ap-
proach of oil droplets, but van
der Waal’s forces favor water
Fig. 1-7. Effect of wedge-shaped surfactant molecules on the convexity coalescence. Thus, the type of
of the oil-water interface.
emulsion formed depends on
the relative kinetics of oil-oil
and water-water coalescence.
Foaming. Food foams are usually made by whipping an aqueous so-
lution of a foaming agent such as a protein (e.g., egg white) or an
emulsifier (e.g., one of the polysorbates). Air is first entrained by the
action of the mechanical element (paddle, whip, or mixer blades),
and then air bubbles are elongated and subdivided into smaller bub-
bles, just as described above for liquid internal phases.
Air is a nonpolar medium. Surfactants concentrate at the air-water
interface, and the hydrophobic portion extends into the gas phase. In
proteins (common foaming agents in foods), some amino acid side
chains are hydrophilic while others are lipophilic. In their natural
configurations, protein chains are usually folded so that the lipo-
Electrical potential—The philic residues are in the interior and the hydrophilic residues are on
magnitude of electrical charge the surface. (A protein molecule has been described as “an oil droplet
difference between two points. surrounded by a water-loving shell.” This characterization has some
van der Waal’s forces —Short-
merit as applied to relatively small albumin and globulin proteins.)
range attractive forces between When a protein such as egg albumen is exposed at an air-water inter-
molecules resulting from the face, it tends to unfold, with the hydrophobic side chains entering
dipole moment of atoms in the the air phase and the hydrophilic chains remaining in the water
molecules. phase (Fig. 1-8). If oil is also present, it will spread at the air-water
 EMULSIONS AND FOAMS \ 9

Fig. 1-8. Unfolding of protein at the air-water interface.

interface, displacing the protein and destabilizing the foam. Traces of

oil (or egg yolk) in egg white, for instance, make it difficult if not im-
possible to whip the egg white into a foam. (For a more detailed dis-
cussion, see Chapters 3 and 5.)

EMULSION STABILIZATION
When two surfaces approach each other, two forces exist: one re-
pulsive and one attractive. Whether or not the surfaces touch and co-
alesce depends on the relative strength of the two forces. This is
equally true for liquids (e.g., oil droplets in an emulsion), solids (e.g.,
finely divided CaCO3), and films (e.g., air bubbles in a foam).
Electrical repulsion forces. Electrical repulsion exists when the sur-
faces carry net charges of the same sign and the continuous phase is
water. For example, if an O/W emulsion is stabilized by an anionic
surfactant, the oil droplets have a negative charge on their surfaces.
Electrical repulsion then tends to keep the droplets from making con-
tact. At the oil surface, the electrical potential (or charge) is denoted
by ψ0. Cations are attracted into the region, partially neutralizing the
surface negative charge. The value of ψ decreases as the distance from
the oil drop surface increases and at some point becomes essentially
zero. The rate of decrease of ψ is directly related to the ionic strength
of the aqueous phase. Ionic strength (µ) is related to the concentra-
tion (c) of individual salt ions and the square of the ionic charge (z)
of each ion:

µ = 1⁄2 Σcizi2 (5) Flocculation —Collection of the

internal phase of an emulsion
Divalent ions are four times as effective as monovalent ions in de- or suspension; clumping.
Flocculated materials are gener-
creasing ψ. Thus, 0.25M zinc sulfate, for example, is as effective as 1M ally somewhat difficult to redis-
sodium chloride in promoting emulsion flocculation or coalescence. If perse, unlike droplets in a
gravity is the only force bringing the droplets together, they will ap- creamed emulsion, which are
proach to a distance at which repulsion caused by ψ is just balanced easily dispersed by simple
by gravitational effects, and the emulsion will then be stable. mixing.
10 / CHAPTER ONE

Attractive forces. Attractive forces, collectively called van der Waal’s

forces, exist between two oil droplets. Simplistically, these forces may
be thought of as the attraction between oil molecules at the O/W in-
terfaces, which have lower energy when in contact with each other
than when in contact with water. Several phenomena are involved.
The most commonly considered, hydrophobic interactions and
London dispersion forces, are unaffected by ionic strength. Sus-
pensions of solids (e.g., cellulose fibers and finely divided CaCO3) are
stabilized in the same way. Ionic surfactants are used that selectively
adsorb to the solid surface, generating a ψ potential and making pos-
sible a stable suspension.
Creaming. Creaming is the collection of the lighter droplets in the
upper part of the mixture. Oil droplets in an O/W emulsion float to
the top, because the density of vegetable oil is about 0.91 g/mL,
0.08 g/mL less than that of water. The rate at which they rise depends
on particle diameter. A drop with a diameter of 1 µm rises at a rate
of 4 cm per day, while one with a 10-µm diameter rises 4 m per
day. Obviously, reducing the average droplet size reduces the
rate of creaming. Fat globules in raw milk have diameters of 0.2–20
µm. After homogenization, the average diameter is <1 µm. In raw
milk, the average flotation rate is 36 cm per day, while in homoge-
nized milk it is 1 cm per day. Creaming brings the oil droplets closer
together, and if contact is not prevented (e.g., by ionic repulsion), co-
alescence occurs. A simple creamed layer of stabilized oil droplets is
readily redispersed by inverting the container a few times.
Ionic stabilization. As discussed above, two surfaces carrying like
charges repel each other. The thickness of the electrical double layer
(the region where ψ > 0) is affected by ionic strength. As long as ionic
strength is low, electrical repulsion is greater than van der Waal’s at-
traction, and the droplets remain suspended. If, by addition of salt
(particularly divalent or trivalent salts), the ψ potential is markedly
suppressed, the surfaces can approach to the point at which van
der Waal’s forces override repulsion, and the droplets can touch and
coalesce. At some intermediate ionic strength, the two forces are ap-
proximately equal, and the droplets will remain separated by about
one droplet diameter. A practical conclusion can be drawn from this:
if the emulsifier used is ionic in nature, the salt concentration of the
aqueous phase markedly affects emulsion stability. Low salt concen-
tration enhances stability, while high salt concentration increases
flocculation and/or coalescence.
Steric hindrance. Another form of stabilization is relatively indepen-
dent of ionic strength: the oil droplets are prevented from making
contact by simple steric hindrance. This may take one of two forms,
either an immobilized water layer at the interface or a solid interfacial
film. Emulsion stabilization by proteins, gums, and polyoxyethylene
derivatives occurs by the first mechanism. Hydrophobic parts of the
stabilizers adsorb at the oil surface, but adjacent large hydrophilic
 EMULSIONS AND FOAMS \ 11

segments are hydrated and form an immobilized

layer approximately of 10–100 nm thick (Fig. 1-9).
As mentioned, these hydrated segments fre-
quently interact to cause flocculation while coa-
lescence of the oil drops is prevented. Such emul-
sions are frequently used as carriers for oil-
soluble flavors, essences, and colorants.
The α-tending emulsifiers such as propylene
glycol monostearate are oil soluble. The emulsifier
adsorbs at the oil-water interface, but under cer-
tain conditions (such as low temperature or the
presence of a free fatty acid), the emulsifier forms
a solid interfacial film (Fig. 1-10). While the oil
droplets may make contact, the film prevents coa-
lescence. The interfacial layer actually appears to
be crystalline and has a well-defined melting
point.
Flocculation. In some emulsions, particularly
those with high molecular weight emulsifying
agents (e.g., proteins and gums), the oil drops rise
to the top and form a layer that is rather resistant
to redispersion. The size (and number) of the oil Fig. 1-9. Immobilization of water by hydrophilic chains
droplets does not change; coalescence does not at the oil-water interface.
occur. The material adsorbed at the interface in-
teracts, probably through hydrogen bonds and
perhaps some ionic bonds, to hold the droplets to-
gether. The phenomenon is termed “flocculation”
or “clumping.” One positive application of this
process is in water treatment plants, where certain
surface-active materials adsorb to solid impurities,
promoting flocculation and allowing easy re-
moval by filtration. Flocculation is much less sig-
nificant in food applications.

FOAM DRAINAGE AND FILM BREAKAGE

Considering the forces involved, a foam is very
similar to an O/W emulsion. The terminology is
somewhat different, but the results are the same:
either a foam is stable or the gas bubbles coalesce Fig. 1-10. Interfacial film formed by an α-tending emul-
sifer. A water drop was suspended in vegetable oil con-
and the foam breaks down. Rather than creaming,
taining 10% propylene glycol monoester. After a few
a foam is said to “drain.” The effect is the same: minutes, some of the water was withdrawn.
the water phase concentrates at the bottom of the
container and the dispersed phase at the top. The
volume fraction (φ) of gas in a foam is usually much
higher than the φ of oil in an emulsion. Whipping Volume fraction —The fraction
egg white, for example, may easily give a 10- to 15-fold expansion of total volume of a system rep-
(φ = 0.9–0.93), while mayonnaise (φ = 0.7–0.8) is the food emulsion resented by one of the discrete
with the highest oil content. phases.
12 / CHAPTER ONE

The mechanism of air in-

corporation and subdivision
in a foam is the same as that
of an emulsion; large bubbles
are elongated, and the unsta-
ble cylinders spontaneously
divide. In a wet foam (φ < 0.7),
the initial drainage of liquid
from the regions between the
bubbles is caused by gravity
and is governed primarily by
Fig. 1-11. Plateau’s border formed at the juncture of air bubbles in a foam. viscosity. Figure 1-11 shows
how the film between three
bubbles meets at a 120° angle after drainage. In three dimensions, four
touching bubbles meet at the tetrahedral angle of 109°28′. In the real
situation, the bubbles assume the shape of regular polyhedra, but the
contact angles remain fairly close to the ideal value. The thicker liquid
in the corners, known as Plateau’s border (named for the Belgian phys-
ical chemist J. Plateau) has a pressure lower than that of the straight
contact films, and liquid moves into these regions. Drainage of a dry
foam (φ > 0.7) is probably through these borders, connected through-
out the foam.
Foam stability and emulsion stability are governed by similar fac-
tors. Thus, in a soap foam, the negative charges located at the air-water
interface result in repulsion as the two surfaces of the film approach
each other, and drainage stops when an equilibrium film thickness is
reached. This thickness is influenced by the ionic strength of the aque-
ous phase; increasing the ionic strength gives foams of lower stability.
Protein stabilizes foams by a combination of steric hindrance and sur-
face viscosity. When egg whites are whipped, the protein molecules
unfold, with the hydrophobic side chains entering the air phase and
the hydrophilic chains remaining in the water phase. In Figure 1-8, the
heavy lines in the magnified section represent unfolded albumin pro-
teins adsorbed at the air-water interface. The portion of the proteins
located in the aqueous phase hold water, preventing it from draining
away from this region and hence preventing the air bubbles from coa-
lescing and destabilizing the foam.
Film breakage is thought to result from random fluctuations (e.g.,
Brownian motion) that momentarily bring the two surfaces into con-
tact, allowing the air bubbles to merge. These fluctuations are mini-
Plateau’s border —The point mized when the surface viscosity is increased. The addition of an al-
at which three or four gas cells cohol to a soap solution (e.g., dodecanol added to sodium laurate)
nearly touch in a foam. increases surface viscosity and also increases foam stability. Surface
viscosity of some (but not all) protein solutions is quite high, and
Brownian motion—The ran-
dom, thermal movement of
there is some correlation between this property and the ability of the
minute, solute particles observ- protein to give a stable foam. Bulk viscosity does not correlate with
able under a microscope and stability of drained films, but if a wet foam is desired, increasing bulk
caused by collision of solvent viscosity (e.g., by adding a high-viscosity gum) extends the usable life
molecules with the particles. of the foam by slowing the drainage rate.
 EMULSIONS AND FOAMS \ 13

WETTING OF SOLID PARTICLES Wetting agents—Agents that

promote spreading of a liquid
Some surfactants are good wetting agents. This property is useful in on a solid surface.
many circumstances: enhancing dispersion of dry mixes in liquid,
improving spreadability of chocolate and cocoa-based coatings, and
incorporation of dietary fiber materials into dressings. Qualitatively,
a drop of water is placed on the solid surface. If the contact angle
θ < 90° (Fig. 1-12), the water does not spread; it is said that the solid
is not wetted. If θ > 90°, the water spreads, and the solid is wetted.
The angle θ is determined by the surface tension at the three inter-
faces involved:

cos θ = (γSV − γSL)/γLV (6)

The spreading coefficient (SL/S) is defined as

SL/S = γSV − γSL − γLV (7)

in which S is solid, L is liquid,

and V is vapor.
When SL/S > 0, wetting oc-
curs, and the liquid spreads. An
efficient wetting agent is one
that minimizes the surface ten-
sion of the air-water and solid-
water interfaces while leaving
the air-solid surface tension un-
changed. This is the situation,
for example, when dry bever-
age powder is added to water.
Sodium lauryl sulfate lowers
the air-water and solid-water
interfacial tensions and en-
hances dispersibility. In the ab-
sence of the surfactant, the
contact angle at many of the
(irregular) solid surfaces is <90°, Fig. 1-12. Contact angle at the liquid-solid-air juncture of nonspreading and
and the powder with its en- spreading liquid drops.
trapped air floats on the top of
the water.
In chocolate coating, the liquid phase is an oil (cocoa butter). The
addition of lecithin aids the wetting of solid cocoa particles by this
oil, most probably by lowering γSL, thereby lowering the viscosity of
the heterogeneous mass and giving a smoother mouthfeel to the final
product.
14 / CHAPTER ONE

Visible light —Light visible to

the human eye. The wave-
Microemulsions
length of visible light is approx- It is possible to make emulsions in which the diameters of the oil
imately 400–700 nm.
droplets range from 1.5 to 150 nm. The droplet size is less than the
Microemulsions—Emulsions wavelength of visible light, and the emulsion appears transparent be-
in which the diameters of the cause no light scattering occurs. Several different strategies for mak-
droplets in the dispersed phase ing microemulsions have been tried, but a simple example in which
are much smaller than the mineral oil and water are used demonstrates the principles involved.
wavelength of visible light. The With pure liquids, γ is 41 mN/m, but the inclusion of 0.001M oleic
droplets do not scatter light; acid in the water phase reduces γ to 31 mN/m, and a moderately sta-
hence, the emulsion appears
ble emulsion may be formed. Neutralization of the acid with 0.001M
transparent.
NaOH lowers γ to 7.2 mN/m and gives a stable emulsion. Making the
water phase 0.001M in NaCl further lowers γ to less than 0.01 mN/m.
This system will spontaneously form an emulsion; Brownian move-
ment provides sufficient shear forces to elongate droplets into cylin-
ders and cause further subdivision.
Spontaneous emulsions such as this one are frequently opalescent,
because some particles have diameters approaching 400 nm, the
wavelength of light. Transparent microemulsions generally require a
surfactant plus a cosurfactant, for example, acetyl monoglyceride
plus hexanol. For use in food, various polyglycerol esters have shown
some promise for making W/O microemulsions. The technology is
promising but needs further refinement before it can be readily ap-
plied to food systems.

Reference
1. Adamson, A. W. 1967. Physical Chemistry of Surfaces, 2nd ed. Interscience
Publishers, New York.
 CHAPTER

Molecular Organization
Fat and Emulsifier Crystals
In This Chapter:
Solid materials can be either crystalline or amorphous. In a crys-
Fat and Emulsifier
talline solid (e.g., salt), the molecules are arranged in a repeating
Crystals
three-dimensional pattern. An amorphous material (frequently called Triglyceride Crystals
a glass) has no such internal organization. A beam of photons (most Emulsifier Crystals
often X rays) directed onto a crystalline material is refracted into a Crystal Modifiers
regular pattern that can be recorded (e.g., on a photographic film)
Mesophases
and analyzed to obtain the dimensions of the crystal unit cell. From Mesophase Structures
this information, the orientation of individual molecules is often in- Surfactant Phase
ferred. If the object of X-ray analysis is a single crystal (not a powder), Diagrams
even more information can be obtained, and often the location of in- Significance for Food
dividual atoms within the unit cell can be determined. Applications

TRIGLYCERIDE CRYSTALS
Crystalline —Pertaining to a
Solid triglyceride molecules resemble an elongated “h” (Fig. 2-1). state in which atoms or mole-
The two parallel chains are the fatty acids at positions 1 and 3 of glyc- cules are arranged in an or-
dered three-dimensional array.
Long-range order is discerned
by X-ray analysis.

Amorphous—Pertaining to the
random arrangement of atoms
or molecules with no dis-
cernible long-range order.

Photon—Basic unit of light

waves.

X rays —A region of light

waves with short wave length
and high-energy photons.

Unit cell—The smallest ordered

unit of a crystal. It may contain
only a few atoms (e.g., sodium
chloride) or several molecules
Fig. 2-1. Chain orientation in fat crystals. Left, paired, double chain length (DCL) ori- (e.g., a fat unit crystal).
entation of a saturated triglyceride. Center, DCL orientation typically found in a satu-
rated monoglyceride. Right, single chain length (SCL) orientation found in unsatu- Triglyceride —Lipid with three
rated monoglycerides and many emulsifiers that have relatively large hydrophilic fatty acids esterified to a glyc-
groups. erol molecule.

15
16 / CHAPTER TWO

erol; the single chain length (SCL), of course, is the chain attached at
position 2. This is sometimes referred to as the “tuning fork” orienta-
tion. In the crystal, the molecules are paired as shown, giving a unit
cell repeating dimension equal to two fatty acid chains, the double
chain length (DCL) configuration. A triple chain length (TCL) con-
figuration is possible in which the single chains of the tuning fork are
paired, but this is rarely seen in natural fats. When it does occur, it is
usually when the fatty acids vary by four or more carbons in chain
length.
When a melted fat is rapidly cooled, it solidifies into a waxy mate-
rial (resembling paraffin wax) termed “α crystals.” If cooling is ex-
tremely slow, the triglycerides in the fat with the highest melting
point have time to form stable β crystals. With intermediate cooling
rates, the fat first forms α crystals, which rather quickly melt and re-
form into the metastable β′ crystals. The difference between the three
crystal types has to do with the arrangement (crystal packing) of the
pairs of fatty acid chains. The order of melting points of the crystal
forms is α < β′ < β. For pure tristearin (glycerol tristearate), the melt-
ing points are 54.7, 63.2, and 73.5°C, respectively. Other factors that
govern fat crystal stability and functionality have been discussed at
greater length (1).
Diglycerides exist in two isomeric forms: the 1,2-diglyceride and the
1,3-diglyceride. The crystal structures of these materials have not
been studied extensively, but it appears that the 1,2 isomer is stable in
the β′ form, while the 1,3 isomer is stable as a β crystal. It has been
suggested that 1,2-diglycerides can be used to stabilize shortenings
and margarines in the desired β′ crystal structure, which imparts
smoothness and plasticity to the fat. Unfortunately, the 1,3 isomer is
thermodynamically more stable than the 1,2 isomer, and isomeriza-
Metastable —Pertaining to a tion occurs at moderately elevated temperatures. No commercial
physical state that is not at the form of 1,2-diglyceride is available today.
lowest possible free energy for
the system. The activation en-
ergy for transition to the more
EMULSIFIER CRYSTALS
stable state is high enough that The structure of triglyceride crystals is governed by the nature of
the system remains in the cur- the fatty acids (saturated or unsaturated and varying chain length)
rent state for a significant
and how these chains interact (fit together) in three dimensions. In
length of time.
emulsifier crystal structure, however, the predominant factor is the
Diglyceride —Lipid with two hydrophilic moiety, which is relatively a much larger part of the mol-
fatty acids esterified to a glyc- ecule. The size of the hydrophilic group, as well as the extent and spa-
erol molecule. tial distribution of hydrogen bonding between adjacent groups, has a
much greater influence on molecular packing in the crystal than does
Monoglyceride —Lipid with the nature of the fatty acid chain. A simple emulsifier such as a mono-
one fatty acid esterified to a
glyceride (e.g., glycerol monostearate [GMS]) generally crystallizes in
glycerol molecule.
the double chain configuration (Fig. 2-1), while those with larger hy-
Polymorphic behavior — drophilic groups (e.g., lactylated monoglyceride) more often crystal-
Ability of a material to crystal- lize in the SCL configuration.
lize in more than one three- 1-Monoglycerides exhibit polymorphic behavior similar to that of
dimensional arrangement. triglycerides. When cooled from a melt, they first form α crystals, and
 MOLECULAR ORGANIZATION \ 17

then on holding at intermediate temperatures, they transform to the α-Tending emulsifier —

β crystal form. Many emulsifiers (called α-tending emulsifiers) are sta- Emulsifier that forms a solid
film at the oil-water interface
ble in the α crystalline form; special techniques (such as crystalliza-
under proper conditions of
tion from a solution) must be used to get the stable β form of these temperature (low) and concen-
materials. Monoglycerides are usually found in the DCL configura- tration (high).
tion, while numerous other emulsifiers are more stable in the SCL
configuration. One cannot generalize about the effects these various
crystal tendencies have on functionality in food systems. Situations
in which a specific crystal form plays a role are discussed later.
Finally, it should be noted that hydrogen bonding between hy-
drophilic head groups imparts stability to emulsifier crystals. The
melting point of a saturated monoglyceride is typically 5–10 degrees
C greater than that of the corresponding triglyceride. Even when
monoglycerides are melted, X-ray diffraction shows the presence of a
certain amount of structure corresponding to the length of the SCL
configuration.

CRYSTAL MODIFIERS
Two types of modification of crystal behavior of fats are of interest
to food technologists: 1) inhibition of crystal formation to prevent
“clouding” (crystallization of solid fat) in salad oils; and 2) inhibition
of crystal polymorphic changes, e.g., β′ to β crystal transformation in
shortening and margarine. Emulsifiers are effective in both of these
roles, although different ones are used for each of the functions.
When salad oils are cooled (held in the refrigerator), the saturated
fat triglycerides begin slowly to form crystals. If the product is a sim-
ple oil and vinegar dressing, this is merely unsightly, but if the food
is an emulsion such as mayonnaise, the crystals can actually lead to
breakdown and separation of the oil phase. To prevent this, the oil is
often “winterized”; i.e., the solid fat triglycerides (generally no more
than 1–2% of the total oil) are extracted by chilling the oil and re-
moving any crystals formed. However, removal is not usually com-
plete, and a crystal inhibitor is also added to the oil. Commonly used
crystal inhibitors are oxystearin and sorbitan monostearate. Other
emulsifiers, for example, polyglycerol esters, sucrose esters, and poly-
oxyethylene sorbitan esters, are also effective in this role. Fat crystals
grow by the addition of molecules (e.g., tristearin) to the surface of
nuclei (small fat crystals) and then incorporation into the growing
face of the crystal. Inhibitors also adsorb to the growing face, but
since they do not match the dimensions of the triglyceride exactly,
they interrupt the addition of more triglyceride molecules, keeping
the crystal small (and essentially invisible to the eye). When the oil is
warmed by removal from the refrigerator, many of the smallest crys-
tals redissolve. Thus, in effect, the shelf life of the oil-containing food
is extended.
Shortening and margarine are manufactured in the metastable β′
crystal form and have a smooth, plastic texture. If this crystal form is
allowed to transform to the stable β crystal (e.g., by storage at some-
18 / CHAPTER TWO

what elevated temperatures or by long-term storage), the product ac-

quires a grainy, nonplastic texture that is considered unsuitable for
most uses. Inhibition of the transformation (or to put it another way,
stabilization in the β′ form) is a topic of interest to both manufactur-
ers and users of these products. The fatty acid chains of the β crystal
are somewhat more closely packed than those of the β′ crystal. If a
small amount (1–3%) of an emulsifier (e.g., sorbitan monostearate or
triglycerol-1-monostearate) is present, it cocrystallizes with the fat,
but it does not fit precisely into the chain packing of the triglyceride.
In other words, the emulsifier introduces a certain (minimal) amount
of distortion into the crystal. Polymorphic transformation of triglyc-
erides can be envisioned as a melting (of β′ crystals) and recrystalliza-
tion (of β crystals), and the emulsifier interferes with this process. The
end result is that the β′ crystals are stabilized and the shelf life of the
product is extended.
Sorbitan tristearate is even more effective as a crystal stabilizer and
is sold primarily for use in confectionery coatings. The development
of bloom on chocolate-coated products is caused by a polymorphic
transformation of the cocoa butter solid phase. Inclusion of an ap-
propriate crystal modifier helps to counteract this unwanted change.
1-Monoglycerides are used in emulsified shortenings and mar-
garines. However, 1-monoglycerides tend to hasten the β′ to β trans-
formation, and the levels of other β′ stabilizers, such as sorbitan tri-
stearate, must be increased to counteract this tendency.

Mesophases
Mixtures of surfactant and water form a number of different phys-
ical structures, depending on the surfactant-water ratio and the tem-
perature. These mixtures are opalescent dispersions often called “liq-
uid crystals,” but they are more properly termed mesophases. This
term (meaning “in-between phases”) reflects the nature of the mix-
ture. On a micro (molecular) scale, the surfactant and the water are
separate phases, but on the macro scale (e.g., >1 µm), the mixture ap-
pears uniform and is stable (i.e., the phases do not separate).

MESOPHASE STRUCTURES
Micelles. Many emulsifiers are soluble in water to a significant degree.
Bloom—A dusty, whitish They exhibit all the colligative properties of dissolved materials, e.g.,
appearance of the surface of freezing point depression, boiling point elevation, and ability to con-
chocolate coatings, caused duct an electric current (if ionic); and, of course, they lower the inter-
by transformation of the fat facial tension of the water. At some concentration, however, these
crystals.
properties cease to change as more of the material is dissolved (Fig.
Mesophase—Opalescent or
1-3.) This point is known as the critical micelle concentration (CMC)
transparent liquid formed by and is an important functional property of water-soluble surfactants.
a mixture of surfactant and A micelle is an aggregation of the emulsifier molecules, oriented
water. with the hydrophobic chains to the inside and the hydrophilic
 MOLECULAR ORGANIZATION \ 19

groups on the surface (Fig.

2-2). It may be thought of
as an inverted cubic meso-
phase, with a high propor-
tion of the continuous
phase (water) present. Mi-
cellization is driven by free
energy considerations and
can be expressed as a reac-
tion of emulsifier mole-
cules Em:

x Em ↔ (Em)x

The value of x varies

with the type of emulsifier Fig. 2-2. Behavior of water-soluble surfactants below (<CMC) and above
considered and may range (>CMC) the critical micelle concentration (CMC).
from less than 100 to more
than 3,000.
The study of micelliza-
tion has contributed great-
ly to our understanding of
hydrophobic interactions
(also sometimes called hy-
drophobic bonds), an im-
portant concept in the
realm of protein conforma-
tion, cell membrane struc-
ture, and other biochemi-
cal interactions. This topic
is discussed with clarity by
Tanford (2).
Lamellar mesophase. A
monoglyceride such as
GMS crystallizes in DCL bi- Fig. 2-3. Steps involved in the formation of lamellar mesophase with a saturated
layers. The thickness of triglyceride. When the pure (distilled) monoglyceride is heated in the presence of
water (left), it melts (fatty acid chains gain mobility), and water intrudes between
each bilayer is defined by
the bilayer leaflets (center). Upon cooling, the chains solidify in the α-crystalline
the length of two mono- configuration (relatively unorganized), resulting in the α gel lamellar mesophase
glyceride molecules end to (right). T = temperature, and m.p. = melting point.
end, which is about 5.5 nm
in GMS (Fig. 2-3, left). Cubic mesophase—Mesophase
When mixed with water and heated, the crystals melt, the thickness in which spheres of water are
of the bilayer decreases to about 3.8 nm (with concomitant lateral ex- found in a cubical arrangement
in a matrix of the surfactant.
pansion), and water begins to intrude between the bilayers along the
plane defined by the glycerol head groups (Fig. 2-3, center). This in- Lamellar mesophase —
trusion results in the formation of the lamellar mesophase. This mate- Mesophase characterized by
rial is rather fluid, but when the mixture is cooled, the lipid layers so- bilayer leaflets of surfactant
lidify in the α-crystalline state, and the material becomes a gel with a separated by layers of water.
20 / CHAPTER TWO

lipid bilayer about 5.5 nm thick (Fig. 2-3, right). This phase is of par-
ticular interest to bakers, because there is evidence that the lamellar
mesophase is the most efficient in promoting the interaction be-
tween monoglyceride and starch, producing the antistaling effects.
Upon further cooling, the α-crystalline layers of monoglyceride
transform into the more stable β-crystalline form. The van der Waal’s
attraction between the bilayers overcomes the tendency of the water
to hydrate the glycerol head groups, and the water is expelled, yield-
ing a suspension of β crystals in water.
With a simple nonionic saturated monoglyceride (i.e., GMS), the
maximum thickness of the water layer in the mesophase is 1.6 nm,
corresponding to 30% water. At this point, the osmotic pressure (fa-
voring hydration of the head groups) is balanced by the van der
Waal’s attraction between the lipid bilayers. If more water is intro-
duced, a dispersion of lamellar mesophase fragments in water is
formed. Commercial distilled monoglycerides contain about 1% free
fatty acid, and if this is neutralized with a base, the situation changes.
The lipid-water interface takes on a negative charge, and electrostatic
repulsion inhibits or slows the collapse and expulsion of water at the
lower temperatures described above. The charged interface also favors
the intrusion of more water into the space between the bilayers, and
the thickness of the water layer increases in direct proportion to the
amount of water added. At 75% water (an amount commonly found
in commercial hydrated monoglyceride), the water layer is about
11 nm thick, twice the thickness of the lipid layer. As expected, this
electrostatic stabilization can be counteracted by adding salts, and
low concentrations (0.3%) in the aqueous phase will counteract the
stabilizing effects of the anionic surfactant. Anionic monoglyceride
derivatives, the succinate and diacetyltartrate esters, form lamellar
mesophases under most conditions. This penchant is enhanced if the
carboxyl group is partially neutralized so that the pH of a water dis-
persion of the surfactant is 4–6, the typical pH range for dough.
Cubic mesophase. At higher temperatures and water concentrations,
the system may shift into the cubic mesophase structure (Fig. 2-4).
The water is present as spheres totally surrounded by monoglyceride.
This phase has a high viscosity and is sometimes called the viscous
isotropic phase in the literature. In the presence of more water than
can be accommodated in the internal spherical phase, a mixture of
lumps of this cubic structure dispersed in excess water is obtained.
With a saturated monoglyceride such as GMS, the lamellar structure
Viscous isotropic phase —
is found most often under practical conditions; with unsaturated
Another name for the cubic
mesophase when the amount
monoglycerides and lower temperatures, the cubic mesophase pre-
of water is sufficient to signifi- dominates. At lower water concentrations, the spherical water mi-
cantly raise the viscosity above celles are farther apart, so the viscosity of the mixture becomes lower,
that of the melted surfactant approaching that of melted pure surfactant. This is the fluid isotropic
alone. mesophase, sometimes referred to as the L2 phase.
 MOLECULAR ORGANIZATION \ 21

Hexagonal II mesophase. The

third important structure, the
hexagonal II mesophase, is formed
by unsaturated monoglycerides
and also by most of the other sur-
factants of interest to bakers. The
hexagonal structure (Fig. 2-4)
consists of rods of the internal
phase arranged hexagonally
within a matrix of the external
phase. In the case of monoglyc-
erides and sodium stearoyl lacty-
late, the internal phase is water,
and the hexagonal II structure
shown in Figure 2-4 is formed.
With highly water-soluble, poly-
oxyethylene-type surfactants (e.g.,
polysorbates and ethoxylated
monoglyceride), the internal
phase is the lipophilic tail of the
material and the external phase
is water, resulting in the hex-
agonal I mesophase.
Liposomes. At higher water lev-
els and within a limited tem-
perature range, the lamellar
mesophase is transformed into
spherical multilamellar vesicles Fig. 2-4. Three types of mesophases formed by emulsifiers. In the lamellar
called liposomes. This process is mesophase, water is sandwiched between bilayers of emulsifier. In the cubic
sometimes called a lamellar dis- mesophase, spheres of water are regularly arranged within the emulsifier
persion and is most readily matrix. The hexagonal II mesophase consists of cylinders of water in the
emulsifier matrix. The reverse of the cubic mesophase (spheres of emulsifier
observed with phospholipids
dispersed in a water matrix) is termed a “micellar dispersion.” The reverse of
(lecithin). As water is added to the hexagonal array, termed “hexagonal I,” has cylinders of emulsifier sur-
the initial lamellar mesophase, rounded by water.
the bilayers start to curve and ul-
timately bend and fuse, forming
a hollow sphere. Water is trapped within the spheres and in the con- Hexagonal II mesophase—
tinuous phase surrounding them. Liposomes are most often used as Mesophase in which cylinders
delivery vehicles (“packaging”) for drugs or cosmetic materials for of water are arranged hexago-
topical application to the skin, where the phospholipid enhances nally in a matrix of the surfac-
tant. When cylinders of surfac-
penetration of the skin and delivery of the internal phase to the tar-
tant are present with water as
get site. the matrix, it is called a hexag-
onal I mesophase.
SURFACTANT PHASE DIAGRAMS
Liposome—Hollow sphere
The exact mesophase structure of a particular surfactant in water formed by bilayers of surfac-
has important implications in industries that use emulsifiers, and a tant, suspended in a water
great deal of research on the effect of water concentration and tem- matrix, and containing water
perature has been done with commercial surfactants. The results are in the center.
22 / CHAPTER TWO

A 100 B 100
Fluid
Isotropic Cubic Fluid
Cubic + Water Isotropic

80 80
Hexagonal II + Water
Temperature, °C

Hexagonal

Temperature, °C
Lamellar II
Dispersion
60 60
α-gel + Water

40 40 Cubic
β−crystals + Water Cubic + Water

La-
20 mellar
20
0 20 40 60 80 100 0 20 40 60 80 100

% Water % Water
Fig. 2-5. Phase diagrams of two kinds of monoglycerides: saturated monoglyceride (distilled glycerol monostearate) (A) and
distilled unsaturated monoglyceride (sunflower oil monoglyceride) (B).

usually shown as phase diagrams, with temperature on the y-axis and

percent water on the x-axis. The interior of the graph is divided into
regions that represent the various mesophases (Fig. 2-5). Phase dia-
grams provide guidance to researchers who are trying to produce sur-
factant systems that are functional under use conditions. They are
used to characterize detergent systems and industrial applications of
surfactants as well as food emulsifiers.
As shown in Figure 2-5A, a saturated monoglyceride forms a cubic
mesophase at relatively low water concentrations (and above its melt-
ing point) and a lamellar mesophase at somewhat lower temperatures.
Unsaturated monoglycerides, on the other hand, form predominantly
the hexagonal II mesophase (Fig. 2-5B); the lamellar mesophase is
found only at low water concentration and low temperatures. The in-
clusion of a nonpolar triglyceride (oil) in the system tremendously
complicates the phase diagrams. For example, GMS forms a lamellar
mesophase with water, as was noted above, but when soybean oil is
added, the system converts into the hexagonal II structure.
Ternary phase diagrams from combinations of flour lipids, water,
and salt have been studied. The structures listed above were all found
in some region of the phase diagram. The studies are interesting, but
as of this writing, the direct relevance to the practical application of
surfactants in dough systems is not clear.

SIGNIFICANCE FOR FOOD APPLICATIONS

Phase diagram—A method The mesophase structure of an emulsifier often influences its inter-
of showing which mesophase action with other food components such as starch and protein and
structures are present at various
hence its functionality in the food. The best-studied example of this
water concentrations and
temperatures.
is the interaction of monoglycerides with gelatinized starch. It is well
known that the helical structure of starch can form a complex with
 MOLECULAR ORGANIZATION \ 23

linear hydrocarbons such as fatty acids. This is thought to be the basis

for the antistaling activity of monoglycerides in bread. In numerous
studies, Niels Krog (Grindsted Co., Denmark) has shown that this
complexation takes place most readily when the monoglyceride is
present in the lamellar mesophase. On the basis of this hypothesis,
one can infer that the reason a saturated monoglyceride (such as
GMS) is a more effective antistaling agent than an unsaturated mono-
glyceride is simply that there is a much larger range of temperature
and water concentration where the lamellar phase is present. This
can be seen by comparing the two phase diagrams in Figure 2-5.
Studies of the interaction of mesophases with proteins in foods are
few, and most statements about such interactions are speculative
rather than substantive. It has been found that wheat gliadin (a
rather hydrophobic protein) is solubilized in the cubic phase of
monoolein-water mixtures, but the significance of this for dough for-
mation is unknown. Many of the emulsifiers used to strengthen
dough, such as sodium stearoyl lactylate and polysorbates, form
lamellar mesophases at the water content and temperatures found
during dough mixing and proofing, and it has been suggested that in
this form, they can contribute to the integrity (strength) of the gluten
film. While lipid-protein interactions play a large role in the proper-
ties of many dairy foods, the significance of the mesophase behavior
of the lipid has not been explored to any extent.

References
1. Stauffer, C. E. 1996. Fats and Oils. American Association of Cereal Chemists,
St. Paul, MN.
2. Tanford, C. 1973. The Hydrophobic Effect. John Wiley & Sons, New York.

Supplemental Reading
Friberg, S. E., and Larsson, K., Eds. 1997. Food Emulsions, 3rd ed. Marcel Dekker,
New York.
 CHAPTER

Food Emulsifiers
Emulsifier Types
In This Chapter:
Actual commercial food emulsifiers are seldom exactly like the or-
Emulsifier Types
ganic chemical structures that are discussed in this section. Rather,
Monoglycerides
they are mixtures of similar compounds derived from natural raw Monoglyceride
materials. The hydrophobic fatty acid (or fatty alcohol) chain reflects Derivatives
the nature of the hydrogenated fat or oil used during manufacture. Sorbitan Derivatives
For example, glycerol monostearate (GMS) made from hydrogenated Polyhydric Emulsifiers
tallow has a saturated fatty acid composition of about 3% C14, 28% Anionic Emulsifiers
C16, 68% C18, and 1% C20, reflecting the chain length distribution Lecithin
in the source fat. If it is made from hydrogenated soybean oil, the Hydrophilic/Lipophilic
chain length distribution is somewhat different (more C18 and less Balance
C16). In addition, the ratio of 1-monoglyceride to 2-monoglyceride Basic Principle of the
Concept
varies depending on the temperature during manufacture.
Experimental
Many emulsifiers are the result of rather complex condensation Determination of HLB
and polymerization reactions. Sorbitan monostearate is made by
heating sorbitol and stearic acid together. Sorbitol cyclizes (dehy- Proteins
Foaming Agents
drates) to a mixture of sorbitans and isosorbides, which in turn is es- Emulsifying Agents
terified to various extents by the stearic acid. By strict control of reac-
tion conditions, the composition of the final product can be kept in Regulations
a relatively narrow (and consistent) range, but it is still a mixture.
One should keep in mind, therefore, that the chemical structures
shown here represent the major components in the commercial ma-
terial and that related molecular species are also present.
Sorbitol—Sugar alcohol pro-
MONOGLYCERIDES duced by reduction of glucose,
Roughly 22 million kg (50 million lb) of monoglyceride are used consisting of a chain of six car-
annually in the United States in yeast-raised goods to retard staling. bons with a hydroxyl group on
each carbon.
At least an equal amount finds its way into cakes, icings, and other
applications. The third major use is in the manufacture of margarine. Sorbitan—Cyclic structure
Overall, monoglycerides make up the single most important group formed by linking the hydroxyls
for food uses, representing about 75% of total emulsifier production. at the 1 and 4 positions of sor-
The use of monoglycerides in baking began during the 1930s, bitol through an ether linkage.
when “super-glycerinated shortening” became commercially avail-
able. Glycerin was added to ordinary shortening along with a small Isosorbide —Bicyclic structure
formed from sorbitol, involving
amount of alkaline catalyst. The mixture was heated, causing some an ether linkage between hy-
interesterification of triglyceride with the glycerin, and the catalyst droxyls at the 1 and 4 positions
was removed by neutralization and washing with water. The resulting and hydroxyls at the 3 and 6
emulsified shortening contained about 3% monoglyceride and was positions.

25
26 / CHAPTER THREE

widely used for making cakes, particularly those containing high lev-
els of sugar. The effectiveness of monoglyceride in retarding staling
(crumb firming) in bread became known at about the same time, and
bread bakers sought a more concentrated source of monoglyceride.
This need was met by suppliers of plastic monoglyceride, which is
made by increasing the ratio of glycerin to fat to achieve a final con-
centration of 40–60% monoglyceride. Most of the remainder is
diglyceride. When industrial-scale molecular distillation processes
were developed, it was logical to subject the plastic monoglyceride to
this step, producing distilled monoglyceride containing a minimum
of 90% (typically, about 95%) monoglyceride (the rest of the mixture
is composed of diglyceride and small amounts of fatty acids and glyc-
erol). The next stage was to make a lamellar mesophase product from
H O this distilled monoglyceride, adding some anionic surfactant (usually
sodium stearoyl lactylate [SSL]) to stabilize the hydrated monoglyc-
H-C-O-C-(CH 2 ) 16 CH 3 eride, which contains roughly 25% monoglyceride, 3% SSL, and 72%
water. More recently, manufacturers have developed a powdered dis-
H-C-OH tilled monoglyceride, in which the composition of the original feed-
stock fat is balanced between saturated and unsaturated fatty acids.
H-C-OH The resulting powder is hydrated fairly rapidly during the process of
dough mixing and is functional in complexing with gelatinized
H starch. Today, bakers use all three monoglyceride types (plastic, hy-
drated, and powdered distilled) with about equally good results.
1-Monostearin The monoglyceride structure shown in Figure 3-1 is 1-monostearin,
also called α-monostearin. If the fatty acid is esterified at the middle
Fig. 3-1. Glycerol 1-mono-
hydroxyl, the compound is 2-monostearin, or β-monostearin. Both
stearate, also referred to as
monostearin or GMS. isomers are equally effective at retarding bread staling. In technical
specifications, manufacturers usually give the monoglyceride con-
tent of their product as the percentage of α-monoglyceride. The routine
analytical method for monoglyceride detects only the 1-isomer;
quantitation of the 2-isomer requires the use of gas chromatography.
Staling —Phenomenon that The total monoglyceride content of a product is about 10% higher
occurs in baked products than the reported α-monoglyceride content. In a practical sense,
during storage. Stale product however, when various products are compared for functionality and
has a firmer crumb structure cost effectiveness, the α-monoglyceride content is a useful number,
than fresh product; the crumb since for most products it equals about 91% of the total mono-
has a dry, harsh texture; and glyceride present.
the flavor impact is significantly
reduced.
The fatty acid composition of a monoglyceride reflects the makeup
of the triglyceride fat from which it is made. Commercial GMS may
α-Monoglyceride — contain as little as 65% stearate if it is made from fully hydrogenated
Monoglyceride in which the lard or as much as 87% stearate if it is made from fully hydrogenated
fatty acid is esterified to the 1 soybean oil. The other major saturated fatty acid is palmitic acid, and
position of glycerol. Esterifica- because complete hydrogenation (to an iodine value of 0) is not prac-
tion at the 2 position results in tical, a small percentage of unsaturated (oleic and/or elaidic) acid is
a β-monoglyceride.
also usually present. A typical commercial GMS has an iodine value
Iodine value —A measurement of about 5. Iodine values for powdered distilled monoglycerides range
of the number of double bonds from 19 to 36 and for plastic monoglycerides, typically from 65 to 75.
in a fat or oil. A higher value The unsaturated fatty acids are a mixture of oleic and linoleic acids
means more double bonds. and their trans isomers. The phase diagram of a highly unsaturated
 FOOD EMULSIFIERS \ 27

monoglyceride is quite different from that of a saturated monoglyc- Dough strengthener—

eride (Fig. 2-4), but the higher melting point of the partially hydro- Material added to bread dough
to increase the ability of the
genated monoglyceride (both saturated and unsaturated) makes its
gluten to retain gas during
phase behavior much more like that of GMS than that of the sun- proofing and baking.
flower monoglyceride. To the extent that mesophase behavior gov-
erns monoglyceride functionality, the plastic monoglycerides are α-Tending emulsifier —
quite adequate. Emulsifier that forms a solid
film at the oil-water interface
MONOGLYCERIDE DERIVATIVES under proper conditions of
temperature (low) and concen-
The derivatives of monoglyceride shown in Figures 3-2 and 3-3 are tration (high).
of two types: 1) dough strengtheners (succinyl monoglyceride [SMG],
ethoxylated monoglyceride [EMG], and diacetyl tartrate ester of
monoglyceride [DATEM]) and 2) α-tending emulsifiers (acetylated
monoglyceride [AcMG], lactylated monoglyceride [LacMG], and

H O
H-C-O-C-(CH 2 ) 16 CH 3
Ethoxylated
H-C-OH
monoglyceride
H-C-O(CH 2 CH 2 O) n H (EMG)

H O
H-C-O-C-(CH 2 ) 16 CH 3
Succinyl
H-C-OH monoglyceride
(SMG)
H-C-OCCH 2 CH 2 COOH
H O

O OCCH 3 Diacetyl tartrate ester of

monoglyceride (DATEM)
MG-OC-CHCHCOO -

OCCH 3
O
Fig. 3-2. Emulsifiers used as dough strengtheners. In the DATEM structure, MG =
monoglyceride.
28 / CHAPTER THREE

propylene glycol monoester

H O [PGME]). In each case, the
structure shown is the main,
H-C-O-C-(CH 2 ) 16 CH 3 Acetylated but not the only, component
monoglyceride of the mixture. The primary hy-
H-C-OH (AcMG) droxyl (3-hydroxyl) of mono-
glyceride is chemically more
H-C-O-C-CH 3 reactive than the secondary (2
position) hydroxyl. Thus, acety-
H O H O lation gives mainly 3-acetyl
1-monoglyceride, but there is
Lactylated H-C-O-C-(CH )
2 16 CH 3 also a certain amount of
monoglyceride 2-acetyl 1-monoglyceride plus
H-C-OH OH 1-acetyl 2-monoglyceride. In
(LacMG)
addition, any diglyceride pres-
H-C-O-C-CH-CH 3 ent can also be acetylated.
H O SMG is made by reacting
succinic anhydride with mono-
H-C-O-C-(CH 2 ) 16 CH 3 H O
glyceride. The reaction is fairly
straightforward. The various
H-C-OH positional isomers mentioned
Propylene glycol for acetylated monoglyceride
H-C-H monoester (PGME) can also be found in succiny-
lated monoglyceride.
DATEM is produced in two
H
steps. First, tartaric acid (a by-
Fig. 3-3. α-Tending emulsifiers. These emulsifiers form solid films at the oil- product of wine making) is
water interface under conditions of low temperature and high concentration.
reacted with acetic anhydride,
acetylating the two hydroxyl
groups and converting the tartaric acid to an anhydride. This is then
reacted with monoglyceride. The major product is the structure
shown in Figure 3-2, although numerous other closely related com-
pounds are present. The four main reaction products are mono-(di-
Primary hydroxyl —Hydroxyl acetyl tartaric acid) ester of monoglyceride, di-(diacetyl tartaric acid)
group on the terminal carbon ester of monoglyceride, mono-(diacetyl tartaric acid) ester of diglyc-
atom of a compound. That car- eride, and mono-(diacetyl tartaric acid) monoacetyl ester of mono-
bon atom is connected to only glyceride. The ratio of these four components in a given DATEM
one other carbon.
preparation depends mainly on the content of diacetyl tartaric anhy-
Secondary hydroxyl—
dride and the type of monoglyceride used in the reaction. The func-
Hydroxyl group on a carbon tionality of the emulsifier depends to a large extent on its composi-
atom that is attached to two tion, so it is necessary to use a rather stringent raw material
other carbons. specification in order to ensure that performance remains consistent
from lot to lot. Important indicator properties are saponification value
Saponification value —Weight and acid value.
in milligrams of the potassium
The structure of EMG is even more random. Monoglyceride is
hydroxide required to saponify
1 g of a lipid. It characterizes a
treated with ethylene oxide gas under pressure in the presence of al-
lipid by quantifying the propor- kaline catalyst and at elevated temperatures. Ethylene oxide is poly-
tion of ester groups relative to merized via a series of ether linkages and also forms ether bonds with
the total molecular weight. the free hydroxyl groups on monoglyceride. The average chain
 FOOD EMULSIFIERS \ 29

length is about 20 units (n = 20 in Fig. 3-2). Both the number 2 (β) Acid value —Weight in milli-
and number 3 (α) positions of the monoglyceride may be derivatized, grams of potassium hydroxide
required to neutralize the titrat-
although because of its greater chemical reactivity, the primary hy-
able groups in 1 g of lipid. It
droxyl (the α position) is more likely to be derivatized than the sec- characterizes a lipid by quanti-
ondary hydroxyl (the β position). The exact distribution of polymer fying the proportion of titrat-
chain lengths and distribution between α and β positions are func- able acidic groups.
tions of reaction conditions, e.g., catalyst type and concentration, gas
pressure, temperature, agitation, and length of reaction time. Of
course, any diglyceride present may also be ethoxylated.
The second group of monoglyceride derivatives, the α-tending
emulsifiers, are used mainly in cake production. These emulsifiers are
dissolved in the shortening phase of the cake formulation, and they
contribute to the emulsification of the shortening in the water phase
and promote incorporation of air into the fat phase. The particular
property of these emulsifiers that makes them valuable in liquid
shortening cakes is that they form a solid film at the oil-water inter-
face. This stabilizes the emulsion; but more importantly, it prevents
the lipid phase from destabilizing the protein-stabilized foam during
cake batter mixing (air incorporation).
The production of AcMG and PGME is straightforward organic
chemistry. Treatment of monoglyceride with acetic anhydride results
in the acetylated product, with the various kinds of isomers listed
above. PGME can be made either by direct esterification of propylene
glycol with fatty acids or by interesterification of fat (triglycerides)
with propylene glycol. The direct esterification product typically
contains about 55–60% monoester, and the remainder is diester.
While a product containing >90% monoester is made by molecular
distillation, the extra cost of this process is not warranted for most
commercial (cake mix production) uses. The interesterified product
is more complex, containing not only mono- and diesters of propy-
lene glycol, but also about 10–15% monoglyceride and a small
amount of diglyceride. As with DATEM, because such a wide range of
product compositions is possible from different manufacturing
processes, it is advisable to have stringent raw material specifications
for this ingredient.
Lactic acid esters of monoglyceride are usually made by reacting
lactic acid with a distilled monoglyceride. The complication here is
that lactic acid contains a hydroxyl group, and the fatty acid moiety
may migrate. For example, if lactic acid is heated with 1-monostearin,
the main initial product is 3-lactoyl-1-stearoyl glycerol. However,
during the reaction, some portion of the stearic acid may migrate to
the lactyl hydroxyl, resulting in glyceryl 3-(stearoyl)-lactylate. In ad-
dition, lactic acid can polymerize (form lactoyl lactic esters), and lac-
toyl dimers and trimers may also be present. Thus, the reaction prod-
uct mixture from heating lactic acid with a monoglyceride is a
complex mixture containing as many as 10 identifiable molecular
species. Production parameters must be tightly controlled to obtain a
product with consistent functionalities.
30 / CHAPTER THREE

Hydrophilic/lipophilic balance SORBITAN DERIVATIVES

(HLB) —Ratio of an emulsifier’s
hydrophilic and lipophilic When the sugar alcohol sorbitol is heated with stearic acid in the
tendencies. presence of a catalyst, two reactions occur: sorbitol cyclizes to form
the five-membered sorbitan ring and the remaining primary hy-
droxyl group is esterified by the acid. The resulting sorbitan mono-
stearate (Fig. 3-4) is oil soluble and has a rather low hydrophilic/
lipophilic balance (HLB) value (HLB is discussed later in this chapter).
It is an approved additive for food use in many countries. Other im-
portant esters are sorbitan monooleate and sorbitan tristearate. A pe-
tition has been filed for affirmation as generally recognized as safe
(GRAS) status for sorbitan tristearate, but until it is acted upon by the
U.S. Food and Drug Administration (FDA), sorbitan tristearate is
being sold as a self-affirmed GRAS crystal modifier.
Any of the three esters may be reacted with ethylene oxide to ob-
tain polyoxyethylene derivatives (Fig. 3-5). The monostearate deriva-
tive is known as Polysorbate 60, the tristearate is Polysorbate 65, and
the monooleate is Polysorbate 80. The discussion above of EMG re-
garding the length and location of the polyoxyethylene chains
applies to these compounds. The average number of oxyethylene
monomers is 20 (n = 20), and in the case of the monoesters, chains
may be located on more than one hydroxyl group of the sorbitan ring
(with the triester, of course, only one hydroxyl group is available for
derivatization).
Sorbitan monostearate is a good emulsifier for use in making icings
with superior aeration, gloss, and stability characteristics. It is also
used as part of the emulsifier system in whipped toppings and coffee
whiteners. The polyoxyethylene derivatives have found more accep-
tance; the monostearate Polysorbate 60 is the most widely used of the
group. At a level of 0.25% (flour basis), the ability of Polysorbate 60
to strengthen dough against mechanical shock is greater than that of

H O
H O H-C-O-C-(CH 2 ) 16 CH 3
H-C-O-C-(CH 2 ) 16 CH 3 OH-C-H
O
H
OH-C-H
C C
O H H H H H
C C C C
H H H H
C C H 3 C(CH 2 ) 16 C-O O-C-(CH 2 ) 16 CH 3
HO OH O O
Sorbitan monostearate Sorbitan tristearate
Fig. 3-4. Sorbitan esters. Note the mono- and tristearate esters of the sorbitan ring.
 FOOD EMULSIFIERS \ 31

SMG and about equal to that of EMG and SSL. Polysorbate 60 has also
been used in fluid oil cake shortening systems, generally in combina-
tion with GMS and propylene glycol monostearate.

POLYHYDRIC EMULSIFIERS
Polyglycerol esters. Polyglycerol esters (Fig. 3-6) have a variety of
applications as emulsifiers in the food industry. The polyglycerol por-
tion is synthesized by heating glycerol in the presence of an alkaline
catalyst, and ether linkages are formed between the primary hydrox-
yls of glycerol. In the structure depicted in Figure 3-6, n may take any
value; but for food emulsifiers, the most common are n = 3 (triglyc-
erol), n = 6 (hexaglycerol), n = 8 (octaglycerol), and n = 10 (decaglyc-
erol). (In all cases, n is an average value for the molecules present in
the commercial preparation.) The polyglycerol backbone is then es-
terified to varying extents, either by direct reaction with a fatty acid
or by interesterification with a triglyceride fat. Again, the number of

H O
H-C-O-C-(CH 2 ) 16 CH 3
H(OCH 2 CH 2 ) n -OCH Polyoxyethylene (20)
O
H sorbitan monostearate
C C (Polysorbate 60)
H H H H
C C
HO OH

H O

H-C-O-C-(CH 2 ) 16 CH 3
H(OCH 2 CH 2 ) n -OCH Polyoxyethylene (20)
O H sorbitan tristearate
C C (Polysorbate 65)
H H H H
C C
H 3 C(CH 2 ) 16 C-O O-C-(CH 2 ) 16 CH 3

O O
Fig. 3-5. Polysorbate emulsifiers. Reacting the sorbitan ester with ethylene oxide
forms the hydrophilic polyoxyethylene side chain.
32 / CHAPTER THREE

OH acid groups esterified to a polyglycerol molecule varies around some

central value, so an octaglycerol octaoleate really should be under-
stood as an (approximately octa)-glycerol (approximately octa)-oleate
H-C-H ester. By good control of feedstocks and reaction conditions, manu-
OH-C-H facturers manage to keep the properties of their various products rela-
tively constant from batch to batch.
The HLB of these esters depends on the length of the polyglycerol
H-C-H chain (i.e., the number of hydrophilic hydroxyl groups present) and
the degree of esterification. For example, decaglycerol monostearate
O has an HLB of 14.5, while triglycerol tristearate has an HLB of 3.6.
Intermediate species have intermediate HLB values, and any desired
H-C-H value may be obtained by appropriate blending, as described below.
The wide range of possible compositions and HLB values makes these
OH-C-H materials versatile emulsifiers for food applications.
Sucrose esters. Sucrose has eight free hydroxyl groups,
H-C-H which are potential sites for esterification to fatty acids.
Compounds containing six or more fatty acids per su-
Polyglycerol
O n-2 crose molecule are marketed as noncaloric fat substi-
monostearate tutes under the name Olestra; this material acts like a
H-C-H triglyceride fat and has no surfactant properties.
Compounds containing one to three fatty acid esters
(Fig. 3-7), on the other hand, do act as emulsifiers and
OH-C-H O are approved for food use in that capacity. They are
manufactured by the following steps:
H-C-O-C-(CH 2 ) 16 CH 3
1. An emulsion is made of fatty acid methyl ester
in a concentrated aqueous sucrose solution.
H 2. The water is removed under vacuum at ele-
Fig. 3-6. Basic structure of the polyglycerol esters. vated temperature.
The free hydroxyls on the polyglycerol can be es- 3. Alkaline catalyst is added, and the temperature
terified to fatty acids to varying extents, resulting
in emulsifiers with a wide range of hydrophilic/
of the dispersion is raised slowly to 150°C
lipophilic balance values. under vacuum, distilling off methanol formed
during transesterification.
4. The reaction mixture is cooled and purified.
H O

H-C-O-C-(CH 2 ) 16 CH 3

H O H
H HOH 2 C O
H
OH O
H O H HO
HO CH 2 O-C-(CH 2 ) 16 CH 3

H OH OH H
Sucrose diester
Fig. 3-7. One possible positional isomer of a sucrose diester.
 FOOD EMULSIFIERS \ 33

TABLE 3-1. Ester Distribution in Sucrose Ester Emulsifiers

Percentage of Ester Type

Designation Monoester Diester Triester Tetraester HLBa
F-160 71 24 5 0 15
F-140 61 30 8 1 13
F-110 50 36 12 2 11
F-90 46 39 13 2 9.5
F-70 42 42 14 2 8
F-50 33 49 16 2 6
a
Hydrophilic/lipophilic balance.

The degree of esterification is controlled by the reaction condi-

tions, especially the ratio of sucrose to methyl ester, and the final
product is a mixture of esters (Table 3-1). The HLB value of a particu-
lar product is lower (more lipophilic) as the degree of esterification
increases, as would be expected.

ANIONIC EMULSIFIERS
In addition to SMG and
DATEM, some other anionic O
surfactants (Fig. 3-8) have
been tried as dough strength- CH 3 (CH 2 ) 16 C-O
eners. SSL is currently the one O Sodium stearoyl
most widely used in the lactylate (SSL)
United States. Sodium stearyl H 3 C-C-C-O - Na +
fumarate did not find accep-
tance, and sodium lauryl sul- H
fate (SLS) is used mainly as a
whipping agent with egg
whites.
Lactic acid, with both a car- O O
boxylic acid and a hydroxyl Sodium stearyl
function on the same mole- CH 3 (CH 2 ) 17 -O-C-C=C-C-O - Na + fumarate
cule, readily forms an ester
with itself. In commercial con- H H
centrated solutions, almost all
the acid is present in this poly-
lactylic form, and to get free
lactic acid, it must be diluted O
with water and refluxed for a
period of time. When stearic CH 3 (CH 2 ) 11 -O-S-O - Na + Sodium
acid is heated with polylactic
dodecyl sulfate
acid under the proper reaction O
conditions and then neutral- (SDS)
ized with sodium hydroxide, a Fig. 3-8. Three anionic emulsifiers. SSL and the fumarate are dough condition-
product with the structure ers, and SDS is used to solubilize proteins.
34 / CHAPTER THREE

shown in Figure 3-8, is obtained. The monomer lactylic acid shown

represents the predominant product; the dilactylic dimer is also pre-
sent as well as lactylic trimers and tetramers. As with all compounds
based on commercial stearic acid derived from hydrogenated fats,
some percentage of the fatty acid is palmitic and small amounts of
myristic and arachidic acids are also present. SSL is readily water solu-
ble, but the calcium salt is practically insoluble. In this respect, it mim-
ics a soap; e.g., sodium stearate is water soluble, but calcium stearate is
oil soluble. Either form may be used, depending on the details of the
intended application, but as a dough strengthener, the sodium salt is
more common. As a stabilizer for hydrated monoglyceride, the
sodium form is used because ionization in the water layer is necessary.
Stearyl fumarate is a half ester of fumaric acid with stearyl alcohol
(octadecanol). Although stearyl fumarate might be expected to have
dough-strengthening properties similar to those of SSL, this was not
found to be so in practice, and the product was not a commercial suc-
cess. Stearyl fumarate is still approved by the FDA for use in bread.
The third structure shown in Figure 3-8 is sodium dodecyl sulfate
(SDS), often used by research workers for solubilizing proteins. It is a
sulfate ester of the C12 alcohol dodecanol. The relationship between
the pure compound (SDS) and the commercial surfactant (SLS) is as
follows. Reduction of coconut oil yields a mixture called lauryl alcohol
(from lauric acid, the predominant fatty acid in coconut oil). Sulfation
and neutralization result in SLS. The alcohol portion of SLS is a mix-
ture of chain lengths; the approximate composition of the common
commercial form is 8% C8, 7% C10, 48% C12, 20% C14, 10% C16,
and small amounts of longer chains. The most common food use of
SLS is as a whipping aid. The compound is added to liquid egg whites
at a maximum concentration of 0.0125% or to egg white solids at a
level of 0.1%. It promotes the unfolding of egg albumin at the air-water
interface and stabilization of the foam.

LECITHIN
Egg albumin —Soluble protein
found in egg white. The lecithin generally used by food processors is a by-product of
the processing of crude soybean oil; it is the “gum” that is removed
Crude gum—Material removed during the degumming step of oil refining. The crude gum is treated
during the degumming phase
and purified to give the various commercial lecithin products that are
of vegetable oil refining. Water
is added to the crude oil, and
available today. Crude soybean oil contains about 2% lecithin. Crude
the polar components (such corn and cottonseed oils contain about 1% lecithin, but because
as phospholipids) become hy- smaller amounts of these oils are processed in the United States (com-
drated and associated with the pared with soy oil), the amount of gum obtained is usually too small
aqueous phase, which is then for economical processing for human food uses. Instead, it is added
separated by centrifugation. back to animal feed formulations as a valuable source of energy.
Egg yolk contains about 20% phospholipid, which accounts for its
Phospholipid —Diglyceride
esterified at the 3 position to
excellent emulsifying functionality, for example, in mayonnaise.
phosphoric acid, which in turn However, isolated lecithin from egg yolk is too expensive to be used
is often esterified to another for food manufacture.
group. The crude gum is dehydrated (to remove water used during degum-
ming), and then insoluble fines are removed by filtration. The crude
 FOOD EMULSIFIERS \ 35

material is brown to dark brown (depending on the amount of heat Acetone insolubles—
applied during processing) and contains some pigments extracted Specification of the amount
from the original soybean. It is bleached to attain a more acceptable of phospholipids in “gums,”
based on the fact that the other
light brown color. Treatment with up to 1.5% hydrogen peroxide re-
constituents normally present
sults in a product known as single-bleached lecithin, and addition are soluble in acetone.
of benzoyl peroxide up to 0.5% yields double-bleached lecithin.
Reaction with hydrogen peroxide at even higher levels plus lactic
acid hydroxylates unsaturated fatty acid side chains at the double
bond (e.g., yielding dihydroxystearic acid from oleic acid). The hy-
droxylated lecithin that is formed is more dispersible in cold water
than the other types and is more effective as an emulsifier for
oil/water (O/W) emulsions.
Phospholipids are insoluble in acetone, and the phospholipid con-
tent of lecithin is specified as acetone insolubles (AI). The standard
commercial lecithin has a minimum AI content of 65%. Crude
bleached lecithin is quite viscous. The addition of vegetable oil flu-
idizes lecithin, and commercial fluid lecithin products are standard-
ized to have a viscosity of 7,500–10,000 cP at 25°C. A fully deoiled
lecithin, a granular, free-flowing product with a typical AI content of
95–98%, is also produced.
The structures of the main surface-active components of lecithin
are shown in Figure 3-9. The phosphatidyl group is a phosphate ester

-CH 2 CH 2 N + H 3
O ethanolamine

CH 3 (CH 2 ) 16 C-O-CH 2
O -CH 2 CH 2 N + (CH 3 ) 3

CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 C-O-CH O - choline

H 2 C-O-P-O-
O OH OH
Phosphatidyl
H H H OH

-O OH H H

H OH
inositol
Fig. 3-9. Structure of the major components of soy lecithin. Serine is another possible substituent,
but phosphatidylserine is found mainly in animal phospholipids, such as that from egg yolk.
Removing one fatty acid from the phosphatidyl moiety results in a lysophospholipid.
36 / CHAPTER THREE

of diglyceride. The fatty acid composition of the diglyceride is similar

to that of the basic oil, so a number of different fatty acids are found,
not just the stearic and oleic acids depicted. The three species are
found in approximately equal amounts. Phosphatidylethanolamine
(PE) and phosphatidylcholine (PC) are amphoteric surfactants, while
phosphatidylinositol (PI) is anionic. Other surface-active materials
are also found at somewhat lower concentrations. These include
phosphatidic acid (the phosphatidyl moiety plus a hydrogen atom),
lysophosphatides (the above species but with one fatty acid re-
moved), and glycolipids (a sugar residue, either galactose or digalac-
tose, attached to the free hydroxyl of a diglyceride).
The HLB values of the three types vary: PC has a high HLB, PE an
intermediate value, and PI a low value. The HLB of the natural blend
is 9–10, and emulsifier mixtures with values in this range tend to form
either O/W or water/oil (W/O) emulsions, although neither type is
highly stable. However, emulsifiers with intermediate HLB values are
excellent wetting agents, and this is a major application for lecithin.
The emulsifying properties of lecithin can be improved by ethanol
fractionation. PC is soluble in ethanol, PI is rather insoluble, and PE
is partially soluble. Adding deoiled lecithin to ethanol results in a sol-
uble and an insoluble fraction. The phosphatide composition of the
ethanol-soluble fraction is 60% PC, 30% PE, and 2% PI plus glyco-
lipids, and that of the ethanol-insoluble fraction is 4% PC, 29% PE,
and 55% PI plus glycolipids. The remaining small percentage of both
fractions includes oil, free fatty acids, and lysophosphatides. The sol-
uble fraction is effective in promoting and stabilizing O/W emul-
sions, while the insoluble portion promotes and stabilizes W/O emul-
sions. Chromatography of the ethanol-soluble fraction can be
performed to obtain a material containing 90% PC that is used to
make an egg yolk replacer. The emulsifying ability of egg yolk results
in part from its high HLB (70% PC and 15% PE in the total yolk phos-
pholipid) plus the protein. The fractionation process is currently used
by several European companies to produce industrial food-grade
emulsifiers with special functionalities.

Hydrophilic/Lipophilic Balance
BASIC PRINCIPLE OF THE CONCEPT
As discussed in Chapter 1, emulsifiers consist of a hydrophilic por-
tion (consisting of a wide variety of structures) and a lipophilic por-
tion (usually a fatty acid or occasionally a fatty alcohol). The balance
between these two governs the functionality of the emulsifier at in-
terfaces and hence its utility in foods. This balance, called the hy-
Glycolipid—Diglyceride drophilic/lipophilic balance (HLB), attaches a number to emulsifiers
connected to a sugar moiety that guides the food technologist in choosing one for a particular
(usually galactose or galactosyl-
application.
galactose) at the 3 position and
common in cereal and legume
The initial proposal was to calculate HLB as
seeds.
 FOOD EMULSIFIERS \ 37

HLB = L/T × 20 TABLE 3-2. Hydrophilic/Lipophilic Balance

Functional Group Numbers
in which L is the molecular weight of the hydrophilic
part of the molecule and T is the total molecular Group Group Number
weight. Thus, a pure hydrocarbon would have an HLB Hydrophilic
of 0, while a pure hydrophile (e.g., sugar) would have -SO4Na 38.7
an HLB of 20. -COOK 21.1
Another method of calculating HLB is to add up con- -COONa 19.1
tributions by various functional groups. The functional Sulfonate ~11
groups and their associated group numbers are listed in -N(CH3)3 9.4
Table 3-2. The group values for the hydrophilic and
Ester (sorbitan ring) 6.8
lipophilic functions in the emulsifier are summed and
Ester (others) 2.4
inserted into the equation:
-COOH 1.9
HLB = Σ (hydrophilic values) – Σ (lipophilic values) + 7 -OH (sorbitan ring) 0.5
The agreement between calculated and experimen- -OH (other) 1.9
tally determined HLB values is generally within a few -(CH2-CH2-O)- 0.33
tenths. Considering that neither method is highly pre- Lipophilic
cise, one cannot expect much better, and the calcu- -CH- …

lated value gives a good indication of HLB for a new -CH2- 0.475
emulsifier under investigation. -CH3 …

HLB values provide a guide to the functionality of =CH- …

the emulsifier system. The following guidelines are
based on experience:
• HLB of 3–6: a good water-in-oil emulsifier;
• HLB of 7–9: a good wetting agent; and
• HLB of 10–18: a good oil-in-water emulsifier.

EXPERIMENTAL DETERMINATION OF HLB

While theoretical calculations are fine, emulsifiers are used in food
systems that, for the most part, are anything but theoretically simple.
For practical purposes, determination of optimum HLB for a particu-
lar system is best done experimentally. This approach starts with the
concept that the HLB of a blend of emulsifiers is the algebraic sum of
their contributions. For example, a blend of sorbitan monostearate
(HLB = 4.7) and Polysorbate 60 (HLB = 14.9) is used to determine the
optimum HLB for a salad dressing formulation. A 50/50 mixture of
the two has an HLB of 9.8 (0.5 × 4.7 + 0.5 × 14.9), a 25/75 blend has
an HLB of 12.35 (0.25 × 4.7 + 0.75 × 14.9), etc. While this is a straight-
line relationship, it should be noted that in practice the prediction
does not hold precisely true.
The first step is to prepare a series of emulsifier blends at intervals of
0.5 HLB units. The range should be selected on the basis of the desired
product characteristics (W/O or O/W emulsion) and according to the
guidelines above. An excess of emulsifier (approximately 10% of the
weight of the oil phase) is used to ensure emulsion formation. The
emulsifier is dissolved in the oil, the aqueous components are added,
38 / CHAPTER THREE

Response surface methodol- and emulsions are made for each trial by using a standardized agita-
ogy—Method of experimental tion technique. The emulsions are allowed to stand and are then
design to determine the opti- assessed for stability, e.g., by measuring the thickness of the oil (or
mum values for two or more
water) layer formed at various times. (If all the emulsions are too sta-
variables in a product by using
a limited number of experi- ble to break down in a reasonable length of time, the experiment
ments and making interpola- should be repeated with less emulsifier.) The result is an approximate
tions based on the experimen- optimum HLB range for the system.
tal data. The next step is to choose the best chemical type of emulsifiers to
use. Experience shows that a blend of two emulsifiers (one lipophilic
and one hydrophilic) generally produces the most stable emulsions.
Numerous such pairs are available, e.g., sorbitan monostearate plus a
polysorbate, monoglyceride plus a fatty acid salt (sodium or potas-
sium), triglycerol tristearate plus decaglycerol monostearate, and su-
crose esters (e.g., F-160 plus F-50).
In addition, the nature of the fatty acid chain (e.g., chain length
and degree of unsaturation) can sometimes make a difference that is
readily seen by comparing some of the entries in Table 3-3. The melt-
ing point can be a factor in some processing systems; solid mono-
stearin may be difficult to add, whereas liquid monoolein (with the
same HLB) may be more convenient to use. If the sys-
tem is acidic (e.g., a salad dressing), acid-stable emulsi-
TABLE 3-3. HLBa Values of Food Emulsifiers fiers such as the sorbitans or polyglycerols may be the
best choices. If the pH is in the neutral range, the
Emulsifier Experimental HLB
monoglyceride plus fatty acid salt pair may be the
Sodium lauryl sulfate 40 most effective.
Sodium stearoyl lactylate 22 The various combinations are then subjected to
Potassium oleate 20 emulsifying trials as described above, but blends that
Sucrose monoester 20 are in the middle of the apparent optimum HLB range
Sodium oleate 18 are used. These trials should include relatively small
Polysorbate 60 15 HLB variations (i.e., optimum and ±0.5 HLB units) and
Polysorbate 80 15 limited variation in concentrations. The goal is to
Decaglycerol monooleate 14 choose the emulsifier system that provides the best
Decaglycerol monostearate 13
stability at the lowest usage level.
After the type of emulsifier is selected, the system can
Ethoxylated monoglyceride 13
be fine-tuned by running a series of trials at intervals of
Decaglycerol dioleate 12
0.1 HLB units and at various concentrations to find the
Polysorbate 65 11 minimum amount that yields the desired emulsion sta-
Hexaglycerol dioleate 9 bility. At this stage of testing, using response surface
Decaglycerol hexaoleate 7 methodology maximizes information gained while mini-
Triglycerol monostearate 7 mizing the amount of work needed.
Glycerol monolaurate 7 Two final points must be emphasized. First, HLB is
Sorbitan monostearate 5.9 an empirical system for characterizing emulsifiers, and
Sucrose triester 5 the values assigned to emulsifiers (as in Table 3-3) are
Propylene glycol monolaurate 4.5 necessarily somewhat imprecise. Thus, if a particular
Propylene glycol monostearate 3.4 emulsifier combination provides the best results at an
Glycerol monostearate 3.8
HLB of 11.4, a different combination might function
best at an HLB of 11.7. The effects of any substitutions
Sorbitan tristearate 2.1
must be evaluated, although the use of the HLB system
a
Hydrophilic/lipophilic balance. greatly decreases the amount of work needed. Second,
 FOOD EMULSIFIERS \ 39

emulsifiers interact with other food ingredients, and if formula

changes are made (additions or subtractions), the assessment of opti-
mum HLB must be repeated. This is especially true if the changes in-
volve proteins or gums.

Proteins
Proteins are surface-active molecules. They unfold (i.e., denature,
or lose their native three-dimensional structure) at water-air or water-
oil interfaces, adsorbing at the interface and stabilizing the foam or
emulsion. Their contribution to foam stability is briefly discussed in
Chapter 1, and the properties and forces contributing to unfolding
and adsorption are discussed here.

FOAMING AGENTS
The best-known example of proteins as foam stabilizers is the
whipping of egg white to make meringue. Ovalbumin (the main pro-
tein in egg white) readily denatures and spreads at the air-water in-
terface. When whipping is continued to the “dry-peak” stage, all the
water is immobilized in the interstitial spaces and the meringue does
not drain, even after an extended period of time. Air bubble size has
been reduced (and numbers increased), generating enough interfacial
area to accommodate all the protein in the unfolded state. Many
other soluble proteins can also be whipped, but the resulting foam is
less stable. Drainage occurs, and after a period of time, the foam be-
gins to break down. The difference may be attributed to reversibility
of the unfolding process. For ovalbumin, the process is essentially ir-
reversible, and it stabilizes the interface, even though system energy
is high. Soluble soy protein unfolds, but with time (and under the
energetic influence to lower free energy by diminishing interfacial
area), the adsorbed protein is slowly forced back into the aqueous
phase, causing the foam to collapse. Acetylation of soy protein (con-
verting basically charged lysine amino groups into uncharged aceta-
mido groups) provides a soluble protein in which the resolubilizing
tendency is greatly reduced, and stable, dry-peak foams can be made
from such a protein.
In cake batters, the soluble flour proteins (and, of course, any
added egg whites) act as foaming agents. In cakes made with oil, pro-
teins are the main agents of air incorporation. The destabilization of
foams in these cakes must be prevented by using an α-tending emul-
sifier that encapsulates the oil (see Chapter 4). In cakes made with
fractionated and reconstituted flours, omission of the soluble protein
fraction results in failures (1).
Polypeptide —A polymer
EMULSIFYING AGENTS consisting of amino acids
connected by an amide bond,
Proteins at interfaces. A protein is a polypeptide (i.e., a chain of amino involving the carboxylic acid
acids joined by amide linkages) in which some of the amino acid side and α amino groups.
40 / CHAPTER THREE

chains are hydrophilic and

some are hydrophobic.
The chain is coiled upon
itself in such a way that
most of the hydrophobic
side chains are in the inte-
rior of the protein (and not
in contact with water) and
the hydrophilic chains are
on the exterior surface
where they can interact
with water (Fig. 3-10, left).
A protein has been charac-
terized as “an oil drop sur-
rounded by a hydrated
Fig. 3-10. Left, protein dissolved in water, folded into its native configuration. Right, shell.” This conformation
protein unfolded at an interface. The hydrophobic parts of the chain (light gray sec-
is not rigid, and under the
tions) penetrate the oil side of the interface while the hydrophilic parts (black sec-
tions) remain in the water. right conditions it can un-
fold. If an interface is pre-
sent, the hydrophobic
parts of the chain will penetrate the air (or oil) side of the interface
while the hydrophilic parts remain in the water (Fig. 3-10, right). The
protein acts as an amphiphile, and the surface (or interfacial) tension
is lowered.
Both soluble and insoluble proteins can emulsify oil. Myosin, a low
molecular weight protein related to hemoglobin, emulsifies fat dur-
ing the grinding of meat to make sausage. Other proteins such as iso-
lated soy protein are also often added to the mix, emulsifying fat (and
increasing its contribution to sausage net weight) as well as holding
water during cooking (thereby increasing yield).
The lipoproteins in egg yolk are the main emulsifying agents in
mayonnaise (see Chapter 6). Lipoproteins from other sources (e.g.,
peanut flour) can also emulsify oil, and a type of mayonnaise has
been made with such preparations. The emulsification capabilities of
egg yolk lipoproteins are enhanced by the lower pH that results from
the vinegar and/or lemon juice used in such dressings.
A major difference between proteins and ordinary emulsifiers (e.g.,
a sodium soap) relates to size. The molecular weight of milk proteins
is 20,000–300,000, while that of sodium oleate is 307. Thus, soap dif-
fuses to the interfacial region much more quickly than a protein.
When the protein reaches the interface, the unfolding of the chains
and partitioning of the segments between the two phases also take
time. If oil is added to a dilute soap solution and to a dilute protein
solution, the former system reaches its final interfacial tension value
within a matter of seconds, while the latter interface may take up to
an hour to reach final equilibrium. Temperature, pH, and different
Complexation—Combination
types and concentrations of salts also greatly affect the time required
of two different molecular
species. for the protein to complete its adsorption at the interface.
 FOOD EMULSIFIERS \ 41

Protein-emulsifier interactions. Protein and emulsifier molecules

can interact in two ways: complexation, which is usually observed
when both types of molecules are in solution, and competition,
which represents the interaction at interfaces.
Since a protein is partially hydrophobic in nature, it is not surpris-
ing that it can interact with the hydrophobic portion of an emulsifier.
The binding of amphiphiles such as SDS or fatty acid to blood serum
albumin has been studied in great detail, in part because the protein
is readily available in a pure state, allowing easier interpretation of ex-
perimental data. A more practical example is the complexation of a
dough strengthener such as SSL to gluten (see Chapter 4).
At low levels of interaction, up to about 10 moles of emulsifier per
mole of protein, there is no alteration in protein configuration, but as
the binding ratio increases, the protein begins to lose its native con-
figuration. As the amount of complexed emulsifier increases, the
amount of the hydrophobic component of the emulsifier becomes
significant compared with the amount of hydrophobic region in the
protein, and the influence of amino acid side chains in maintaining
the native protein configuration (through hydrophobic bonding) is
lessened. The influence of the ionic charge of the emulsifier hy-
drophilic group is much more disruptive. As the binding ratio ap-
proaches 100, the negative charges contributed by the emulsifier (as-
suming it is SDS or a soap) overcome the charged amino acid side
chains, and the protein-emulsifier complex takes on a fairly high
charge density. The ionic interactions (e.g., carboxylate-amino group
pairs) that contribute to the stability of the native protein configura-
tion are disrupted, and the protein unfolds. The unfolded complex
has been called the “necklace on a string” model (Fig. 3-11). Micelles
of the emulsifier incorporate hydrophobic regions of the protein.

Box 3-1. SDS-PAGE

The ability of 1% SDS in buffer to convert most proteins to
rod-shaped molecules with lengths proportional to their mol-
ecular weights has been used to estimate protein size by poly-
acrylamide gel electrophoresis (PAGE). The gel is a spongy
structure containing buffer. A sample of SDS-denatured pro-
tein is placed at one end of the gel slab, and an electrical po-
tential is applied. The complex migrates toward the anode
(positively charged pole). The rate at which the complex
makes its way through the gel is proportional to its length—
small rods travel faster than large ones. After an appropriate
time, the gel slab is removed from the electrophoretic appara-
tus, and a protein stain is applied so that the extent of migra-
tion can be measured. This is compared with the migration
rates of a standard mixture of proteins of known molecular
weight (run in the gel at the same time), and the molecular
weight of the unknown protein can be estimated.
42 / CHAPTER THREE

Since these micelles are all negatively charged, they are mutually re-
pulsive, and the necklace is rod shaped.
The binding described occurs only above the critical micelle con-
centration (CMC) of the emulsifier (see Chapter 2). The binding mode
is termed “cooperative”; i.e., the initial binding (and unfolding of a
small region of the protein) enhances further binding and unfolding.
Nonionic emulsifiers complex with proteins, although the effect is
small, since in general the emulsifiers are relatively insoluble in water.
The interaction of a moderately soluble emulsifier, octyl glucoside,
with many proteins has been studied. Cooperative binding of more
than 100 molecules of the emulsifier per molecule of protein was ob-
served. However, there was no measurable disruption of protein con-
figuration, which highlights the importance of the charge disruption
to the unfolding described above.
As mentioned above, proteins can unfold and adsorb at interfaces
(either air-water or oil-water). If another emulsifier is also present in
the system, it too adsorbs at the interface. Several reactions are
possible.
• Competitive adsorption: The two surface-active molecules com-
pete for the available interfacial area.
• Displacement: The more surface-active compound displaces the
less active material from the interface.
• Enhancement: A complex of the small molecule with the pro-
tein increases the interfacial action of the protein.
• Reinforcement: Interaction at the interface results in more effi-
cient packing of the ele-
ments involved (the hy-
drophobic regions of the
protein and the hydrophilic
ends of the emulsifier), in-
creasing the total interfacial
concentration and decreas-
ing interfacial tension even
further.
Numerous permutations
and combinations of these
possibilities have been ob-
served, mainly at air-water
interfaces but also occasion-
Fig. 3-11. The “necklace on a string” model for
ally at oil-water interfaces.
interaction of a surfactant with an unfolded pro- The proteins studied have
tein molecule. The surfactant (black circles plus ranged from purified (e.g.,
hydrophobic chains) forms micelles around the ovalbumin and lactoglobu-
hydrophobic segments of the protein (light lin) to complex (e.g., gluten
gray sections), stretching out the hydrophilic and meat extracts), and all
(black) parts of the protein chain. types of emulsifiers have
 FOOD EMULSIFIERS \ 43

been examined, although most reports involve either nonionic or an-

ionic food emulsifiers. A typical example of each case follows.
At low concentration, proteins tend to be more surface active than
emulsifiers. The addition of a mixture of protein (e.g., β-casein) plus
a surfactant such as SDS (at a concentration below its CMC) results in
a surface tension that is about the same as that of protein alone.
Raising the surfactant concentration to near its CMC allows it to be-
come the dominant surface-active molecule, and the surface tension
then becomes the same as that of SDS alone.
In a drained protein foam, the unfolded protein stabilizes the film
between air bubbles and prevents foam breakdown. If a small amount
of a nonionic emulsifier (e.g., monocaproin) is present in the liquid,
the foam is rather unstable and tends to collapse quickly after it
drains. The small molecules lower surface tension (so the foam can be
formed) but are not able to prevent the formation of holes in the film
that lead to collapse.
If the water-soluble emulsifier binds to the protein, it may actually
enhance the unfolding and surface-adsorption phenomenon. This is
the case with SLS and egg white protein. The surfactant, present at
low level, presumably destabilizes the protein conformation, leading
to quicker adsorption at the air-water interface and better whippabil-
ity of the egg white.
Surface tension decreases as SDS concentration increases up to the
CMC of SDS and then remains constant (Fig. 1-3). In the presence of
ovalbumin, for instance, the surface tension is less than that of SDS
alone up to the CMC, but at concentrations above the CMC, surface
tension continues to decrease. This must result from additional ad-
sorption of the protein-SDS complex at the surface.
Most studies of surfactants include measurements of interfacial
tension (see Chapter 1). However, adsorbed proteins usually show
a large increase in interfacial viscosity, presumably because they are
macromolecules. Often, this is the property that makes the protein
functional in the food system of interest. A viscous film at the oil-
water interfaces in an emulsion, for instance, greatly increases the re-
sistance to coalescence of oil droplets. Certain surfactants may dis-
place (or disrupt) the protein film, lowering interfacial viscosity while
at the same time producing the same or lower interfacial tension. An
emulsion made with protein alone is more stable (i.e., less coales-
cence is observed) than an emulsion made with the protein plus a
small amount of the displacing surfactant.
These considerations play a role in many types of food systems:
bakery batters, meat (sausage) emulsions, and egg yolk-stabilized
dressings and sauces. The influence of protein at interfaces, however,
is most pervasive in dairy products (see Chapter 5).

Interfacial viscosity —
Resistance to flow in the two
dimensions of the interface.
44 / CHAPTER THREE

Regulations
Emulsifiers are additives to traditional foods, and as such their use
is regulated by most governments. In the United States, they are ap-
proved by the FDA in one of three categories (approved additives,
GRAS materials, or affirmed as GRAS compounds) and listed in the
Code of Food Regulations, Title 21. In Canada, emulsifiers that may
be used are listed in Table IV, Division 16, of the Canadian Food and
Drug Regulations. In Europe, the European Union issues European
Parliament and Council Directives that list food additives authorized
for use in human foodstuffs.
Most of the emulsifiers commonly used in foods are listed in Table
3-4. This table should be used only as a guide to the regulations.
Many emulsifiers are approved only for certain kinds of food prod-
ucts, and often the allowable amount is limited. Before a large-scale
product-development project is begun, the actual regulations con-
cerning the emulsifiers to be used should be consulted to make sure
that the final product meets all regulatory guidelines.

Reference
1. Howard, N. 1972. Bakers Dig. 46(5):28-30, 32, 34, 36-37, 64.

Supplemental Reading
Friberg, S. E., and Larsson, K., Eds. 1997. Food Emulsions, 3rd ed. Marcel Dekker,
New York.
 FOOD EMULSIFIERS \ 45

TABLE 3-4. Regulatory Status of Emulsifiers

United European
Emulsifier Statesa Canadab Unionc
Mono- and diglycerides (GRAS)d 182.4505 M.4, M.5 E 471
Succinyl monoglyceride 172.830 …e …

Acetylated monoglyceride 172.828 A.2 E 472a

Lactylated monoglyceride 172.852 L.1 E 472b
…
Monoglyceride citrate 172.832 E 472c
…
Monoglyceride phosphate (GRAS) 182.4521 A.94, C.7
Diacetyl tartrate ester of
monoglyceride (GRAS) 182.4101 A.3 E 472e
Stearyl monoglyceride citrate 172.755 S.19 E 472f
… …
Polyoxyethylene monoglyceride 172.834
… …
Polyoxyethylene (8) stearate P.5
Propylene glycol monoester 172.854 P.14 E 477
Lactylated propylene glycol
… …
monoester 172.850
Sodium, potassium salts of fatty
…
acids 172.863 E 470
Sorbitan monostearate 172.842 S.18 E 491
…
Sorbitan tristearate S.18B E 492
Polysorbate 60 172.836 P.3 E 435
Polysorbate 65 172.838 P.4 E 436
Polysorbate 80 172.840 P.2 E 433
…
Calcium stearoyl lactylate 172.844 E 482
Sodium stearoyl lactylate 172.846 S.15A E 481
…
Stearoyl lactylic acid 172.848 L.1A
… …
Stearyl tartrate E 483
Stearoyl propylene glycol hydrogen
… …
succinate (succistearin) 172.765
… …
Sodium stearyl fumarate 172.826
… …
Sodium lauryl sulfate 172.822
… …
Dioctyl sodium sulfosuccinate 172.810
Polyglycerol fatty acid esters 172.854 P.1A E 475
Sucrose fatty acid esters 172.859 S.20 E 473
… …
Sucrose glycerides E 474
Lecithin (GRAS) 184.1400 L.2 E 322
Hydroxylated lecithin 172.814 H.1 E 322
… …
Oxystearin 172.818
… …
Triethyl citrate (GRAS) 182.1911
a
Code of Food Regulations, Title 21.
b
Canadian Food and Drug Regulations, Table IV, Division 16.
c
European Parliament and Council Directive 95/2/EC, 20 February 1995.
d
Generally recognized as safe.
e
Not listed by this jurisdiction.
 CHAPTER

Bakery Products
Surfactants used in the production of bakery goods are usually re-
ferred to as either “emulsifiers” or “dough strengtheners.” From a In This Chapter:
physical chemist’s point of view, the way these terms are used is im- Antistaling Agents
precise. The interfacial role of these materials is spelled out in this Starch Gelatinization
section, but in the remainder of this chapter, current bakery termi- Starch Retrogradation
nology is used for the sake of convenience. Bread Staling
Strictly speaking, an emulsifier is a surfactant that promotes the Emulsifier-Starch
formation of an emulsion; that is, it aids in the subdivision of parti- Complexation
cles of the discontinuous phase. In bakery usage, this function is most Dough Strengtheners
important in the production of batters for cake, cake doughnuts, waf- Aeration Agents
fles, etc.
The term “emulsifier” is also applied to compounds (i.e., crumb Troubleshooting
softeners) that interact with molecules and granules of gelatinized
starch and slow the rate at which they recrystallize, thereby con-
tributing to the retention of crumb softness. Surfactants that perform
this role react at the solid-liquid, not the liquid-liquid, interface.
Dough strengtheners are surfactants that presumably interact
with gluten proteins and enhance the dough characteristics that
bakers call “strength.” Again, the functionality is at the solid-liquid
interface.
All bakery surfactants aid the incorporation and subdivision of air
into the liquid phase; that is, they promote foam formation. This is
important in cake production and in the generation of fine-grained
crumb in bread. Compounds used for this purpose are usually called
emulsifiers, although they are actually foaming agents that function
at the gas-liquid interface.
Finally, it should be noted that any given surfactant may function
in all the ways listed, even though it is used primarily for one specific
function. For example, sodium stearoyl lactylate (SSL) is used mainly
for its dough-strengthening effect, but it also promotes emulsifica-
tion, air incorporation and subdivision, and retention of crumb soft-
ness. Again, in the viewpoint of the physical chemist, a bakery dough
or batter is a “messy” system with a multitude of interfacial interac-
tions occurring simultaneously. It is helpful to isolate each type of in-
teraction for discussion, realizing that ultimately all functions must
be considered together to realistically assess the effects of surfactants
on bakery foods.

47
48 / CHAPTER FOUR

Antistaling Agents
Emulsifiers were first used in bread to extend shelf life, i.e., to re-
tard staling. Monoglycerides are the primary antistaling additives
used today and account for about one-third of the emulsifiers used in
the baking industry. Staling is a complicated process that involves
changes in all the components of bread and is actually a sensory re-
sponse (older bread tastes “stale”) to these changes. A decrease in fla-
vor impact or a drier mouthfeel can be measured by taste panels, but
the consumer commonly uses the “squeeze test.” Staleness is equated
with resistance to manual squeezing of a loaf of bread. Bakery qual-
ity-control laboratories and research groups usually assess staleness
by measuring the resistance of the crumb to compression in an in-
strument such as the Baker Compressimeter, the Instron Universal
Testing Machine, or the penetrometer. Crumb compression correlates
with panel ratings; there is an excellent linear relationship between
panel freshness score (which includes flavor and mouthfeel as well as
texture) and the logarithm of the elastic modulus, or crumb modulus
(resistance to compression).
From the extensive research done on staling, three conclusions are
important:
1. Staling is not related to moisture loss from the bread. A five-day-
old stale loaf (stored under the proper conditions) has the same
moisture content as fresh bread, although it gives a drier mouth-
feel impression.
2. Staling is related to the recrystallization (retrogradation) of the
starch molecules gelatinized during the baking process.
Elastic modulus —Relationship 3. Other bread components (e.g., gluten protein and pentosans)
between stress (force) applied may play a role, but the extent and the nature of their contribu-
to a sample and the strain
tion to staling is uncertain.
(deformation) in the sample;
a more general rheological This section is concerned with the role emulsifiers (mainly mono-
term than crumb modulus. glycerides) play in retarding bread staling. To begin the discussion,
the current understanding of the involvement of starch in staling is
Crumb modulus —Synonym
for elastic modulus.
first reviewed.

Starch granules —Naturally STARCH GELATINIZATION

occurring, partially crystalline,
discrete aggregates of amylose
Native starch granules are ordered structures possessing a high de-
and amylopectin. gree of crystallinity. They are made up of two types of polyglucoside
chains: amylose, in which the linkages between monomers are of the
Amylose —Linear polyglucose α-1,4 type, and amylopectin, in which there are both α-1,4 and α-1,6
chains in starch. linkages. Amylose is a linear chain polymer with a molecular weight
of 100,000–300,000. Amylopectin is a branched structure with a mo-
Amylopectin —Branched
lecular weight of 10,000,000–40,000,000. Segments of several adja-
polyglucose chains in starch.
cent chains may order themselves in a crystalline structure (crystal-
Crystallites—Small regions lites), while other parts of the molecules are more random. The
of crystalline starch within a internal structure of the starch granule is still under discussion, but it
granule. may be roughly characterized as containing both crystalline and
 BAKERY PRODUCTS \ 49

amorphous regions. The crystallinity is evidenced by X-ray diffrac- Differential scanning

tion patterns of native starch, by a sharp melting endotherm when calorimetry (DSC) —A method
starch granules are heated in water in a differential scanning calorime- for measuring energy uptake
as a sample is heated. When
ter (DSC), and by the birefringence (Maltese cross) seen when native
a phase change occurs (e.g.,
starch is viewed microscopically in polarized light. When starch is melting or freezing), the plot
heated in water, crystallinity begins to disappear at a temperature shows the temperature at
that varies depending on the source of the starch, and it is almost which the change occurred and
completely lost at a point about 6–8 degrees C higher. This loss of the amount of heat energy
structure is called gelatinization (1): involved.

Starch gelatinization is the collapse (disruption) of molecular or- Birefringence —Ability of

ders within the starch granule manifested in irreversible changes crystalline materials to rotate
in properties such as granular swelling, native crystallite melting, polarized light.
loss of birefringence, and starch solubilization. The point [tem-
Gelatinization—Collapse (dis-
perature] of initial gelatinization and the range over which it oc-
ruption) of molecular orders
curs is governed by starch concentration, method of observation, within the starch granule mani-
granule type, and heterogeneities within the granule population fested by irreversible changes
under observation. in properties such as granular
swelling, native crystalline melt-
When starch granules are heated in water, the first change noted ing, loss of birefringence, and
microscopically is a gradual increase in granule volume, or swelling. starch solubilization.
Generally, the granules take up available water, and the loss of crys-
tallinity is progressive. At intermediate stages of heating or in situa-
tions where water is limited (a starch-water ratio of two or more),
some birefringence persists.
When the granules are swollen and the crystallites are melted, the
amylose molecules are freed to migrate into the surrounding aqueous
matrix. In a limited-water system such as bread, only a small percent-
age of the starch is rendered soluble. In a fresh-baked product such as
bread or cake, the starch granules are swollen, some of the amylose
has migrated into the aqueous phase, and more of the amylose is at
the granule surface, as are portions of some of the amylopectin mol-
ecules. The resulting granules have the appearance of hairy billiard
balls. Several other factors influence the process, including the starch-
water ratio, the presence of solutes such as sugar and salts, other com-
ponents that compete with starch for water, and lipids that complex
with the starch.
The temperature at which starch crystallites melt depends upon
the amount of water available. At least two parts water to one part
starch (by weight) are needed for all the starch to gelatinize in the
normal temperature range (about 60–70°C for wheat starch). Bakery
products all contain a water-starch ratio lower than this, so the tem-
perature necessary to complete gelatinization is higher. For example,
in a cake baked with 80% of the normal water content, the granules
reach the first swelling stage at 96°C and never fully gelatinize. In a
cake containing 120% of the normal water level, the granules swell at
88°C, and the cake is fully set before the end of the bake cycle. At the
other extreme is a cookie dough that contains only 22% water. After
baking, almost none of the starch granules are gelatinized. DSC stud-
ies of gelatinization at varying water-starch ratios indicate that when
50 / CHAPTER FOUR

Gelatinization temperature— adequate water is present, the melting of starch crystallites is assisted
A narrow temperature range at by the solvent; i.e., they are hydrated as they melt. This occurs at
which starch granules begin to
what is usually called the gelatinization temperature (about 65°C for
swell, lose crystallinity, and vis-
cosify the cooking medium.
wheat starch). With limiting amounts of water, some portion of the
Starches from different sources starch crystallites melts and hydrates near 65°C, and the remaining
have different characteristic portion melts during an anhydrous process that occurs over a tem-
gelatinization temperatures. perature range of up to 115°C.
Sugar and salt also raise gelatinization temperatures. In amylograph
tests, the addition of 2% sodium chloride raised the peak gelatiniza-
tion temperature from 82 to 91°C. The elevation of gelatinization
temperature by sugar depends in
part upon the particular sugar
used. In a 50% sucrose solution,
the gelatinization temperature of
wheat starch is raised by 26 de-
grees C, while in 50% glucose it
increases by 20 degrees. This ef-
fect is particularly important in
cake baking, in which coordina-
tion between the timing of starch
granule swelling and the release
of leavening gas, both of which
are governed by internal batter
temperature, is crucial for obtain-
ing a satisfactory cake.
The presence of other hydrat-
able materials in a dough or bat-
ter decreases the amount of free
water available for starch gela-
Fig. 4-1. Amylograph curves for wheat starch in the presence of diacetyl tar- tinization. Studies on mixtures of
trate ester of monoglyceride (DATEM), sodium stearoyl lactylate (SSL), and
glycerol monostearate (GMS).
gluten and starch showed that
the gluten bound approximately
75% of its weight in water, and in
a marginal system (0.91 g of water per gram of starch), this decrease
in free water decreased the proportion of starch that gelatinized at the
normal temperature (about 61°C) and increased the fraction that
melted at a higher temperature. No doubt this also occurs when gums
are added to cake batters for viscosity control.
Emulsifiers modify the gelatinization behavior of starch. Figure 4-1
shows the changes in amylograph gelatinization curves for wheat
starch caused by the inclusion of various emulsifiers at a level of
Amylograph —An instrument 0.5%. Of the three emulsifiers shown, diacetyl tartrate ester of mono-
used to study starch gelatiniza- glyceride (DATEM) is the least interactive, raising the swelling tem-
tion. A slurry is heated from
perature by about 5 degrees C but not changing the viscosity of the
room temperature to 95°C at
a set rate, held for a period of gelatinized starch. Glycerol monostearate (GMS) has the most effect,
time, and then cooled at a set raising swelling temperature by about 18 degrees C and increasing
rate. The viscosity of the slurry the paste viscosity. SSL has less effect on the inhibition of swelling,
is recorded as a function of but it increases paste viscosity to about the same level as that caused
time (hence, of temperature). by GMS.
 BAKERY PRODUCTS \ 51

SSL and GMS reduce the level of solubilization of starch granules

upon heating in excess water. At 85°C, 10% of the starch from a con-
trol sample is solubilized, but in the presence of 2% SSL or GMS, only
1.7% of the starch is solubilized. Monoglyceride produces this effect
at higher temperatures, but at 95 and 120°C, starch solubility is the
same in the presence of SSL as in the control. Measurements of
swelling follow the same pattern. X-ray diffraction patterns of the in-
soluble portion of wheat starch heated in the presence of excess water
and SSL or GMS show marked amylose-emulsion complex formation.
The interaction can take place at the surface of the granules, and the
starch-emulsion complex apparently serves to stabilize the granule,
retarding water penetration and swelling as the temperature is raised.
This occurs primarily with amylose. The inclusion of monoglyceride
in a bread formula decreases soluble amylose in the crumb by about
one-half but does not significantly change the amount of amylo-
pectin that is solubilized.

STARCH RETROGRADATION
Amylose dissolved in water forms in-
soluble crystals, usually within hours. By
contrast, amylopectin crystallizes much
more slowly, taking days to do so. The
difference in rate is probably caused by
the relative differences in molecular mo-
bility. The low molecular weight amy-
lose is free to take different conforma-
tions and move around in solution, thus
achieving molecular alignment and crys-
tallization more readily than the high
molecular weight amylopectin, which is
sterically more hindered by branching.
This reassociation is called retrogradation
(1):
Starch retrogradation is a process which
occurs when starch chains begin to re- Fig. 4-2. Changes in starch molecules in bread during retrograda-
associate in an ordered structure. In its tion (staling). In bread immediately out of the oven, both amylose
initial phases, two or more starch and amylopectin are gelatinized and randomly oriented. During
chains may form a simple juncture cooling, the amylose molecules align and crystallize. During stor-
age, amylopectin reforms crystallites. (Reprinted from Stauffer,
point which then may develop into
C. E., 1996, Fats & Oils, American Association of Cereal Chemists,
more extensively ordered regions. St. Paul, MN)
Ultimately, under favorable conditions,
a crystalline order appears.
The picture that best fits our present understanding of what occurs
in baked products is shown in Figure 4-2. When bread or cake leaves
the oven, the starch granules are gelatinized and a portion of the
amylose is in the surrounding matrix. As the product cools, a signifi- Retrogradation—Recrystal-
cant portion (one-third or more) of the amylose crystallizes. During lization of gelatinized starch.
52 / CHAPTER FOUR

storage, the remainder of the amylose crystallizes, although this

process appears to have relatively little to do with the increase in
crumb firmness. The amylopectin forms crystallites during the sev-
eral days of storage, causing the granules to become firmer (less com-
pressible) and contributing markedly to increased crumb firmness.
The system is analogous to a sprayed concrete
mesh structure in which the solid aggregate
(gravel) contributes greatly to the strength and
incompressibility of the whole system. If the
gravel is omitted, the mesh is weaker and can
be crushed more easily. The point of present
interest is the change in slab compressibility as
the “aggregate” changes from a soft gel to a
firm, crystalline form.
Two physical phenomena are causally
linked in this example: degree of crystallinity
and elastic modulus (firmness). Quantitative
X-ray analysis, differential thermal analysis, and
the related DSC measurements provide infor-
mation about crystallinity, while the various
compression methods mentioned earlier mea-
sure elastic modulus. Data from several studies
on bread and gelatinized starch gels show sim-
Fig. 4-3. Simple first-order rate process for the increase in
firmness of bread crumb with time. E0 is firmness at zero
ilar rate constants for the respective changes;
time, E∞ is firmness at infinite time, and Et is the measure- the temporal correlation of crystallinity (indi-
ment made at time t minus the zero time value. T is the re- cated by thermal analysis) and firmness is
ciprocal of the rate constant, and t1⁄2 is the time for the value good. On the other hand, a study that mea-
of E∞ – Et to be reduced by half. sured increases in firmness and crystallinity

Box 4-1. Avrami Equation

Theoretical analyses of staling measurements are often
done by using the modified Avrami equation to determine
the level of crystallization in a restricted (solid) matrix. It
considers that the fraction of crystallization that remains to
take place, q, is an exponential function of some power of
time, t (Fig. 4-3). That is
q = (E∞ − Et)/(E∞ − E0) = exp(−kt n)
in which E0 is the initial value (of firmness, heat absorption,
or other measure), E∞ is the final or limiting value, and k is
the rate constant.
While the ordinate in Figure 4-3 is labeled firmness, it can
be any appropriate measure such as the index of crystallinity
Differential thermal by X ray, heat absorption by DSC, or elastic modulus. For
analysis —Method for measur- bread crumb and starch gels, a convenient unit of time t is
ing energy uptake as a sample days, usually resulting in k values of 0.1–1.
is heated; similar to differential (continued on next page)
scanning calorimetry.
 BAKERY PRODUCTS \ 53

Box 4-1. (continued)

The exponent of time, n, is called the Avrami exponent and is related to
the mode of crystallization. When the melted material contains no crystal
nuclei, nucleation occurs sporadically because of random molecular motion.
This happens in solutions that can be supercooled before some random
event initiates crystallization. Instantaneous nucleation occurs when micro-
scopic nuclei still exist in the melt and is often found in solutions that have
been crystallized and then reheated. An example familiar to many bakers is
high-fructose corn syrup. As it comes from the supplier, it remains clear even
if it is cooled to below the nominal crystallization temperature for the glu-
cose present, but if crystallization occurs, the syrup must be heated to a
relatively high temperature and held for a long time to redissolve all the
microcrystals of dextrose. The theoretical value of the Avrami exponent is
the sum of two numbers: the first value equals the number of dimensions in
which crystal growth occurs (1, linear; 2, circular; or 3, spherical) and the
second value is 1 when instantaneous nucleation occurs and 0 when spo-
radic, random nucleation occurs.
An Avrami analysis of data requires a “double log” plot:
ln[ln(1/q)] = ln(k) + n ln(t)
The logarithm of the logarithm of the reciprocal of the fraction of change
is plotted versus the logarithm of time. The intercept is the logarithm of the
rate constant, and the slope of the plot equals n. In most studies of bread
firming and starch gel retrogradation, the value found for n is 0.85–1. This
seems correct for starch recrystallization. One would not expect all the inter-
molecular alignments (crystal nuclei) in starch to be totally disrupted, par-
ticularly under the condition of limited water that occurs during baking. The
growth of the crystal (i.e., the addition of portions of the starch chains to the
structure) would be expected to be one dimensional because of the linearity
of the chains.
It is not clear from the basic theory what a value of n < 1 means in a phys-
ical sense. When a set of data is constructed by using the sum of two first-
order reactions with rate constants that differ by a factor of 10 and the data
are plotted according to the double log plot, a slope of <1 is obtained. Starch
gels involve two different polymeric structures (amylose and amylopectin),
and in bread, the complications are even greater. It appears that the com-
plexity of the system may lead to an incorrect estimation of n. Overall, it is
probably justifiable to assume a value of 1 for n in studies on bread and cake
staling and starch gel retrogradation.
When n = 1, the Avrami equation is a first-order decay curve. This curve is
completely described by the three terms E0, E∞, and k. Determining the pa-
rameters of a first-order reaction curve from experimental data can be easily
done on a personal computer with one of the many simple programs avail-
able for this purpose. Frequently a value called the time constant, T, is re-
ported (T = 1/k). At the point T (Fig. 4-3), 63.2% of the reaction has occurred.
Another reference point often used is the half-life, t1⁄2, which equals ln(2)/k.
At one half-life, the reaction is 50% complete, and T = 1.44 × t1⁄2.
54 / CHAPTER FOUR

Specific volume —In baking (by X-ray analysis) on bread stored at 4 and 21°C found that the rate
research, the weight of the constant for crystallinity increase was about twice that of the rate for
cooled loaf divided by its
increase in firmness. It was also found that if the enzyme α-amylase
volume.
is included in the dough, the relationship does not seem to hold. We
may tentatively hypothesize a cause-and-effect relationship between
starch crystallization and an increase in elastic modulus, realizing
that the question still is not unequivocally settled. A more extensive
discussion of this question has been published (2).
Starch retrogradation is influenced by a number of factors. Three of
special interest to bakers are temperature, specific volume, and mois-
ture content of the bread.
Staling has a negative temperature coefficient; that is, it accelerates
as temperature decreases. This has been demonstrated many times.
An Arrhenius plot of rate constant for staling (compression measure-
ments) versus 1/temperature
(°K) is shown in Figure 4-4. The
plot is linear between 10 and
66°C, indicating that the rate of
firming is a straightforward
physical chemical phenomenon
(the point on the right was ob-
tained at –1°C). The straight line
is fitted to the circled points,
which represent bread made by
the Chorleywood bread process.
The triangles are points for
bread made by a straight dough
process with fermentation. This
is objective proof of the general
observation that bread stales
faster when refrigerated.
Specific volume (g/cm3) does
not affect the rate constant for
firming, but as specific volume
increases, the total change in
Fig. 4-4. Arrhenius plot of the effect of temperature on the first-order rate firmness (E∞ – E0) decreases. The
constant for the firming of bread crumb. dependence of E∞ – E0 on spe-
cific volume is also process de-
pendent. Chorleywood process
bread shows a somewhat lower limiting firmness than fermented
straight dough bread when the two are compared at the same specific
volume. In addition, bread with a higher specific volume has a lower
initial firmness, so at all stages it is softer than a more compact loaf.
Chorleywood bread Starch retrogradation slows when the moisture content of the
process —A rapid bread-
making process, developed at
starch gel is high. To relate this to bread, remember that there is a
the Chorleywood Laboratories moisture gradient in bread. In one study, the rate of retrogradation of
in England, in which dough is crumb from the center of a loaf and from the region near the crust
mixed in a high-intensity mixer was determined by DSC. The center crumb had a moisture content of
for a short period of time. about 43% (45% initially and 42% after five days of storage at 21°C),
 BAKERY PRODUCTS \ 55

and the crumb near the crust had a moisture content of approxi-
mately 32% (33% at day 1 and 31% at day 5). The firming of crumb
from the center had a rate constant, k, of 0.22 per day, while that of
crumb near the crust was 0.38 per day. The total amount of change
was the same in both cases, 1.8 J/g. This confirms the general obser-
vation that moist bread stales less rapidly.

BREAD STALING
Several factors that are thought to influence bread staling rate are
considered here briefly before the main discussion of the effect of
surfactants on starch retrogradation and staling. These factors—
moisture content, protein content, and processing variables—are
not negligible from a practical standpoint.
Increasing the moisture content of bread increases its shelf life (as
judged by the squeeze test). An obvious example is reduced-calorie
bread, which contains 45–50% moisture versus the 38% level in stan-
dard U.S. white pan bread. The initial firmness of the high-moisture
bread is slightly lower, and the compression curve remains lower
throughout the normal shelf life. No data have been published that
indicate whether there is a difference in the rate constant for firming
and whether the total amount of firmness increase differs for regular
bread and high-moisture reduced-calorie bread. As a rule, decreasing
the finished moisture content of bread by 2% (e.g., by increasing bake
time) shortens the shelf life by one day.
The major components of baked bread that bind moisture are heat-
denatured gluten and gelatinized starch. Moisture migration within
the bread crumb during cooling and storage has been studied, but re-
sults are contradictory. One group of researchers found that moisture
migrates, if at all, from the retrograding starch to gluten, while an-
other group, using a different approach, found migration to be in the
opposite direction. In either case, the change in moisture of the
starch portion is small, approximately 2%. Other indirect evidence
for the role of moisture migration has been published, but the extent
of the projected effect is minimal compared with the overall increase
in crumb firmness.
It is known that increasing the protein content of bread tends to
result in a softer loaf, which may be caused by simple dilution of the
starch. Of course, increasing protein content also usually increases
specific volume with attendant increased softness. An alternate hy-
pothesis is that more protein binds more water, decreasing the mois-
ture level in the starch phase and decreasing the rate or extent of
starch crystallinity. However, this theory is not consistent with the
known effect of moisture content on starch retrogradation. The role
played by gluten protein in bread firming is not yet clear.
Processing parameters can markedly influence the shelf life (staling
rate) of bread. Both overmixing and undermixing shorten shelf life,
and long fermentation times extend shelf life. Slow baking shortens
shelf life (moisture content is lower), while a fast bake lengthens shelf
56 / CHAPTER FOUR

life (moisture content is higher). All of these factors are understood

by industrial bakers, and adjustments in the baking process to opti-
mize economic factors and production efficiency also tend to maxi-
mize shelf life.

EMULSIFIER-STARCH COMPLEXATION
Although starch and gluten proteins are usually thought of as hy-
drophilic molecules, readily wetted by water and becoming water sol-
uble as the molecular size is reduced, they are in fact amphiphilic.
Starch molecules are polymers composed of α-D-glucopyranosidyl
residues joined primarily by 1,4
acetal linkages (1,6 linkages occur
at the branch points in amy-
lopectin). Glucopyranoside is a six-
membered ring. It is not flat but
is puckered in what is called the
“chair” configuration (Fig. 4-5a).
The bond angles from each car-
bon are such that the hydrophilic
hydroxyl groups project outward
to the side of the plane of the
ring, while the hydrogen atoms
project either above or below this
plane. The perimeter of the ring
is hydrophilic, and the two faces
are hydrophobic. The bond angle
of the α-1,4 acetal linkage is such
that the starch chain coils to
form a helix, with about six
residues per turn (Fig. 4-5b). It is
difficult to draw the details of
Fig. 4-5. Structures of α-D-glucopyranoside (a), the amylose helix this helix, but molecular models
(b), and the inclusion complex of amylose with straight-chain
show that the plane of the
lipids (c).
residue ring lies parallel to the
wall of this helix and that the hy-
Acetal linkages—Bonds be- drogen atoms on carbons 3 and 5 (circled in Fig. 4-5a) project into
tween sugar residues in poly-
mers, linking the carbonyl
the interior of the helix. The result is a hollow cylinder that has a hy-
group of one residue to a drophilic outer surface and a hydrophobic inner surface. This inner
hydroxyl group on the other space is about 4.5 Å in diameter, and straight-chain alkyl molecules
sugar. such as stearic acid can fit into it (Fig. 4-5c), as can other molecules
such as iodine. The blue color of an iodine-starch complex demon-
Glucopyranoside —Glucose in strates that iodine is in a nonpolar environment; iodine dissolved in
its usual molecular form of a chloroform is blue, but in water it is brown. The complex of amylose
six-membered ring.
with n-butanol crystallizes much more readily than amylose alone,
Helix —Three-dimensional and this behavior has been used to separate amylose from
arrangement of many biologi- amylopectin.
cal polymers, including starch. The n-alkyl portion of emulsifiers such as GMS forms a complex
It is analogous to a coil spring. with helical regions of starch. This interaction has been measured
 BAKERY PRODUCTS \ 57

Table 4-1. Starch-Lipid Complex Formation

Excess Emulsifier Excess Emulsifier

with Amylosea with Amylopectina Excess Amylose
(mg/g complexed) (mg/g complexed) (ACI)b
1-Monocaprin … … 63
1-Monolaurin … … 95
1-Monomyristin 23.4 … 100
1-Monopalmitin 37.4 5 72
1-Monostearin 33.9 8.3 87
1-Monoarachidin … 11 …
1-Monobehenin … … 16
1-Monoolein 24.6 … 9
1-Monoelaidin … … 75
1-Monolinolein 12.2 … 0
a
Data from (3).
b
Data from (4) and (5). ACI = amylose complexing index

quantitatively but with two different approaches: excess emulsifier

and excess starch (Table 4-1). In the first approach, 1 g of amylose or
amylopectin was heated with 100 mg of monoglyceride. The mixture
was cooled, and the amount of uncomplexed monoglyceride was de-
termined. The results were given as milligrams of lipid bound per
gram of starch. In the second approach, 100 mg of amylose was
heated with 5 mg of emulsifier. Upon cooling, the amylose-emulsifier
complex precipitated, and the amount of dissolved, uncomplexed
amylose was quantitated by its affinity for iodine. The results were ex-
pressed as an amylose complexing index (ACI), which is the percent-
age of the amylose complexed by 5 mg of emulsifier.
The results can be summarized as follows:
1. Saturated fatty acids (12–20 carbons long) are the best complex
formers.
2. cis Unsaturated C18 fatty acids are very poor complex formers.
3. trans Unsaturated C18 fatty acids are good complex formers.
There is a definite correlation between the ability of a monoglyc-
eride to form a complex with starch and its ability to retard the rate
of staling (i.e., the increase in crumb firmness). This has been con-
firmed in several studies, which showed, for instance, that 1%
monopalmitin or monostearin increased shelf life by as much as two
days, whereas bread made with 1% monoolein or monolinolein
staled at the same rate as the control. Also, the monoglyceride should
Synergistic —Pertaining to a
be present in the dough as the lamellar mesophase. This may account combination of two materials
for the synergistic functionality of some mixed systems (e.g., GMS that displays more functionality
plus SSL or GMS plus Polysorbate 60). than would be expected by
The mechanism by which emulsifiers slow crumb firming (staling) simply summing the individual
may be summarized as follows: functionalities of the materials.
58 / CHAPTER FOUR

1. Crumb firmness increases during storage primarily (though not

exclusively) because of retrogradation of amylopectin molecules.
2. Emulsifiers form complexes with gelatinized amylopectin, hin-
dering its ability to recrystallize.
3. Emulsifiers also form complexes with solubilized amylose and
may hinder its ability to contribute to formation of a solid inter-
granular starch matrix.
The model of staling resulting from starch retrogradation was de-
veloped by T. Schoch during the 1950s, and the role of emulsifiers in
retarding staling was explicated during the 1960s and 1970s, mainly
by W. Knightly and N. Krog. Subsequent work has indicated some
particular subareas of this phenomenon that are still puzzling, but
the main concept seems to be valid.
As discussed in Chapter 3, monoglyceride is added to bread and
rolls to decrease the rate of staling. Shelf life extension increases up to
a level of about 0.75–1% monoglyceride (flour basis); more emulsifier
produces relatively little effect. In using the various forms of mono-
glyceride, the baker should keep in mind that they contain different
levels of the active material. The ap-
proximate relationship is 4 oz. of pow-
dered distilled monoglyceride = 8 oz. of
plastic monoglyceride and diglyceride =
16 oz. of hydrated monoglyceride.
It should also be remembered that
both 1- and 2-monoglycerides are effec-
tive antistaling agents. Some product
analyses report total monoglyceride,
while others report only 1-monoglyc-
eride (sometimes called α-monoglyc-
eride), which represents about 92% of
the total monoglyceride.

Dough Strengtheners
Some of the amino acid side chains in
proteins are hydrophobic, generally
buried in the interior of the folded pro-
tein molecule but exposed if the protein
Fig. 4-6. Influence of pH and anionic surfactant molecules on gluten is unfolded. Frequently, these hydro-
protein. The crosshatched areas depict nonpolar patches on the phobic regions are partially exposed,
protein surface. SSL = sodium stearoyl lactylate. even in the native folded protein, and
are referred to as hydrophobic patches
on the protein surface (Fig. 4-6). The
lipophilic parts of surfactants interact
Hydrophobic patches—Areas
with these hydrophobic regions, sometimes contributing to unfold-
on the surface of a protein mol-
ecule, in contact with sur- ing (denaturation) of the protein and further binding of surfactant.
rounding water, that are Gluten protein contains about 40% hydrophobic amino acids, and it
lipophilic in nature. interacts strongly with lipid-type materials. In a mixed dough, more
 BAKERY PRODUCTS \ 59

than half the native lipid plus any added surfactant is bound to the Fluorescent probes—Small
protein, while the rest is uncomplexed and freely extractable. The molecules that fluoresce in a
surfactant SSL binds to gluten proteins as do fluorescent probes for hy- nonpolar medium but not in a
polar medium such as water.
drophobic environments. It can safely be said that gluten proteins
When these probes are mixed
have rather large hydrophobic regions on their surfaces, and some of with proteins, for example, the
the properties of gluten may be explained on this basis. appearance of fluorescence im-
Two of these gluten characteristics are depicted in Figure 4-6. plies that a probe has bound to
When acid is added to a flour-water dough, some of the protein solu- a hydrophobic region of the
bilizes. This is most likely a charge effect. At a dough pH of about 6, protein.
the gluten proteins carry a low charge density resulting from an ap-
Ovenspring —Increase in the
proximate equality between the cationic amino acids (lysine, argi-
volume of a loaf of bread dur-
nine, and histidine) and the anionic amino acids (glutamic and as- ing baking; i.e., the final loaf
partic acids). As the pH is lowered, many of the anionic carboxylates volume minus the volume of
are protonated (i.e., become un-ionized), and the protein molecule the dough at the end of the
takes on an overall positive net charge. At pH 6, the hydrophobic proof.
patches can interact, and the protein molecules aggregate via hy-
drophobic interaction. At pH 3, the net positive charges cause the
molecules to repel each other, and solubilization occurs. This situa-
tion has many similarities to that of emulsified oil droplets stabilized
by an ionic surfactant, where the surface charge prevents droplet con-
tact and coalescence. Likewise, salt represses the electrostatic repul-
sion, and protein aggregation is favored. Most dough strengtheners
are anionic surfactants, and when the lipophilic tail of the surfactant
binds to the protein hydrophobic patches, it incorporates this nega-
tive charge into the complex, moving the overall charge closer to zero
and promoting aggregation in the dough (Fig. 4-6). Salt and SSL have
similar effects on mixograph curves, and it might be said that salt
suppresses the electrostatic repulsion while SSL neutralizes it. The
final effect in both cases is the same, i.e., hydrophobic aggregation of
the gluten protein and an increase in dough strength.
An excess amount of surfactant can solubilize proteins, and addi-
tional adsorption to the protein generates an excess net charge, even
if the protein net charge is near zero. Sodium stearate (4 mg per 10
mg of glutenin) renders glutenin proteins completely soluble in dis-
tilled water. Cationic surfactants also solubilize glutenin, but non-
ionic or amphoteric surfactants (e.g., Tweens, Span, and lecithin)
have little or no solubilizing effect.
The usual test of a dough strengthener is a bake test, in which the
loaf volume increment resulting from the inclusion of the surfactant
being tested is determined. This change in loaf volume appears to
have more to do with the interaction of the surfactant with the starch
granule than with the effect upon gluten protein. The final loaf vol-
ume of a dough with 3% shortening is greater than that of a control
loaf containing no shortening, because the loaf containing shortening
expands for a longer time during the bake cycle. The presence of short-
ening delays the swelling of starch granules (and perhaps the denatu-
ration of the gluten protein), and this delay translates into a larger loaf
volume (i.e., larger ovenspring). The addition of a surfactant such as SSL
or DATEM to dough also produces this delay in the setting mechanism
60 / CHAPTER FOUR

and thus increases the loaf volume. Numerous studies with a variety of
emulsifiers (e.g., sucrose mono- and diesters, calcium stearoyl lactylate
[CSL], DATEM, and GMS) report similar results. It should be noted
that the surfactants are about 10 times more effective than triglyc-
erides in producing loaf volume enhancement by this mechanism;
0.2–0.4% surfactant gives the same effect as 3% shortening.
A more meaningful test of the dough-strengthening capabilities of
a surfactant involves subjecting the proofed loaf to mechanical abuse
before putting it into the oven. The pan containing the proofed
dough is placed on blocks of wood 3.75 in. high. The blocks are
pulled from under the pan, allowing it to fall to the counter top. This
procedure is conducted two more times, and then the doughs are
baked, depanned, and cooled, and the volume is measured. In a study
in which this technique was employed and the use level of all
strengtheners was 0.25%, CSL produced the best volume improve-
ment (approximately 260 cm3 in a 1-lb loaf), ethoxylated monoglyc-
eride was the second most effective, Polysorbate 60 and SSL were
roughly equivalent (about 210 cm3), and succinyl monoglyceride
showed the least improvement (about 125 cm3) compared with the
control loaf. This test is designed to simulate the rough handling,
such as sudden starts and stops on the conveyor line or being struck
by a loading or unloading bar, that proofed doughs often undergo in
a commercial bakery. A more reproducible test is to allow the pan to
slide down an inclined plane (a short section of the conveyor) and hit
a stop bar at the bottom. Although the literature is replete with data
on delaying starch swelling and volume improvements such as those
discussed above, when a dough strengthener is evaluated for com-
mercial use, some sort of abuse test of the proofed dough is the best
way to determine dough-strengthening capabilities of a surfactant.
The basic mechanism by which dough strengtheners work appears
to be enhancement of gluten protein aggregation, either by charge
neutralization (anionic surfactants) (Fig. 4-6) or by some sort of hy-
drogen bonding (ethoxylated surfactants). The surfactants are bound
rather strongly to the native gluten protein, but they are not bound
to the heat-denatured protein after baking. CSL has little effect on the
mixing requirements of dough but increases its tolerance to overmix-
ing, while the anionic surfactant sodium dodecyl sulfate markedly in-
creases the mixing tolerance of a dough in the mixograph.
It might be that the fatty acids of dough strengtheners form a com-
plex with gelatinized starch and thus contribute to antistaling activ-
ity. SSL and DATEM are reported to have ACI values of 72 and 49, re-
spectively. Reports from baking and storage tests in which these
surfactants were used indicate that they do indeed retard crumb firm-
ing compared with the control. However, in most such studies, loaf
specific volume was not controlled, which muddles interpretation of
the results.
Studies with lidded bake pans (which keep loaf specific volume
constant) indicate that DATEM does preserve crumb softness. The ef-
fect of combining DATEM with GMS appears to be roughly multi-
 BAKERY PRODUCTS \ 61

plicative: at day 7, the bread containing 1% DATEM had 53% of the

firmness of the control; the loaves with 1% GMS had 40% of the firm-
ness of the control; and the bread containing 1% GMS plus 1%
DATEM registered 22% of the firmness of the control. This relation-
ship implies that the two emulsifiers are exerting their antistaling ef-
fects through different mechanisms and are not competing for the
same complexing sites in the gelatinized starch. The researchers pro-
pose that DATEM reduces crumb firmness by affecting crumb cell
wall thickness and elasticity and that its effect on starch retrograda-
tion is limited. In other words, the gluten protein in bread crumb
plays some role in staling, and emulsifiers such as DATEM and SSL
modify this contribution.

Aeration Agents
Air is entrained in most bakery products during the preparation
stages. In baked items (excluding icings and the like), the degree of
subdivision of the air bubbles determines the nature of the finished
crumb. The air bubbles are nuclei for the leavening gases generated
during baking. If the air is present as a few large bubbles, the finished
product will have a coarse crumb, while if the air is divided into
many small bubbles, the finished crumb will be smooth and fine
grained. The presence of emulsifiers (either natural or added) aids in
air dispersal and inhibits coalescence of the
bubbles during the processing period before
baking. This was first demonstrated for bread
in 1940 and subsequently for other products
such as cakes, doughnuts, and cookies.
Successful manufacture of a good-quality
layer cake requires dispersal of air through-
out the batter and retention of the bubbles
until the starch has swollen and the cake
structure is set. Traditionally, air has been en-
trained in the shortening phase during the
first stage of making a cake. This method is
not an efficient way to incorporate air, be-
cause it depends primarily upon the ability
of the plastic shortening to trap air bubbles
during creaming. The “superglycerinated”
shortenings containing monoglycerides, de-
veloped in about 1930, enable the baker to
subdivide the air bubbles, creating smaller
bubbles that are more efficiently retained by
the shortening phase and that give more
Fig. 4-7. High-ratio cake batters made by three-stage mixing.
uniform nucleation for leavening gases A, Plastic shortening, no emulsifier, batter specific gravity 0.85
throughout the batter during baking. The g/ml. B, Plastic shortening containing 4.5% monoglyceride,
final crumb grain, therefore, is closer and the batter specific gravity 0.81 g/ml. C and D, Cakes baked from A
overall volume is larger (Fig. 4-7). These and B, respectively.
62 / CHAPTER FOUR

shortenings also enable the production of high-ratio cakes (i.e., cakes

containing more sugar than flour).
This traditional approach involves at least three stages in batter
preparation: first, shortening and sugar are creamed vigorously to in-
corporate air; second, eggs are blended into this whipped material;
and third, the flour, milk (or water), flavors, and other ingredients are
added and blended to make the final batter. The development of dry
cake mixes for home and industrial use dictated a different approach
to air incorporation. Using a liquid vegetable oil in place of plastic
shortening results in a moister cake and a longer shelf life. However,
a liquid oil is not well suited to entrapping air bubbles. It was found
that the addition of certain emulsifiers to the oil before it was incor-
porated into the cake mix produced high-ratio cakes with good vol-
ume, fine grain, and excellent keeping qualities. These cakes can be
mixed in one stage. All the ingredients are placed in a bowl, the liq-
uid is added, and the batter is mixed at low speed (to blend ingredi-
ents) and then at high speed to incorporate air.
The most useful emulsifiers for this purpose are the α-tending
emulsifiers, because they tend to solidify in a stable α-crystalline
form. Those used on a commercial basis today include acetyl mono-
glycerides (AcMG), lactyl monoglycerides (LacMG), and propylene
glycol monoester (PGME). A number of other emulsifiers have also
been used, including Polysorbate 60, stearoyl lactylic acid, and su-
crose esters, but most commercial cake emulsifiers now offered by
suppliers are based upon PGME and/or AcMG, perhaps in
combination with other emulsifiers that enhance their func-
tionality.
When dissolved in the oil phase, α-tending emulsifiers
lower interfacial tension, but their effectiveness in cake bat-
ters is not the result of this property. Rather, at concentrations
above a certain level, these emulsifiers form a solid film at the
oil-water interface. This behavior is seen when one suspends
a drop of water from a syringe tip in the oil, waits a few min-
utes for film formation, and then withdraws some of the
water (Fig. 1-10). The film appears to be caused by crystalliza-
tion of the emulsifier at the interface in the α form. There is a
defined relationship between temperature and the minimum
bulk concentration of the emulsifier that produces a film; the
minimum concentration increases as temperature increases
(Fig. 4-8). The addition of a second surfactant may enhance
film formation. A mixture of propylene glycol monostearate
(PGMS) and stearic acid (80:20) forms a stronger film than
pure PGMS at the same weight concentration.
In a one-stage cake batter, air incorporation is primarily a
Fig. 4-8. Effect of temperature on film function of foam stabilization by the protein contributed by
formation by 1-acetyl-3-monostearin at
the oil-water interface. The sharp rise in
flour, milk, and egg whites. As discussed earlier, the presence
the tensiometer reading indicates the of oil inhibits this foam formation, and the solid film at the
presence of the solid film. CSO = cotton- oil-water interface effectively encapsulates the oil during air
seed oil. incorporation, thus preventing destabilization.
 BAKERY PRODUCTS \ 63

Simply lowering cake batter density by incorporating more air is

not enough to ensure a good final volume. In a comparison of two su-
crose esters in a sponge cake formula batter, densities were 0.65 and
0.55 for F-110 and F-160, respectively, but F-110 gave a larger finished
volume than F-160 (see Table 3-1). Similarly, stearoyl lactylic acid de-
creases batter density markedly as its usage level is increased from
0 to 4% (flour basis), but the best finished cake volume is achieved at
1.5% emulsifier. These results merely confirm the earlier remark that
not only is it necessary to incorporate air into a cake batter during
mixing, but also that air bubbles must remain in the batter during
baking, serving as nuclei for the gases released from the chemical
leavening system.
Air incorporation is also important in obtaining a fine grain in
cookies, cake doughnuts, and similar products. If a cookie is made
with nonemulsified plastic shortening, for example, it will have a
more open texture than the same product made with an emulsified
shortening (containing 3% α-monoglyceride). The aeration of creme
icings is enhanced by the presence of an emulsifier in the shortening
used. However, while initial aeration increases as α-monoglyceride
concentration is increased up to 4%, the best icing stability is observed
at 2% emulsifier. At higher levels, the air escapes more readily from
the icing during storage. The reason for this behavior is not known.
Whipping aids such as sodium lauryl sulfate (SLS) or triethyl citrate
enhance foam formation when egg whites are whipped. The surfac-
tant aids the unfolding of the protein, which is the actual foam sta-
bilizer. A small amount of the surfactant is effective. SLS is added at a
maximum level of 1% to dried egg whites for this functionality.

Troubleshooting
In bakery products, emulsifiers work with the fat phase, protein, and starch to produce a good
final product. Often, a mixture of emulsifiers works better than a single emulsifier. For many prob-
lems, the solution may require adjustments not only to the emulsifier system but also to the other
ingredients or the processing parameters. In emulsion systems, troubleshooting is still more an art
than a science, because many of the interactions taking place between the ingredients and the pro-
cessing parameters are specific to each food product. While the following table suggests adjustments
to be made in emulsifier use, the reader can also consult the troubleshooting sections in the Fats &
Oils handbook that deal with shortening-related problems.
64 / CHAPTER FOUR

BREAD
Symptom Cause Changes to Makea
Sidewall weakness Inadequate strength of crumb Add dough strengthener (e.g., SSL or DATEM)
(“keyholing”) structure and low elasticity up to legal limit (0.5% flour basis for SSL and
good manufacturing practice for DATEM).
Open grain Inadequate gluten strength Add dough strengthener (e.g., SSL or DATEM).
Low volume (some- Inadequate gluten strength Add dough strengthener (e.g., SSL or DATEM).
times noted when
substituting oil for
plastic shortening)
Short shelf life Insufficient staling inhibitor Use up to 0.5% actual α-monoglyceride (flour basis).
Use easily dispersible form. (Excess could cause
open cell defect.)
Sticky dough Gluten not fully developed; process Adjust water pH (e.g., with lactic acid or
water too soft or too alkaline monocalcium phosphate).
YEAST-RAISED DOUGHNUTS
Symptom Cause Changes to Make
Short shelf life Inadequate fat absorption Add 0.5% α-monoglyceride to base dough.
Collapse on cooling Weak gluten structure Add SSL or DATEM up to legal limits.
CAKES
Symptom Cause Changes to Make
Tunnels in the cake Inadequate emulsification Use emulsified shortening (e.g., 3.5–5%
α-monoglyceride).
Add emulsifier with a high HLB (e.g., 0.25%
Polysorbate 60) to the batter.
Too hot an oven Lower oven temperature.
Excess leavening Lower leavening level.
Inadequate hydration and dispersion Allow enough time to make up batter.
of ingredients
Low volume; Inadequate emulsification; poor Use an emulsified shortening (e.g., 3.5–5%
center dip creaming of fat α-monoglyceride).
Poor foam stability (oil cakes) Increase level of α-tending emulsifier (e.g., PGME
or AcMG) at 12–14% of oil.
Excess liquid Decrease water level.
a
AcMG = acetylated monoglyceride; DATEM = diacetyl tartrate ester of monoglyceride; HLB = hydrophilic/lipophilic bal-
ance; PGME = propylene glycol monoester; and SSL = sodium stearoyl lactylate.
 BAKERY PRODUCTS \ 65

CAKE DOUGHNUTS
Symptom Cause Changes to Make
Excessive fat Excess emulsification Reduce amount of emulsifier in the formula.
absorption Cold batter Use warmer water during batter make-up.
Batter viscosity too high Increase amount of water in batter formula.
Under mixed Increase mixing time to fully hydrate ingredients.
Fryer temperature too low Raise fryer temperature to recommended level.
Make sure heater can keep up with rate of batter
deposition.
Fat breakdown If fryer is not in continuous use, lower fryer
temperature between fries.
If use is continuous, match doughnut production
with fryer size to get complete fat turnover in 8 hr.
Low fat absorption Insufficient emulsification Add 0.5% α-monoglyceride or 1% lecithin to the
formula.
Hot batter Use cold water (or ice) to reduce batter temperature.
Batter viscosity too low Reduce water in batter formula.
Over mixed Decrease mixing time.
Too much floor time before depositing Balance batch size and mixing schedule with rate of
production in fryer.
Fryer temperature too high Lower fryer temperature to recommended level.
New (untempered) fat When refilling fryer (after cleaning), use old (not
degraded) fat equal to one-fourth of fryer capacity.
If old fat is not available, add 1.5 oz free fatty acids
per 100 lb new fat.
CREME ICINGS
Symptom Cause Changes to Make
Low aeration (high Inadequate emulsification Use shortening with 2–3% α-monoglyceride.
specific gravity) Use an emulsifier with a high HLB (e.g., up to 0.46%
Polysorbate 60 based on total icing).
Fat too soft to entrap air Use shortening with a high solid fat index profile.
Inadequate creaming Increase first stage mixing time of fat plus sugar.
Loss of aeration Unbalanced formula Rebalance HLB of emulsifier system.
during storage Add hydrocolloid stabilizer.
Excess monoglyceride Use shortening with a maximum of 3%
monoglyceride.
Over or under whipping Adjust whipping time.
66 / CHAPTER FOUR

References
1. Atwell, W. A., Hood, L. F., Lineback, D. R., Varriano-Marston, E., and Zobel,
H. F. 1988. Cereal Foods World 33:306-311.
2. Hebeda, R. E., and Zobel, H. F., Eds. 1996. Baked Goods Freshness. Chapter 1,
The Staling Mechanism, and Chapter 2, Surfactants. Marcel Dekker, New
York.
3. Lagendijk, J., and Pennings, H. J. 1970. Cereal Sci. Today 15:354-356, 365.
4. Krog, N. 1971. Starch/Stärke 23:206-210.
5. Riisom, T., Krog, N., and Eriksen, J. 1984. J. Cereal Sci. 2:105-118.

Supplemental Reading
Stauffer, C. E. 1990. Functional Additives for Bakery Foods. Chapter 3, Emulsifiers
and Dough Strengtheners. Van Nostrand Reinhold, New York.
Thomas, D. J., and Atwell, W. A. 1999. Starches. American Association of Cereal
Chemists, St. Paul, MN.
 CHAPTER

5
Dairy and Nondairy
Products
Milk is a protein-stabilized oil/water (O/W) emulsion. The presence
of protein at the interface complicates the interpretation of experi- In This Chapter:
mental results and the understanding (at the molecular level) of the Milk
events that occur when milk-derived and milk-related products are
Butter and Margarine
processed. These complications increase when emulsifiers such as
Butter
those discussed in Chapter 3 are added to the system. How proteins Margarine
act at air-water and oil-water interfaces is also discussed in Chapter 3.
Whipped Cream and
Nondairy Whipped
Milk Toppings
Whipped Cream
Milk proteins are divided into two groups: casein and the whey pro- Nondairy Whipped
teins. Casein (the protein that precipitates to make cheese) is a com- Toppings
plex containing four major proteins, αs1-, αs2-, β-, and κ-casein, in the Ice Cream
rough proportion of 40:10:40:10. The molecular weights of the ca- Coffee Whiteners
seins range from 24,000 for β-casein to 121,000 for α-casein. In addi-
tion, the caseins aggregate to form micelles with molecular weights of Troubleshooting
approximately 1 × 109. Casein is often dissolved at alkaline pH and
then neutralized and dried to create compounds such as sodium ca-
seinate, which has an estimated molecular weight of 250,000. In
whey, the main proteins are α-lactalbumin (approximate molecular
weight, 17,000) and β-lactoglobulin (approximate molecular weight,
45,000); numerous others are present in minor amounts. The ratio of
hydrophobic to hydrophilic amino acid residues varies greatly. As a
rule, the larger the protein, the greater the proportion of hydrophobic
residues. Given these disparities in size and relative hydrophobicity,
one would predict that interfacial behavior might vary widely among
Casein —The main protein
different proteins, and this is indeed the case. The behavior of whey
component of milk, accounting
protein concentrate differs from that of sodium caseinate, which in for about 80% of the total
turn differs from that of β-casein. When the numerous possible com- proteins.
binations of proteins at the interface are also considered, it is easy to
understand why the interfacial chemistry of milk is so complex. Whey—The liquid left after ca-
Milk fat droplets are synthesized in the endoplasmic reticulum of sein has been precipitated from
mammary epithelial cells. They are released into the glandular intra- milk. In addition to protein, it
contains lactose (milk sugar)
cellular region after being surrounded by a plasma membrane, which
and ash (inorganic salts).
is a highly complex, stratified structure consisting mainly of polar
lipids and proteins. The two major proteins of the membrane are xan- Milk fat —The natural fat found
thine oxidase (molecular weight, 155,000) and a hydrophobic glyco- in milk consisting of a mixture
protein, butyrophilin (molecular weight, 67,000). The structure of of glycerides.

67
68 / CHAPTER FIVE

this membrane is different in the milk from various mammalian

species. This discussion relates only to cow’s milk.
The diameters of milk fat droplets in native milk range from 0.2 to
20 µm; 90% of the diameters are 1–8 µm, and the average diameter is
about 3 µm. Since the droplets are less dense than the aqueous por-
tion, they rise to the top of unagitated milk within a day and are
known as “cream.” The droplets are highly resistant to coalescence,
and the cream can be easily redispersed by simply inverting the con-
tainer a few times. Cooling milk enhances the creaming tendency by
causing an interaction between the milk membrane proteins and
some immunoglobulins present in the aqueous phase. Centrifuga-
tion of milk accelerates the separation of the fat phase and is done
routinely. The fat content of unprocessed milk may vary from 2.5 to
4%, but for consumer sales, the fat content is standardized at speci-
fied levels (0, 0.5, 1, 2, or 3.5%). The cream is processed separately for
other products.
After the fat content is standardized, the milk is homogenized by
forcing it at high pressure through a valve homogenizer. The typical
average fat droplet diameter decreases from 3 to <1 µm, and the sur-
face area per milliliter of fat increases. The additional interfacial area
requires stabilization, which is supplied by proteins from the aqueous
phase. About 95% of this protein is casein, some in the form of the
various individual casein species and some as deformed casein mi-
celles. Whey proteins (lactalbumin and lactoglobulin) are incorpo-
rated into the interfacial protein membrane in varying proportions
depending on homogenization conditions, especially temperature.
Denaturation of whey protein leads to formation of casein-whey
complexes, which adsorb more readily at the interface. The adsorbed
protein layers are quite stable. Simple desorption of protein from an
oil-water interface is quite slow (a period of days), and there is also
some evidence that crosslinking occurs between the adsorbed pro-
teins, which further increases stability.
Heat treatment of the milk promotes flocculation of the fat glob-
ules, presumably through interaction of heat-unstable whey proteins
in the interfacial layers. Again, the fat droplets do not coalesce but
clump together and are readily redispersed by mild agitation.

Butter and Margarine

BUTTER
Churning cream to make butter is essentially a phase inversion, i.e.,
transformation of an O/W emulsion into a water/oil (W/O) emulsion
(Fig. 5-1). The basic process has been used for millennia, but it has
been modified extensively in recent years to make it more amenable
Phase inversion —Conversion to large-scale industrial butter production.
of the continuous phase of an During churning, the fat globules are forced together, some degree
emulsion to the discontinuous of membrane removal occurs, and the fat coalesces. This process con-
phase and vice versa. tinues until the fat forms a discrete clump with some entrained aque-
 DAIRY AND NONDAIRY PRODUCTS \ 69

Whey Butterfat

Cream Churned to Butter

Fig. 5-1. Coalescence of milk fat globules during churning, resulting in an inversion
from an oil/water emulsion to a water/oil emulsion.

ous phase. When all the fat has been transformed in this fashion, it is
separated from the residual buttermilk; additives (e.g., salt and color-
ing) are added; and it is kneaded into a smooth, homogenous mass.
In most countries, there are regulations about the composition of
butter (e.g., a minimum of 80% milk fat).
The temperature during churning is an important processing para-
meter. Fat globules coalesce from the liquid phase, but the solid fat
fraction of the milk fat stabilizes the clump and keeps the entrained
aqueous droplets separate. The solid fat content of milk fat is lower
during the winter than during the summer, and this difference must
be accounted for in the churning operation. If the milk fat is too
hard, the protein membrane does not desorb sufficiently to allow co-
alescence; if it is too soft, the aqueous phase and air (about 3–5% of
the total mass by volume) are not incorporated. (The proper water
and air content is important for the flavor and spreadability of the
butter.)
Two things contribute to the stability of the water droplets: the fat
protein membrane and crystals of high-melting-point triglycerides
from the fat. When an emulsion inverts, the emulsifier tends to re-
main at the interface. As shown in Figure 5-1, the curvature of the
membrane simply reverses and appears to encase the aqueous phase
rather than the fat phase. The reason for desorption of the membrane
is not fully understood, but it is probably the result of mechanical
forces rather than interfacial energetics. As mentioned above, protein
Solid fat content—A measure
desorption from an interface is a slow process, but during churning,
of the amount of solid fat in a
it occurs quickly. Thus, it seems likely that when two fat globules col- fat at various temperatures, de-
lide, the membrane is physically ruptured (made easier because the termined by nuclear magnetic
fat phase is semiliquid), allowing the globules to make contact and resonance.
70 / CHAPTER FIVE

Margarine—A substitute for coalesce. The involvement of fat crystals is somewhat less easy to ex-
butter, originally formulated to plain but is not an unknown phenomenon. Solid particles tend to
mimic butter as closely as possi- stabilize an interface, probably by simply interfering with the contact
ble, but using other fat sources
and coalescence of the dispersed phase.
in place of milk fat.

MARGARINE
Originally invented as an inexpensive substitute for butter, mar-
garine today is purchased for its own characteristics. It is a W/O emul-
sion. The oil is generally some blend of partially hydrogenated veg-
etable fats, chosen to meet a specified solid fat content profile. The
water phase varies greatly from reconstituted nonfat dry milk to
water with some added flavors.
Standard margarine contains at least 80% fat; the rest is a skim
milk, whey, or water solution containing salt and flavors. In prepar-
ing margarine, there are six steps:
1. blending base stocks plus other oil-soluble components;
2. mixing milk or water with salt and other water-soluble
ingredients;
3. mixing the two phases to form a W/O emulsion;
4. chilling and plasticizing the emulsion;
5. forming the margarine into prints or placing it into plastic
tubs; and
6. finish packaging and cold storage of the finished product.
In step 1, the oils to be used are weighed into a tank (at 5 degrees
C above their melting points), and emulsifier (lecithin, mono- and
diglyceride, or a combination), oil-soluble vitamins (A, D, and E) and
colorants (β-carotene and annatto) are added. The oil is mixed,
preferably under a nitrogen atmosphere to prevent oxidation and fla-
vor deterioration.
When the oil-soluble ingredients are thoroughly mixed, the water
phase is added. This can be whole milk, skim milk, reconstituted non-
fat dry milk solids, or water. Salt and flavors such as diacetyl and
starter distillate are included in the water phase. Antimicrobial agents
(sodium benzoate and potassium sorbate) and/or heavy metal chelat-
ing agents (citric acid or EDTA) are added if needed and if the law al-
lows it. The water phase is slowly added to the oil with agitation to
form a W/O emulsion. Sometimes the emulsion is pasteurized at 73°C
for 16 sec to ensure freedom from pathogenic bacteria.
The emulsion is quickly chilled in a swept-surface heat exchanger.
The violent agitation and kneading in this unit produce an extremely
fine dispersion of the water phase droplets. Diameters of the droplets
at this point range from 2 to 20 µm; the average is about 5 µm. Marga-
rine is a stable emulsion because the continuous phase (the fat) is solid.
The chilled emulsion is then held in a quiescent tube, and the marga-
 DAIRY AND NONDAIRY PRODUCTS \ 71

rine is allowed to solidify for a period of time before being extruded to

the packaging line. The emulsified water droplets plus a small amount
of entrained air provide the desired opacity to margarine.

Whipped Cream and Nondairy

Whipped Toppings
Flavorful, airy toppings produced by whipping an emulsion have
long been used for desserts by pastry chefs. Foam formation is basi-
cally an interfacial phenomenon, but the generation of a good
whipped product (including ice cream, which is basically a frozen
whipped cream) is somewhat unusual in that whipping involves a
controlled deemulsification correlated with crystallization of the fat
to stabilize the air cells. The various processes discussed next will be
considered from this viewpoint.

WHIPPED CREAM
By centrifugation, the milk fat portion of milk is concentrated to
make cream. In the United States, three standards of identity apply to
cream:
1. light cream (coffee cream or table cream) contains 18–30%
milk fat;
2. light whipping cream (whipping cream) contains 30–36% milk
fat; and
3. heavy cream (heavy whipping cream) contains 36% or more
milk fat.
The producer may also add approved emulsifiers, stabilizers, nutri-
tive sweeteners, and flavors, if desired. Other countries set their own
standards for “cream,” so these specifications may be different out-
side the United States. After concentration, the cream is homoge-
nized, pasteurized, and packaged for the consumer.
To whip properly, the cream must contain sufficient fat (30% min-
imum), it must be held for at least 24 hr at refrigeration tempera-
tures, and the quantity must not be too large (i.e., the mixer must not
be overfilled). The importance of each of these factors will become
apparent.
Whipped cream is a foam in which the air bubbles are stabilized by
agglomerated fat globules. During the early stages of mixing, air is in-
corporated into the cream and divided into large bubbles. Fat glob-
ules concentrate at the air-water interface and stabilize the bubble.
(This results from the partial removal of the membrane, exposing
some fat and forcing it into the air phase.) At the same time, fat glob- Agglomerate—To remain in
ules in the aqueous phase agglomerate, partly through membrane- close proximity but, because of
membrane interactions and partly through binding of membrane any of a variety of forces, not
protein to milk proteins. The fat globules must agglomerate but not coalesce; e.g., individual parti-
coalesce (as they do during churning). Thorough cooling of the cles in a suspension.
72 / CHAPTER FIVE

cream solidifies the fat to prevent coalescence. (If the cream is too
warm, the result may well be butter rather than whipped cream.)
Most of the air incorporation occurs during the first stage of mix-
ing (before significant viscosity has developed). Further mixing
shears and subdivides the air bubbles, and the new air-water interface
area is stabilized by the fat globule agglomerates. (Keep in mind that
partial removal of the fat membrane exposes hydrophobic fat sur-
faces that collect at the air-water interface.) Viscosity results from the
increase in the number of (subdivided) bubbles and continued ag-
glomeration of fat globules to form a network throughout the system.
As viscosity slowly develops, the shear stress on the air bubbles in-
creases, contributing to further subdivision, and the whipped cream
rapidly becomes stiff (the end point of the whipping process). If the
mixer is overfilled, it takes longer to effect fat agglomeration and thus
longer to reach the internal shear stress that contributes to comple-
tion of whipping.
Emulsifiers may be added to cream to increase overrun and final
stiffness. In one study in which combinations of polysorbates were
used, it was found that a 50:50 mixture of Polysorbate 60 (the mono-
stearate) and Polysorbate 65 (the tristearate) at 0.5% concentration
produced the stiffest cream with an overrun of about 200% (i.e., two
volumes of air per volume of cream) (1). Polysorbate 80 (the mono-
oleate) in place of Polysorbate 60 produced much less overrun and a
softer whipped cream. Studies in which monoglycerides and two de-
rivatives (the citric and lactic acid esters) were used at the 0.2% level
have also been reported (1). Monoglycerides alone had poor results,
and a blend of citric acid ester and monoglyceride had good results.
Lactylated monoglyceride produced a very stiff foam with a high
overrun, which may have resulted from its interfacial film-forming
tendencies. The overrun with simple whipping cream tends to be
about 100%, and emulsifiers apparently increase air incorporation
during the early mixing stages.

NONDAIRY WHIPPED TOPPINGS

Consumers have three concerns about using cream for whipping:
the cost, the high level of saturated fatty acids in milk fat, and the
cholesterol content. These concerns were addressed by food technol-
ogists, who developed whipped toppings made with vegetable fats.
Unlike cream, these fats do not have a natural emulsifier, so the nec-
essary emulsifiers are added during production. However, producing a
nondairy whipped topping is more complicated than simply combin-
ing an emulsified fat with an aqueous protein solution and whipping
the mixture. The fat must have the proper solid fat content profile so
that the “correct” amount of solid fat is present to stabilize the air
bubbles. Also, the emulsifier used must interact with the protein,
Overrun —Increase in volume coating the fat so as to produce the necessary degree of controlled de-
of a whipped material resulting sorption of the protein layer. Finally, the emulsion is frequently spray
from the incorporation of air. dried for storage and then reconstituted with cold water before whip-
 DAIRY AND NONDAIRY PRODUCTS \ 73

ping. The emulsifier, protein, and any other ingredients (e.g., sugar,
flavors, and maltodextrins) must rehydrate in the proper fashion to
produce an emulsion that is whippable. In short, the development of
a good nondairy whipped topping is not a simple assignment.
A basic whipped topping powder formula is 25% partially hydro-
genated fat and 5% emulsifier melted together and 50% water in
which 15% maltodextrin and 5% sodium caseinate are dissolved. The
two phases are mixed, homogenized, and then spray dried. The emul-
sion is stabilized by the combined effects of the emulsifier and pro-
tein. The powder is held at 5°C for 1 hr to solidify most of the fat and
then stored at temperatures below 20°C.
For whipping, the powder is dispersed in an equal weight of cold
water. Agitation initiates many of the same events that occur during
whipping of dairy cream—fat globule agglomeration, partial desorp-
tion of protein from the fat-water interface, air incorporation (stabi-
lized by fat globules), and air subdivision resulting in formation of a
stable foam.
The nature of the fat seems to be crucial. Best results are obtained
with partially hydrogenated lauric fats (e.g., coconut or palm kernel
fat) plus partially hydrogenated vegetable oils (e.g., soybean or sun-
flower oil). The hydrophobic segments of the protein, which pene-
trate the fat globule, appear to inhibit crystallization of the fat, so the
fat in the powder itself is a supercooled phase. Upon desorption (which
is aided by the presence of emulsifier), the fat rapidly crystallizes.
Crystallization concurrent with protein desorption appears to be nec-
essary for proper agglomeration and concentration of the fat at the
air-water interface, resulting in stabilization of the air bubbles. This
phenomenon appears to be connected with short-chain C12 fatty
acids; it occurs with lauric fats but not if the fat phase contains solely
the C18 vegetable oils. A partially hydrogenated C18 fat, exhibiting
no supercooling phenomenon, produces a poor whipped topping, as
does a partially hydrogenated C12 fat with a low melting point (little
or no fat crystal formation occurs at the temperature of the mixture
being whipped).
α-Tending emulsifiers such as propylene glycol monostearate or
lactylated monostearin have been used with good success, and
Polysorbate 60 (the monostearate derivative) is frequently used in
commercial nondairy whipped toppings. Both types form a rather
thick layer at the fat-water interface. The α-tending emulsifiers form
a multilayer of emulsifier, and Polysorbate 60 forms a layer of ad-
sorbed water (held by the polyoxyethylene chain). These properties
promote partial protein desorption, and yet a “sticky” surface is
maintained on each fat globule that enhances agglomeration. Supercooled—Pertaining to a
solution that is cooled below
the temperature at which crys-
Ice Cream tals would ordinarily begin to
form but do not because of the
The basic interfacial phenomena that occur during the manufac- absence of nucleation or the
ture of ice cream are similar to those that occur during whipping. presence of crystal inhibitors.
74 / CHAPTER FIVE

Again, the aim is the subdivision of air bubbles and stabilization by

adsorbed fat globules. However, in ice cream production, the temper-
ature regime is quite different, so one would expect differences in the
emulsifiers used.
After the initial ice cream emulsion is prepared, it is aged for 4–24
hr at ~5°C. This is an important step. During the aging, partial de-
sorption of the fat globule membrane takes place and the globules ag-
glomerate. Desorption is aided by the presence of emulsifiers. As in
whipped toppings, it appears that the fat is supercooled, and solidifi-
cation is connected with the desorption. During agitation and freez-
ing, the fat globules collect at the air-water interface and stabilize the
air bubbles. Studies have shown that increasing the degree of desorp-
tion (by the addition of a monoglyceride) gives a “drier” ice cream
with smaller average air bubble diameter.
The emulsifiers commonly used in ice cream manufacture are
monoglyceride (mono- and diglycerides seem to work equally well)
and Polysorbate 80 (the monooleate derivative). The effectiveness of
the unsaturated emulsifier compared with that of the saturated vari-
ety used in whipped toppings is undoubtedly connected to the much
lower processing temperature. The emulsifiers are used at a 0.2–0.4%
level (compared with the level of 3–5% in whipped toppings). Again,
these details relate to the temperature differences. Gums (e.g., guar,
carrageenan, and tragacanth) are also frequently used in ice cream
mixes. They improve the body and mouthfeel of the product, but
their main purpose is to act as crystal modifiers. They inhibit the
growth of ice crystals and lactose crystals in frozen ice cream, pre-
venting the gritty mouthfeel that can develop, particularly when the
product is stored for a long time.

Coffee Whiteners
Cream in coffee is enjoyed by many people. Today, however, the
cream pitcher has disappeared from the table, replaced by a powder,
which when stirred into a cup of coffee, mimics the effect of cream.
The restaurant trade uses small, individual packets of liquid whitener,
while the powder (a spray-dried emulsion stable at room tempera-
ture) is more popular for home use.
A wide range of formulations appears in the literature, but a typi-
cal spray-dried whitener contains vegetable fat, 37%; corn syrup
solids (dextrose equivalent, 42), 56%; sodium caseinate, 5%; dipotas-
sium phosphate, 1.6%; monoglyceride (e.g., glycerol monostearate),
0.3%, Polysorbate 65, 0.1%; and flavor and anticaking agent as de-
sired. The emulsifiers are added to the fat, the other materials are dis-
solved in water, and an emulsion of the two phases is homogenized
and then spray dried. The powder must be held under cool condi-
tions for a tempering period so that the fat solidifies and clumping is
avoided.
 DAIRY AND NONDAIRY PRODUCTS \ 75

The fat for coffee whitener usually has a melting point of about Feathering—Streaks of fat and
42–45°C, but it has a rather steep solid fat content profile. Such a fat precipitated protein that form
melts completely at coffee temperature (thus leaving no waxy mouth- in a liquid such as coffee when
improperly stabilized whitener
feel) but is relatively solid at room temperature, so the powder does
is added; caused by breakdown
not clump during storage. Corn syrup solids provide body during pro- of the emulsion.
cessing, and the dried matrix separates the fat particles.
The added emulsifier serves two purposes: during homogenization,
it facilitates formation of fine fat globules (average diameter, 1 µm),
and in conjunction with the protein, it prevents feathering, which oc-
curs if the emulsion breaks down and the fat separates (oils out) when
the whitener is dissolved in the coffee. The protein helps emulsify the
fat, and the proper emulsifier can stabilize the protein layer when the
whitener is added to the coffee. The protein layer can be destabilized
by calcium ions and organic acids in the coffee, and dipotassium
phosphate counteracts this tendency. One patent recommends the
use of sodium stearoyl lactylate rather than Polysorbate 65 because its
protein-complexing behavior apparently makes the protein more
effective (2).

Troubleshooting
The main role of emulsifiers in ice cream and whipped toppings is to destabilize the natural pro-
teinaceous film surrounding milk fat globules, allowing the solid milk fat to agglomerate around the
air bubbles and thus stabilize the three-dimensional physical structure. Interaction of emulsifier
with the fat can change the finished properties. One has to keep in mind that defects may not be
caused by the emulsifier system and may have other causes.

ICE CREAM
Symptom Causes Changes to Makea
Inadequate overrun Air bubble instability caused by Use aerating emulsifiers (e.g., GMS) or α-tending
poor fat agglomeration emulsifiers (e.g., PGMS).
Too soft; shiny, Insufficient agglomeration of fat Use emulsifiers containing unsaturated fatty acids
wet looking globules in the freezer (e.g., GMO or Polysorbate 80).
Too firm; “dry” looking Excessive agglomeration Adjust emulsifier blend to contain more saturates
(e.g., GMS or Polysorbate 65).
Mix viscosity too high Homogenization temperature too low Increase homogenization temperature.
Worn homogenizer valves Regrind valves.
Mix acidity too high Adjust pH.
Homogenizer pressure too high Adjust pressure.
Mix viscosity too low Hold time before freezing too short Adjust hold period.
Curdled meltdown Protein destabilization caused by Add dipotassium phosphate or sodium citrate.
high acidity
Homogenizer pressure too high Lower homogenizer pressure.
a
DATEM = diacetyl tartrate ester of monoglyceride; GMO = glycerol monooleate; GMS = glycerol monostearate; PGMS =
propylene glycol monostearate; and SSL = sodium stearoyl lactylate.
76 / CHAPTER FIVE

WHIPPED TOPPINGS
Symptom Causes Changes to Make
Insufficient overrun Poor emulsification Increase the amount of emulsifier with a high
hydrophilic/lipophilic balance (e.g., sorbitan
monostearate, Polysorbate 60 and/or 65).
Check homogenizer valves for wear.
Whipping temperature too high Adjust whipping temperature.
Soft whipped product Poor fat agglomeration Use an unsaturated fatty acid emulsifier (e.g., GMO)
for part of the system.
Use an α-tending emulsifier (e.g., PGMS).
Poor homogenization Decrease valve clearance.
Increase pressure.
Make multiple passes.
COFFEE WHITENER
Symptom Causes Changes to Make
Feathering Emulsion breakdown Use SSL or DATEM as the emulsifier.
Protein destabilization Add dipotassium phosphate or sodium citrate.
Clumping Untempered fat Make sure the heat of fat crystallization is released
before packaging.
Soft fat Use a fat that remains solid at room temperature.

References
1. Sogo, Y., and Kako, M. 1989. Whipping cream emulsifiers. In: Food Emulsifiers.
G. Charalambous and G. Doxastakis, Eds. Elsevier, Amsterdam.
2. Miller, D. E., and Werstak, C. E. 1983. U.S. patent 4,415,600.

Supplemental Reading
Chandan, R. 1997. Dairy-Based Ingredients. American Association of Cereal
Chemists, St. Paul, MN.
 CHAPTER

Dressings and Sauces

Dressings and sauces are a part of traditional cuisines of all types.
In terms of interfacial chemistry, they range from the very simple In This Chapter:
(e.g., an oil and vinegar salad dressing) to the complex (e.g., mayon- Polysaccharides at
naise). A common ingredient is oil, which gives a smooth mouth- Interfaces
feel and extended flavor impact to the food. To function effectively, Gums
the oil should be present in a finely divided (i.e., emulsified) state. Modified Starch
The means for accomplishing this are many and often involve ma- Cellulose Derivatives
terials other than (or in addition to) the emulsifiers discussed in Salad Dressings
Chapter 3. These materials may be proteins (see Chapter 3) or vari- Pourable Salad Dressings
ous polysaccharides. Spoonable Salad
The polysaccharides are often referred to as “stabilizers,” and they Dressings
work in different ways to maintain the oil in small droplets. Some Mayonnaise
gums, for example, actually adsorb to the oil-water interface, forming Reduced-Fat Dressings
a film with good interfacial viscosity and preventing droplet coales- and Sauces
cence. Other polysaccharides inhibit creaming (see Chapter 1) of the
emulsified drops by greatly increasing the viscosity of the aqueous Troubleshooting
phase, while still others prevent creaming by gelling, i.e., forming a
semisolid matrix that prevents flotation of the oil drops. Thus, in the
strict sense of the word, few of these materials are true “emulsifiers”
(surfactants that lower interfacial tension), but they still perform the
needed function of stabilizing the dressing or sauce by preventing
separation of the oil phase.

Polysaccharides at Interfaces
Polysaccharide —A carbohy-
GUMS drate containing several hun-
dred, thousand, or hundred
Obtained from plant exudates, seaweed extracts, and bacterial poly- thousand sugar units (from the
meric products, gums are high molecular weight polysaccharides that Greek poly, meaning “many”).
dissolve in water to form viscous solutions and, in some cases and
under the proper conditions, gels. They are widely used in food prod- Gum—Polysaccharide that
ucts, usually at low levels (0.1–1%), for many different functional rea- markedly increases viscosity
sons. Some gums have a high water-binding capacity and are used to when dissolved or dispersed in
water.
control water migration in the finished product. These gums also act
to inhibit growth of ice crystals in frozen products. In other in- Plant exudate —Droplets of
stances, the viscosity imparted by the gum is necessary for the inter- hardened gum exuded by a
mediate material (e.g., a cake batter) to perform properly when baked plant to seal a break in the
or cooked. Gum viscosity is often used as a means of classification. bark.

77
78 / CHAPTER SIX

TABLE 6-1. Viscosities of Gums Common food-grade gums and the viscosities
of 1% solutions are listed in Table 6-1.
Gum Viscositya
The molecular structure of gums is a long
Low viscosity polysaccharide chain with numerous side
Arabic 2–5 branches of sugars or oligosaccharides. Fre-
Ghatti 4–10 quently, the sugar units include carboxylic
Larch 2–10 (uronic) acids, e.g., D-glucuronic, D-man-
Medium viscosity nuronic, or D-galacturonic acid. In a few in-
Sodium alginate 25–800 stances, sulfate esters provide an anionic
Propylene glycol alginate 100–500 character. Many different saccharides are
Tragacanth 200–500 found in gums, including the hexoses D-glu-
Xanthan 800–1,400 cose, D-mannose, and D-galactose and the
pentoses D-arabinose, D-xylose, and D-rham-
High viscosity
nose. The highly branched structure con-
Guar 2,000–3,500
tributes to water solubility, and the anionic
Karaya 2,500–3,500
gums often form gels in the presence of
Locust bean 3,000–3,500 cations such as Ca++.
Cellulose gums The low-viscosity gums (arabic, ghatti, and
Sodium carboxymethylcellulose 50–5,000 larch) are used mainly as water-binding
Hydroxypropyl methylcellulose 20–50,000 agents; e.g., they prevent syneresis, or weep-
Methylcellulose 10–2,000 ing, in baked meringues. The gums readily
Gel-forming gums dissolve in water, and a concentrated solution
Agar Gel (10–50%) of the gum is often used to emulsify
Calcium alginate Gel hydrophobic flavor oils such as citrus or cin-
Carrageenan Gel namon oil. The gum forms a layer at the oil-
water interface, and spray drying the emul-
Furcelleran Gel
sion results in an encapsulated flavor that has
Gellan Gel
many uses in food product development.
Pectin Gel
The medium-viscosity gums (sodium algi-
a
Viscosity of a 1% aqueous solution of the gum, in centipoise. nate, propylene glycol alginate, tragacanth,
(Water viscosity = 1 centipoise.) and xanthan), when used in foods at the
usual levels, impart body to the product. They
also have emulsifying properties and are often found in pourable
Oligosaccharide —Short poly- dressings, e.g., oil and water types that are emulsified just before use
mer of sugar having three to by shaking the bottle. They can also be used in flavor oil emulsions,
eight sugar units. particularly the liquid types often used in bakeries.
High-viscosity gums (guar, karaya, and locust bean) are used as
Uronic acids —Derivatives of
a sugar, in which the terminal
thickening or stabilizing ingredients. They greatly increase the vis-
-CH2OH group is oxidized to a cosity of the aqueous phase of the food product and aid in air incor-
carboxylic acid. D-Glucuronic poration in whipped toppings. High-viscosity gums are often used in
acid is derived from D-glucose, low-fat or fat-free pourable dressings. The enhanced viscosity (or
D-mannuronic acid from D- body) results in a mouthfeel that is similar to that of fat-containing
mannose, and D-galacturonic dressings.
acid from D-galactose. Gel-forming gums (agar, calcium alginate, carrageenan, fur-
Hexose—Sugar containing six
celleran, gellan, and pectin) are used mainly in foods such as jellies
carbon atoms. and fruit fillings that require a semisolid nature. These gums also im-
part freeze-thaw stability to many products. Many frozen whipped top-
Pentose—Sugar containing pings and ice creams include one or more of the gums listed, particu-
five carbon atoms. larly carrageenan or alginate.
 DRESSINGS AND SAUCES \ 79

Most dressings and many sauces contain vinegar and thus are Syneresis —Separation of a liq-
acidic. The effect of pH on gums is quite variable, and suppliers can uid from a gel; weeping.
provide information on the performance of gums under a range of
Body—A qualitative measure-
pH conditions. Some gums are somewhat susceptible to acid hydrol- ment determined in sensory
ysis, but again this varies (tragacanth is reasonably stable at pH 2, tests as the ability to “fill the
whereas arabic begins to depolymerize at pH 4). Most gums (e.g., the mouth” with the characteristic
carboxylic acid groups or sulfate esters) are acidic in nature, and a cer- being measured.
tain sensitivity to pH would be expected. For example, the viscosity
of a sodium alginate solution is constant from pH 4 to 10, but at Freeze-thaw stability—The
ability of a product to be
lower pH, the carboxylate groups are converted (un-ionized) to car-
frozen, thawed, and refrozen
boxylic acids and the polymer chains begin to interact, resulting in several times without notice-
an increase in viscosity. Propylene glycol alginate ester, on the other able changes in physical
hand, is relatively insensitive to pH, and the viscosity increase at characteristics.
lower pH is much less than that of sodium salt.
Crosslinked starch —Starch in
MODIFIED STARCH which hydroxyl groups on adja-
cent chains are joined by a co-
As described in Chapter 4, starch is made of two types of mole- valent linkage.
cules: linear amylose and branched amylopectin. In native starch,
these molecules exist partly as amorphous chains and partly in crys-
tallites (regions of crystallized starch). When starch is heated with a
liquid, gelatinization occurs. The starch first hydrates (swells), and
then the crystallites melt into the water solvent. Upon cooling, ret-
rogradation (recrystallization) of the gelatinized starch takes place,
and a gel is formed, the properties of which depend upon the starch-
water ratio of the mixture and the amylose-amylopectin ratio of the
starch. Starches can be modified to make them more useful in the
food industry.
Crosslinked starch is starch that has been treated with one or more
reagents to form bonds between glucose residues in adjacent starch
chains. Sodium trimetaphosphate or phosphorus trichloride form a
phosphate diester:
2 Starch-OH + PO3Cl (NaOH) → Starch-O-P(=O)(-O–)-O-Starch Na+
Epichlorohydrin forms a diether bridge, where the central moiety is a
hydroxypropyl group:
Starch-O-CH2-CH(-OH)CH2-O-Starch
The differences in reactivity of phosphate esters and ethers lead to
differences in the chemical stability of the two kinds of modified
starch. They both are generally useful, and each has advantages in
certain situations, such as extremes of pH and temperature.
Crosslinking raises the gelatinization temperature of starch, but
more important, the gel that is formed is stable under varying condi-
tions of temperature, low pH, and shear. Of course, the degree of sta-
bilization depends on the degree of crosslinking (i.e., the amount of
reagent used during the modification reaction). Crosslinked starch is
less likely to lose viscosity at low pH than other kinds of starch. This
makes crosslinked starch useful in salad dressing, in which the pH is
80 / CHAPTER SIX

Stabilized starch —Starch in 3–4. However, the starch degrades somewhat when it is cooked at low
which hydroxyl groups form pH, so it is precooked (gelatinized) at neutral pH before it is combined
ester or ether bonds with other
with the oil, vinegar, and spices.
small molecules.
Stabilized starch is derivatized without crosslinking. Reaction with
Shear thinning—Decrease in propylene oxide, for example, produces hydroxypropylated starch.
the viscosity of a suspension as Sodium tripolyphosphate, under the proper reaction conditions,
shear rate increases. makes phosphate monoester derivatives, and acetic anhydride yields
acetylated starch. Stabilized starches have lower gelatinization tem-
Crystal inhibitors —Small mol- peratures and higher viscosities than the native starches, but they are
ecules that interfere with the
often less resistant to shear thinning. A major advantage of stabilized
deposition of dissolved mole-
cules on the growing face of a
starches is that because of the subtitution along the starch chains,
crystal, thus inhibiting growth they are less inclined to retrograde upon cooling. Retrogradation ren-
of the crystal. ders the starch opaque (rather than translucent) and much firmer,
possibly generating a gritty or rubbery mouthfeel.

CELLULOSE DERIVATIVES
Cellulose is insoluble in water, but substitution of certain groups
along the glucose backbone render it soluble. The three forms most
commonly used in foods are substituted with carboxymethyl, methyl,
and hydroxypropyl plus methyl groups. The degree of substitution
varies depending upon the cellulose-reactant ratio, and products with
a wide range of viscosities are possible. Methylcellulose has a modest
degree of surface activity and acts as an emulsifier in oil-in-water sys-
tems. Hydroxypropyl methylcellulose forms a film at oil-water inter-
faces and stabilizes oil emulsions. Certain grades of hydroxypropyl
methylcellulose form gels even at room temperature and can be used
in some types of fat-free pourable dressings to add body.
Microcrystalline cellulose is a highly purified fraction of regular cel-
lulose. It absorbs several times its own weight of water and is added to
some low-fat dressings for body. A suspension of microcrystalline cel-
lulose is thixotropic; i.e., it flows very slowly at low shear rates, or has
a high apparent viscosity. For this reason, it is often added to condi-
ment sauces (e.g., ketchup and barbecue sauce) to enhance “cling”;
i.e., the sauce remains where it is applied and does not run down the
sides of the food item.

Salad Dressings
POURABLE SALAD DRESSINGS
According to U.S. standards of identity, french dressing is a mixture
of vegetable oil (minimum 35% by weight), acidifying ingredients
(e.g., vinegar, lemon juice, or lime juice), and other permissible ingre-
dients (salt, sugars, spices, monosodium glutamate, tomato products,
eggs, colorants, thickeners, citric and/or malic acids, sequestrants, and
crystal inhibitors). Thus, a wide range of products is included, from the
simplest vinaigrette (oil, vinegar, and a few spices) to relatively com-
plex products marketed under a variety of names.
 DRESSINGS AND SAUCES \ 81

Salad dressing oil is a refined, bleached, deodorized oil that has

been winterized to inhibit development of cloudiness during refrigera-
tion. A crystal inhibitor is often added to lengthen the time that
elapses before such cloudiness begins to develop. The molecular struc-
ture of crystal inhibitors is similar to that of triglycerides but different
in some specific manner. When the crystal inhibitors deposit on the
faces of growing fat microcrystals, this difference in molecular struc-
ture interferes with the further deposition of fat molecules. Two com-
pounds, oxystearin and polyglycerol esters, are approved by the U.S.
Food and Drug Administration specifically for this use. Oxystearin is
made by blowing air through cottonseed or soybean oil (hydro-
genated to an iodine value of about 35) at 200°C. The product con-
tains many polymeric and breakdown products, and its exact compo-
sition is unknown. Its maximum permissible use concentration is
0.125% by weight. Several emulsifiers, including sucrose esters, glu-
cose esters, and sorbitan tristearate, also inhibit crystal formation.
Before a dressing is added to the salad greens, the bottle is shaken to
make an emulsion, i.e., an even distribution of the oil and water
phases. Many nonstandard dressings are rather complex mixtures that
also contain dairy products (e.g., buttermilk powder or blue cheese),
spices (e.g., ground mustard or turmeric powder), dried vegetable
pieces (e.g., onion or green and red peppers), and other items. They
also often include Polysorbate 60 in their formulations at the maxi-
mum permissible level of 0.3% by weight of the total dressing to en-
hance “home emulsification.” An emulsion stabilizer helps maintain
uniformity of this complex mixture and increases the product appeal.
The viscosity of a simple emulsion of 35% oil in water is almost
that of water. For many dressings, a higher viscosity is desired so that
the dressing does not drain quickly from the salad greens and collect
in the bottom of the salad bowl. Soluble gums are used at a concen-
tration of 0.05–0.3% to give the desired viscosity. Some of the names
commonly seen on labels include propylene glycol alginate, xanthan
gum, modified cellulose gum, and carrageenan. Besides contributing
the desired viscosity, the gum must be stable in an acidic environ-
ment; hydrolysis at low pH decreases viscosity.
Microcrystalline cellulose may be used at 1–2% concentration and
increases viscosity by decreasing the amount of continuous (water) Winterize—To cool salad oil
phase in the formulation. It is most often used in dressings that con- until high-melting-point triglyc-
tain tomato products, where it gives a smooth texture and imparts a erides form crystals. These crys-
certain degree of thixotropy to the mixture so that the dressing clings tals are removed so that the
next time the oil is cooled, the
to the surface of the salad greens.
cloudiness that results from
crystallization will not occur.
SPOONABLE SALAD DRESSINGS
Bingham plastic —A suspen-
Spoonable, starch-based salad dressing was first developed as a low-
sion that does not flow when
cost alternative to mayonnaise. Today, it is accepted as a somewhat subjected to a shear stress
different product, purchased and judged by consumers on its own lower than the yield value but
merits. While it is similar to mayonnaise in rheology (it is a Bingham does flow at any shear stress
plastic, and its yield value is a factor in acceptability), its characteris- above the yield value.
82 / CHAPTER SIX

Box 6-1. Yield Value

Spoonable dressing is a “Bingham plastic” in rheological
terms (Fig. 6-1). When shear stress (stirring) is applied at low
levels, the dressing acts like a solid; i.e., it does not flow, al-
though it may fracture (break). At some level of shear force,
called the “yield value,” the dressing begins to act like a liq-
uid. Put another way, if a block of dressing is simply cut, the
vertical edge does not flow, because the shear stress of gravity
is less than the yield value. However, the dressing can be
spread smoothly with a knife on a slice of bread because the
shear force applied by the knife blade is greater than the yield
value. The yield values of spoonable dressing and mayonnaise
are important factors in the quality of the products.

tics are dependent on the nature of the food starch used and not on
the state of emulsification of the oil.
A salad dressing meeting the U.S. standard of
identity contains vegetable oil (minimum 30%
by weight), egg yolk (minimum 4% by weight),
acidifiers (vinegar, lemon juice, or lime juice), a
Newtonian
paste prepared from a suitable food starch, and
other ingredients (salt, sugar, spice, monosodium
Shear Rate

glutamate, thickeners, citric and/or malic acid,

sequestrants, and crystal inhibitors). A typical
commercial product might contain (by weight)
Bingham plastic
35% salad oil, 4% liquid egg yolk, 2% salt, 11%
Yield value sugar (or 15.5% high-fructose corn syrup), 0.5%
mustard flour, 11% vinegar (100 grain), 6% mod-
ified starch, spices, and water to total 100%.
The starch is the key component in this formu-
lation, providing the desired structure and creamy
Shear Stress texture to the finished product. The starch most
Fig. 6-1. Rheological stress-strain curve of a Bingham often used is a waxy maize starch, which is essen-
plastic. tially 100% amylopectin, crosslinked with sodium
trimetaphosphate and stabilized, usually by hy-
droxypropyl substitution. The starch has a relatively high gelatiniza-
tion temperature and sets to a soft gel upon cooling. The crosslinking
prevents hydrolysis in the low pH environment of the finished dress-
Waxy maize starch —Starch ing; without crosslinking, the starch gel would soften during storage.
from genetically modified corn; The stabilization interferes with recrystallization of the side chains and
contains almost no amylose. maintains a creamy texture in the finished dressing during storage,
particularly if the dressing is held at refrigerator temperatures or even
Lipoprotein —A complex of a
protein with a lipid (generally frozen.
a phospholipid) found in many Spoonable salad dressing is made in several stages. First, the oil is
plants. The most common in emulsified with the egg yolk and some of the water and vinegar. The
food processing is from egg egg yolk lipoproteins are the surface-active materials that stabilize this
yolk. emulsion, which is rather coarse because of the relatively large diam-
 DRESSINGS AND SAUCES \ 83

eter of the oil drops. Meanwhile, the starch is gelatinized by heating Colloid mill —Machine used to
it with water. After it is cooled, the other ingredients such as vinegar, decrease the size of suspended
sugar, salt, and spices are mixed in to form a paste. The cooled paste particles or droplets.
is then fed into the premixer and blended into the oil-egg emulsion.
This soft mass is pumped to a colloid mill, where the final high viscos-
ity and smooth texture are generated. The gelatinization procedure is
crucial in attaining good final product quality, and the details of time
and temperature depend to a large degree upon the specific starch
used. Information about the proper operation of the starch cooker is
best obtained from the starch supplier.

Mayonnaise
Standardized mayonnaise contains vegetable oil (minimum 65%
by weight), acidifiers (vinegar, lemon juice, or lime juice), egg yolks
(liquid, frozen, or as whole egg), and other ingredients (salt, sugars,
spices, monosodium glutamate, sequestrants, citric and/or malic
acid, and crystal inhibitors). Mayonnaise is an oil-in-water emulsion,
stabilized by the lipoprotein components of egg yolk. While the legal
minimum for the oil content is 65%, mayonnaise at this oil level is
rather thin (i.e., has low viscosity). Thus, the usual commercial prod-
uct today contains 77–82% oil. Liquid egg yolk (45% solids) is the
emulsifier and is used at 5.3–5.8% of total formula weight. Sometimes
whole eggs (25% solids) are substituted for egg yolks on a total solids
basis (i.e., whole eggs at 9.5–10.4% of the total formula weight). This
produces a somewhat “stiffer” product than egg yolks because the egg
albumin is denatured at the interface and forms a matrix in the aque-
ous phase, increasing the Bingham yield value of the product.
Oil is the internal phase in the emulsion. If all the droplets are
spherical and incompressible and have the same diameter, the maxi-
mum volume percentage of oil is 74.05%. (For example, if a 1,000-ml
container were filled with small, uniform ball bearings, 260 ml of
water would be needed to fill the space between the bearings.)
If the oil volume percentage exceeds 74%, the emulsion inverts (i.e.,
the oil droplets coalesce, and the emulsion becomes a water-in-oil
emulsion). However, if the droplets differ in diameter, small droplets
can fill the spaces between large drops. This is what happens in
mayonnaise.
This “filling in the spaces” also has a major effect on the rheologi-
cal (flow) characteristics of the product. Mayonnaise is a Bingham
plastic, and the yield value is related to the amount of internal (oil)
phase in excess of the 74% (by volume) theoretical limit. Thus, a
mayonnaise with the legal minimum of 65% oil by weight has a very
low yield value and is considered too “thin” by users. Mayonnaise
with 80–84% oil by weight has a high yield value and is considered
dry or rubbery by home consumers, although it is preferred for insti-
tutional use because it does not soak into bread in sandwiches or
soften and flow over salads.
84 / CHAPTER SIX

As mentioned above, the lipoproteins in egg yolk are the main

emulsifying agents in mayonnaise. They are partially denatured by
the low pH of the vinegar used, and their emulsification capabilities
are enhanced. If whole eggs are used, the egg white albumins are also
denatured by the low pH and provide some emulsification, giving the
aqueous phase a somewhat meringuelike quality. The resulting may-
onnaise may be slightly fluffier than mayonnaise made with only
yolk, and the yield value is slightly greater. The choice between the
two products is mainly a matter of consumer preference.
An oil that resists clouding is essential for mayonnaise. After the jar
is opened, it is stored in the refrigerator. If fat crystals form, the bal-
ance of emulsion-stabilizing forces is disrupted and the emulsion
breaks down. In addition to winterization of the oil, crystal inhibitors
may be used to further inhibit clouding.
The preparation of mayonnaise is difficult, and science is less im-
portant than the experience and skill of the equipment operators in
making an acceptable final product. Nevertheless, there are certain
basic principles that apply. Understanding them can help to solve
production problems when they arise.
A planetary mixer (e.g., a Hobart) with a paddle is used in tradi-
tional mayonnaise production. The yolk and other dry ingredients
are blended, and then the oil is added while mixing continues, slowly
at first and then more rapidly when the mass begins to thicken (with-
out allowing any puddles of oil to form). After all the oil is incorpo-
rated, the vinegar is added and the mixture is thoroughly blended.
This method is used in homes and in gourmet restaurants that have
their own special blends.
Commercial manufacture is a two-step process. First, a premix sim-
ilar to that in the traditional method is made. Often mayonnaise
from a previous batch is placed in the mixer to give a high-viscosity
medium into which the mixer blades can readily disperse the oil. The
egg and dry ingredients are added, mixing is initiated, and the oil and
vinegar are pumped in at a controlled rate (the flow of vinegar is not
completed until after all the oil is in). The viscosity of the premix de-
pends in part upon the characteristics of the particular batch of egg
being used and can be adjusted by changing the timing and rate of
the oil and vinegar addition. In the second step, this rather soft pre-
mix is pumped to a colloid mill, which reduces the diameter of the oil
droplets. The viscosity of the final product depends upon the degree
of subdivision attained in the mill, which in turn depends upon mill
settings (e.g., clearance between rotor and stator and speed of the
rotor) and the premix viscosity. The ideal, of course, is to obtain a
high degree of subdivision but large variation in droplet diameters. If
too much subdivision occurs and all droplet diameters approach the
theoretical minimum (governed by interfacial tension), variable
space filling is lost, and since the volume percentage of oil is greater
than 74%, the emulsion inverts (breaks down). As stated earlier, the
ability of the operator to adjust the mill to achieve the proper degree
of subdivision depends more on skill and experience than on science.
 DRESSINGS AND SAUCES \ 85

Reduced-Fat Dressings and Sauces

The first reduced-fat dressing was a spoonable, starch-based prod-
uct developed during the 1930s as a less expensive alternative to may-
onnaise. With less than half the oil of mayonnaise, this product
would qualify for a “reduced fat” label today, although that was not
the original intent of the developers. The appearance of “low-fat” and
“fat-free” salad dressings (both pourable and spoonable types) during
the 1990s has been in response to the consumer trend toward lower-
ing fat in the diet. This trend is not confined to dressings, of course.
Bakery, dairy, confectionery, and numerous other food products have
also been developed.
The challenge in all areas is to mimic the functionality of fat while
reducing its level in the product. Since fat contributes many of the
positive gustatory characteristics of foods, this has not been easy to
do. In dressings, for example, some of the major contributions of fat
are body (viscosity and cling), creaminess (smoothness), lubricity
(slipperiness), sheen (appearance), and flavor (intensity and dura-
tion). The search for nonfat materials to mimic each of these features
has produced some successes but no one (or even two) materials that
do the whole job.
Emulsified oil increases the viscosity of the dressing, although the
increase is not great, except in mayonnaise. Still, this viscosity in-
crease is desirable because it slows drainage of the dressing from the
salad greens. Gums, modified starches, and solid fibers all increase
viscosity. By themselves, however, they do not make a satisfactory
product. Some gums, for example, increase viscosity, but the dressing
has a “slimy” rather than a smooth or slippery mouthfeel. The most
popular gums used today in low-fat or fat-free dressings are xanthan,
propylene glycol alginate, and hydroxypropyl methylcellulose (la-
beled simply as cellulose gum). They are used in part because of their
high resistance to hydrolysis during storage at the low pH of the
dressing. While these materials do improve cling, that alone is not
sufficient.
A fat mimetic comes closer to providing the needed creaminess and
lubricity. The first successful one was Simplesse, a product made from
egg and dairy proteins in the form of spherical particles about
0.5–2 mm in diameter. The claim was that these gave a “ball bearing”
effect on the palate. Soon after, starch gels containing soft (de-
formable) particles appeared that produced a similar creamy effect.
The sheen caused by a thin layer of oil is desirable in certain prod-
ucts, particularly condiment sauces. This appearance has not been
achieved with starches, gums, or protein derivatives. However, by
using a strongly surface-active emulsifier, such as one of the polysor-
bates, a very small amount of oil is enough to produce this surface ef-
fect. If the level of oil plus emulsifier is such that a serving of the Fat mimetic —Fat substitute
product contains less than 0.5 g of fat (by analysis), it may be labeled that mimics the properties of
“fat free.” fat.
86 / CHAPTER SIX

Flavor notes—Small mole- The main problem with reducing or removing fat is in the area of
cules, usually volatile hydrocar- flavor. Fat plays an important role in the perception of flavor. It mod-
bons, that interact with taste ifies the way flavor notes interact with taste receptors on the tongue.
receptors and are experienced
It influences the order of release of these flavors and slows down the
as flavors.
rate of interaction. Since many of the flavor notes derived from spices
are fat soluble, they are affected by these factors. A fat-free, vinegar-
based dressing containing spices (e.g., oregano, marjoram, and sage)
has a large, immediate flavor impact that rapidly fades, leaving only
the acidity of the vinegar on the palate. The corresponding dressing
with oil has a longer, less intense flavor impact. The flavor notes in-
teract with the sourness in a more pleasing sequence, and the con-
sumer has a more favorable final perception. In the flavor chemist’s
terms, the result is a more “rounded” flavor. Also, the oil tends to
mask low-level off-flavors and mitigates unfavorable interactions be-
tween flavor notes. Many flavor molecules are volatile hydrocarbons
and are rather unstable in an aqueous environment.
This entire area is still under investigation. Simply using the same
spices and other flavors in a fat-free version of an existing regular
dressing is inadequate. The formulator must do an extensive rebal-
ancing of the formula to achieve an acceptable result. In dressings, as
in the other food applications, experience is showing that low-fat or
reduced-fat formulations are often much more acceptable to the con-
sumer than fat-free products and can contribute to bringing the calo-
ries from the fat portion of the diet below the recommended 30% of
total calories.

Troubleshooting
SPOONABLE DRESSINGS
Symptom Causes Changes to Make
Oil separates during Crystal formation in oil Use a winterized (non-clouding) oil.
storage Add a crystal inhibitor to the oil.
Stabilizer breakdown due to low pH Use a stabilized (hydroxypropyl) starch.
Use propylene glycol alginate gum.
Insufficient stabilizer Add a solid particle stabilizer such as mustard flour.
Breaks down during Excess shear force Increase clearance in homogenizer.
processing Decrease homogenizer rotor speed.
Use shear-resistant starch.
 DRESSINGS AND SAUCES \ 87

POURABLE DRESSINGS
Symptom Causes Changes to Makea
Oil separates too Inadequate emulsification Add emulsifier (e.g., Polysorbate 60 up to 0.3% or
quickly DATEM).
Use some protein stabilizer (e.g., whey isolates).
Low viscosity Add a pH-stable, high-viscosity gum (e.g.,
hydroxypropyl methylcellulose).
Lacks “cling” Low viscosity; poor flocculation Add a fibrous thickener (e.g., microcrystalline
cellulose or xanthan gum).
REDUCED-FAT DRESSINGS
Symptom Causes Changes to Make
“Slimy” mouthfeel Viscosity too high Switch to lower viscosity gum stabilizer.
Evanescent flavor Insufficient lipid phase Rebalance flavor system.
impact Add emulsifier(s) that form a mesophase or micelles
(e.g., SSL + GMO).
a
DATEM = diacetyl tartrate ester of monoglyceride; GMO = glycerol monooleate; and SSL = sodium stearoyl lactylate.

Supplemental Reading
Whistler, R. L., and BeMiller, J. N. 1996. Carbohydrate Chemistry for Food Scientists.
American Association of Cereal Chemists, St. Paul, MN.
 CHAPTER

Beverages
Soft drinks are consumed by people around the world. The most
popular flavors are citrus (orange first, followed by lemon). In the In This Chapter:
United States, cola flavor holds the number one spot, followed by or- Flavor Emulsions
ange and lemon. Citrus flavors are essential oils extracted from the Oil Phase
fruit peel and are insoluble in water. The beverages made with these Emulsion Stabilizers
oils consist of dilute oil/water (O/W) emulsions in dilute solutions of Emulsion Preparation
sugar (which may be carbonated). At the bottling plant, a concen- Stability
trated emulsion is mixed with the aqueous phase, packaged in bottles Creaming
or cans, and delivered to the vendor. The dilute emulsion must re- Flocculation
main stable for at least six months and often must survive intermedi- Coalescence
ate storage under either warm (>40°C) or cold (<10°C) conditions. Microemulsions
A characteristic desired in some beverages is cloudiness. For these Troubleshooting
drinks, the emulsion includes a flavorless oil called a weighting agent,
which has a density higher than that of the flavor oil. Adjustments
are made so that the density of the oil droplets approaches that of the
dilute sugar solution, keeping the emulsion droplets uniformly dis-
tributed throughout the beverage during storage and consumption.

Flavor Emulsions Essential oils —Aromatic and

flavorous oils obtained from
OIL PHASE various plant sources and origi-
nally known as “essences,”
Citrus flavor oils are mainly mixtures of monoterpenes (typically mainly in the perfume industry.
more than 90%) and sesquiterpenes. By themselves, these hydrocar-
bons are nearly odorless and flavorless, but they are carriers for the Weighting agent —An oil-
compounds—alcohols, aldehydes, ketones, acid, and esters—that soluble material that has a den-
provide the citrus aromas and flavors of orange, lemon, grapefruit, sity greater than that of water.
etc. The selection and blending of citrus oils to produce the desired
Monoterpenes—Aliphatic
flavor and odor is done by flavor chemists and is outside the scope of compounds, containing 10 car-
this book. It is a highly developed expertise and is basic to the design bon atoms, formed biologically
of a product that is acceptable to consumers. by combination of two mole-
The terpenes have specific gravities of 0.845–0.890 g/cm3, well cules of isoprene (2-methyl
below the specific gravity of 1.04–1.048 g/cm3 of the 10–12% sugar butadiene), with subsequent
solution of the beverage. The need for inclusion of a weighting agent modification to give the various
members of this group.
to make an emulsion with a neutral density (one that does not cream)
is apparent. However, the selection of a weighting agent has been Sesquiterpenes —Similar to
complicated by government regulations in various countries. Some monoterpenes but containing
agents are permitted in one country but not in another. Thus, no sin- 15 carbon atoms; formed by
gle weighting agent is universally applicable. reaction of three isoprene units.

89
90 / CHAPTER SEVEN

CH3 Brominated vegetable oil (BVO) was first used

in the 1940s. It has a specific gravity of about
1.33 g/cm3, the highest of the agents presently
in use, and thus is the most efficient. Unfor-
CH3 tunately, in 1970, several European countries
withdrew permission for its use, and shortly
H3C thereafter, Canada and the United States lim-
ited it to a maximum level of 15 ppm in bev-
H erages, about one-tenth that necessary to
make a neutral-density emulsion. These ac-
tions presented the industry with a major
problem. The weighting agents most used
H today are ester gum, damar gum, and sucrose ace-
tate isobutyrate, although none of them are ap-
H3C COOH proved for use in all countries.
Fig. 7-1. Structure of abietic acid, one of the main diter- Ester gum is produced by esterification of
penoid carboxylic acids present in purified wood resin. wood resin with glycerol. Wood resin is ob-
tained by purification of the oleoresin from
pine trees and consists mainly of diterpenoid
carboxylic acids, e.g., abietic acid (Fig. 7-1) and pimaric acid.
Esterification with glycerol produces a mixture of the mono-, di-, and
triglycerides. After purification (by steam sparging and vacuum distil-
lation), a flavorless, colorless, oil-soluble resin is obtained. Since a
typical density of this resin is 1.08 g/cm3, the oil phase requires a
much higher proportion of this product than of BVO to obtain neu-
Brominated vegetable oil— tral density. Ester gum is approved for use in the United States at a
Oil made by treating an unsat- maximum level of 100 ppm but is not approved in Canada or most
urated vegetable oil with mole- European countries.
cular bromine. Addition of HBr Damar gum is a resinous plant exudate from shrubs belonging to
across double bonds gives
these oils a high density.
the genus Shorea. It is a complex mixture of triterpenes, other low
molecular weight polymers, and numerous acids, esters, and ketones
Ester gum —Gum made by derived from these compounds. The crude exudate is deodorized by
esterifying the acids of purified solvent extraction and/or fractional distillation to remove low mole-
wood resin with glycerol. cular weight terpenes that might impart a flavor or odor to beverages.
Damar gum is completely soluble in essential oils and has a typical
Damar gum —A shrub exudate specific gravity of 1.05–1.08 g/cm3. It is permitted for use in European
consisting mainly of triterpenes
(containing 30 carbon atoms)
countries as an all-natural, chemically unmodified, vegetable gum
but with numerous other re- resin. It is not approved in the United States for use as a food additive.
lated compounds also present. Sucrose acetate isobutyrate is a mixture of sucrose esters, mainly
the diacetate hexaisobutyrate isomer. It is prepared by esterification
Sucrose acetate isobutyrate— of sucrose with the two acid anhydrides, acetic anhydride and butyric
The octaester of sucrose with anhydride, followed by purification. Its specific gravity is 1.146
acetic and isobutyric acids. g/cm3, higher than that of ester gum or damar gum, and thus it is a
Diterpenoid carboxylic
more efficient weighting agent. It is permitted for use in several coun-
acids—Tricyclic compounds tries (e.g., Canada, Sweden, Norway, and Brazil), but regulators in the
containing 20 carbon atoms United States and the European Community are waiting for the re-
and with a carboxylic acid func- sults of long-term safety studies. Given the structure of the molecule
tion attached. (and its obvious relationship to the recently approved Olestra), ap-
 BEVERAGES \ 91

proval can be expected, but obviously no time frame can be predicted Centipoise—An older unit of
for such action. viscosity (1 centipoise = 1
mPa˙sec [SI unit], the approxi-
mate viscosity of water at room
EMULSION STABILIZERS temperature).
Gum arabic is the most widely used stabilizer for beverage emul-
sions. As discussed in Chapter 6, a relatively concentrated solution
has a low viscosity, facilitating the production process. A 30% solu-
tion in water (a typical concentration for making these emulsions)
has a viscosity of less than 100 centipoise (about the viscosity of veg-
etable oil). The hydrophilic/lipophilic balance (HLB) of gum arabic
has been reported as 8 and as 12. The discrepancy is not surprising
(applying the HLB scale to a gum takes it somewhat outside its origi-
nal design purpose), but either number indicates that gum arabic
should be a modest to good emulsifier for O/W emulsions. While
gum arabic lowers interfacial tension, its effectiveness as a stabilizer
results mainly from the interfacial film it forms and the resultant
high interfacial viscosity.
Gum tragacanth is also sometimes used in beverage emulsion sys-
tems. It is a medium-viscosity gum, but in combination with gum
arabic, the viscosity of the overall solution is less than that of either
of the gums alone. However, the two in combination form a mixed
interfacial film, providing a more effective stabilizer than either gum
alone.
A particular type of modified starch, which has
been reacted with a derivatized succinic anhy- O
dride, is also suggested for use as a beverage emul-
sifier. The derivative consists of a lipophilic alkyl Na + -O-C
or alkenyl chain located at carbon 2 of the suc-
cinic acid. In the United States and several other
countries, modified starch substituted with 2- HCH
(1-octenyl)-succinic anhydride (Fig. 7-2) has been
approved for food use. The starch has at least two HC-CH=CH-(CH 2 ) 5 CH 3
advantages over gum arabic as an emulsifier for
beverage systems. First, as a modified corn starch,
it is “cleaner” (i.e., less likely to have off-flavors or Starch-O-C
odors) than the average gum preparation. Second,
because of the added lipophilic character result- O
ing from the substituent molecule, less modified Fig. 7-2. Structure of 2-(1-octenyl) succinic acid, esteri-
starch is needed for stabilization of the beverage fied to a hydroxyl group in starch to produce a modified
emulsion. starch for flavor emulsion stabilization.

EMULSION PREPARATION
Making a beverage emulsion follows the basic principles of emul-
sion production. The oil phase (flavors and weighting agents) is pre-
pared and mixed with two to four times its volume of the aqueous
phase. A mixer is used to produce a crude emulsion with droplet di-
ameters of approximately 20 µm. The crude emulsion is then ho-
mogenized (in an apparatus similar to that used for homogenizing
92 / CHAPTER SEVEN

milk), reducing the average droplet diameter to 0.5–1 µm. This emul-
sion is packaged and shipped to the bottler.

Stability
Instability in emulsions is evidenced by three phenomena: cream-
ing, flocculation, and coalescence. Beverage emulsion concentrates
may exhibit all three, but in the finished, bottled beverage, only the
first is likely to be noticed by the consumer after the drink has been
stored for a period of time.

CREAMING
Creaming occurs when the dispersed phase of an emulsion is
lighter than the continuous phase and the dispersion remains quies-
cent for a period of time. The collected, oil-rich cream layer is usually
easily redispersed by gentle agitation of the total container contents.
In soft drinks, creaming is often referred to as “ringing,” because the
flavor oil droplets collect around the neck of the bottle in a creamy
ring.
The rate at which the particles rise is determined by Stokes’s law:
v = 2gr2(ρ1 – ρ2)/9η
in which v is the rate of creaming (or sedimentation, if the droplets
are heavier than water), g is the gravitational constant, r is droplet ra-
dius, ρ1 and ρ2 are the densities of the oil and water phases, respec-
tively, and η is the viscosity of the water phase. The water viscosity
can be considered essentially constant, although it is slightly higher
for a 10–12% sugar solution than for a diet drink in which a nonnu-
tritive sweetener is used. Likewise, g is a constant factor. Thus, phase
densities and droplet radius are the manipulable parameters.
The densities of 10 and 12% sugar solutions are 1.04 and 1.048
g/cm3, respectively. The only notable difference is in a diet drink,
where the density is about 1 g/cm3. As mentioned earlier, citrus oils
have a typical density of 0.85 g/cm3. This density is increased by the
addition of weighting agents, but the amount of these agents that
can be used is regulated. Using the maximum level of weighting
agent allowed by law raises the oil density to about 0.95–0.98, which
means that the droplets still rise in the beverage. Another factor,
however, is that the stabilizer (gum arabic or modified starch) is heav-
ier than water. Thus, the interfacial film of the stabilizer used also in-
creases droplet density. Because the exact film thickness is not gener-
ally known and because the ratio of oil to polysaccharide varies with
droplet size (oil volume varies as the cube of the radius, while surface
area varies as the square of the radius), a precise value for overall
droplet density cannot be calculated. This is one reason that a gum
stabilizer is preferable to a small-molecule emulsifier (such as a
polysorbate).
 BEVERAGES \ 93

Droplet radius is reduced as much as possible by the homogeniza-

tion step. In studies in which some ringing was observed, compar-
isons of the particle size of the collected material with that of the
droplets still in the main body of the drink showed that the majority
of the creamed particles were 1–8 µm in diameter, while the sus-
pended particles were nearly all less than 1 µm in diameter. A cream-
ing velocity of 1 µm/24 hr is usually offset by Brownian motion (ran-
dom thermal convection) in the drink, and no ringing is seen. In a
practical sense and given ordinary values for oil droplet density, this
means that droplets with a radius of less than about 0.5 µm will not
produce a visible ring in the bottle neck.

FLOCCULATION
In a concentrated emulsion, where the dispersed phase may con-
stitute 20–35% of the total volume, the droplets make contact. The
hydrophilic layers interact loosely through van der Waal’s and ionic
forces, and a loose, low-density floc is formed. These aggregates, or
clumps, act like large droplets and tend to rise more rapidly than in-
dividual drops. The sizes of individual drops remain unchanged;
there is no coalescence of two drops into one. Flocculated emulsions,
like creamed ones, are fairly readily redispersed by simple agitation,
although flocculated emulsions may require a bit more vigor to ac-
complish this. The only practical concern caused by flocculation oc-
curs at the bottling plant. The workers must be sure that each pack-
age (drum or carboy) of concentrated emulsion is thoroughly mixed
before the emulsion is introduced into the bottling line; otherwise,
the flavor level may be inconsistent in the bottles or cans of drink.

COALESCENCE
Gum (or modified starch) emulsion stabilizers form a film around
the oil droplets. Such films develop a definite viscoelastic nature after
a few days and can be observed macroscopically. A drop of oil is ex-
truded into a gum solution and allowed to age for several hours.
Some of the oil is then withdrawn with a syringe and a needle, and a
crumpled envelope is seen. The phenomenon is much like that
shown by α-tending emulsifiers, discussed in Chapter 3. Because of
this interfacial film, true coalescence of oil droplets is seldom seen in
flavor emulsions.

Microemulsions
The conditions necessary for spontaneous emulsification (i.e., the
formation of microemulsions) are discussed in Chapter 1. Such emul-
sions would seem to be natural choices for the citrus-flavored bever-
ages in which transparency is desired. A great deal of research has
been done in this area, mainly in the laboratories of companies in-
94 / CHAPTER SEVEN

terested in producing such beverages, but little or nothing has yet ap-
peared in the marketplace.
The main problem is to find two food-grade cosurfactants that pro-
duce the required low interfacial tension. Some that have been ex-
plored include acetyl monoglyceride and polyglycerol esters, but the
usual cosurfactant has been something like a medium-chain-length
alcohol (e.g., hexanol), which is not allowed in foods. Further funda-
mental work is likely to reveal a combination of surfactants that will
produce acceptable food microemulsions, but none are commonly
known at this time.

Troubleshooting
Emulsifiers are not used in beverage flavor emulsions because of the bitter flavors often noted.
Emulsion stabilization depends primarily on gums.

Symptom Causes Changes to Make

“Ringing” Large emulsion drops Increase amount of gum.
Improve homogenization methods.
Low density of oil drops Increase the amount of weighting agent (insofar as
legally possible).
Increase amount of gum.
Glossary
Acetal linkages—Bonds between sugar residues in poly- Bingham plastic—A suspension that does not flow when
mers, linking the carbonyl group of one residue to a hy- subjected to a shear stress lower than the yield value but
droxyl group on the other sugar. does flow at any shear stress above the yield value.

Acetone insolubles—Specification of the amount of phos- Birefringence—Ability of crystalline materials to rotate po-
pholipids in “gums,” based on the fact that the other con- larized light.
stituents normally present are soluble in acetone.
Bloom—A dusty, whitish appearance of the surface of
Acid value—Weight in milligrams of potassium hydroxide chocolate coatings, caused by transformation of the fat
required to neutralize the titratable groups in 1 g of lipid. It crystals.
characterizes a lipid by quantifying the proportion of titrat-
able acidic groups. Body—A qualitative measurement determined in sensory
tests as the ability to “fill the mouth” with the characteristic
Agglomerate—To remain in close proximity but, because being measured.
of any of a variety of forces, not coalesce; e.g., individual
particles in a suspension. Brominated vegetable oil—Oil made by treating an unsat-
urated vegetable oil with molecular bromine. Addition of
a-Monoglyceride—Monoglyceride in which the fatty acid HBr across double bonds gives these oils a high density.
is esterified to the 1 position of glycerol. Esterification at the
2 position results in a b-monoglyceride. Brownian motion—The random, thermal movement of
minute, solute particles observable under a microscope and
a-Tending emulsifier—Emulsifier that forms a solid film at caused by collision of solvent molecules with the particles.
the oil-water interface under proper conditions of tempera-
ture (low) and concentration (high). Casein—The main protein component of milk, accounting
for about 80% of the total proteins.
Amorphous—Pertaining to the random arrangement of
atoms or molecules with no discernible long-range order. Centipoise—An older unit of viscosity (1 centipoise = 1
mPa·sec [SI unit], the approximate viscosity of water at
Amphiphilic—“Both loving.” Pertains to molecules that room temperature).
possess both lipophilic (“fat-loving”) and hydrophilic
(“water-loving”) regions. Chorleywood bread process—A rapid bread-making
process, developed at the Chorleywood Laboratories in
Amylograph—An instrument used to study starch gela- England, in which dough is mixed in a high-intensity mixer
tinization. A slurry is heated from room temperature to 95°C for a short period of time.
at a set rate, held for a period of time, and then cooled at a
set rate. The viscosity of the slurry is recorded as a function Coalesce—To combine; usually refers to two liquid (e.g.,
of time (hence, of temperature). oil) drops combining into one drop.

Amylopectin—Branched polyglucose chains in starch. Colloid mill—Machine used to decrease the size of sus-
pended particles or droplets.
Amylose—Linear polyglucose chains in starch.
Complexation—Combination of two different molecular
species.

95
96 / GLOSSARY

Continuous phase—The undispersed phase of an emulsion. Diterpenoid carboxylic acids—Tricyclic compounds con-
In an oil-in-water emulsion, water is the continuous phase. taining 20 carbon atoms and with a carboxylic acid function
attached.
Critical micelle concentration (CMC)—Concentration of a
surfactant in aqueous solution at which colligative properties Dough strengthener—Material added to bread dough to
cease to change with increase in concentration. increase the ability of the gluten to retain gas during proof-
ing and baking.
Crosslinked starch—Starch in which hydroxyl groups on
adjacent chains are joined by a covalent linkage. Egg albumin—Soluble protein found in egg white.

Crude gum—Material removed during the degumming Elastic modulus—Relationship between stress (force) ap-
phase of vegetable oil refining. Water is added to the crude plied to a sample and the strain (deformation) in the sam-
oil, and the polar components (such as phospholipids) be- ple; a more general rheological term than crumb modulus.
come hydrated and associated with the aqueous phase,
which is then separated by centrifugation. Electrical potential—The magnitude of electrical charge
difference between two points.
Crumb modulus—Synonym for elastic modulus.
Emulsifiers—Molecules that promote and/or stabilize emul-
Crystal inhibitors—Small molecules that interfere with the sification, i.e., dispersion of one liquid in another (nonmisci-
deposition of dissolved molecules on the growing face of a ble) liquid.
crystal, thus inhibiting growth of the crystal.
Essential oils—Aromatic and flavorous oils obtained from
Crystalline—Pertaining to a state in which atoms or mole- various plant sources and originally known as “essences,”
cules are arranged in an ordered three-dimensional array. mainly in the perfume industry.
Long-range order is discerned by X-ray analysis.
Ester gum—Gum made by esterifying the acids of purified
Crystallites—Small regions of crystalline starch within a wood resin with glycerol.
granule.
Fat mimetic—Fat substitute that mimics the properties of
Cubic mesophase—Mesophase in which spheres of water fat.
are found in a cubical arrangement in a matrix of the
surfactant. Feathering—Streaks of fat and precipitated protein that
form in a liquid such as coffee when improperly stabilized
Damar gum—A shrub exudate consisting mainly of triter- whitener is added; caused by breakdown of the emulsion.
penes (containing 30 carbon atoms) but with numerous
other related compounds also present. Flavor notes—Small molecules, usually volatile hydrocar-
bons, that interact with taste receptors and are experienced
Differential scanning calorimetry (DSC)—A method for as flavors.
measuring energy uptake as a sample is heated. When a
phase change occurs (e.g., melting or freezing), the plot Flocculation—Collection of the internal phase of an emul-
shows the temperature at which the change occurred and sion or suspension; clumping. Flocculated materials are gen-
the amount of heat energy involved. erally somewhat difficult to redisperse, unlike droplets in a
creamed emulsion, which are easily dispersed by simple
Differential thermal analysis—Method for measuring mixing.
energy uptake as a sample is heated; similar to differential
scanning calorimetry. Fluorescent probes—Small molecules that fluoresce in a
nonpolar medium but not in a polar medium such as water.
Diglyceride—Lipid with two fatty acids esterified to a glyc- When these probes are mixed with proteins, for example,
erol molecule. the appearance of fluorescence implies that a probe has
bound to a hydrophobic region of the protein.
Discontinuous phase—The dispersed (internal) phase in an
emulsion. In an oil-in-water emulsion, oil is the discontinu- Free energy—The thermodynamic energy of a closed sys-
ous phase. tem. Absolute free energy is not easily measured, but the
change in free energy when the system is changed (e.g.,
when oil is dispersed in water) is more easily established.
 GLOSSARY \ 97

Freeze-thaw stability—The ability of a product to be Iodine value—A measurement of the number of double
frozen, thawed, and refrozen several times without notice- bonds in a fat or oil. A higher value means more double
able changes in physical characteristics. bonds.

Gelatinization—Collapse (disruption) of molecular orders Ionic strength—Measure of the ionic character of an aque-
within the starch granule manifested by irreversible changes ous solution of salts. Ionic strength plays a role in numerous
in properties such as granular swelling, native crystalline physical phenomena such as conductance of electrical cur-
melting, loss of birefringence, and starch solubilization. rent, folding of protein molecules, and degree of repulsion
of charged surfaces in water.
Gelatinization temperature—A narrow temperature
range at which starch granules begin to swell, lose crys- Isosorbide—Bicyclic structure formed from sorbitol, involv-
tallinity, and viscosify the cooking medium. Starches from ing an ether linkage between hydroxyls at the 1 and 4 posi-
different sources have different characteristic gelatinization tions and hydroxyls at the 3 and 6 positions.
temperatures.
Lamellar mesophase—Mesophase characterized by bilayer
Glucopyranoside—Glucose in its usual molecular form of a leaflets of surfactant separated by layers of water.
six-membered ring.
Lipophilic—“Lipid loving.” Pertains to the nonpolar parts of
Glycolipid—Diglyceride connected to a sugar moiety (usu- molecules that dissolve readily in a nonpolar medium such
ally galactose or galactosyl-galactose) at the 3 position and as vegetable oil. Generally synonymous with “hydrophobic.”
common in cereal and legume seeds.
Lipoprotein—A complex of a protein with a lipid (generally
Gum—Polysaccharide that markedly increases viscosity a phospholipid) found in many plants. The most common in
when dissolved or dispersed in water. food processing is from egg yolk.

Helix—Three-dimensional arrangement of many biological Liposome—Hollow sphere formed by bilayers of surfactant,

polymers, including starch. It is analogous to a coil spring. suspended in a water matrix, and containing water in the
center.
Hexagonal II mesophase—Mesophase in which cylinders
of water are arranged hexagonally in a matrix of the surfac- Margarine—A substitute for butter, originally formulated to
tant. When cylinders of surfactant are present with water as mimic butter as closely as possible, but using other fat
the matrix, it is called a hexagonal I mesophase. sources in place of milk fat.

Hexose—Sugar containing six carbon atoms. Mesophase—Opalescent or transparent liquid formed by a

mixture of surfactant and water.
Hydrophilic—“Water loving.” Pertains to the (polar) parts
of molecules that readily dissolve or disperse in a polar Metastable—Pertaining to a physical state that is not at the
medium such as water. lowest possible free energy for the system. The activation
energy for transition to the more stable state is high enough
Hydrophilic/lipophilic balance (HLB)—Ratio of an emulsi- that the system remains in the current state for a significant
fier’s hydrophilic and lipophilic tendencies. length of time.

Hydrophobic patches—Areas on the surface of a protein Microemulsions—Emulsions in which the diameters of the
molecule, in contact with surrounding water, that are droplets in the dispersed phase are much smaller than the
lipophilic in nature. wavelength of visible light. The droplets do not scatter light;
hence, the emulsion appears transparent.
Hydrophobic—“Water hating.” Pertains to the (nonpolar)
parts of molecules that do not readily enter a polar medium Milk fat—The natural fat found in milk consisting of a mix-
such as water. ture of glycerides.

Interfaces—Boundaries between two phases. Various types Monoglyceride—Lipid with one fatty acid esterified to a
of interfaces occur in foods: solid-liquid, gas-liquid, gas- glycerol molecule.
solid, and liquid-liquid (two immiscible liquids).
Monoterpenes—Aliphatic compounds, containing 10 car-
Interfacial viscosity—Resistance to flow in the two dimen- bon atoms, formed biologically by combination of two mol-
sions of the interface.
98 / GLOSSARY

ecules of isoprene (2-methyl butadiene), with subsequent Saponification value—Weight in milligrams of the potas-
modification to give the various members of this group. sium hydroxide required to saponify 1 g of a lipid. It charac-
terizes a lipid by quantifying the proportion of ester groups
Oligosaccharide—Short polymer of sugar having three to relative to the total molecular weight.
eight sugar units.
Secondary hydroxyl—Hydroxyl group on a carbon atom
Ovenspring—Increase in the volume of a loaf of bread dur- that is attached to two other carbons.
ing baking; i.e., the final loaf volume minus the volume of
the dough at the end of the proof. Sesquiterpenes—Similar to monoterpenes but containing
15 carbon atoms; formed by reaction of three isoprene
Overrun—Increase in volume of a whipped material result- units.
ing from the incorporation of air.
Shear thinning—Decrease in the viscosity of a suspension
Pentose—Sugar containing five carbon atoms. as shear rate increases.

Phase diagram—A method of showing which mesophase Solid fat content—A measure of the amount of solid fat in
structures are present at various water concentrations and a fat at various temperatures, determined by nuclear mag-
temperatures. netic resonance.

Phase inversion—Conversion of the continuous phase of Sorbitan—Cyclic structure formed by linking the hydroxyls
an emulsion to the discontinuous phase and vice versa. at the 1 and 4 positions of sorbitol through an ether linkage.

Phospholipid—Diglyceride esterified at the 3 position to Sorbitol—Sugar alcohol produced by reduction of glucose,

phosphoric acid, which in turn is often esterified to another consisting of a chain of six carbons with a hydroxyl group
group. on each carbon.

Photon—Basic unit of light waves. Specific volume—In baking research, the weight of the
cooled loaf divided by its volume.
Plant exudate—Droplets of hardened gum exuded by a
plant to seal a break in the bark. Stabilized starch—Starch in which hydroxyl groups form
ester or ether bonds with other small molecules.
Plateau’s border—The point at which three or four gas
cells nearly touch in a foam. Staling—Phenomenon that occurs in baked products dur-
ing storage. Stale product has a firmer crumb structure than
Polymorphic behavior—Ability of a material to crystallize fresh product; the crumb has a dry, harsh texture; and the
in more than one three-dimensional arrangement. flavor impact is significantly reduced.

Polypeptide—A polymer consisting of amino acids con- Starch granules—Naturally occurring, partially crystalline,
nected by an amide bond, involving the carboxylic acid and discrete aggregates of amylose and amylopectin.
a amino groups.
Sucrose acetate isobutyrate—The octaester of sucrose
Polysaccharide—A carbohydrate containing several hun- with acetic and isobutyric acids.
dred, thousand, or hundred thousand sugar units (from the
Greek poly, meaning “many”). Supercooled—Pertaining to a solution that is cooled below
the temperature at which crystals would ordinarily begin to
Primary hydroxyl—Hydroxyl group on the terminal carbon form but do not because of the absence of nucleation or the
atom of a compound. That carbon atom is connected to presence of crystal inhibitors.
only one other carbon.
Surface excess—The concentration of a surfactant in the
Response surface methodology—Method of experimental interfacial region compared with its concentration in the
design to determine the optimum values for two or more bulk phase in which it is dissolved.
variables in a product by using a limited number of experi-
ments and making interpolations based on the experimental Surface tension—The component of total free energy in a
data. closed system caused by the presence of an interface.

Retrogradation—Recrystallization of gelatinized starch. Syneresis—Separation of a liquid from a gel; weeping.

 GLOSSARY \ 99

Synergistic—Pertaining to a combination of two materials Visible light—Light visible to the human eye. The wave-
that displays more functionality than would be expected length of visible light is approximately 400–700 nm.
by simply summing the individual functionalities of the
materials. Volume fraction—The fraction of total volume of a system
represented by one of the discrete phases.
Thermodynamic activity—A factor accounting for the fact
that the concentration-dependent properties of dissolved Waxy maize starch—Starch from genetically modified
molecules often deviate from a strictly linear dependence. corn; contains almost no amylose.
For surfactants below the critical micelle concentration, this
deviation is usually negligible. Weighting agent—An oil-soluble material that has a den-
sity greater than that of water.
Triglyceride—Lipid with three fatty acids esterified to a
glycerol molecule. Wetting agents—Agents that promote spreading of a liq-
uid on a solid surface.
Unit cell—The smallest ordered unit of a crystal. It may
contain only a few atoms (e.g., sodium chloride) or several Whey—The liquid left after casein has been precipitated
molecules (e.g., a fat unit crystal). from milk. In addition to protein, it contains lactose (milk
sugar) and ash (inorganic salts).
Uronic acids—Derivatives of a sugar, in which the terminal
-CH2OH group is oxidized to a carboxylic acid. D-Glucuronic Winterize—To cool salad oil until high-melting-point
acid is derived from D-glucose, D-mannuronic acid from triglycerides form crystals. These crystals are removed so
D-mannose, and D-galacturonic acid from D-galactose. that the next time the oil is cooled, the cloudiness that
results from crystallization will not occur.
van der Waal’s forces—Short-range attractive forces be-
tween molecules resulting from the dipole moment of X rays—A region of light waves with short wave length and
atoms in the molecules. high-energy photons.

Viscous isotropic phase—Another name for the cubic

mesophase when the amount of water is sufficient to signifi-
cantly raise the viscosity above that of the melted surfactant
alone.
Index
Abietic acid, 90 in ice cream, 74 Foams
Acetone insolubles content, 35 in salad dressings, 81 drainage, 11–12
Acetylated monoglyceride (AcMG), 28, Crystal structures, of mono-, di-, formation, 8–9
29, 62 and triglycerides, 15–17 nondairy whipped toppings, 72–73
Aeration agents, 61–63 Cubic mesophase, 19, 20, 21 whipped cream, 71–72
-Tending emulsifiers stabilization, 39, 43
crystal form, 17 Damar gum, 90 Free energy. See Surface free energy and
interfacial film formed by, 11 Decaglycerol dioleate, 38 Interfacial tension
structures, 28 Decaglycerol hexaoleate, 38
uses Decaglycerol monooleate, 38 Glycerol monolaurate, 38
aeration, 62 Decaglycerol monostearate, 38 Glycerol monostearate (GMS)
cake production, 29 Diacetyl tartrate ester of antistaling effects, 60, 61
nondairy whipped toppings, 73 monoglyceride (DATEM), 27, 28 composition, 25, 26
Amylopectin, 48, 51, 57 antistaling effects of, 60, 61 crystallization, 16
Amylose, 48, 49, 51, 56, 57 as a dough strengthener, 59, 60 effects of, on starch gelatinization,
Anionic emulsifiers, 33–34 effects of, on starch gelatinization, 50 50, 51
Antistaling agents Diacetyltartrate esters, 20 hydrophilic/lipophilic balance, 38
in bread, 55–56 Differential scanning calorimeter, 49 interfacial tension, 4
effects of, on starch Diglycerides, crystal structure of, 16 lamellar mesophase formation, 19, 20
complexation, 56–58 Dough strengtheners, 58–61 phase diagram, 22
gelatinization, 48–51 structures, 27–29 uses
retrogradation, 51–55 uses, 33–34 coffee whiteners, 74
monoglycerides, 20, 23, 26 Drop weight, 5 dough strengthener, 60
Avrami equation, 52–53 Gums
Eggs, 82, 83 in beverages, 90, 91
Bingham plastic, 81, 82, 83 Electrical potential, 8, 9 in dressings and sauces, 77–79, 81
Bloom, 18 Emulsions in reduced-fat products, 85
Bread staling, 51–56 in beverages, 91–92
Brownian motion, 12 flavor emulsions, 89–91 Hexaglycerol dioleate, 38
Butter, 68–70 formation, 6–9 Hexagonal II mesophase, 21
microemulsions, 14, 93–94 Hydrogen bonding, 16, 17
Cake batters, 61–63 spontaneous emulsions, 14, 93 Hydrophilic/lipophilic balance (HLB),
Calcium stearoyl lactylate, 60 stabilization, 9–11, 91, 92–93 30, 36–39
Capillary rise method, 5 Essential oils, 89 of gum arabic, 91
Cellulose, 80, 81 Ester gum, 90 of lecithin, 36
Cetyltrimethylammonium bromide Ethoxylated monoglyceride (EMG) of polyglycerol esters, 32
(CTAB), 2 as a dough strengthener, 60 of sucrose esters, 33
Clouding 17, 84 hydrophilic/lipophilic balance, 38
Coalescence, 7, 93 structure, 27, 28, 30 Ice cream, 73–74
Coffee whiteners, 74–75 Interfacial tension, 3–4, 7
Colloid mill, 83, 84 Fat Interfacial viscosity, 43
Cookies, 63 effects of, on flavor, 86 Ionic stabilization, 10
Creaming, 10, 92–93 mimetics, 85 Ionic strength, 2
Critical micelle concentration, 4, Flavor emulsions, 89–91
18–19, 42 Flavor notes, 86 Lactic acid, 29, 33
Crude gum, 34 Flocculation, 9, 11, 93 Lactylated monoglyceride (LacMG)
Crystal inhibitors (modifiers), 17–18 Fluid isotropic mesophase, 20 and aeration, 62

101
102 / INDEX

structure, 28 nondairy whipped toppings, 73 Specific volume, 54

in whipped cream, 72 salad dressings, 81 Spontaneous emulsification, 14, 93
Lamellar mesophase, 19–20, 21 Polysorbate 65, 30, 31 Starch, 91
Lauryl sulfate, 2 hydrophilic/lipophilic balance, 38 complexation with emulsifiers, 56–58
Laurylsulfonic acid, 4 uses gelatinization, 48–51
Lecithin, 2, 34–36 coffee whiteners, 74 modification, 79–80
lamellar dispersion, 21 whipped cream, 72 retrogradation, 51–55
as a wetting agent, 13 Polysorbate 80, 30 waxy maize starch, 82
Lipoproteins, 40 hydrophilic/lipophilic balance, 38 Stearic acid
in mayonnaise, 84 uses in production of food emulsifiers,
in salad dressings, 82 ice cream, 74 25, 29, 30, 33
Liposomes, 21 whipped cream, 72 structure, 2
Potassium oleate, 38 Stearoyl lactylic acid, 62, 63
Margarine, 70–71 Propylene glycol monoester (PGME) Steric hindrance, 10–11, 12
crystal inhibitors in, 17–18 production, 29 Succinate esters, 20
Mayonnaise, 83–84 structure, 28 Succinyl monoglyceride (SMG)
Mesophases, 18–21 use, 62 as a dough strengthener, 60
phase diagrams, 21–22 Propylene glycol monolaurate, 38 structure, 27, 28
Micellization, 18–19, 41 Propylene glycol monostearate, 11, 38, Sucrose acetate isobutyrate, 90
Microemulsions, 14, 93–94 73. See also Propylene glycol Sucrose esters, 32–33
Milk, 67–68 monoester and aeration, 62, 63
Monoglycerides, 2, 25–27 Proteins as crystal inhibitors, 17
crystal structure, 15–16 as emulsifying agents, 39–43 Sucrose monoester, 38
derivatives, 27–30 as foaming agents, 39 Sucrose triester, 38
hexagonal II mesophase formation, 21 in milk, 67–68 Surface excess, 4–5
phase diagrams, 22 Surface free energy, 3–4
polymorphic behavior, 16–17 Reduced-fat dressings and sauces, 85–86 Surface tension
uses Regulations, 43–44 in foams, 43
aeration, 61 Ring tensiometer, 5–6 measurement, 5–6
antistaling effects, 20, 23, 26
ice cream, 74 Salad dressings, 80–83 Temperature, effects of
shortenings and margarines, 18 Shear, effects of, 6, 7, 72, 80 on emulsifier film formation, 62
Monostearin. See Glycerol monostearate Shortening, 17–18 on starch gelatinization, 49, 50, 51
Sodium chloride, 9, 10 on starch retrogradation, 54
Nondairy whipped toppings, 72–73 Sodium dodecyl sulfate (SDS), 33, 34, on mesophase structure, 21–22
41, 60 Thermodynamic activity, 4, 5
Oriented wedge theory, 8 Sodium lauryl sulfate (SLS), 33, 34 Triglycerides
Oxystearin, 17, 81 hydrophilic/lipophilic balance, 38 crystal structure, 15–16
uses crystallization, 17
Pendant drop, 5 wetting agent, 13 Triglycerol monostearate, 18, 38
pH, effects of, 38 whipping aid, 63
on gluten protein, 58, 59 Sodium oleate, 38 van der Waal’s forces, 8, 10, 20
on viscosity, 79, 80 Sodium stearate, 7, 8 Viscosity
Phase diagrams, 21–22 Sodium stearoyl lactylate (SSL), 33, 34 and emulsion stability, 12
Phase inversion, 68, 69 effects of, on viscosity, 50, 51 and gums, 77, 78
Phosphatidylcholine (PC), 35, 36 hexagonal II mesophase formation, 21 Viscous isotropic phase, 20
Phosphatidylethanolamine (PE), 35, 36 hydrophilic/lipophilic balance, 38 Volume fraction, 11
Phosphatidylinositol (PI), 35, 36 uses
Plateau’s border, 12 dough strengthener, 23, 58, 59, 60 Water, effect of, on mesophase
Polyglycerol esters, 17, 31–32, 81 coffee whiteners, 75 structure, 21–22
Polyglycerol monostearate, 32 Sodium stearyl fumarate, 33, 34 Weighting agents, 89, 92
Polyoxyethylene sorbitan esters, 17 Solid fat content, 69 Wetting agents, 13
Polysaccharides, 77–80 Sorbitan monostearate, 30 Whipped cream, 71–72
Polysorbates, 21, 23 as a crystal inhibitor, 17, 18 Wilhelmy balance, 6
Polysorbate 60, 30, 31 hydrophilic/lipophilic balance, 38 Winterization, 17, 81
hydrophilic/lipophilic balance, 38 production, 25
uses Sorbitan tristearate, 30 Yield value, 82, 83
aeration, 62, 72 as a crystal stabilizer, 18
Zinc distearate, 7, 8
dough strengthener, 60 hydrophilic/lipophilic balance, 38
Zinc sulfate,