Formulation of Emulsions: Marie Wahlgren, Björn Bergenståhl, Lars Nilsson, and Marilyn Rayner

3 Formulation of Emulsions
Marie Wahlgren, Björn Bergenståhl,

Lars Nilsson, and Marilyn Rayner
Contents
3.1 Introduction .................................................................................................... 52
3.2 Functionality that Ingredients should give to Emulsions ............................... 52
3.2.1 Nutrition and Health ........................................................................... 52
3.2.2 Texture and Flavor .............................................................................. 53
3.2.3 Shelf-Life Stability ............................................................................. 54
3.2.3.1 Emulsion Stability................................................................ 54
3.2.3.2 Chemical Stability ............................................................... 56
3.2.3.3 Microbiological Stability ..................................................... 57
3.2.3.4 Freeze-Thaw Stability .......................................................... 58
3.3 Issues to Consider when choosing Ingredients for Emulsions........................ 59
3.4 Key Ingredients in Emulsions......................................................................... 62
3.4.1 Fats and Oils ....................................................................................... 62
3.4.2 Low Molar Mass Emulsifiers.............................................................. 63
3.4.3 Proteins ............................................................................................... 67
3.4.4 Polysaccharides................................................................................... 72
3.4.5 Protein-Polysaccharide Complexes .................................................... 75
3.4.6 Particles .............................................................................................. 76
3.5 Evaluation of Emulsion Formulation and Ingredient Performance ................ 78
3.5.1 Emulsification Capacity ...................................................................... 81
3.5.2 Emulsion Stability Index .................................................................... 83
3.5.3 Assessing Gravitational Separation—Creaming Index......................84
3.5.4 Accelerated and Environmental Stress Tests ...................................... 87
3.5.5 Evaluation of Texture .......................................................................... 89
References ................................................................................................................92
ABSTRACT In this chapter, we describe some of the main concerns when it

comes to formulating emulsions. This includes the choice of ingredients, such as
emulsifiers, oils, preservatives, and thickener. This is done with a focus on how these
ingredients can give the desired properties of the emulsions, such as texture, fla-
vor, nutrition, and stability. Commonly encountered thickeners and emulsifiers are
described, and the methods to characterize the key properties of emulsion and ingre-
dient are discussed.
51
K16909_C003.indd 51 12/31/14 4:14 PM

52 Engineering Aspects of Food Emulsification and Homogenization
3.1 IntroduCtIon
Almost all industrially processed emulsion-based food products are made up of a
wide variety of constituents, including fats and oils, emulsifiers, texture modifiers,
preservatives, antimicrobial agents, antioxidants, pH adjusters, sweeteners, salts,
coloring agents, flavors, and, of course, water. Each of these has been included in the
food product due to its intrinsic function or a combination of functions with other
compounds in the formulation. They are there to provide the overall quality of food
products such as nutritional value, flavor, texture, and shelf life. In this chapter, we
will discuss how the ingredients deliver these quality attributes to emulsion, and
we will also give a more general description of some of the key ingredients in emul-
sions, primarily oils, emulsifiers, and texture modifiers.
Food ingredients can be described on several levels:
1. Molecular (e.g., H2O, glucose, kappa casein, etc.)

2. Nutritional (e.g., proteins, lipids, carbohydrates, minerals, etc.)
3. Composite ingredients or recipe (e.g., milk, eggs, flour, salt, etc.)
4. Functional ingredients (e.g., emulsifiers, thickeners, preservatives, etc.)
Food manufacturers, product developers, and formulators are generally concerned

with the mass fraction of composite ingredients and functional ingredients because
they are normally purchased and used in this form.
3.2 FunCtIonalIty that IngredIents

should gIve to emulsIons
3.2.1 NutritioN aNd HealtH
A key function of any food emulsion is certainly its nutritional value. As emulsions
contain both lipophilic and hydrophilic regions, they have the capability to include
both water-soluble and oil-soluble components of high nutritional value. Emulsions
can increase the bioavailability of lipophilic nutrients such as vitamin E (Mayer,
Weiss, and McClements 2013, Yang and McClements 2013) or other beneficial com-
ponents, such as curcumin, that have low solubility in water (Ting et al. 2014). One of
the main nutritional concerns when it comes to emulsions is the composition of the oil
phase. Health benefits can be obtained, for example, by formulating products contain-
AQ 1 ing omega-3 oils (Berasategi et al. 2014, Moore et al. 2012). Another important health
aspect of food emulsions is the development of low-calorie products. In this case, one
often tries to manufacture products with low oil content, such as low-fat spreads, that
still has a texture similar to the original high-fat product (Chronakis 1997, Kasapis
2000). The aim is to formulate a product with low oil content that still has compa-
rable texture, flavor, mouthfeel, and visual aspects as its traditional high-fat product.
However, as the volume fraction of oil phase often is important for emulsion struc-
ture, this poses specific problems that need to be addressed; for example, the addition
AQ 2 of texturizing macromolecules (polysaccharides and proteins) will compensate the
lower oil fraction in maintaining the microstructure in low-calorie products.
K16909_C003.indd 52 12/31/14 4:14 PM

Formulation of Emulsions 53
The effectiveness of emulsions as vehicles for the delivery of individual nutritional

compounds is affected by emulsion properties such as the surface area of the oil
droplets and the availability of the oil interface for digestive enzymes. Furthermore,
in the in vivo situation, the properties of the emulsion will also affect the gastric
emptying of the stomach, where emulsions prone to phase separation in the stomach
show a more rapid empting than emulsions that are stable (Golding and Wooster
2010). The structure of the fat used for the emulsion will also affect digestion; for
example, solid fat is digested more slowly than liquid fat (Michalski 2009).
3.2.2 texture aNd Flavor

In this section, a short overview of the area is given, and for a more thorough read-
ing, we recommend some recent reviews on the topic (Chung and McClements 2013,
Stokes, Boehm, and Baier 2013). The texture of emulsions is strongly dependent
on its rheological properties. Rheology of the emulsion is in turn dependent on the
volume fraction of the dispersed phase, the degree of flocculation of the dispersed
phase, and rheological properties of the continuous phase. In most cases, especially
if the drops are small, the rheological properties of the dispersed phase are less
important. Another factor that influences the mouthfeel and taste is how the emul-
sion may aggregate and coalesce in the mouth due to mixing with saliva, interactions
with the mucosa, the change in temperature, and the mechanical treatment while
eating (Benjamins et al. 2009).
In oil-in-water (O/W) emulsions, the rheological properties of the continuous
phase are often modified by the addition of polymers. As the degree of flocculation
of the oil droplets may also influence rheology, factors that affect flocculation such
as the type of emulsifier, pH, and salt should also be considered. The physical prop-
erties of dispersed oil phase could affect the rheology by the formation of crystal-
line bridges between different oil droplets leading to semicoalesced drops (Fredrick,
Walstra, and Dewettinck 2010). Thus, the melting temperature of the oil phase may
affect the texture. The fraction of oil also influences mouthfeel, where high-fat O/W
emulsions are usually perceived to have high creaminess, to be smooth and rich in
flavor (Chung and McClements 2013). The critical level of fat content to achieve the
mouthfeel related to fattiness seems to be around 15% (Malone, Appelqvist, and
Norton 2003). In low-fat products, increasing the viscosity in the continuous phase
can to some degree compensate the low-fat content and give products that have simi-
lar flavor and mouthfeel as high-fat products. However, the key parameter may not
be the rheology as a bulk property but more on the rheology of the film formed in the
mouth cavity upon eating the food product (Malone, Appelqvist, and Norton 2003).
In the case of water-in-oil (W/O) emulsions, such as spreads, the state of the fats
are important not only for mouthfeel but also for spreadability. The ratio between
liquid and solid fat will thus affect the rheology. Also, for these types of products,
the type of polymorphic form of the lipid crystals will influence the property of the
product, as a transition from β′ crystals (preferred in margarine-type products) to
β crystals is associated with larger crystals (greater than20 µm), giving a gritty or
sandy mouthfeel, low spreadability, and oil–fat separation (Heertje 2014, Sato and
Ueno 2011). Mouthfeel of emulsions can also be altered by the presence of particles
K16909_C003.indd 53 12/31/14 4:14 PM

or fat crystals. Large particles will give a sandy mouthfeel usually described as
tallowness (Watanabe et al. 1992).
When it comes to flavor, the release of flavoring components from the dispersed
phase is important. The release will be affected by how these molecules are trans-
ported out of the dispersed phase and thus by properties such as diffusion coefficient
of the component, droplet size of the dispersed phase, and interaction with other
ingredients in the emulsions (such as the emulsifier). The release will also be influ-
enced by partitioning of the flavoring ingredient into two phases and thus be affected
by the concentration of the dispersed phase. This is especially important for O/W
emulsions, as it is the concentration of aroma in the water phase and the head space
(gas phase above the emulsion) that influences its taste. Low-fat products can show a
burst of flavor due to the quick release of the oil-soluble components whereas high-
fat products often display a more continuous release of components that partition
to the oil phase (Bayarri, Taylor, and Hort 2006). When designing and producing
low-fat products, the release profile of the oil-soluble components may have to be
modulated, for example, by encapsulation.
It has also been seen that in systems that have the same release of aroma com-
ponents into the gas phase, changes in the rheology of the emulsion still can affect
taste. This could be attributed to the difference in the release pattern between volatile
aroma compounds and more water-soluble taste compounds such as sugar (Bayarri
et al. 2006), where the latter is more sensitive to the rheology. When it comes to the
water-soluble components, they will predominately be in the water phase, and thus
O/W emulsions will have a quick influence on the taste. However, if taste masking
is desired, the water-soluble components can sometimes be encapsulated in double
emulsions.
3.2.3 SHelF-liFe Stability

The shelf-life stability of food emulsions is governed by factors that affect both
chemical and microbiological stability, in addition to issues that have to do with the
stability of the emulsion as such. There are also special issues, for instance, the sta-
bility of emulsions in frozen food, which are of technical and industrial importance.
3.2.3.1 emulsion stability

In Chapter 2 Bergenståhl describes factors that lead to the destabilization of emul-
sions in more detail. Destabilization of emulsions is mainly caused by creaming/
AQ 3 sedimentation, coalescence, and Ostwald ripening. For macroscopic emulsions,
creaming/sedimentation occurs due to the density difference between the oil and
water fraction; it can partially be reduced by decreasing the droplet size of the
emulsion, increasing the viscosity of the continuous phase, or by decreasing the dif-
ference in densities between the two phases (see Section 3.5.3). Coalescence leads
to the formation of larger oil droplets, which may eventually lead to a complete
AQ 4 phase separation of the emulsion. This can mainly be controlled by the adsorp-
tion of surface-active compounds to the interface that hinders drop–drop con-
tact through either a steric barrier or an electrostatic repulsion, thus resulting in
K16909_C003.indd 54 12/31/14 4:14 PM

the process of coalescence. Increased viscosity of the continuous phase can also
decrease coalescence (as well as the rate of creaming/sedimentation) to some extent.
Another mechanism that drives the evolution of droplet size is caused by the pres-
sure difference between the inside and outside of a curved surface. This so-called
Laplace pressure is higher for a more curved surface, for example, small droplets;
this is the driving force Ostwald ripening, which leads to an increase in particle
size of the emulsions at the expense of smaller droplets. In this case, the solubility
of the dispersed phase in the continuous phase is of major importance; that is, a low
solubility slows down or prevents Ostwald ripening. Hence, Ostwald ripening is
typically not observed in triglyceride O/W emulsions but, for instance, can occur
for more soluble oils such as aromatic and essential oils. Ostwald ripening can also
be decreased by increasing the viscosity in the continuous phase (decreases diffu-
sion) and systems with low curvature. Pickering emulsions, for example, have been
suggested to decrease Ostwald ripening, as they might have a local zero curvature
(Tcholakova, Denkov, and Lips 2008).
Flocculation is the aggregation of droplets. Flocculated systems may have desired
properties for formulation such as beneficial rheology, but extensive flocculation
might lead to increased creaming and thus may lead to coalescence. Changes in the
degree of flocculation can also affect the rheology of the emulsions, changing prop-
erties such as mouthfeel.
The colloidal stability of the emulsion will be governed by the repulsive/attractive
forces between individual droplets of dispersed phase, the energy and rate of droplet
collisions, the viscoelastic properties of the interface between oil and water, and the
solubility of the dispersed phase in the continuous one. The choice of an emulsifier
could influence all of these, and a proper choice of viscosity modifier will influence
all kinetic factors such as collision of droplets and diffusion of dissolved molecules.
The most important repulsive and attractive forces between emulsions droplets
are summarized as follows:
Hydrophobic effect. This is the main reason for the instability of emulsions.
The hydrophobic interaction is based on the exclusion of nonpolar compo-
nents from water.
van der Waals attraction. These forces exist in all systems. Between small
molecules, van der Walls forces are of short range and the decay with the AQ 5
distance between the molecules as the power of minus six. However, in a
colloidal system, they can be of a much more long range, decaying with the
reciprocal of distance. Together with the electrostatic forces, it is the basis
for the DLVO theory (Verwey and Overbeek 1948). AQ 6
Electrostatic repulsion. This can be an important stabilizing force for food
emulsions. Both proteins and ionic emulsifiers can be charged, depend-
ing on the pH, and when adsorbed, at the droplet interface giving rise
to electrostatic repulsion. Emulsions stabilized by electrostatic repulsions
are sensitive to salt and, in many cases, sensitive to pH. This sensitivity
toward salt is due to the decay in the range of the electrostatic repulsion
caused by the presence of ions and the effect strongly increases with the
K16909_C003.indd 55 12/31/14 4:14 PM

valance of the ions. Thus, it is the ionic strength that is the key issue when
it comes to stability in emulsions based on ionic emulsifiers. One should
be aware that the ionic strength of buffers changes with pH. In some cases,
there could also be specific ion interactions; for example, an interaction
between calcium ions and casein that leads to aggregation (Dickinson and
Davies 1999).
Depletion attraction and steric repulsion. These interactions are caused by the
presence of macromolecules in the continuous phase. Depletion attraction
is due to the fact that macromolecules (proteins, polymers, and colloidal
particles) having no affinity toward the interface will be excluded in the
space between two approaching emulsion drops; this will lead to an osmotic
pressure gradient, which then favors aggregation. Depletion attraction is
typically observed in emulsions containing dissolved neutral polysac-
charides. Thus, the addition of polysaccharides to alter the rheology or to
form complexes with emulsifying agents may lead to depletion aggregation
(Magnusson and Nilsson 2011). Steric repulsion is induced by macromol-
ecules adsorbed at the interface; this is mainly due to the excluded vol-
ume effect, as adsorbed molecules come close together (Israelachvili 1985).
Steric repulsion thus requires not only the affinity of the macromolecule to
the interface but also a high solubility of the macromolecule in the continu-
ous phase. The latter allows parts of the adsorbed macromolecule to pro-
AQ 7 trude into the continuous phase, giving rise to steric hindrance. Nonionic
emulsifiers both low molecular and polymers might stabilize the emulsion
through steric repulsion. These systems are less sensitive to salt and pH
than electrostatic stabilized emulsions.
3.2.3.2 Chemical stability

One key issue for the chemical stability of emulsions is the oxidation of fats;
especially fats with a high degree of unsaturation are susceptible to this problem
(Moore et al. 2012, Waraho, McClements, and Decker 2011). The most common
cause of fat oxidation in O/W emulsions is the interaction between transition met-
als and lipid hydroperoxides located at the oil–water interface, which produces
highly reactive peroxyl and alkoxyl radicals (Frankel 1998, McClements and
Decker 2000).
One way to handle fat oxidation could be to add antioxidants such as vitamin E
or phenolic substances, but a proper choice of ingredients and ingredient quality
can also be of importance. For example, Charoen et al. (2012) showed that different
biopolymers used as emulsifiers for rice oils differed in their capability to protect
AQ 8 the oil from oxidation. They speculate that this could partly be due to the degree
of specific binding of iron to the polymers, but they could not exclude that it was
caused by impurities such as heavy metal ions used in the polymers. This illustrates
that it is important to be aware of the oxidative impurities in the ingredients that are
AQ 9 used; this could be heavy metal ions as well as peroxides. Waraho, McClements,
AQ 10 and Decker (2011) review the oxidation of lipids in emulsions and point out that
there will be a difference in the oxidation process in pure oil when compared with
one in an emulsion. This is because the water phase in the emulsion may include
K16909_C003.indd 56 12/31/14 4:14 PM

oxidative agents such as transition metals and iron and ingredients such as EDTA AQ 11
and iron-binding proteins (e.g., lactoferrin) that may decrease oxidation in emul-
sions (Waraho, McClements, and Decker 2011). Phenolic compounds have been
seen to be pro-oxidatives, especially in the presence of iron (Medina et al. 2012,
Sørensen et al. 2008).
Antioxidants can, as mentioned, be added to the formulation, and the activity of
these antioxidants will depend on their location in the emulsion and solution condi-
tions such as pH. It has been shown that nonpolar antioxidants are more effective
in emulsions as compared to nonpolar oxidants, which are more effective in bulk
oils (Frankel 1998). This is called the polar paradox and is probably related to the
fact that the antioxidant has to be close to the lipids that it should protect. There
is a growing interest to use naturally occurring phenolic compounds such as caf-
feine, coumaric acid, and rutin as antioxidants (Kikuzaki et al. 2002, Medina et al.
2012, Sørensen et al. 2008). These compounds have, however, also been seen to,
at some conditions, be pro-oxidative (Sørensen et al. 2008), again highlighting the AQ 12
importance to know the function of the specific additive at the conditions used for
each food product. Another problem with several phenolic compounds is their low
solubility (Löf, Schillén, and Nilsson 2011) and, in these cases, their existence as
dispersed particles in the continuous phase, which, of course, reduces there antioxi-
dative capacity.
3.2.3.3 microbiological stability

Microbiological stability is especially important for O/W emulsions as they often
have a high water activity. The shelf life from a microbiological viewpoint will be
dependent on packaging, processing (e.g., pasteurization), and the choice of ingredi-
ents. When it comes to ingredients, both their intrinsic microbiological load and their
ability to function as antimicrobiological ingredients are important. Furthermore,
from a formulation viewpoint, ingredients other than preservatives can give bacte-
ricidal effects. For example, components in essential oils are antimicrobial (Burt
2004) and so are some emulsifiers, for example, lysozyme–xanthan gum conjugates
(Hashemi, Aminlari, and Moosavinasab 2014) and monocaprylate (Hyldgaard et al.
2012). Some of the more common food preservatives such as ascorbic acids and its
salts (Lück 1990) are also used in emulsions. Other bactericides are the peptide nisin
(Castro et al. 2009) that is common in several food emulsions such as dairy prod-
ucts and sausages (Abee, Krockel, and Hill 1995). When choosing preservatives, it
is important to understand how the property of the emulsions such as pH and salt
content will affect the preservative. The choice of other ingredients and their concen-
tration might also affect the action of the preservative. Nisin, for example, has been
seen to be strongly affected by the composition of the emulsion such as oil content
and oil/surfactant ratio (Castro et al. 2009). The homogenization as such may also
affect the preservative, especially if it is sensitive to surface adsorption, heat, or shear
(Zapico et al. 1999).
In W/O emulsions, the microbiological growth is reduced due to the limited space
in the water droplets and the inability for the microorganisms to transport them-
selves in between droplets; however, as pointed out by others, W/O emulsions such
as margarine and spreads also need to show how microbiological safety is obtained
K16909_C003.indd 57 12/31/14 4:14 PM

during the shelf life (Charteris 1996, Delamarre and Batt 1999). For these products,
spoilage is often due to moulds and can be reduced by the addition of preservatives
such as sorbates and benzoates (Delamarre and Batt 1999).
3.2.3.4 Freeze-thaw stability

A special case of stability is the freeze-thaw stability of emulsions (Degner et al.
2014). It is often seen that frozen emulsions changes when thawed, for example,
manifested as a full phase separation or that the emulsion becomes grainy and
watery. There are several reasons for these effects; one is that the lipid crystals
can form and lead to partial coalescence of the semifrozen emulsion, which upon
reheating goes forward to full coalescence and phase separation. Crystallization
pattern of the lipids is one of the main factors that will determine if a freeze-stable
emulsion can be obtained. Magnusson, Rosén, and Nilsson (2011) have shown that
for high dispersed volume fraction O/W emulsions, oils contain high amounts
of unsaturated fatty acids, have a high percentage of crystallized triglycerides at
−25°C, and thus have a high rate of susceptibility for freeze-thaw instabilities. The
volume fraction of oil will also affect the freeze-thaw stability; in an unpublished
study, it was shown that the freeze-thaw stability of mayonnaise was increased by
decreasing the oil fraction. This is probably because of the reduced contact time
between oil droplets. Another mechanism that is seen for emulsions with oils that
do not crystallize before ice formation is that coalescence is triggered by increas-
ing the concentration of the dispersed phase when larger and larger volumes of the
water phase are removed due to ice formation. In this case, freeze-thaw instabili-
ties can be decreased by not only the right freezing conditions but also the right
choice of the product composition. The freeze-thaw stability of emulsions can be
increased by the addition of cryprotectants such as polyols (sucrose, glucose, fruc-
tose, trehalose, and maltose), antifreeze proteins, gelatin, and some carbohydrates
(Degner et al. 2014). These alter the crystallization of water and the morphology
of the ice crystals; however, some of them can also function by increasing the vis-
cosity, and thus decreasing the number of oil droplet collisions leading to coales-
cence. Addition of polysaccharides has also been seen to improve the freeze-thaw
stability. This could be due to several factors; however, an increased viscosity of
the nonfrozen phase and the capability of some polysaccharides to form protec-
tive layers around the dispersed phase hindering coalescence play a major role
(Degner et al. 2014). The emulsifier is critical when it comes to destabilization
due to increased concentration, but can also be important for lipid crystallization-
induced freeze-thaw instabilities. Emulsifiers are able to stabilize the emulsion
also at a high concentration, for example, some Pickering emulsions using quinoa
starch granules or egg yolk granules (Marefati et al. 2013, Rayner et al. 2014) pro-
teins such as caseins (Degner et al. 2014) and hydrophobic starch that give a thicker
interfacial coatings around the fat droplets are good in this sense.
In frozen and cold-stored foods, it is especially important to understand how the
emulsifier itself is affected by the decrease in temperature; for example, several low-
molecular emulsifiers lose their solubility below the so-called Kraft point and thus
the function of these emulsifiers will decrease.
K16909_C003.indd 58 12/31/14 4:14 PM

3.3 Issues to ConsIder when ChoosIng

IngredIents For emulsIons
One of the key ingredients to choose for an emulsion formulation is the emulsifier.
The emulsifier lowers the surface energy between the two phases and thus affects the
size of the emulsion droplets. It should also create a barrier for coalescence and drop-
let growth during storage. Emulsions can be stabilized by low-molecular emulsifiers,
proteins and other polymers, and particles. Table 3.1 gives a comparison between
them. As a rule-of-thumb, low-molecular emulsifiers lowers the surface tension more
than surface-active macromolecules, but they adsorb reversibly to the interface; they
often form complexes with other ingredients in products such as proteins, and might
be less good than high-molecular emulsifiers when it comes to reducing coalescence
during storage. When choosing an emulsifier, it is important to consider its compat-
ibility with other ingredients of the product; many components, such as some preser-
vatives, are surface active themselves and might interact with the interface. Another
issue is salt concentration and pH. Both charged small emulsifiers and proteins are AQ 13
strongly affected by salt concentration and proteins are especially strongly affected
by pH.
When choosing ingredients for a multicomponent system as an emulsion, it is
very important to not only understand the solubility of components in the two phases
but also to partition the ingredients into each phase and to the interface between
the two phases. For example, whatever thickener is used, it should be partitioned
into the continuous phase of the formulation. One also has to be aware that the
partitioning of components might change the phase behavior of the ingredient. One
simple example of this is that the partitioning of small surface-active substances to
the oil–water interface will shift the apparent critical micelle concentration (CMC)
for these components to a higher concentration, which is dependent on the surface
area of the dispersed phase, and thus affected by the droplet size and the amount of
dispersed phase.
For shelf life, the purity of the ingredient is critical, especially components that
trigger oxidation of the oil, for example, heavy metal ions or peroxides. One should
also be aware of the concentration of surface-active substances such as fatty acids
in the oil. The latter could interact in different ways with the mechanisms of sta-
bilization of the oil droplets either by competing with the chosen emulsifier at the
oil–water interface or by interacting with it thus changing its properties. This is of
special importance for particles, but could also likely affect, for example, fatty acid-
binding proteins or biopolymers that form inclusion complex with the surface-active
components.
Also, the stability of the ingredients during homogenization has to be considered.
As discussed previously, the homogenization process negatively affects the preserva-
tive effect of nisin. Another example is the hydrophobically modified starch, which
has been shown to decrease its molecular weight during homogenization (Modig
et al. 2006, Nilsson, Leeman et al. 2007). Soy proteins have shown disruption as
well as aggregation induced by high-pressure homogenization (Roesch and Corredig
2003). Several issues such as heat, shearing, and the adsorption into surfaces of the
K16909_C003.indd 59 12/31/14 4:14 PM

60
K16909_C003.indd 60
taBle 3.1
Comparison of Functional Characteristics and Formulation attributes of various general Classes of emulsifiers
used in Food emulsions
general Class small molecular weight surfactants macromolecules Particles
Approx. size ~0.4 to 1 nm 2–200 nm 10 nm to 10 µm
Surface active Yes Yes Yes—via partial dual wettability
Amphiphilic Yes (head and tail) Yes (hydrophobic and hydrophilic No (unless Janus particles)
regions)
Adsorption kinetics Fast in dynamic equilibrium Medium partially irreversibly Slow but essentially irreversible
Desorption energy Low < 10 kT High and increasing if Exceptionally high greater than
conformational changes occurs at several thousand to tens of
the interface, several thousand kT million kT, depending on particle
size and contact angle
Chemical types Nonionic HLB 12–16 Nonionic HLB Ionic Proteins Polysaccharides Colloidal solids Colloidal
7–10 θ < 90° solids θ > 90°
Food examples Polysorbates Monoglycerides Phospholipids Caseinates egg Modified Modified starch Fat crystals
proteins starches, and cellulose
celluloses in crystals/particles
Engineering Aspects of Food Emulsification and Homogenization
solution
12/31/14 4:14 PM
Basic structure at
Water OH Oil Water Water
K16909_C003.indd 61
interface (not to HO
O O Monoglyceride
scale) O
Lecithin θ
Particle
O O O
O O
O O O
O N
O
O OH
O Oil
HO O O OH
θ < 90° oil in water emulsion
Oil Water Oil (or if θ > 90° water in oil emulsion)
Polysorbate
Solubility/ Water Oil Water Water Water Water Oil

dispersibility
Formulation of Emulsions
Emulsion type O/W W/O O/W O/W O/W O/W W/O

Usage level (g/goil) ~0.05 ~0.05 ~0.05 ~0.05 ~1 to 1.5 ~0.02 to 1 ~0.02 to 1
pH stability Good Good Depends on pKa Poor Good Variable Good
AQ 14 Salt stability Good Good Poor at I > CFC Poor at I > CFC Good Variable Good
61
12/31/14 4:14 PM
equipment can affect the ingredients in the emulsion. Another issue could be that
the surface-active components might induce the leakage of components from gas-
kets and other plastic and rubber parts of the equipment. Thus, an incompatibility
between the process and the ingredients used has to be considered during the devel-
opment process.
In food products, a further complication is that many of the ingredients used are
often very complex mixtures, for example, mixture of proteins, polar lipids, and
polysaccharides. One good example here is egg yolk, which is used to stabilize
mayonnaise-type emulsions. In such cases, it may be difficult to know which ingredi-
ent actually contributes to the emulsification and stabilization actions; to complicate
things further, the components at the interface can vary with solution properties such as
pH (Magnusson and Nilsson 2013, Nilsson et al. 2006, Nilsson, Osmark et al. 2007).
The interaction between ingredient components may enhance the stability of emulsions
as well as cause instability, and the effect of adding individual ingredients can be dif-
ficult to predict.
Finally, one should be aware of the variation and inhomogeneity of the ingredi-
ents and at least have some knowledge if this might affect batch-to-batch variation
of products. Several commercial emulsifiers are mixtures that show a variation in
chain length of the hydrophobic tail (cf. sorbitan esters and ethoxylated sorbitan
esters) or variation in molecular weight (cf. all polymers) and even variation in the
composition, for example, lecithin and whey proteins. These variations can affect
the composition of the molecules at the interface and could influence issues such as
shelf-life stability, rheology, droplet size, and so on.
3.4 Key IngredIents In emulsIons

3.4.1 FatS aNd oilS
Oil is not only often the major source of energy in a food emulsion, but it also acts
as the phase where key nutritional components such as antioxidants and fat-soluble
vitamins will be dissolved. Thus, the choice of fats used in the emulsion process will
influence the nutritional value of the final product. Generally speaking, a high degree
of saturated lipids, especially omega-3 and omega-6 lipids, is considered to be linked
to health benefits, and a factor that is used to improve the nutritional value of some
foods (Berasategi et al. 2014, Moore et al. 2012, Sørensen et al. 2008)
The most common oils in food emulsions are triglycerides (see Figure 3.1). The
properties of the triglycerides are governed by the chain length and the degree of
saturation of the lipophilic part of the molecule (Larsson 1986).The longer the chain
length and the more saturated fatty acids are in a triglyceride, the higher will be the
melting point. Triglycerides are often classified depending on the chain length of the
fatty acid part into high- (>12), medium- (6–12), and low-chain (<6) triglycerides.
Table 3.2 shows some of the more common food oils and fats.
As described in Chapter 2, the character of the oil phase will influence emul-
sion stability when it comes to oxidation, coalescence, and Ostwald ripening.
Furthermore, the crystallinity of the oil affects both the stability and the organoleptic
properties of the emulsion. Thus, the key properties are the temperature at which the
K16909_C003.indd 62 12/31/14 4:14 PM

α β′ β
Hexagonal Orthorhombic Triclinic
FIgure 3.1 Schematic description of crystalline structures for triglycerides with unsatu-
rated fatty acid side chains.
oil will crystallize and the type of polymorph that is formed during crystallization.
Triglycerides exist in several polymorphic forms, where β is the most stable one. Due
to the differences in treatment, for example, cooling rate, the crystals can be locked
into other less stable polymorphic forms, where α and β′ are the most common ones
for triglycerides; this is considered in several textbooks and in a recent review by
Sato et al.(2013). As discussed previously, β′ has more appealing organoleptic prop-
erties than β. The different polymorphic forms also have different melting points,
which can be important for the stability of the emulsions. As a rule of thumb, the
less stable polymorphic forms, the lower the melting temperature. In more com-
plex systems, the crystallization will be dependent on the mixture of triglycerides
and the addition of other components. One example is the addition of diacylglycerol
to blends of palm super olein to increase the onset temperature for crystallization
(Ng et al. 2014).
Apart from triglycerides, most oils also contain traces of numerous other com-
ponents such as diacylglycerol, monoacylglycerols, free fatty acids, phospholipids,
tocopherols, and minerals. As reviewed by Chen, McClements, and Decker (2011),
these can affect the stability of the oil when it comes to oxidation but also when it AQ 15
comes to emulsion stability. For example, free fatty acids, mono and diglycerides
as well as phospholipids are surface active and can cause foaming upon mixing, or
destabilization of protein-stabilized emulsions. However, the effect on lipid oxida-
tion of these compounds, as described by Chen, McClements, and Decker (2011), is
not straightforward, although free fatty acids have been seen to accelerate the oxida-
tion of triacylglycerols. Tocopherols, on the other hand, have a beneficial effect on
reducing the oxidation as they work as antioxidants.
3.4.2 low Molar MaSS eMulSiFierS

Low-molecular emulsifiers are characterized by having regions of the molecule that
are more water loving (hydrophilic) and regions that are more water hating (hydro-
phobic). This is the main driving force for these molecules to adsorb into the inter-
face between oil and water, where they lower the surface tension between the two
K16909_C003.indd 63 12/31/14 4:14 PM

64
K16909_C003.indd 64
taBle 3.2
Common Food oils/lipids
Production vitamin e saturated lipids monounsaturated Polyunsaturated
name [million tons (may 2014)]a (mg/100g)b (g/100g)b (g/100g)b (g/100g)b melting Pointc
Oil, Coconut 3.43 0.09 86 6 2 25
Oil, Cottonseed 4.99 35.3 26 18 52 −1
Oil, Olive 3.19 14.4 14 73 10 −6
Oil, Palm 62.35 15.9 43 37 9 35
Oil, Palm Kernel 7.23 3.81 81.5 11 2 24
Oil, Peanut 5.84 15.7 17 46 32 3
Oil, Rapeseed 26.02 −10
Oil, Soybean 46.34 8.1 16 23 58 −16
Oil, Sunflower 15.52 41.8 10 45 40 −17
Fish oil 1 30 27 34
Butter fat 2.8 60 28 4 32–35
Lard 0.6 40 45 11 41
AQ 16 Sources: a Agriculture, U.S.D.O., World Production, Markets, and Trade Reports: Oilseeds, United States Department of Agriculture, 2014.
b http://ndb.nal.usda.gov/ndb/foods.
AQ 17
c http://www.engineeringtoolbox.com/oil-melting-points-d_1088.html.
12/31/14 4:14 PM
CPP < 1/3 1/2 < CPP < 2 CPP > 2
V: volume of hydrophobic chain

CPP = V l: length of hydrophobic chain
al
a: area of head group
FIgure 3.2 Schematic description of some self-assembled lipid structures and an explana- AQ 18
tion of packing parameter: (a) CPP < 1/3, (b) CPP = 1, (c) CPP > 2.
phases. The amphiphilic character of these molecules also triggers the formation
of different self-assembled structures in solution (see Figure 3.2). The type of self-
assembled structures that are obtained depends on the concentration of the emulsifi-
ers, as well as is partly affected by the intrinsic properties of the molecules. The type
of structures formed ranges from micellar structures to reversed structures (reversed
micelles, L2 phases, or reversed hexagonal phases). Emulsifiers with an even bal- AQ 19
ance between hydrophilic and hydrophobic parts often form lamellar liquid crystals,
which forms vesicles when dispersed in water. The critical packing parameter (CPP)
is a generalization of the self-assembling properties of surfactants, describing the
properties as a geometrical balance between the area needed for the polar group
relative and the area needed for the hydrophobic group (Israelachvili, Mitchell, and
Ninham 1976) (see Figure 3.2). This can be used to estimate what type of structure
an emulsifier will give. When CPP is equal to one, it will favor lamellar structure,
whereas if the CPP is lesser than 1/3, it will favor micelles; a CPP of above 2 will
favor reversed micelles. For more details on the liquid crystalline phases formed
by common food emulsifiers, there is a review by Krog (1997). Friberg and Wilton
K16909_C003.indd 65 12/31/14 4:14 PM

(1970) suggested that the presence of lamellar liquid crystalline phases is a strong
indication of a good emulsifier in simple systems.
The functionality of low-molecular emulsifiers is, in a wide interpretation, deter-
mined by their solution properties. Although the character of low-molecular emulsi-
fiers is such that they contain regions that are water soluble and those that are more
lipophillic, their overall character can make them more soluble in one of the two
phases. Thus, emulsifiers can be found in a range from highly soluble in the oil to
more soluble in the water phase. The effect of solubility on emulsion character was
AQ 20 first expressed in the Bancroft (1913) rule, stating that “hydrophilic colloid will tend
to make water the dispersing phase while a hydrophobic colloid will tend to make
water the disperse phase.” To describe the degree of hydrophilicity contra lipophi-
licity, it is very popular to use the hydrophilic–lipophilic balance system according
AQ 21 to Griffin (1954). The HLB ratio is expressed as a number based on the molecular
weight of hydrophobic components compared to the molecular weight of the mole-
cule. The HLB number can also be estimated from the chemical structure according
to molecular group contributions as stated by Davies (1957):
HLB = ∑ Hydrophilic group numbers − ∑ Hydrophobic group numbers + 7 (3.1)
The HLB value of an emulsifier is often used as a rule of thumb (see Table 3.3). However,
one should be aware of the fact that solution conditions might change the HLB balance
of a system; for example, the addition of salt can screen charge groups, making the
system appear less hydrophilic. Another factor of importance is the temperature. The
effective HLB value is strongly temperature dependent. For ethoxylated emulsifiers,
the emulsifier gets less hydrophilic with increasing temperature and finally becomes
insoluble in water at a temperature denoted as the cloud point. In an emulsion sys-
tem, this can be followed by the phase inversion temperature (PIT), which corresponds
to the temperature at which the effective HLB is about 6 (Shinoda and Sato 1969).
Emulsions stored at a temperature of 25°C–60°C below the PIT are usually more stable.
However, in food applications, this is rarely used, as ethoxylated surfactants are uncom-
mon for food applications. Another important temperature to consider for emulsifiers is
the Krafft point (Krafft and Wiglow 1895). The Krafft point is the temperature below
taBle 3.3
hlB values as Predictor for the use of emulsifiers
hlB value applications example of emulsifiersa
3.5–6 W/O emulsifier Glycerol monostearate
7–9 Wetting agent Sorbitan monolaurate
8–18 O/W emulsifier Tween 80
13–15 Detergent Tween 81
15–18 Solubilization Sodium Oleate
Source: Davies, J.T., Proceedings of 2nd International Congress Surface Activity,

a
Butterworths, London, 1957.
K16909_C003.indd 66 12/31/14 4:14 PM

which the surfactant has low solubility and, hence, cannot form micelles. Technical
functionality (such as foaming and emulsifying action) is only obtained above the
Krafft temperature. High-melting fat bases (fully hardened C18-dominated fats) or long
paraffinic chains creates high-melting emulsifiers with Krafft temperatures in the range
of 40°C–60°C. Precipitating emulsifiers may contribute to fat crystallization and solid
emulsifier may have a textural functionality; however, for most applications, such high
melting points are unsuitable. Intermediate melting fat bases (C14–C18 fats with some
unsaturation) give emulsifiers with Krafft or transition temperatures between 30°C
and 50°C. These emulsifiers could be used to create stable α-gels and usually display
well-performing properties in baking applications. Low-melting fat (highly unsaturated
fat), branched hydrocarbons and inclusion of aromatic groups, gives low Krafft points,
sometimes below 0°C. Table 3.4 summarizes some examples and usages of common
low-molecular weight emulsifiers.
3.4.3 ProteiNS
Proteins function both as emulsifiers and as rheological modifiers in the formulation
of food emulsions. The character of proteins in emulsions will be based on their
tertiary structure in the solution and at the interface, their size, the net charge and
charge distribution, their capability to form gels, and the distribution of hydrophilic
and hydrophobic groups. There are numerous proteins that are used in emulsion,
and the choice of protein emulsifier is often not only based on function but also
based on what food group the emulsion is related. There are several traditional or
natural-occurring emulsions that, at least, are partially stabilized by proteins, such
as mayonnaise, dairy products, and sausages. Table 3.5 presents some of the more
common protein emulsifiers. Most of these emulsifiers are mixtures of several differ-
ent protein species. Thus, depending on the production and formulation conditions,
the actual proteins at the interface may differ although the same protein emulsifier
is used. Factors affecting the protein adsorption into the interface during competi-
tive adsorption from solution are size, charge and hydrophobicity of the protein, the
transport conditions of proteins to the surface during emulsification, if adsorbed
proteins can be exchanged by proteins in solution, and the degree of conformational
changes of the protein at the interface (Nilsson et al. 2006, Nilsson, Osmark et al.
2007, Wahlgren and Arnebrant 1991). Thus, it is a complex issue to understand
what proteins are actually adsorbed at the interface. Magnusson and Nilsson (2013)
reviewed this recently for egg yolk in high internal phase emulsions and discussed
that the main property governing adsorption was the hydrophobicity of the proteins
and that there is a preference for HDL and LDL proteins to adsorb at the interface.
In the case of milk proteins, Surel et al. (2014) have seen that in mixtures of casein
micelles and whey proteins, casein dominates at the interface when the fraction of
casein in the solution is above 25%.
Proteins get their amphiphilic character from the mixture of hydrophilic and
hydrophobic amino acids. The amino acid sequence (secondary structure) also gives
the template for the three-dimensional structure of the protein (tertiary structure).
However, one should be aware that the tertiary structure will vary due to solution
conditions, and that proteins in solution have a well-defined tertiary structure, which
K16909_C003.indd 67 12/31/14 4:14 PM

68
K16909_C003.indd 68
taBle 3.4
Common low-molecular weight emulsifiers
number
AQ 22 name eu/usa solubility uses Comment
Lecithin E322 Dispersible but insoluble in water, Margarine, chocolate, breads and cakes, bubble gum, Mixture of phosphoric acid, choline,
184.1400 where it swells on hydration. salad dressings, and sauces fatty acids, glycerol, glycolipids,
Soluble in oils and fats. triglycerides, and phospholipids
Fatty acid salts E470 Sodium and potassium salts are Baked goods (e.g., bread and cakes), confectionery, Charged at normal and low pH
172.863 soluble in water. Calcium salts dairy products, margarines, spreads, shortenings,
are insoluble in water. salad dressings, and sauces
Sodium stearoyl E481 Dispersible in warm water and Fine bakery wares, emulsified liqueur, fat emulsions, Negatively charged
lactylate 172.846 soluble in hot edible oils and fats. desserts, beverage whiteners, and minced and diced
canned meat products
Citric acid esters E472 Dispersible in hot water, insoluble Fats for stabilizing, also as synergists for antioxidants, Negatively charged
of MG 172.832 in cold water, and soluble in baking fat emulsions, bakery margarines and
edible oils and fats. shortening for stabilizing, margarine, mayonnaise,
salad dressings, sauces, and in low-calorie foods
Mono and E471 Oil Baked goods, confectionery (e.g., chewing gum, Nonionic
diglycerides 184.1505 toffees, and caramels), dairy products, creams,
desserts, edible ices, margarines, shortenings
12/31/14 4:14 PM
Polyglycerol E475 Water Cakes and icings, margarine, and salad oils Nonionic
K16909_C003.indd 69
esters of FA 172.854
Propylene glycol E477 Oil Whippable icing Nonionic
esters of FA 172.856
Polyoxyethylene E435 Water Fine bakery wares, fat emulsions for baking purposes, Nonionic cloud point around
(20) sorbitan 172.836 milk and cream analogues, emulsified sauces, soups,
monooleate dietary food supplements, carriers and solvents for
colors, fat-soluble antioxidants, and antifoaming agents
Polyoxyethylene E433 Water Fine bakery wares, fat emulsions for baking purposes, Nonionic cloud point around
(80) sorbitan 172.840 milk and cream analogues, emulsified sauces, soups,
monostearate dietary food supplements, dietetic foods, carriers
and solvents for colors, fat-soluble antioxidants, and
antifoaming agents
69
12/31/14 4:14 PM
taBle 3.5
Common Commercial Proteins emulsifiers and example
of Proteins that are Part of the emulsifier
AQ 23 emulsifier Key Proteins molecular weight IP
Whey protein a
β-lactoglobulin 18.6 5.3
α-lactalbumin 14.2 4.8
Bovine serum albumin 66 5.1
Caseinsb α1-Casein 23 4.1
α2-Casein 25 5.3
β-Casein 24 5.1
κ-Casein 19 5.6
Egg whitec Ovalbumin 45 4.5
Ovotransferrin 77.7 6.0
Ovomucoid 28 4.1
Lysozyme 14.3 10.7
Egg yolkc Phosvitin 160–190
Low-density lipoproteins 16–135
Cobalamin-binding proteins 39
Riboflavin-binding proteins 37
Biotin-binding proteins 72
α- and β-Lipovitellins 400
Soy proteind α-Conglycinin 18–33
β-Conglycinin 104
σ-Conglycinin 141–171
Glycinin 317–360
Sources: aKinsella, J.E. and Whitehead, D.M., Advances in Food and Nutrition
Research, Academic Press, San Diego, CA 1989.

b Swaisgood, H.E., J. Dairy Sc., 76, 10, 3054–3061, 1993.
c Awade, A.C., Z. Lebensm. Unters. For., 202, 1–14, 1996.
d Clarke, E.J. and Wiseman, J., J. Agr. Sci., 134, 111–124, 2000.
could be considerably changed and even lost when adsorbing at an interface. Proteins
are often divided into different categories based on their tertiary structure. The most
common structures are random coil (casein), globular proteins (whey proteins and
egg proteins), and rod-like structures (fibrinogen, collagen, and gelatin). In many
cases, the protein has a defined molecular weight but for some food proteins such as
gelatin, this is not the case. The distribution of hydrophobic groups within the poly-
mer is important. For globular proteins, the hydrophobic groups are mainly found
inside the core of the protein shielding them from water. Upon adsorption into the
oil–water interface, these hydrophobic groups could orient themselves toward the oil,
which might lead to conformational changes of the protein. A few proteins especially
κ-Casein has very distinctive hydrophilic and hydrophobic domains, which together
K16909_C003.indd 70 12/31/14 4:14 PM

with its semirandom coil structure makes them especially suitable as emulsifiers.
The casein proteins α1−, α2−, β−, κ−Caseins form complex called casein micelles.
Although these proteins play a large biological and a technical role, the structure of
the casein micelles is still debated (Dalgleish 2011, Horne 2002).
The main difference between low-molecular weight emulsifiers and proteins is
that while the adsorption of the former is completely reversible, when the concentra-
tion is lowered, proteins have a tendency to adsorb irreversibly. This makes them less
sensitive to changes such as dilution. However, even if the adsorption is irreversible
toward the lowering of concentration, the protein could still be exchanged by other
species (proteins or low-molecular ones) that have higher driving force for adsorp-
tion, for example, a higher reduction of the surface tension at the oil–water interface.
The kinetics of these events and the conformational changes of the proteins can be
slow, on the time scale of hours to days, and can lead to postproduction changes
of the emulsion. Furthermore, proteins are sensitive to heat, enzymes, and solution
conditions such as pH and ionic strength, which lead to degradation, aggregation,
and other protein changes. These events can also lead to long-term change of emul-
sions stabilized by proteins. Another difference between low molar mass (or small)
emulsifiers and proteins is the rheology of the adsorbed layer. Proteins often form
thicker, more viscous layers than small emulsifiers (Bosa and van Vlieta 2001). This AQ 24
is in most cases positive for the long-term stability of the emulsion. Proteins might
stabilize emulsions through electrostatic repulsion and, thus, several protein sys-
tems show tendencies to aggregate at pH close to the isoelectric point of the pro-
tein emulsifier. If such aggregation does not lead to coalescence, it could lead to an
increase in the viscoelasticity of the emulsion (Wu, Degner, and McClements 2013).
In systems where both small molecular emulsifiers and proteins are present, there
might be a competition between the components at the interface or there might be
a cooperative adsorption (Maldonado-Valderrama and Patino 2010, Nylander et al.
2008, Rodríguez, García, and Niño 2001, Waninge et al. 2005). The competitive AQ 25
adsorption of proteins and small emulsifiers are strongly concentration dependent,
and at concentrations below the CMC of the emulsifiers, proteins often dominate at
the interface (Wahlgren and Arnebrant 1992). The order in which the components
reach the surface might also be important as small surface-active components can-
not always remove already adsorbed proteins (Karlsson, Wahlgren, and Trägårdh
1996, Wahlgren 1995). Cooperative adsorption may occur when the protein com-
plexes with the low-molecular emulsifier, which, for example, is common for many
ionic surfactants (Maldonado-Valderrama and Patino 2010). It is often seen that the
adsorption of low-molecular emulsifiers to protein-stabilized emulsions have a detri-
mental effect on the emulsion stability (Wilde et al. 2004). Furthermore, there could
be strong interactions between proteins and surfactants in solution, changing the
structure and behavior of the proteins (Nylander et al. 2008).
Proteins also have the capability to change the rheology of the emulsions, espe-
cially if they are triggered to aggregate and to form a gel. Gel formation is often
induced by heating and denaturation of the proteins but could also be an effect of
pH, for example, the change in the rheology between milk and yoghurt. For example,
increased viscosity through the addition of proteins is important in low-fat products
such as margarines, sausages, and spreads (Chronakis 1997). Common proteins used
K16909_C003.indd 71 12/31/14 4:14 PM

to form gel structures are milk-based systems such as whey proteins (Chronakis 1997,
Youssef and Barbut 2011) and soy proteins (Youssef and Barbut 2011).
3.4.4 PolySaccHarideS
Polysaccharides primarily function as viscosity modifiers in emulsions. However,
hydrophobically modified polysaccharides are also used as emulsifiers. A thorough
description of polysaccharides is given in Food Polysaccharides and Their Applications
(Stephen, Phillips, and Williams 2006). The properties of a polysaccharide is given by
the structure of the smallest repeating saccharide units, the degree of branching of the
polymer, and its molecular size. Differing from proteins, polysaccharides typically
have a high degree of polydispersity when it comes to branching and molecular weight.
There can also be a large batch-to-batch variation, which might lead to variation in
performance. Table 3.6 presents some of the more common polysaccharide groups and
these will also be discussed subsequently.
AQ 26 Traditionally, exudate gums, such as gum arabic, have been used as emulsifiers
especially in flavored beverages (Dickinson 2003). These are natural polysaccharides
that are produced by plants as a protection against bacteria and dehydration. One has to
be aware that there is a very high variation in the composition between gums obtained
from different species (Stephen, Phillips, and Williams 2006) and that this variation
might affect the emulsion produced. These contain a heterogeneous mixture of highly
branched polysaccharides and a small amount of proteins (2% for gum arabic) cova-
lent attached to the polysaccharides. Gum arabic is thought to have a water blossom
structure built up of an amino acid core of around 400 units onto which bulky poly-
saccharide units of 250 kDaltons are grafted (Stephen, Phillips, and Williams 2006).
It is the protein moieties of the exudated gums that make them surface active. Alftrén
showed that for gum arabic and mesquite gum, the amount of protein in the polysac-
charide fraction increased with increasing molecular mass and that these high protein
content/high-molecular weight fractions were preferentially adsorbed into emulsion
droplets (Alftrén et al. 2012; Evans, Ratcliffe, and Williams 2013). The emulsification
capacity of gum arabic is lost upon heating (Williams, Phillips, and Randall 1990).
Another group of polysaccharide that is dependent on a protein fraction for its emul-
sifying properties are modified pectins (Akhtar et al. 2002, Dickinson 2003). Although
pectin is mainly used as a rheological modifier in emulsions, if they are modified, they
might work as emulsifiers (Dickinson 2003). The modification is, in most cases, acety-
lation; however, depolymerization using acids has also been used (Dickinson 2003).
Akhtar et al. (2002) have shown that depolymerized citrus pectin of 70% esterifica-
tion gives good stable emulsions, although only 25% of the pectin is adsorbed into the
interface and that upon storage, there are some flocculation that increase particle size.
For example, hydrophobic modification of polysaccharides starch can also pro-
duce molecules that are surface active and can be used as emulsifiers. Nilsson and
Bergenståhl (2006, 2007) have done extensive studies of hydrophobically modified
starch and shown that they are good emulsifiers and that the surface load of OSA-
starch can be as high as 16 mg/m2. They have also shown that it is the high molar
mass components of the polymer that are selectively adsorbed to the emulsion drop-
lets (Nilsson, Leeman et al. 2007).
K16909_C003.indd 72 12/31/14 4:14 PM

K16909_C003.indd 73
taBle 3.6
some Key Polysaccharides
name molecular structure Function viscosity modification
Starch amylase Essentially linear (1 → 4)-α-D-glucan Stabilizers, thickener, Starch gelatinization; the ordered crystalline regions
and hydrophobically undergo melting, permitting granule swelling. This

modified starches, can be followed by the recrystallization and
which function as formation of helix structure.
Starch amylopectin Clusters of short (1 → 4)-α-D-Glc chains attached by emulsifiers Modification can make the starch cold, swelling or
a-linkages of 0–6 of other chains nonswelling.
Modified starches Native starch both amylose and amylopectin-modified
by chemicals for example acetate, phosphate, and
sodium octenyl succinate
Carboxymethylcellulose HO2CCH2-groups at 0–6 of linear Stabilizer, thickener, Semisoluble polymer with a wide range of viscosities,
(1 → 4)-β-D-glucan and water retention viscosity decreases with temperature.
Chitosan (1 → 4)-2-acetamido-2-deoxy-β -D-glucose and Emulsifier and Positively charged, partly hydrophobized polymer that
2-amino-2-deoxy-b-D-glucose rheological modifier can gel depending on pH and the presence of
multivalent negative ions
Carrageenans Sulfated D-galactans, units of (1 → 3)-β-D-Gal and Stabilizer, thickener, Forms salt- or cold-setting reversible gels in an
(1 → 4)-3,6-anhydro-a-D-Gal alternating; pyruvate and gelation aqueous environment. Gelling ability is seen for
and Me groups Carrageenans that form helical structures.
(Continued)
73
12/31/14 4:14 PM
74
K16909_C003.indd 74
taBle 3.6 (Continued )
some Key Polysaccharides
name molecular structure Function viscosity modification
Gum arabic Acidic L-arabino-, (1 → 3)- and (1 → 6)-β- D-galactan, Emulsifier, Low viscosity at high concentrations, less than 40%
highly branched with peripheral L-Rhap attached to encapsulating agent, rheology strongly affected by pH and electrolyte.
D-GlcA. Minor components of glycoproteins stabilizer, and
thickener
Pectins Linear and branched (1 → 4)-α-Dgalacturonan (partly Gelation, thickener, High-molecular weight pectins form gels at low pH
methyl esterified and acetylated); chains include and stabilizer (2.5–3.5) and in the presence of high sucrose
(1 → 2)-L-Rhap, and branches D-Galp, L-Araf, concentration (>55%), or other cosolutes (e.g.,
D-Xylp, D-GlcA sorbitol, and ethylene glycol)
Xanthan gum Cellulosic structure, D-Manp (two) and GlcA- Stabilizer and thickener Solutions have a thixotropic behavior; gels are formed
containing side chains, acetylated and pyruvylated on at high concentration or in the presence of plant
Man galactomannans such as locust bean gum.
Source: Data from Stephen, A.M. et al., Food Polysaccharides and Their Applications, CRC Press, Boca Raton, FL.
12/31/14 4:14 PM
According to Dickinson (2013), xanthan gum, which has high viscosity at low
shear, is established as the first choice when it comes to using them as rheological
modifiers for stabilizing emulsions, but there are a large range of polysaccharides that
are used for improving texture in food emulsions. Polysaccharides can increase the
viscosity of an emulsion either by some gelation mechanism, such as those triggered by
the addition of calcium ions (alginate, pectins, and carrageenan) and the formation of
double helices and crystallization (starch), or by nonspecific chain–chain interactions
determining the viscosity. Nongelling polysaccharides, especially if they are linear
and are good solvents, often behave as random coil polymers. At low concentrations,
such polymers behave more or less as Newtonian liquids but as the concentration
increases, the polymer chains start to overlap and the rheological behavior of the poly-
mer changes. Above the so-called overlap concentration, the viscosity becomes shear AQ 27
thinning and the viscosity increases more steeply with polymer concentration. Gelling
of polysaccharide can also form continuous water-swollen networks at low concentra-
tions. To obtain such systems, the polysaccharides contain both regions that form the
physicochemical bonds between the polymers and the nonbinding regions that primar-
ily hold the water. The regions that form the bonds are usually well ordered, allowing
for helices, egg-box, ribbon–ribbon, and double helix–ribbon structures.
In complex food products, for example, the interaction with the polysaccharides
with other components of the product might lead to segregated networks when pro-
teins and polysaccharides phase segregate. The polysaccharides, especially starch,
can also form inclusion complex with small emulsifiers such as monoglycerides and
fatty acids (Eliasson 1986, Tufvesson, Wahlgren, and Eliasson 2003). These interac-
tions are often stronger than the tendency for the emulsifier to adsorb into interfaces
and thus it will lower the amount of the emulsifier available (Lundqvist, Eliasson,
and Olofsson 2002). The complexes so formed will also have additional properties AQ 28
such as melting point than the double helices normally formed in starch.
3.4.5 ProteiN-PolySaccHaride coMPlexeS

Compatibility between proteins and polysaccharides becomes important during the
modification of textures in food products. Mixtures of proteins and polysaccharides
can lead to three major scenarios (Schuh et al. 2013):
1. A single homogenous phase is formed.

2. The polysaccharide and proteins phase segregates into different phases as
the mixtures are not thermodynamically compatible.
3. Protein and polysaccharides aggregate and form insoluble complex.
In complex food systems, these types of interactions might either lead to the stabili-
zation of the emulsion or, especially in the latter case, destabilization.
Lately, there has been an interest in using the protein–polysaccharide complex
as emulsifiers in food systems (Evans, Ratcliffe, and Williams 2013). As discussed
previously, some traditional polysaccharide emulsifiers are probably protein–
polysaccharide complexes; other methods to obtain such complexes could be the
formation of Maillard conjugates (Akhtar and Dickinson 2007, Zhang, Chi, and
K16909_C003.indd 75 12/31/14 4:14 PM

Li 2013) or electrostatic complexes (Harnsilawat, Pongsawatmanit, and McClements

2006, Koupantsis, Pavlidou, and Paraskevopoulou 2014, Xu et al. 2014). Protein–
polysaccharide complexes are used in the encapsulation of emulsion droplets, lead-
ing to the protection of sensitive substances (Xu et al. 2014), or the encapsulation of
AQ 29 flavors (Koupantsis, Pavlidou, and Paraskevopoulou 2014). Polysaccharide–protein-
stabilized emulsions have been shown to be more stable to stress, for example, heat
than emulsions only stabilized by the protein (Harnsilawat, Pongsawatmanit, and
McClements 2006). They have also been seen to be insensitive to pH and salt con-
centration (Zhang, Chi, and Li 2013).
3.4.6 ParticleS
In addition to small molecular-weight surfactants and macromolecules, colloidal
particles can be utilized to stabilize emulsions. Particle-stabilized emulsions (com-
monly referred to as Pickering-type emulsions) are possible as a result of the proper-
ties of the particles, where a combination of size, form, and partial dual wettability
of both the oil and water phases confers Pickering particles several useful properties
and the ability to create emulsion droplets that are highly stable against coalescence
(Rayner et al. 2014). Particle-stabilized emulsions in general, and in food-based
particles in particular, have received an increasing interest in recent years and for
this reason, a separate chapter has been devoted to particle-stabilized emulsions in
this book (see Chapter 4). However, particle-stabilized emulsions are by no means a
recent discovery, being reported in the scientific literature during the early twentieth
century. One of the first particle-stabilized food products was mayonnaise, a popular
condiment based on an O/W emulsion, which was first formulated in 1756, where the
finely ground (and somewhat hydrophobic) mustard particles adsorb at the oil–water
interface and cover a fraction of the oil droplets preventing coalescence, in addition
to other surface-active components found in egg and other ingredients (Binks 2007).
The commonly used types of particles in fundamental studies (where there is an
abundance of literature to be found in fields of soft matter and physical chemistry)
are often inorganic/synthetic such as clays, silica, alumina, titanium oxides, and latex-
based particles (Aveyard, Binks, and Clint 2003). However, there has been a recent
and an increasing trend toward developing suitable food-based particles, which are not
only edible but also maintain the consumer perception of being wholesome or natu-
ral. Three general approaches can be taken to obtain food-based particles. They can
be built up or synthesized from molecules extracted from food-based materials (e.g.,
aggregation, crystallization, cross-linking, precipitation, etc.); they can be obtained
by reducing the size of existing structures (e.g., milling, crushing, hydrolyzing, etc.);
and they can be isolated as with their innate biological structures intact. Also, in many
cases, a breaking-down step (i.e., to dissolve the working material) is a precursor for
synthesis. Examples of a synthesis approach for generating edible particles include
starch nanocrystals (Li, Sun, and Yang 2012), chemically modified starch nanospheres
(Li, Sun, and Yang 2012, Tan et al. 2012), flavonoid particles (Luo et al. 2011, 2012),
chitin nanocrystals (Tzoumaki et al. 2011, 2013), soy protein particles (Paunov et al.
2007), whey protein microgels (Destribats et al. 2014), insoluble corn protein (zein) par-
ticles (De Folter, Van Ruijven, and Velikov 2012), solid lipid particles, and fat crystals
K16909_C003.indd 76 12/31/14 4:14 PM

(Gupta and Rousseau 2012). Examples of particles formed from the breakdown of
larger structures include cellulose nanocrystals (Kalashnikova et al. 2011, 2013), cocoa
particles (Gould, Vieira, and Wolf 2013), ethyl cellulose particles (Jin et al. 2012), and
cryomilled fractured modified starch particles (Yusoff and Murray 2011). Examples of
particles directly isolated include lactoferrin nanoparticles (Shimoni et al. 2013), bacte-
ria chitosan networks (Wongkongkatep et al. 2012), natural spore particles (Binks et al.
2005, 2011) hydrophobic bacteria (Dorobantu et al. 2004), egg yolk granules (Ercelebi
and Ibanoglu 2010, Eriksson 2013, Laca et al. 2010, Rayner et al. 2014), and starch
granules isolated from a variety of botanical sources (Li et al. 2013, Rayner, Timgren
et al. 2012, Timgren et al. 2011), with or without hydrophobic modification (Rayner,
Sjöö et al. 2012, Song et al. 2014, Timgren et al. 2013).
Generating food-grade particles for stabilizing emulsions has been of a recent
interest because Pickering-type emulsions are generally more stable against coales-
cence and Ostwald ripening, and have the potential to enhance oxidative stability
(Aveyard, Binks, and Clint 2003, Binks 2002, Kargar et al. 2012). The reason for
their high stability is due to the particles preventing interfacial interaction by vol-
ume exclusion; that is, particles adsorbed at the oil–water interface create a physical
barrier preventing drop–drop contact. Because Pickering particles are often tens to
thousands of nanometres in diameter, this physical layer is quite large in comparison
to surfactant molecules (~1 nm) and protein molecules (~5 nm). As in most types
of emulsion formulations, the size of emulsions droplets in Pickering emulsions is
governed either by the amount of emulsifier relative to the dispersed phase or by the
intensity of the emulsification device (Chevalier and Bolzinger 2013, Tcholakova,
Denkov, and Lips 2008). Generally droplet size decreases with increasing particle
concentration (at fixed dispersed phase content) to a certain extent after which it
levels out, and excess particles begin to accumulate in one of the phases. Beyond this
level of particle-to-dispersed phase ratio, a further reduction in droplet size can only
be achieved by improving the emulsification conditions (Frelichowska, Bolzinger,
and Chevalier 2010). However, in Pickering emulsions, the size of the stabiliz-
ing particles ultimately limits the size of the emulsions drops that can be formed.
Generating small particles is a common objective of many studies, as it reduces the
amount required (milligram of particles per milliliter of dispersed phase) to stabi-
lize a given emulsion droplet interface, that is, emulsification capacity. Requiring a
high concentration of emulsifier for creating a stable emulsion is generally undesir-
able from a formulation viewpoint, as emulsifiers can be expensive, have a negative
impact on the overall taste, or have their concentration limited by regulatory aspects.
On the other hand, if the particles themselves are food components (i.e., starch gran-
ules, egg yolk granules, or fat crystals), this may not necessarily be the case, as the
particles themselves contribute to the nutritional profile, the perceived product qual-
ity, and/or the sensory properties of the formulation in a positive way. Furthermore,
for Pickering emulsions, achieving a small droplet size may not be as crucial as
in conventional emulsion formulations, where small droplet size is often correlated
with improved emulsion stability, as creaming is often a precursor to coalescence. In
contrast, Pickering emulsions droplets of large size (even on the millimeter scale) if
successfully formed, seem to be stable to coalescence over extended periods of time
(Aveyard, Binks, and Clint 2003, Binks 2007, Laredj-Bourezg et al. 2012, Marku
K16909_C003.indd 77 12/31/14 4:14 PM

et al. 2012, Timgren et al. 2013). However, large droplets are also susceptible to
creaming, which is a major drawback of this type of emulsion. Some examples of
how gravimetric separation is reduced in Pickering formulations include the careful
AQ 30 choice of particle size and the amount to generate droplets that are neutral buoy-
ancy (Rayner, Sjöö et al. 2012), or in cases where particle properties create weak
gel (Dickinson 2010, 2012), which is further improved in cases having high level of
dispersed phase (drops + particles), that is, space-filling conditions.
Particles as emulsion stabilizers have enabled formulators in the reduction or the
removal of low-molecular weight surfactants, which, in some cases, have a limit on
the amount that can be used in food emulsion recipes. Due to the relatively large
size of the stabilizing particles (in comparison to molecular surfactants and poly-
mers emulsifiers), they make up a significant volume fraction of the emulsion for-
mulation per se, and once adsorbed at the oil–water interface, they are essentially
thermodynamically trapped there (Aveyard, Binks, and Clint 2003). Furthermore,
if they possess a sufficient level hydrophobicity, it can also lead to particle aggrega-
tion. Because if it is energetically favorable for a particle to adsorb at the oil–water
interface, it is also favorable for the particles to adsorb to each other and tend to
exist in a state of weak aggregation in the continuous phase (Dickinson 2013), and
the particles may form a network or a gel-like structure with increased viscoelastic
moduli (Dickinson 2013).This can also result in the emulsion having a yield stress,
which, even if relatively small, will assist in preventing creaming, drop–drop con-
tact, and coalescence under quiescent storage conditions (Dickinson 2012). This may
also prove to be the reason why particle-stabilized emulsions, even when the surface
coverage of particles at the oil–water interface is much less than a closely packed
monolayer, can remain stable over several years of storage (Timgren et al. 2013).
Rheological properties resulting from particle–particle interactions may also have
the added benefit of reducing the need for additional thickeners and viscosity modi-
fiers in particle-stabilized formulations (Dickinson 2013).
3.5 evaluatIon oF emulsIon FormulatIon

and IngredIent PerFormanCe
The evaluation and characterization of emulsions and ingredient performance in food
formulations can be performed on several different time and length scales. The com-
plexity of these expensive type measurements or characterization methods can vary
from using simple visual observations of creaming in a glass container to elaborate
neutron scattering experiments. In any case, the method and time window of evalua-
tion should reflect the formulations’ fitness of intended use. For example, diary emul-
sions as refrigerated products need to be stable over the span of its best before date
(due to microbial spoilage), but not necessarily too much beyond that. Furthermore,
the emulsions should remain stable when exposed to likely environmental stresses
encountered during processing, packaging, storage, and consumption.
There are numerous methods to characterize emulsions and the ingredients
making up emulsion formulations, all of which cannot be described in detail
here. For a more thorough description of characterization method, we recom-
mend McClements’s (2005a) work and references therein. However, in Table 3.7,
K16909_C003.indd 78 12/31/14 4:14 PM

K16909_C003.indd 79
taBle 3.7
Characterization of emulsion Ingredient Properties
Key Properties (reviews) examples of methods Comments
Surface tension of biopolymers, surfactants Wilhelm plate, drop volume, Pendent drop Pendent drop works well for soluble substances and for
AQ 31 and proteinsa oil–water interface. It is also good for measuring dynamic

change in surface tension. Wilhelm plate are easier to use
for nonsoluble materials
Interfacial rheology that is especially Interfacial rheology can be measured as dilatational The methods listed here are suitable for measurements
important for biopolymers and proteinsb. deformation (oscillating increase and decrease of close to equilibrium
Presence of low-molecular emulsifiers often surface, for example, a pendant drop) Langmuir trough gives both dilatation and shearing
decrease interfacial elasticityc Shearing deformation where the area is constant but the deformation
shape is changed (deep-channel surface viscometer)
Crystallinity and polymorphismd X-ray diffraction is the preferred method for identifying The use of synchrotron radiation enables analyses on a
AQ 32 crystalline structure but DSC, and FTIR can be used as short time scale and thus kinetic phenomena can be
complementary techniques studied. X-ray can also be used to study self-associated
structures of lipids and synchrotron radiation can be used
to study structures at interfacese
Melting point and amount of solid materialf DSC, ultrasonics, and heat-controlled microscopy One should be aware that the scanning rate used in DSC
sometimes are too fast to have the sample in equilibrium
and this can affect the measured melting temperature
(Continued)
79
12/31/14 4:14 PM
80
K16909_C003.indd 80
taBle 3.7 (Continued )
Characterization of emulsion Ingredient Properties
Key Properties (reviews) examples of methods Comments
Molecular weight/mass distribution is critical There are numerous methods for molecular weight Size exclusion and FFF can be linked to light-scattering
properties especially for proteins and determination; for high-molecular weight molecules, detectors to get additional information such as shape. FFF
polysaccharides. Information on branching FFFg, size exclusionh, gel electrophoreses, rheology of is especially well suited for larger polymers and proteins
and shape can also be important to diluted solutions, and analytical ultracentrifugation can such as starch molecules. MALDI TOF is primarily used
understand biopolymers be used. Mass spectroscopy such as MALDI TOFi to get composition and structural information
AQ 33 Sources: a Drelich, J. et al., Encyclopedia of Surface and Colloid Science, Marcel Dekker, 2002.
b Pelipenko, J. et al., Acta Pharm., 62, 2,123–140, 2012.
c Maldonado-Valderrama, J. and Patino, J.M.R., Curr. Opin. Colloid Interface Sci., 15, 4, 271–282, 2010.
d Sato, K., Chem. Eng. Sci., 56, 2255–2265, 2001.
e Cristofolini, L., Curr. Opin. Colloid Interface Sci., 19, 3, 228–241, 2014.
f McClements, D.J., Food Emulsions Principles, Practices, and Techniques, CRC Press, Boca Raton, FL, 2005a.
g Nilsson, L., Food Hydrocolloids, 30, 1, 1–11, 2013.
h Hagel, L., Protein Purification, John Wiley & Sons, Inc., 2011.
i Harvey, D.J., Mass Spectrom. Rev., 30, 1:1–100, 2011.
DSC, differential scanning calorimetry; FFF, field flow fractionation; FTIR, Fourier transform infrared spectroscopy.
12/31/14 4:14 PM
we summarize some of the more important ingredient properties investigated and

their possible characterization.
On a microstructural level, the emulsion droplet size distribution is perhaps the
most central quantifying measure in emulsion science, as emulsion characteristics
and performance are highly dependent on the droplet size distribution. There are
numerous methods to assess particle size distributions in emulsions, including direct
droplet measurement by microscopy (light, confocal, electron, etc.), automated
particle counters (i.e., Coulter counter), light scattering (i.e., Malvern Mastersizer),
dynamic light scattering, diffusional wave spectroscopy, nuclear magnetic reso-
nance, and sedimentation or centrifugation (Walstra 2005). These techniques vary
with respect to the range of sizes covered, measurement principles, degree of sample
preparation and dilution, as well as physical limitations of the methods. The inter-
ested reader is directed to comprehensive and critical reviews on emulsion charac-
terization techniques for more details (Dalgleish 2003, Dickinson 2013, McClements
2005b, 2007, Sherman 1995, Walstra 2005).
From a consumers’ perspective, aside from taste, the two most important emul-
sion properties are physical appearance (creaming, sedimentation, phase separation,
graininess, etc.) and texture (mouthfeel, viscosity, etc.). These macroscopic proper-
ties are a result of microstructure and molecular interactions within the emulsion
formulation (Corredig and Alexander 2008) and are closely related to the ability
of the formulation to stabilize and maintain the stability of the emulsion droplets,
as well as the rheology of the resulting dispersion. For this reason, in the develop-
ment of food-based emulsions, the effectiveness of emulsifiers and the evaluation of
texture are often studied. From the material presented in the earlier sections of this
chapter, it is apparent that there is a large variety of emulsifiers that can be used in
formulating food-based emulsions. The fundamental performance of an emulsifier
can be described by the emulsifying capacity (EC) as the minimum amount required
to produce a stable emulsion and its ability to produce small drops during homogeni-
zation. The emulsion stability index (ESI) is a measure of the ability of an emulsifier
to prevent droplets from aggregating, flocculating, and coalescing over time.
3.5.1 eMulSiFicatioN caPacity

When formulating a food emulsion, it is useful to know the minimum amount of
emulsifier required to create a stable emulsion. The EC of a water-soluble emulsi-
fier is defined as the maximum amount of oil that can be dispersed in an aqueous
solution containing a specific amount of emulsifier without the emulsion breaking
down or inverting into a W/O emulsion (Sherman 1995). The EC of an oil-soluble
emulsifier is determined in a similar way, except that water is added to the oil phase
and it would invert into an O/W emulsion. This test is practically carried out by
placing the continuous phase containing the emulsifier into a vessel with a high-
speed mixer (e.g., ultra-turrax) and carefully titrating the dispersed phase into the
vessel. Phase inversion can be monitored via electrical conductivity (Allouche et al.
2004, Gu et al. 2000) or optically using a colorimeter or spectrophotometer in reflec-
tance mode (McClements 2002) or by adding a dye to one of the phases (Timgren
et al. 2013). The larger the volume of oil that can be added before phase inversion,
K16909_C003.indd 81 12/31/14 4:14 PM

the higher will be the EC of the emulsifier. This test is widely used due to its relative
simplicity, but has several drawbacks that prevent its application as a standardized
procedure (Dalgleish 2003, McClements 2005b, 2007, Sherman 1995). The main
problem identified with the procedure is that the amount of emulsifier required to
stabilize an emulsion depends on the oil–water interfacial area rather than the oil-
volume fraction, thus EC depends on the size of the droplets produced during agita-
tion. This in turn is highly sensitive to the type of mixing/homogenization apparatus
used, its energy intensity (see Chapter 1), the volume of emulsion being processed,
the viscosity of the oil phase, and the temperature of processing. As such, EC should
be regarded as a qualitative index that depends on the specific setup and conditions
used to carry out the test that can be used to compare different emulsifiers tested
under the same conditions.
An alternative way of estimating the amount of emulsifier required to form an
emulsion that takes into account the amount of interfacial area generated is via the
surface load, Γs, which corresponds to the mass of emulsifier required to stabilize a
unit area of droplet surface (Dickinson 1992). This is determined by first generating
a stable emulsion by homogenizing a known amount of oil, water, and emulsifier.
Then the amount of emulsifier adsorbed at the oil–water interface is determined
via a mass balance of the emulsifier; that is, the amount adsorbed at the oil–water
interface, which is found by considering the initial concentration of emulsifier in the
continuous phase, Cini , minus the amount remaining in the continuous phase after
emulsification, Cend . This is carried out experimentally by carefully separating the
droplets from the continuous phase by centrifugation or filtration and determining
the remaining concentration of the emulsifier (Tcholakova et al. 2002). The interfa-
cial area to which the emulsifiers are adsorbed is found by measuring the specific
surface area of the emulsion by either microscopy or an automated particle size ana-
lyzer. The specific surface area, S, is determined from the surface mean diameter, d32
d32 =
∑Nd i
3
i i
(3.2)
∑Ndi
2
i i
where:
Ni is the number of drops with diameter di
Because the specific surface area, S, is the sum of all the surface areas of all drops
divided by the sum of all their volumes (m2/m3), we can calculate S from d32:
4π(d32 /2)2 6
S= = (3.3)
(4/3)π(d32 /2)3
d32
Now, including this into the mass balance or the emulsifier over the continuous phase
and interface, we get
Vcts (Cini − Cend ) (1 − φ) d32

ΓS = = (Cini − Cend ) (3.4)
Vdisp S φ 6
K16909_C003.indd 82 12/31/14 4:14 PM

Here, Vcts and Vdisp are the volumes of the continuous and dispersed phases,
respectively, and ϕ is the volume fraction of dispersed phase, that is,
Vdisp
φ= (3.5)
Vcts + Vdisp
Typically, the values of ΓS for molecular food emulsifiers is around a few milligram
per square meter, but is much larger for particles, hundreds to thousands milligram per
square meter, as ΓS is also directly related to the thickness of the interfacial layer. These
estimates of surface load values provide some knowledge with respect to the minimum
amount of emulsifier that is required to make an emulsion having droplets of a given
size and the dispersed phase fraction. However, in practice, an excess of emulsifier is
often used, as not all emulsifiers are ideally adsorbed into the oil–water interface during
homogenization due to kinetic limitations, as well as due to the partitioning equilibrium
conditions between the interface and the continuous phase. Furthermore, the surface
load of some types of emulsifiers is also sensitive to formulation conditions such as ionic
strength, pH, the concentration of macromolecules, temperature, and so on.
3.5.2 eMulSioN Stability iNdex

The emulsification capacity, presented in Section 3.5.1, gives information on the
ability to create an emulsion with a given formulation, but does not necessarily take
into account the evolution of emulsion stability over time. One expression of the
emulsion stability over time is the ESI, which is based on particle size measurements
performed at given time intervals and is defined as
d( 0 )t
ESI = (3.6)
d( t ) − d( 0 )
where:
d( 0 ) is the initial mean droplet diameter of the emulsion
d( t ) is the mean droplet diameter measured after a storage time, t (McClements
2005b)
Some of the main strengths of this method include that the mean droplet diameter
can be readily determined in analytical instruments, the evolution of particle size
microstructure is often a precursor to quality deterioration on the macrostructure
(creaming and phase separation, etc.) and can re-repeated over relevant time scale for
the shelf life of the product. A similar index is also sometimes used that compares
the specific surface area of the emulsions rather than just mean droplet size as a mea-
sure of how much coalescence has taken place. This surface coalescence index (SCI)
is more sensitive to the fate of smaller drops (as they have a relatively larger surface
are to volume ratio) and can be calculated by
S( 0 ) − S( t )
SCI = (3.7)
S( 0 )
K16909_C003.indd 83 12/31/14 4:14 PM

where:
S( 0 ) is the initial specific surface area of the emulsion
S( t ) is new specific surface area of the emulsion measured after a storage time,
t (Anton, Beaumal, and Gandemer 2000)
S is calculated directly from 6/d32
It should be noted that there is no compelling evidence that a single index such as
EC, ESI, or SCI can be used to ultimately compare the effectiveness or the stability
of emulsifiers if they have been produced under different homogenization condi-
tions. Still, these indices are very useful when comparing a series of emulsifiers
of emulsion formulations produced under standardized conditions or in situations
when the influence of specific changes are being made to the formulation, pro-
cessing conditions, or functionality of a specific ingredient that is being studied
(McClements 2005b).
3.5.3 aSSeSSiNg gravitatioNal SeParatioN—creaMiNg iNdex

Gravitational separation of emulsions is one of the most common instability mecha-
nisms encountered in food and personal care products, thus formulators need to
know at what degree creaming or sedimentation is likely to occur over the shelf life
of a relevant product. Due to the fact that emulsion droplets in the context of food
emulsions typically never have the same density as the continuous phase and are
large enough for the buoyant forces to overcome viscous resistance and Brownian
motion, they allow gravitational separation to be observed on a relevant time scale.
As most edible oils at room temperature have a lower density than aqueous solu-
tions, oil droplets in O/W emulsions will tend to rise to the top of the container in
a process referred to as creaming, leaving the depleted layer by an emulsion drop at
the bottom of the container, often referred to as serum. These terms likely originate
from the prevalence of diary emulsions. For W/O emulsions, the sedimentation of
water droplets is observed, although generally at a much slower rate due to the higher
viscosity of the oil. However, the opposite can be observed, where the sedimentation
of oil droplet can occur if fat crystals or other weighing agents are added to the oil
phase, or in some cases, in particle-stabilized emulsions, where a higher density of
the stabilizing particle layer increases the overall density of the droplet causing them
to settle (Rayner, Timgren et al. 2012).
The rate at which a single spherical droplet or particle will cream (or settle) in a
Newtonian fluid can be predicted by the Stokes velocity:
2gr 2 (ρ2 − ρ1 )
AQ 34 υStokes = − (3.8)
9η1
where:
g is acceleration due to gravity
r is the particle radius
ρ1 and ρ2 are the densities of the continuous and dispersed phases, respectively
η1 is the continuous phase viscosity
K16909_C003.indd 84 12/31/14 4:14 PM

The settling or creaming rate of drops and particles indicated by Stokes equation is
somewhat idealized, as in reality, emulsions drops are not all the same size and will be
interacting during creaming or settling. Furthermore, Stokes law is mainly applicable
at low concentrations of the dispersed phase. However, Stokes equation does provide an
illustration of the factors that have the most impact on the gravitational tendency, specif-
ically the viscosity of the fluid surrounding the droplets, their relative density, and, to a
large degree, the droplet size due to the exponent. For example, an oil droplet creams at
a rate of 0.1 mm/day if its diameter is 0.1 µm, and will cream at a rate of 10 mm/day if the
diameter is 1 µm, if all other conditions remain constant. In many practical situations,
these conditions are not constant and are more complex; for example, there is often an
increase in the effective particle size during creaming due to coalescence, flocculation,
or Ostwald ripening (see Chapter 2), which results in Stokes under predicting the rate AQ 35
of gravitational separation (McClements 2007). Therefore, it is often more practical to
directly quantify gravitational separation of the emulsions during storage.
The extent of creaming or sedimentation in an emulsion can be monitored by
visual observation. This method is cheap and straightforward, only requiring the
emulsions to be stored in an appropriate environment in clear glass vials or test
tubes. The layer formed by creamed emulsion droplets can be readily seen, and often
the serum layer is transparent or optically distinct to such a degree that its height can
be determined, or its volume estimated. The emulsion index (EI) is a measure of the
volume of an emulsion layer formed relative to the total volume given by the follow-
ing equation, with the volumes defined in Figure 3.3:
Vemuls
EI = (3.9) AQ 36
Vtotal
The relative heights of the creamy layer is also used to define the creaming index (CI):
Hserum
CI = × 100% (3.10)
Hemuls
Vemuls Hrel oil Released oil layer
Vtotal Hemuls Creamed emulsion
Vserum Serum layer

Hserum
Vemuls Hserum
EI = CI = × 100%
Vtotal Hemuls
FIgure 3.3 (a) Test tube showing creamed emulsions as defined in EI; (b) schematic test AQ 37
tube showing layers as defined in CI.
K16909_C003.indd 85 12/31/14 4:14 PM

Assuming that there is no significant coalescence or creation of an oil later (called

oiling-off, schematically illustrated in Figure 3.3b), the CI will start at zero and will
increase until all the emulsion drops are packed into the creamy layer, after which
the CI index reached a final value. The height of the final creamy layer depends on
the volume fraction of the oil, ϕ, and the maximum packing parameter droplets,
which is approximately P ~ 0.6, for random closed packing (McClements 2007).
 φ
CI final =  1 −  × 100% (3.11)
 P 
Knowing the expected CI final can be relevant if emulsions with different dispersed
phase volumes are to be compared, as the more dispersed phases, the lesser will be
the serum. This concept had also been extended to adjust for the fact that particles,
and especially the larger food-based ones used in stabilizing Pickering emulsions,
also contribute to the amount of dispersed phase observed. The total amount of non-
separated emulsion can be expressed as the relative occluding volume (ROV).
Vemuls
ROV = (3.12)
Vdisp + Vparticles
where:
Vemuls is the volume of the observed emulsion (i.e., the nonclear fraction) after
emulsification
Vdisp is the known volume of the added dispersed phase
Vparticles is the known volume occupied by the added particle stabilizers
In a completely phase-separated system, ROV equals to 1; that is, there is no

increase in the emulsion layer beyond that of its constituent phases. Figure 3.4
illustrates the differences in EI and ROV for starch granule-stabilized emulsions
1.1 6
1.0 5
Emulsion index
0.9 4
ROV
0.8 3
0.7 2
0.6 1
0.5 0
0.1 1 10 0.1 1 10
Storage time (weeks) Storage time (weeks)
12.5% oil 16.6% oil 25% oil 33.2% oil
FIgure 3.4 EI and ROV of quinoa starch granule-stabilized oil-in-water emulsions. (Data
from Timgren, A. et al., Procedia Food Sci., 1, 95–103, 2011.)
K16909_C003.indd 86 12/31/14 4:14 PM

with varying dispersed phase fraction (oil content 12.5%–33.2%), but at constant
starch-to-oil ratio of 214 mg/mL oil. Here, we can see that although the EI
increases as expected with oil content, the ROV is higher for the less tightly
packed systems. It should be noted that in this system, there was no significant
change in droplet size over time or between formulations with different dispersed
phase fractions.
Although the use of digital camera has greatly simplified the analysis of visual
observations of gravitational separations, there are several limitations to the visual
inspection of gravitational separation. It is often difficult to distinguish between the
layers in creaming/settling emulsions by the visual observation of a glass vial or a test
tube. One means to overcome this limitation is using an apparatus that scans the height
of the glass tube with a monochromatic beam of light near infrared part of the spec-
trum while monitoring the amount of scattered and transmitted light. This can give
an improved accuracy with respect to the boundaries between the creamed and serum
layers, as well as the possibility to quantify the concentration of emulsion drops as a
function of height. Some modern commercial instruments have also implemented mul-
tiple light-scattering techniques (e.g., Turbiscan Lab) that enable the measurement of
concentrated emulsions and the measurement of both the particle size and phase thick-
ness continuously over time (Mengual et al. 1999), detecting the creaming long before
it is visible to the naked eye. The other major limitation of the gravitational separation
analysis is that it takes a significantly long time to monitor instability that may occur
after weeks of storage and that the storage conditions in reality are not necessarily those
found in a controlled laboratory environment. This can be overcome in two ways: (1) by AQ 38
increasing the gravitational field where the droplets cream/settle to accelerate storage
and (2) by exposing the emulsions to environmental stresses that may trigger instability.
3.5.4 accelerated aNd eNviroNMeNtal StreSS teStS

The rate of gravitational separation and droplet coalescence can be accelerated
by the centrifugation of emulsions at a fixed speed for a certain length of time
(Sherman 1995). After which, the separation is monitored using the same means
as in a normal storage trial (visual observation, digital imaging, light scattering
etc.). Alternatively, there are commercial analytical instruments that both scan and
centrifuge samples to gain further information (i.e., Lumisizer). However, precau-
tionary measures must be taken while using this approach, especially if there is a
difference in the rate of droplet size evolution between the normally stored and
accelerated samples. For example, if the droplet size is changing due to coales-
cence or Ostwald ripening, which in turn affects the rate of gravitational separation,
then these may or may not be reflected by merely increasing the gravitational field.
Furthermore, if the emulsion has a complex rheology (i.e., not just a Newtonian
continuous phase), increasing the gravitational field may over exaggerate the sepa-
ration. For example, if the emulsion has a weak gel structure (a finite yield stress)
that can be overcome in the centrifuge (but not under normal storage), the emulsion
will be forced to separate in conditions when it normally would not, if it is left to
settle over the normal time frame. For these reasons, it is imperative to compare
the results of accelerated creaming tests with those made using long-term normal
K16909_C003.indd 87 12/31/14 4:14 PM

storage to validate the methods before routinely using an accelerated test for a
given type of formulation (McClements 2007).
In addition to gravitational separation, coalescence can also be accelerated using
centrifugal methods, as these methods essentially force droplets together. In this
case, the coalescence stability is determined by measuring the change in droplet
size distribution and/or the extent of oiling-off after the emulsion has been cen-
trifuged for a specific speed and time. Here, the coalescence stability is quanti-
fied in terms of the maximum centrifugation force that the emulsion can tolerate
before a change in the microstructure is observed (droplet size and or oiling-off).
The particle size distribution of the emulsion droplets can be measured before and
after centrifugation and the data can be represented as either the entire distribu-
tion or ESI. Alternatively, Tcholakova et al. (2002, 2006) have developed a cen-
trifugal method that can provide quantitative data about O/W emulsions stability
to coalescence. An emulsion is added to a transparent centrifuge tube and is loaded
into a centrifuge. This emulsion is then subjected to a centrifugal acceleration at
an appropriate intensity and time. The oils droplets will tend to move toward the
axis of rotation (z direction in Figure 3.5) due to their relatively lower density. This
is the case for almost all food emulsions. Initially, the emulsion droplets form a
AQ 39 creamy layer where they are forced into close proximity but keep their initial form.
As the centrifugal force is increased, they are pressed tighter and tighter together
and eventually the interfacial layer surrounding and stabilizing the droplets will
AQ 40 rupture, releasing a layer of cream on the top of the emulsion column in the tube
(see Figure 3.5).
The critical pressure that the emulsion can withstand before the oil is released
CR
when the film ruptures is described as a critical osmotic pressure, POSM . For a full
derivation, refer to Tcholakova et al. (2002, 2006) and references therein.
Hc
(Voil tot − Voil rel )
∫
= ∆ρgk φ( z)dz = ∆ρgk
CR
POSM (3.13)
ATT
0
0 ζ0 ζ1 ζ2 ζ
ω
Cream
Oil Serum
Hrel HC
Z 0
FIgure 3.5 Schematic image of the thickness of the oil layer released during a forced
coalescence test.
K16909_C003.indd 88 12/31/14 4:14 PM

where:
Δρ is the density difference between the oil and aqueous phases
gk is the centrifugal acceleration
φ(z) is the local volume fraction of oil along the z direction along the centrifugal
field
Voil tot is the total volume of oil in the emulsion
Voil rel is the volume of oil released
ATT is the interior cross-sectional area of the test tube containing the emulsion
After centrifugation, the height of the creamy layer, HC and oil released Hoil rel can
be easily measured, where Hoil rel = Voil rel / ATT . POSM
CR
may be readily calculated from
experimental data, if one assumes that the centrifugal field is homogenous through
the column of creamed emulsion, HC, and can be represented by the square of the
angular frequency, ω times the mean distance of the emulsion layer from the axis of
rotation, ζ:
ω2 (ζ1 + ζ 2 )
gk ≈ = constant (3.14)
2
Tcholakova et al. (2002, 2006) have proven that this is a reasonable assumption, as
more precise calculations that take into the account the spatial variation of the field
compared to using a mean distance gives a relatively small difference in the result,
and the imposed error is within the experimental accuracy of the measurements. This
method has been demonstrated to be particularly useful for monitoring the coales-
cence stability of different types of protein-stabilized emulsion with various composi-
tions (Denkov, Tcholakova, and Ivanov 2006, Tcholakova et al. 2002, 2003, 2006).
In addition to centrifugation, other types of accelerated coalescence tests include
subjecting the emulsions to other types stress such as mechanical forces (extended
homogenization, pumping, vibration, shearing, extruding, whipping, shaking, and
mixing) environmental stresses (freeze-thaw cycling, thermal processing, and heat
abuse), as well as compositional stresses (drying causing a change in solute com-
position, changes in pH and ionic strength, etc.). All of which with the purpose
of emulating some sort of typical event, environmental stress, or process that the
emulsion under consideration should withstand during processing, transport, shelf
life, and use. The formulation in general—and the performance of its emulsifier in
particular—is evaluated in a variety of conditions depending on its application to
establish a design space, in which a particular emulsifier is expected to successfully
function. Examples of test methods and experimental conditions/protocols can be
found in McClements (2007) and references therein.
3.5.5 evaluatioN oF texture

As pointed out previously, the rheology of an emulsion is important not only to the
taste, texture, and mouthfeel (Le Révérend et al. 2010) but also for the creaming
stability and coalescence (Tadros 2004). In this chapter, we only give a short over-
view of the rheology of an emulsion; for a more extensive review, we recommend
K16909_C003.indd 89 12/31/14 4:14 PM

Derkach (2009), Tabilo-Munizaga and Barbosa-Cánovas (2005), and Tadros

(2004)). Texture can be evaluated using techniques such as rheological and texture
analyzers. Although texture analyzers can give a quick information and comparison
of systems, the information gained especially from oscillating rheology gives more
knowledge.
Emulsions droplets can, from a rheological viewpoint, in most cases be consid-
ered as hard spheres. The rheology of such systems are strongly dependent on the
concentration at low concentrations; where there are no droplet–droplet interactions,
the system will follow Einstein’s (1906) law for hard spheres. However, at moderate
concentrations, the interactions between the droplets will affect the rheology and in
these regimes, the rheology can be described by semiempirical equations such as the
Krieger–Dougherty equation (Krieger 1972).
−[( 5 / 2 ) φc ]
 φ 
η = η0  1 − e  (3.15)
 φc 
where:
η0 is the viscosity of the continuous phase
φc is the is the volume fraction at random close packing of spheres
φe is the volume fraction of oil in the emulsion.
Addition of rheological modifiers will further complicate the rheological proper-

ties of emulsions; for emulsions in the concentrated regime or emulsions containing
viscosity modifiers, the system will often become viscoelastic. For such systems,
measuring the rheology using oscillating measurements can further elucidate the
character of the emulsion. This allows for the use of small strains and stresses on
the material leading to measurements that does not destroy the structure of the sam-
ples. The sample is subjected to a sinusoidal shear deformation and the resultant
stress response is measured. The frequency and the strain/stress on the sample can
normally be varied and the response is divided into a viscous component G″ (loss
module) and an elastic component G′ (storage module). Such measurements can give
information of the viscoelastic character of the emulsion and, for example, describe
if the emulsion has a gel-like character or not. A characteristic for gels is that G′ is
higher than G″.
Oscillating measurements can, for example, be used to follow the buildup of a gel
during heating or cooling. In oscillating measurements, one can either change the
frequency of the oscillation or the strain/stress. Figure 3.6 shows typical frequency
measurements of Pickering emulsions for weak and strong gels and Figure 3.7 shows
a strain curves for the same samples. The frequency curve gives information on how
the emulsions react to stress during different time frames (time is proportional to
1/frequency). Stress or strain test are often used for gel-like emulsions and preferably
measured at a frequency where the rheological properties of the gel are in a linear
region. Typically, in strain tests, the strain is increased until the structure of the emul-
sions is broken and the gel starts to flow, which is shown as a rapid decease of G′.
As can be seen in Figures 3.6 and 3.7, even if the gel is stiffer (high G′) and has a
smaller linear gel region (frequency), it might still flow at lower strains.
K16909_C003.indd 90 12/31/14 4:14 PM

100000
10000
1000
G′ and G′′ (Pa)
100
10
0
0.1 1 10
Frequency, f (Hz)
FIgure 3.6 Elastic modulus (G′, in Pa) and viscous modulus (G″, in Pa) versus frequency
(f, in Hz) for Pickering emulsions with 19% Miglyol oil-in-water (O/W) emulsion stabilized
by chitosan G″(closed squares), G′ (open squares) with 55% Miglyol O/W emulsion stabilized
by OSA-modified quinoa starch G″ (closed circles), G′ (open circles). AQ 41
10000
1000
100
G′ and G′′ (Pa)
10
0.1
0.01
1.00E − 01 1.00E + 00
Complex shear strain
FIgure 3.7 Elastic modulus (G′, in Pa) and viscous modulus (G″, in Pa, versus complex
shear strain) for Pickering emulsions with 19% Miglyol O/W emulsion stabilized by chitosan
G″ (closed squares), G′ (open squares) with 55% Miglyol O/W emulsion stabilized by OSA-
modified quinoa starch G″ (closed circles), G′ (open circles).
The rheology of emulsions is especially important to avoid creaming in nonspace

filled systems. Thus, it is of interest to estimate the viscosity needed to arrest cream-
ing. The bouncy force on a droplet will be F = VΔρg stress is F/A thus the stress AQ 42
exerted by the droplet will be RΔρg/3. The stress asserted by normal emulsions
droplets will thus be normally below 0.1 Pa. Therefore, to arrest creaming, gelling
K16909_C003.indd 91 12/31/14 4:14 PM

polymers only have to withstand the stress asserted by the droplet. Furthermore, this
also means that to predict the resistance of the system to creaming, the rheology has
to be measured at a low stress, which can be obtained by constant stress or creep
measurements. However, normally we would like the system to flow when handled;
therefore, a good rheological modifier should yield at higher stresses. In this respect,
stress curves are more informative.
reFerenCes
Abee, T., L. Krockel, and C. Hill. 1995. “Bacteriocins: Modes of action and potentials in food
preservation and control of food poisoning.” International Journal of Food Microbiology
28:169–185.
AQ 43 Agriculture, U.S.D.O. 2014. World Production, Markets, and Trade Reports: Oilseeds. United
States Department of Agriculture.
Akhtar, M., and E. Dickinson. 2007. “Whey protein–maltodextrin conjugates as emulsi-
fying agents: An alternative to gum arabic.” Food Hydrocolloids 21 (4):607–616.
doi:10.1016/j.foodhyd.2005.07.014.
Akhtar, M., E. Dickinson, J. Mazoyer, and V. Langendorff. 2002. “Emulsion stabilizing prop-
erties of depolymerized pectin.” Food Hydrocolloids 16 (3):249–256. doi:http://dx.doi
.org/10.1016/S0268-005X(01)00095-9.
Alftrén, J., J.M. Peñarrieta, B. Bergenståhl, and L. Nilsson. 2012. “Comparison of molecu-
lar and emulsifying properties of gum arabic and mesquite gum using asymmetri-
cal flow field-flow fractionation.” Food Hydrocolloids 26 (1):54–62. doi:10.1016/
j.foodhyd.2011.04.008.
Allouche, J., E. Tyrode, V. Sadtler, L. Choplin, and J.L. Salager. 2004. “Simultaneous conductiv-
ity and viscosity measurements as a technique to track emulsion inversion by the phase-
inversion-temperature method.” Langmuir 20 (6):2134–2140. doi:10.1021/la035334r.
Anton, M., V. Beaumal, and G. Gandemer. 2000. “Adsorption at the oil–water interface and
emulsifying properties of native granules from egg yolk: Effect of aggregated state.”
Food Hydrocolloids 14 (4):327–335. doi:10.1016/s0268-005x(00)00009-6.
Aveyard, R., B.P. Binks, and J.H. Clint. 2003. “Emulsions stabilised solely by colloidal par-
ticles.” Advances in Colloid and Interface Science 100–102:503–546.
Awade, A.C. 1996. “On hen egg fractionation: Applications of liquid chromatographyt o the
isolation and the purification of hen egg white and egg yolk proteins.” Z lebensm Unters
Forsch 202:1–14.
Bancroft, W.D. 1913. “The theory of emulsification, V.” Journal of Physical Chemistry
17 (6):501–519.
Bayarri, S., A.J. Taylor, and J. Hort. 2006. “The role of fat in flavor perception: Effect of par-
tition and viscosity in model emulsions.” Journal of Agricultural and Food Chemistry
54:8862−8868.
Benjamins, J., M.H. Vingerhoeds, F.D. Zoet, E.H.A. de Hoog, and G.A. van Aken. 2009.
“Partial coalescence as a tool to control sensory perception of emulsions.” Food
Hydrocolloids 23 (1):102–115. doi:10.1016/j.foodhyd.2007.11.017.
Berasategi, I., M. Garcia-Iniguez de Ciriano, I. Navarro-Blasco, M.I. Calvo, R.Y. Cavero,
I. Astiasaran, and D. Ansorena. 2014. “Reduced-fat bologna sausages with improved
lipid fraction.” Journal of the Science of Food and Agriculture 94 (4):744–751.
doi:10.1002/jsfa.6409.
Binks, B.P. 2002. “Particles as surfactants—Similarities and differences.” Current Opinion in
Colloid & Interface Science 7 (1–2):21–41.
Binks, B.P. 2007. “Colloidal particles at liquid interfaces.” Physical Chemistry Chemical
Physics 9 (48):6298–6299. doi:10.1039/b716587k.
K16909_C003.indd 92 12/31/14 4:14 PM

Binks, B.P., A.N. Boa, M.A. Kibble, G. MacKenzie, and A. Rocher. 2011. “Sporopollenin
capsules at fluid interfaces: Particle-stabilised emulsions and liquid marbles.” Soft Matter
7 (8):4017–4024.
Binks, B.P., J.H. Clint, G. Mackenzie, C. Simcock, and C.P. Whitby. 2005. “Naturally occurring
spore particles at planar fluid interfaces and in emulsions.” Langmuir 21 (18):8161–8167.
Bosa, M.A., and T. van Vlieta. 2001. “Interfacial rheological properties of adsorbed protein lay-
ers and surfactants: A review.” Advances in Colloid and Interface Science 91:437–471.
Burt, S. 2004. “Essential oils: Their antibacterial properties and potential applications in
foods—A review.” International Journal of Food Microbiology 94 (3):223–253.
doi:10.1016/j.ijfoodmicro.2004.03.022.
Castro, M.P., A.M. Rojas, C.A. Campos, and L.N. Gerschenson. 2009. “Effect of preservatives,
tween 20, oil content and emulsion structure on the survival of Lactobacillus fructiv-
orans in model salad dressings.” LWT—Food Science and Technology 42 (8):1428–1434.
doi:10.1016/j.lwt.2009.02.021.
Charoen, R., A. Jangchud, K. Jangchud, T. Harnsilawat, E.A. Decker, and D.J. McClements.
2012. “Influence of interfacial composition on oxidative stability of oil-in-water emul-
sions stabilized by biopolymer emulsifiers.” Food Chemistry 131 (4):1340–1346.
doi:10.1016/j.foodchem.2011.09.128.
Charteris, W.P. 1996. “Microbiological quality assurance of edible table spreads in new prod-
uct development.” Journal of the Society of Dairy Technology 49:87–98.
Chen, B., D.J. McClements, and E.A. Decker. 2011. “Minor components in food oils: A
critical review of their roles on lipid oxidation chemistry in bulk oils and emulsions.”
Critical Reviews in Food Science and Nutrition 51 (10):901–916. doi:10.1080/104083
98.2011.606379.
Chevalier, Y., and M.-A. Bolzinger. 2013. “Emulsions stabilized with solid nanoparticles:
Pickering emulsions.” Colloids and Surfaces A: Physicochemical and Engineering
Aspects 439:23–34. doi:10.1016/j.colsurfa.2013.02.054.
Chronakis, I.S. 1997. “Structural–functional and water-holding studies of biopolymers in low
fat content spreads.” Lebensmittel-Wissenschaft und -Technologie 30:36–44.
Chung, C., and D.J. McClements. 2013. “Structure–function relationships in food emul-
sions: Improving food quality and sensory perception.” Food Structure 1:106–126.
doi:10.1016/j.foostr.2013.11.002.
Clarke, E.J., and J. Wiseman. 2000. “Developments in plant breeding for improved nutritional
quality of soya beans I. Protein and amino acid content.” Journal of Agricultural Science
134:111–124.
Corredig, M., and M. Alexander. 2008. “Food emulsions studied by DWS: Recent advances.”
Trends in Food Science and Technology 19 (2):67–75.
Cristofolini, L. 2014. “Synchrotron X-ray techniques for the investigation of structures and
dynamics in interfacial systems.” Current Opinion in Colloid & Interface Science
19 (3):228–241. doi:10.1016/j.cocis.2014.03.006.
Dalgleish, D.G. 2003. “Food emulsions.” In Food Emulsions. CRC Press. AQ 44
Dalgleish, D.G. 2011. “On the structural models of bovine casein micelles—Review and pos-
sible improvements.” Soft Matter 7 (6):2265. doi:10.1039/c0sm00806k.
Davies, J.T. 1957. “A quantitative kinetic theory of emulsion type. I. Physical chemistry of AQ 45
the emulsifying agent.” Gas/liquid and liquid/liquid interfaces. Proceedings of 2nd
International Congress Surface Activity, Butterworths, London.
De Folter, J.W.J., M.W.M. Van Ruijven, and K.P. Velikov. 2012. “Oil-in-water Pickering emul-
sions stabilized by colloidal particles from the water-insoluble protein zein.” Soft Matter
8 (25):2807–2815.
Degner, B.M., C. Chung, V. Schlegel, R. Hutkins, and D.J. McClements. 2014. “Factors influ-
encing the freeze-thaw stability of emulsion-based foods.” Comprehensive Reviews in
Food Science and Food Safety 13 (2):98–113. doi:10.1111/1541-4337.12050.
K16909_C003.indd 93 12/31/14 4:14 PM

Delamarre, S., and C.A. Batt. 1999. “The microbiology and historical safety of margarine.”
Food Microbiology 16:327–333.
AQ 46 Denkov, N.D., S. Tcholakova, and I.B. Ivanov. 2006. “Globular proteins as emulsion
stabilizers—Similaries and differences with surfactants and solid particles.” 4th World
Congress on Emulsions, Lyon, France.
Derkach, S.R. 2009. “Rheology of emulsions.” Advances in Colloid and Interface Science
151 (1–2):1–23. doi:10.1016/j.cis.2009.07.001.
Destribats, M., M. Rouvet, C. Gehin-Delval, C. Schmitt, and B.P. Binks. 2014. “Emulsions
stabilised by whey protein microgel particles: Towards food-grade Pickering emul-
sions.” Soft Matter 10: 6941–6954. doi:10.1039/C4SM00179F.
Dickinson, E. 1992. Introduction to Food Colloids. Oxford: Oxford University Press.
Dickinson, E. 2003. “Hydrocolloids at interfaces and the influence on the properties of dis-
persed systems.” Food Hydrocolloids 17:25–39.
Dickinson, E. 2010. “Food emulsions and foams: Stabilization by particles.” Current Opinion
in Colloid & Interface Science 15 (1–2):40–49. doi:10.1016/j.cocis.2009.11.001.
Dickinson, E. 2012. “Use of nanoparticles and microparticles in the formation and stabilization
of food emulsions.” Trends in Food Science and Technology 24 (1):4–12. doi:10.1016/
j.tifs.2011.09.006.
Dickinson, E. 2013. “Stabilising emulsion-based colloidal structures with mixed food ingredients.”
Journal of the Science of Food and Agriculture 93 (4):710–721. doi:10.1002/jsfa.6013.
Dickinson, E., and E. Davies. 1999. “Influence of ionic calcium on stability of sodium casein-
ate emulsions.” Colloids and Surfaces B-Biointerfaces 12:203–212.
Dorobantu, L.S., A.K.C. Yeung, J.M. Foght, and M.R. Gray. 2004. “Stabilization of oil-water
emulsions by hydrophobic bacteria.” Applied and Environmental Microbiology 70
(10):6333–6336.
AQ 47 Drelich, J., Ch. Fang, and C.L. White. 2002. “Measurement of interfacial tension in fluid-fluid
systems.” In Encyclopedia of Surface and Colloid Science, 3152–3166. Marcel Dekker.
Einstein, A. 1906. “Eine neue Bestimmung der Moleküldimensionen.” Annalen der Physik
324 (2):289–306. doi:10.1002/andp.19063240204.
Eliasson, A.-C. 1986. “On effects of Surface active agents on the gelatinization of starch—a
calorimetric investigation.” Carbohydrate Polymers 6:463–476.
Ercelebi, E.A., and E. Ibanoglu. 2010. “Stability and rheological properties of egg yolk gran-
ule stabilized emulsions with pectin and guar gum.” International Journal of Food
Properties 13 (3):618–630. doi:10.1080/10942910902716984.
AQ 48 Eriksson, M. 2013. “Pickering emulsions based on food grade biological particles.” MSc,
Department of Food Technology, Engineering and Nutrition, Lund University (KLT
920, 2013).
Evans, M., I. Ratcliffe, and P.A. Williams. 2013. “Emulsion stabilisation using polysaccharide–
protein complexes.” Current Opinion in Colloid & Interface Science 18 (4):272–282.
doi:10.1016/j.cocis.2013.04.004.
Frankel, E.N. 1998. Lipid Oxidation. Dundee, Scotland: Oily Press.
Fredrick, E., P. Walstra, and K. Dewettinck. 2010. “Factors governing partial coalescence in
oil-in-water emulsions.” Advances in Colloid and Interface Science 153 (1–2):30–42.
doi:10.1016/j.cis.2009.10.003.
Frelichowska, J., M.A. Bolzinger, and Y. Chevalier. 2010. “Effects of solid particle content
on properties of o/w Pickering emulsions.” Journal of Colloid Interface and Science
351 (2):348–356. doi:10.1016/j.jcis.2010.08.019.
Friberg, S., and I. Wilton. 1970. “Liquid crystals—the formula for emulsions.” American
Perfumer and Cosmetics 85:27–30.
Golding, M., and T.J. Wooster. 2010. “The influence of emulsion structure and stability on
lipid digestion.” Current Opinion in Colloid & Interface Science 15 (1–2):90–101.
doi:10.1016/j.cocis.2009.11.006.
K16909_C003.indd 94 12/31/14 4:14 PM

Gould, J., J. Vieira, and B. Wolf. 2013. “Cocoa particles for food emulsion stabilisation.” Food
& Function 4 (9):1369–1375. doi:10.1039/c3fo30181h.
Griffin, W.C. 1954. “Calculation of HLB values of non-ionic surfactants.” Journal of the
Society of Cosmetic Chemists 5 (4):249–256.
Gu, Y.X., Y.H. Huang, B. Liao, G.M. Cong, and M. Xu. 2000. “Studies on the characterization
of phase inversion during emulsification process and the particle sizes of water-borne
microemulsion of poly(phenylene oxide) ionomer.” Journal of Applied Polymer Science
76 (5):690–694. doi:10.1002/(sici)1097-4628(20000502)76:5<690::aid-app11>3.0.co;2-q.
Gupta, R., and D. Rousseau. 2012. “Surface-active solid lipid nanoparticles as Pickering
stabilizers for oil-in-water emulsions.” Food & Function 3 (3):302–311. doi:10.1039/
c2fo10203j.
Hagel, L. 2011. “Gel filtration: Size exclusion chromatography.” In Protein Purification, AQ 49
51–91. John Wiley & Sons.
Harnsilawat, T., R. Pongsawatmanit, and D.J. McClements. 2006. “Stabilization of model
beverage cloud emulsions using protein−polysaccharide electrostatic complexes formed
at the oil−water interface.” Journal of Agricultural and Food Chemistry 54:5540−5547.
Harvey, D.J. 2011. “Analysis of carbohydrates and glycoconjugates by matrix-assisted laser
desorption/ionization mass spectrometry: An update for the period 2005–2006.” Mass
Spectrometry Reviews 30 (1):1–100. doi:10.1002/mas.20265.
Hashemi, M.M., M. Aminlari, and M. Moosavinasab. 2014. “Preparation of and studies on the
functional properties and bactericidal activity of the lysozyme–xanthan gum conjugate.”
LWT—Food Science and Technology 57 (2):594–602. doi:10.1016/j.lwt.2014.01.040.
Heertje, I. 2014. “Structure and function of food products: A review.” Food Structure 1 (1):
3–23. doi:10.1016/j.foostr.2013.06.001.
Horne, D.S. 2002. “Casein structure, self-assembly and gelation.” Current Opinion in Colloid
& Interface Science (7):456–461.
http://ndb.nal.usda.gov/ndb/foods. AQ 50
http://www.engineeringtoolbox.com/oil-melting-points-d_1088.html.
Hyldgaard, M., D.S. Sutherland, M. Sundh, T. Mygind, and R.L. Meyer. 2012. “Antimicrobial
mechanism of monocaprylate.” Applied and Environmental Microbiology 78
(8):2957–2965. doi:10.1128/AEM.07224-11.
Israelachvili, J.N. 1985. Intermolecular and Surface Forces: With Applications to Colloidal
and Biological Systems. London: Academic Press.
Israelachvili, J., D.J. Mitchell, and B. Ninham. 1976. “Theory of selfassembly of hydrocar-
bon amphiphiles into micelles and bilayers.” Journal of the Chemical Society, Faraday
Transactions 2 72:1525–1568.
Jin, H., W. Zhou, J. Cao, S.D. Stoyanov, T.B.J. Blijdenstein, P.W.N. De Groot, L.N. Arnaudov,
and E.G. Pelan. 2012. “Super stable foams stabilized by colloidal ethyl cellulose par-
ticles.” Soft Matter 8 (7):2194–2205. doi:10.1039/c1sm06518a.
Kalashnikova, I., H. Bizot, P. Bertoncini, B. Cathala, and I. Capron. 2013. “Cellulosic nanorods
of various aspect ratios for oil in water Pickering emulsions.” Soft Matter 9 (3):952–959.
doi:10.1039/c2sm26472b.
Kalashnikova, I., H. Bizot, B. Cathala, and I. Capron. 2011. “New Pickering emulsions stabi-
lized by bacterial cellulose nanocrystals.” Langmuir 27 (12):7471–7479. doi:10.1021/
la200971f.
Kargar, M., K. Fayazmanesh, M. Alavi, F. Spyropoulos, and I.T. Norton. 2012. “Investigation
into the potential ability of Pickering emulsions (food-grade particles) to enhance the
oxidative stability of oil-in-water emulsions.” Journal of Colloid and Interface Science
366 (1):209–215. doi:10.1016/j.jcis.2011.09.073.
Karlsson, C.A.-C., M.C. Wahlgren, and A.C. Trägårdh. 1996. “Time and temperature aspects
of β-lactoglobulin removal from methylated silica surfaces by sodium dodecyl sulphate.”
Colloids and Surfaces B: Biointerfaces 6 (4):317–328.
K16909_C003.indd 95 12/31/14 4:14 PM

AQ 51 Kasapis, S. 2000. “Novel uses of biopolymers in the development of low fat spreads and
soft cheeses.” In Novel Macromolecules in Food Systems, edited by G. Doxastakis and
V. Kiosseoglou. ElsevierScience, B.V.
Kikuzaki, H., M. Hisamoto, K. Hirose, K. Akiyama, and H. Taniguchi. 2002. “Antioxidant
properties of ferulic acid and its related compounds.” Journal of Agricultural and Food
Chemistry 50:2161−2168.
Kinsella, J.E., and D.M. Whitehead. 1989. “Proteins in whey: Chemical, physical, and func-
tional properties.” In Advances in Food and Nutrition Research, edited by E. Kinsella
John, 343–438. San Diego, CA: Academic Press.
Koupantsis, T., E. Pavlidou, and A. Paraskevopoulou. 2014. “Flavour encapsulation in
milk proteins—CMC coacervate-type complexes.” Food Hydrocolloids 37:134–142.
doi:10.1016/j.foodhyd.2013.10.031.
Krafft, F., and H. Wiglow. 1895. “Ueber das Verhalten der fettsauren Alkalien und der Seifen
in Gegenwart von Wasser, III. Die Seifen als Krystalloide.” Berichte der deutschen
chenischen Gesellschaft 28:2566–2573.
Krieger, I.M. 1972. “Rheology of monodisperse lattices.” Advances in Colloid and Interface
Science 3:111.
Krog, N. 1997. “Food emulsifiers.” In Food Emulsions, edited by S. Friberg and K. Larsson,
141–188. New York: Marcel Dekker.
Laca, A., M.C. Saenz, B. Paredes, and M. Diaz. 2010. “Rheological properties, stability and
sensory evaluation of low-cholesterol mayonnaises prepared using egg yolk granules
as emulsifying agent.” Journal of Food Engineering 97 (2):243–252. doi:10.1016/
j.jfoodeng.2009.10.017.
Laredj-Bourezg, F., Y. Chevalier, O. Boyron, and M.A. Bolzinger. 2012. “Emulsions sta-
bilized with organic solid particles.” Colloids and Surfaces A: Physicochemical and
Engineering Aspects 413:252–259. doi:10.1016/j.colsurfa.2011.12.064.
Larsson, K. 1986. “Physical properties—Structural and physical characteristics.” In The Lipid
Handbook, edited by F.D. Gunstone, J.L. Harwood, and F.B. Padley, 321–384. London:
Chapman and Hall.
Le Révérend, B.J.D., I.T. Norton, P.W. Cox, and F.Spyropoulos. 2010. “Colloidal aspects of
eating.” Current Opinion in Colloid & Interface Science 15 (1–2):84–89. doi:10.1016/
j.cocis.2009.11.009.
Li, C., Y. Li, P. Sun, and C. Yang. 2013. “Pickering emulsions stabilized by native starch gran-
ules.” Colloids and Surfaces A: Physicochemical and Engineering Aspects 431:142–149.
doi:10.1016/j.colsurfa.2013.04.025.
Li, C., P. Sun, and C. Yang. 2012. “Emulsion stabilized by starch nanocrystals.” Starch−Stärke
64 (6):497–502. doi:10.1002/star.201100178.
Löf, D., K. Schillén, and L. Nilsson. 2011. “Flavonoids: Precipitation kinetics and
interaction with surfactant micelles.” Journal of Food Science 76 (3):N35–N39.
doi:10.1111/j.1750-3841.2011.02103.x.
Lück, E. 1990. “Food applications of sorbic acid and its salts.” Food Additives & Contaminants
7 (5):711–715. doi:10.1080/02652039009373936.
Lundqvist, H., A.-C. Eliasson, and G. Olofsson. 2002. “Binding of hexadecyltrimethylam-
monium bromide to starch polysaccharides. Part I. Surface tension measurements.”
Carbohydrate Polymers 49 (1):43–55.
Luo, Z., B.S. Murray, A.L. Ross, M.J.W. Povey, M.R.A. Morgan, and A.J. Day. 2012. “Effects
of pH on the ability of flavonoids to act as Pickering emulsion stabilizers.” Colloids and
Surfaces B: Biointerfaces 92:84–90. doi:10.1016/j.colsurfb.2011.11.027.
Luo, Z.J., B.S. Murray, A. Yusoff, M.R.A. Morgan, M.J.W. Povey, and A.J. Day. 2011. “Particle-
stabilizing effects of flavonoids at the oil-water interface.” Journal of Agricultural and
Food Chemistry 59 (6):2636–2645. doi:10.1021/jf1041855.
K16909_C003.indd 96 12/31/14 4:14 PM

Magnusson, E., and L. Nilsson. 2011. “Interactions between hydrophobically modified starch
and egg yolk proteins in solution and emulsions.” Food Hydrocolloids 25 (4):764–772.
doi:10.1016/j.foodhyd.2010.09.006.
Magnusson, E., and L. Nilsson. 2013. “Emulsifying properties of egg yolk.” In Eggs: Nutrition, AQ 52
Consumption and Health, 69–85.
Magnusson, E., C. Rosén, and L. Nilsson. 2011. “Freeze–thaw stability of mayonnaise
type oil-in-water emulsions.” Food Hydrocolloids 25 (4):707–715. doi:http://dx.doi.
org/10.1016/j.foodhyd.2010.08.024.
Maldonado-Valderrama, J., and J.M.R. Patino. 2010. “Interfacial rheology of protein–surfactant
mixtures.” Current Opinion in Colloid & Interface Science 15 (4):271–282. doi:10.1016/
j.cocis.2009.12.004.
Malone, M.E., I.A.M. Appelqvist, and I.T. Norton. 2003. “Oral behaviour of food hydrocolloids
and emulsions. Part 1. Lubrication and deposition considerations.” Food Hydrocolloids
17 (6):763–773. doi:10.1016/s0268-005x(03)00097-3.
Marefati, A., M. Rayner, A. Timgren, P. Dejmek, and M. Sjöö. 2013. “Freezing and freeze-
drying of Pickering emulsions stabilized by starch granules.” Colloids and Surfaces
A: Physicochemical and Engineering Aspects 436:512–520. doi:http://dx.doi.
org/10.1016/j.colsurfa.2013.07.015.
Marku, D., M. Wahlgren, M. Rayner, M. Sjöö, and A. Timgren. 2012. “Characterization
of starch Pickering emulsions for potential applications in topical formulations.”
International Journal of Pharmaceutics 428:1–7.
Mayer, S., J. Weiss, and D.J. McClements. 2013. “Behavior of vitamin E acetate delivery sys-
tems under simulated gastrointestinal conditions: Lipid digestion and bioaccessibility
of low-energy nanoemulsions.” Journal of Colloid and Interface Science 404:215–222.
doi:10.1016/j.jcis.2013.04.048.
McClements, D.J. 2002. “Colloidal basis of emulsion color.” Current Opinion in Colloid &
Interface Science 7 (5–6):451–455. doi:10.1016/s1359-0294(02)00075-4.
McClements, D.J. 2005a. “Characterization of emulsions.” In Food Emulsions Principles, AQ 53
Practices, and Techniques. Boca Raton, FL: CRC Press.
McClements, D.J. 2005b. Food Emulsions Principles, Practices, and Techniques, edited by AQ 54
F.M. Clydesdale, CRC Series in Contemporary Food Science. Boca Raton, FL: CRC
Press.
McClements, D.J. 2007. “Critical review of techniques and methodologies for characterization
of emulsion stability.” Critical Reviews in Food Science and Nutrition 47 (7):611–649.
doi:10.1080/10408390701289292.
McClements, D.J., and E.A. Decker. 2000. “Lipid oxidation in oil-in-water emulsions: Impact
of molecular environment on chemical reactions in heterogeneous food systems.”
Journal of Food Science 65 (8):1270–1282. doi:10.1111/j.1365-2621.2000.tb10596.x.
Medina, I., I. Undeland, K. Larsson, I. Storrø, T. Rustad, C. Jacobsen, V. Kristinová, and
J.M. Gallardo. 2012. “Activity of caffeic acid in different fish lipid matrices: A review.”
Food Chemistry 131 (3):730–740. doi:10.1016/j.foodchem.2011.09.032.
Mengual, O., G. Meunier, I. Cayré, K. Puech, and P. Snabre. 1999. “TURBISCAN MA
2000: Multiple light scattering measurement for concentrated emulsion and suspen-
sion instability analysis.” Talanta 50 (2):445–456. doi:http://dx.doi.org/10.1016/
S0039-9140(99)00129-0.
Michalski, M.C. 2009. “Specific molecular and colloidal structures of milk fat affecting
lipolysis, absorption and postprandial lipemia.” European Journal of Lipid Science and
Technology 111:413–431.
Modig, G., L. Nilsson, B. Bergenståhl, and K.G. Wahlund. 2006. “Homogenization-induced deg-
radation of hydrophobically modified starch determined by asymmetrical flow field-flow
fractionation and multi-angle light scattering.” Food Hydrocolloids 20 (7):1087–1095.
K16909_C003.indd 97 12/31/14 4:14 PM

Moore, R.L., S.E. Duncan, A.S. Rasor, W.N. Eigel, and S.F. O’Keefe. 2012. “Oxidative
stability of an extended shelf-life dairy-based beverage system designed to contribute to
heart health.” Journal of Dairy Science 95 (11):6242–6251. doi:10.3168/jds.2012-5364.
Ng, S.P., O.M. Lai, F. Abas, H.K. Lim, B.K. Beh, T.C. Ling, and C.P. Tan. 2014. “Compositional
and thermal characteristics of palm olein-based diacylglycerol in blends with palm super
olein.” Food Research International 55:62–69. doi:10.1016/j.foodres.2013.10.035.
Nilsson, L. 2013. “Separation and characterization of food macromolecules using field-
flow fractionation: A review.” Food Hydrocolloids 30 (1):1–11. doi:10.1016/
j.foodhyd.2012.04.007.
Nilsson, L., and B. Bergenståhl. 2006. “Adsorption of hydrophobically modified starch at oil/
water interfaces during emulsification.” Langmuir 22:8770–8776.
Nilsson, L., and B. Bergenståhl. 2007. “Adsorption of hydrophobically modified anionic starch
at oppositely charged oil/water interfaces.” Journal of Colloid and Interface Science
308 (2):508–513. doi:10.1016/j.jcis.2007.01.024.
Nilsson, L., M. Leeman, K.G. Wahlund, and B. Bergenståhl. 2007. “Competitive adsorption
of a polydisperse polymer during emulsification: Experiments and modeling.” Langmuir
23:2346–2351.
Nilsson, L., P. Osmark, C. Fernandes, and B. Bergenståhl. 2006. “Competitive adsorption
of water soluble plasma proteins from egg yolk at the oil/water interface.” Journal of
Agricultural and Food Chemistry 54 (18):6881–6887.
Nilsson, L., P. Osmark, C. Fernandes, and B. Bergenståhl. 2007. “Competitive adsorption of
proteins from total hen egg yolk during emulsification.” Journal of Agricultural and
Food Chemistry 55:6746−6753.
Nylander, T., T. Arnebrant, M. Bos, and P. Wilde. 2008. “Protein/emulsifier interactions.” In
Food Emulsifiers and Their Applications, edited by G.L. Hasenhuettl and R.W. Hartel.
New York: Springer Science + Business Media.
Paunov, V.N., O.J. Cayre, P.F. Noble, S.D. Stoyanov, K.P. Velikov, and M. Golding. 2007.
“Emulsions stabilised by food colloid particles: Role of particle adsorption and wettabil-
ity at the liquid interface.” Journal of Colloid and Interface Science 312 (2):381–389.
doi:10.1016/j.jcis.2007.03.031.
Pelipenko, J., J. Kristl, R. Rosic, S. Baumgartner, and P. Kocbek. 2012. “Interfacial rheology:
An overview of measuring techniques and its role in dispersions and electrospinning.”
Acta Pharmaceutica 62 (2):123–140. doi:10.2478/v10007-012-0018-x.
Rayner, M., D. Marku, M. Eriksson, M. Sjöö, P. Dejmek, and M. Wahlgren. 2014. “Biomass-
based particles for the formulation of Pickering type emulsions in food and topical
applications.” Colloids and Surfaces A: Physicochemical and Engineering Aspects.
458:48–62. doi:http://dx.doi.org/10.1016/j.colsurfa.2014.03.053.
Rayner, M., M. Sjöö, A. Timgren, and P. Dejmek. 2012. “Quinoa starch granules as stabilizing
particles for production of Pickering emulsions.” Faraday Discussions 158:139–155.
Rayner, M., A. Timgren, M. Sjöö, and P. Dejmek. 2012. “Quinoa starch granules: A candidate
for stabilising food-grade Pickering emulsions.” Journal of the Science of Food and
Agriculture 92 (9):1841–1847. doi:10.1002/jsfa.5610.
Rodríguez, P.J.M., J.M.N. García, and M.R.R. Niño. 2001. “Protein–lipid interactions at the
oil–water interface.” Colloids and Surfaces B: Biointerfaces 21:207–216.
Roesch, R.R., and M. Corredig. 2003. “Texture and microstructure of emulsions prepared
with soy protein concentrate by high-pressure homogenization.” LWT—Food Science
and Technology 36 (1):113–124. doi:10.1016/s0023-6438(02)00208-6.
Sato, K. 2001. “Crystallization behaviour of fats and lipids * a review.” Chemical Engineering
Science 56:2255–2265.
Sato, K., L. Bayés-García, T. Calvet, M.À. Cuevas-Diarte, and S. Ueno. 2013. “External fac-
tors affecting polymorphic crystallization of lipids.” European Journal of Lipid Science
and Technology 115 (11):1224–1238. doi:10.1002/ejlt.201300049.
K16909_C003.indd 98 12/31/14 4:14 PM

Sato, K., and S. Ueno. 2011. “Crystallization, transformation and microstructures of

polymorphic fats in colloidal dispersion states.” Current Opinion in Colloid & Interface
Science 16 (5):384–390. doi:10.1016/j.cocis.2011.06.004.
Schuh, V., K. Allard, K. Herrmann, M. Gibis, R. Kohlus, and J. Weiss. 2013. “Impact of
carboxymethyl cellulose (CMC) and microcrystalline cellulose (MCC) on functional
characteristics of emulsified sausages.” Meat Science 93 (2):240–247. doi:10.1016/
j.meatsci.2012.08.025.
Sherman, P. 1995. “A critique of some methods proposed for evaluating the emulsifying
capacity and emulsion stabilizing performance of vegetable proteins.” Italian Journal of
Food Science 7 (1):3–10.
Shimoni, G., C. Shani Levi, S. Levi Tal, and U. Lesmes. 2013. “Emulsions stabilization by
lactoferrin nano-particles under invitro digestion conditions.” Food Hydrocolloids
33 (2):264–272. doi:10.1016/j.foodhyd.2013.03.017.
Shinoda, K., and K. Sato. 1969. “The stability of O/W type emulsions as functions of tempera-
ture and the HLB of emulsifiers: The emulsification by PIT-method.” Journal of Colloid
and Interface Science 30:258–263.
Song, X., Y. Pei, W. Zhu, D. Fu, and H. Ren. 2014. “Particle-stabilizers modified from indica
rice starches differing in amylose content.” Food Chemistry 153:74–80. doi:http://
dx.doi.org/10.1016/j.foodchem.2013.12.046.
Sørensen, A.D.M., A.M. Haahr, E.M. Becker, L.H. Skibsted, B. Bergenståhl, L. Nilsson,
and C. Jacobsen. 2008. “Interactions between iron, phenolic compounds, emulsifiers,
and pH in omega-3-enriched oil-in-water emulsions.” Journal of Agricultural and Food
Chemistry 56 (5):1740–1750.
Stephen, A.M., G.O. Phillips, and P.A. Williams, eds. 2006. Food Polysaccharides and Their
Applications. Boca Raton, FL: CRC Press.
Stokes, J.R., M.W. Boehm, and S.K. Baier. 2013. “Oral processing, texture and mouthfeel:
From rheology to tribology and beyond.” Current Opinion in Colloid & Interface
Science 18 (4):349–359. doi:10.1016/j.cocis.2013.04.010.
Surel, C., J. Foucquier, N. Perrot, A. Mackie, C. Garnier, A. Riaublanc, and M. Anton. 2014.
“Composition and structure of interface impacts texture of O/W emulsions.” Food
Hydrocolloids 34:3–9. doi:10.1016/j.foodhyd.2013.06.016.
Swaisgood, H.E. 1993. “Review and update of casein chemistry.” Journal of Dairy Science 76
(10):3054–3061. doi:http://dx.doi.org/10.3168/jds.S0022-0302(93)77645-6.
Tabilo-Munizaga, G., and G.V. Barbosa-Cánovas. 2005. “Rheology for the food industry.”
Journal of Food Engineering 67 (1–2):147–156. doi:10.1016/j.jfoodeng.2004.05.062.
Tadros, T. 2004. “Application of rheology for assessment and prediction of the long-term
physical stability of emulsions.” Advances in Colloid and Interface Science 108–109:
227–258. doi:10.1016/j.cis.2003.10.025.
Tan, Y., K. Xu, C. Liu, Y. Li, C. Lu, and P. Wang. 2012. “Fabrication of starch-based nano-
spheres to stabilize Pickering emulsion.” Carbohydrate Polymers 88:1358–1363.
Tcholakova, S., N.D. Denkov, I.B. Ivanov, and B. Campbell. 2002. “Coalescence in
β-lactoglobulin-stabilized emulsions: Effects of protein adsorption and drop size.”
Langmuir 18 (23):8960–8971. doi:10.1021/la0258188.
Tcholakova, S., N.D. Denkov, I.B. Ivanov, and B. Campbell. 2006. “Coalescence stability
of emulsions containing globular milk proteins.” Advances in Colloid and Interface
Science 123–126:259–293. doi:10.1016/j.cis.2006.05.021.
Tcholakova, S., N.D. Denkov, and A. Lips. 2008. “Comparison of solid particles, globular
proteins and surfactants as emulsifiers.” Physical Chemistry Chemical Physics 10 (12):
1608–1627. doi:10.1039/b715933c.
Tcholakova, S., N.D. Denkov, D. Sidzhakova, I.B. Ivanov, and B. Campbell. 2003.
“Interrelation between drop size and protein adsorption at various emulsification condi-
tions.” Langmuir 19 (14):5640–5649. doi:10.1021/la034411f.
K16909_C003.indd 99 12/31/14 4:14 PM

Timgren, A., M. Rayner, P. Dejmek, D. Marku, and M. Sjöö. 2013. “Emulsion stabilizing
capacity of intact starch granules modified by heat treatment or octenyl succinic anhy-
dride.” Food Science & Nutrition 1 (2):157–171. doi:10.1002/fsn3.17.
Timgren, A., M. Rayner, M. Sjöö, and P. Dejmek. 2011. “Starch particles for food based
Pickering emulsions.” Procedia Food Science 1:95–103.
Ting, Y., Y. Jiang, C.-T. Ho, and Q. Huang. 2014. “Common delivery systems for enhancing
in vivo bioavailability and biological efficacy of nutraceuticals.” Journal of Functional
Foods 7:112–128. doi:10.1016/j.jff.2013.12.010.
Tufvesson, F., M. Wahlgren, and A.C. Eliasson. 2003. “Formation of amylose–lipid complexes
and effects of temperature treatment. Part 1. Monoglycerides.” Starch - Stärke 55 (2):61–71.
Tzoumaki, M.V., T. Moschakis, V. Kiosseoglou, and C.G. Biliaderis. 2011. “Oil-in-water emul-
sions stabilized by chitin nanocrystal particles.” Food Hydrocolloids 25 (6):1521–1529.
Tzoumaki, M.V., T. Moschakis, E. Scholten, and C.G. Biliaderis. 2013. “In vitro lipid diges-
tion of chitin nanocrystal stabilized o/w emulsions.” Food & Function 4 (1):121–129.
Verwey, E.J.W., and J.Th.G. Overbeek. 1948. Theory of the Stability of Lyophobic Colloids.
Amsterdam, Netherlands: Elsevier.
Wahlgren, M. 1995. “Removal of T4 lysozyme from silicon oxide surfaces by sodium dodecyl
sulfate.” Surface and Colloid Science Symposium, Lund, Sweden, October 18–19.
Wahlgren, M., and T. Arnebrant. 1991. “Protein adsorption to solid surfaces.” Trends in
Biotechnology 9 (1):201–208.
Wahlgren, M., and T. Arnebrant. 1992. “The concentration dependence of adsorption from a
mixture of b-lactoglobulin and sodium dodecyl sulfate onto methylated silica surfaces.”
Journal of Colloid and Interface Science 148:201–206.
AQ 55 Walstra, P. 2005. “8 Emulsions.” In Fundamentals of Interface and Colloid Science, edited by
J. Lyklema, 1–94. Academic Press.
Waninge, R., P. Walstra, J. Bastiaans, H. Nieuwenhuijse, T. Nylander, M. Paulsson, and
B. Bergenståhl. 2005. “Competitive adsorption between β-casein or β-lactoglobulin and
model milk membrane lipids at oil-water interface.” Journal of Agricultural and Food
Chemistry 53 (3):716–724.
Waraho, T., D.J. McClements, and EA. Decker. 2011. “Mechanisms of lipid oxidation in
food dispersions.” Trends in Food Science and Technology 22 (1):3–13. doi:10.1016/
j.tifs.2010.11.003.
Watanabe, A., I. Tashima, V. Matsuzaki, J. Kurashige, and K. Sato. 1992. “On the formation
of granular crystals in fat blends containing palm oil.” Journal of the American Oil
Chemists’ Society 69:1077–1080.
Wilde, P., A. Mackie, F. Husband, P. Gunning, and V. Morris. 2004. “Proteins and emulsi-
fiers at liquid interfaces.” Advances in Colloid and Interface Science 108–109:63–71.
doi:10.1016/j.cis.2003.10.011.
Williams, P.A., G.O. Phillips, and R.C. Randall. 1990. “Structure-function relationships of
gum arabic.” In Gums and Stabilisers for the Food Industry, edited by G.O. Phillips,
D.J. Wedlock and P.A. Williams, 25. Oxford: IRL.
Wongkongkatep, P., K. Manopwisedjaroen, P. Tiposoth, S. Archakunakorn, T. Pongtharangkul,
M. Suphantharika, K. Honda, I. Hamachi, and J. Wongkongkatep. 2012. “Bacteria
interface Pickering emulsions stabilized by self-assembled bacteria-chitosan network.”
Langmuir 28 (13):5729–5736. doi:10.1021/la300660x.
Wu, B., B. Degner, and D.J. McClements. 2013. “Microstructure & rheology of mixed col-
loidal dispersions: Influence of pH-induced droplet aggregation on starch granule–
fat droplet mixtures.” Journal of Food Engineering 116 (2):462–471. doi:10.1016/
j.jfoodeng.2012.12.020.
Xu, W., W. Jin, C. Zhang, Z. Li, L. Lin, Q. Huang, S. Ye, and B. Li. 2014. “Curcumin loaded
and protective system based on complex of κ-carrageenan and lysozyme.” Food
Research International 59:61–66. doi:10.1016/j.foodres.2014.01.059.
K16909_C003.indd 100 12/31/14 4:14 PM

Yang, Y., and D.J. McClements. 2013. “Vitamin E bioaccessibility: Influence of carrier oil
type on digestion and release of emulsified alpha-tocopherol acetate.” Food Chemistry
141 (1):473–481. doi:10.1016/j.foodchem.2013.03.033.
Youssef, M.K., and S. Barbut. 2011. “Effects of two types of soy protein isolates, native and
preheated whey protein isolates on emulsified meat batters prepared at different protein
levels.” Meat Science 87 (1):54–60. doi:10.1016/j.meatsci.2010.09.002.
Yusoff, A., and B.S. Murray. 2011. “Modified starch granules as particle-stabilizers of oil-in-
water emulsions.” Food Hydrocolloids 25 (1):42–55. doi:10.1016/j.foodhyd.2010.05.004.
Zapico, P., M. de Paz, M. Medina, and M. Nuñez. 1999. “The effect of homogenization of whole
milk, skim milk and milk fat on nisin activity against Listeria innocua.” International
Journal of Food Microbiology 46: 151–157.
Zhang, B., Y.J. Chi, and B. Li. 2013. “Effect of ultrasound treatment on the wet heating
Maillard reaction between β-conglycinin and maltodextrin and on the emulsifying
properties of conjugates.” European Food Research and Technology 238 (1):129–138.
doi:10.1007/s00217-013-2082-y.
K16909_C003.indd 101 12/31/14 4:14 PM

Author Query Sheet
Chapter No: 3
Query No. Queries Response

AQ 1 “omega three” and “omega six” have been set as
“omega-3” and “omega-6,” respectively. Please check
and confirm whether this is okay.
AQ 2 Can “texturizing macromolecules” be changed to
“textured macromolecules” here? Please confirm.
AQ 3 “Creaming/sedimentation occurs for macroscopic
emulsions . . . difference of the oil” has been changed as
“For macroscopic emulsions, creaming/sedimentation
occurs due to the density difference between the oil and
water fraction . . . ” Please confirm whether OK.
AQ 4 In the sentence “This can mainly be . . . ” “that either
through a steric barrier or electrostatic repulsion
hinders drop-drop contact and thus the process of
coalescence” has been changed as “that hinders
drop–drop contact through either a steric barrier or an
electrostatic repulsion and thus resulting in the process
of coalescence.” Please confirm whether OK.
AQ 5 Please clarify “and decay with the distance between
the . . . ”
AQ 6 Please provide an expanded form of DLVO, if
available.
AQ 7 Please advise whether the sentence “Nonionic
emulsifiers both low molecular and polymers . . . ” should
read as “Both low-molecular nonionic emulsifiers and
polymers might . . . ”
AQ 8 Please check whether “degree of specific binding”
could be changed to “degree of specific binding
capacity”
AQ 9 Reference citation “Waraho et al.” has been changed
to “Waraho, McClements, and Decker (2011)” with
respect to reference list. Please check if this is okay.
AQ 10 The sentence “Waraho et al. reviews the oxidation . . . ”
has been changed as “Waraho, McClements, and
Decker (2011) review the oxidation of lipids in
emulsions and point out that there will be a difference
in the oxidation process in pure oil when compared
with one in an emulsion.” Please confirm whether such
changes preserve the intended meaning of the sentence.
K16909_C003.indd 102 12/31/14 4:14 PM

AQ 11 Perhaps explain EDTA?
AQ 12 Please clarify “again highlighting the importance
to know the function of the specific additive at the
conditions used for each food product.”
AQ 13 Please confirm whether “charged small emulsifiers”
could be changed to “charged small-molecule
emulsifiers.”
AQ 14 Perhaps explain CFC?
AQ 15 Please clarify the sense in “these can affect the
stability of the oil when it comes to oxidation but also
when it comes to emulsion stability.”
AQ 16 Please provide publisher location for table source
Agriculture (2014.)
AQ 17 Please provide the organization name, year of
publication, article title and access date for URL
sources “http://ndb.nal.usda.gov/ndb/foods” and
http://www.engineeringtoolbox.com/oil-melting-
points-d_1088.html.
AQ 18 Please check the changes made to the caption of the
figure and confirm whether they are fine.
AQ 19 Please clarify L2 phases.
AQ 20 Please provide a page number for the quote.
AQ 21 Perhaps explain HLB ratio?
AQ 22 Please advise whether the numbers in this column
could be set as E470/172.863 instead.
AQ 23 Explain IP in this table.
AQ 24 Reference citation “Bosa and Vlieta 2001” has been
changed to “Bosa and van Vlieta 2001” with respect to
reference list. Please check if this is okay.
AQ 25 Reference citation “Rodr ́ıguez Patino, Navarro Garc ́ıa,
and Rodr ́ıguez Niño 2001” has been changed to
“Rodríguez, García, and Niño 2001” with respect to
reference list. Please check if this is okay.
AQ 26 “gum arabica” has been changed to “gum arabic”
throughout the chapter. Please check and confirm if it
is okay as set.
AQ 27 Please clarify “the viscosity becomes shear thinning”.
AQ 28 I have changed “the formed complexes” to “complexes
so formed” and “other properties” to “additional
properties”. Please confirm whether OK
K16909_C003.indd 103 12/31/14 4:14 PM

AQ 29 Kindly clarify the sense of the sentence
“Polysaccharide–protein-stabilized . . . ”
AQ 30 Please confirm whether the change to “neutral
buoyancy” from “buoyance neutral.”
AQ 31 Reference citations in table entries have been changed
as table footnote sources. Please check whether this is
okay.
AQ 32 Please check the expansion provided for FTIR in the
table footnote.
AQ 33 Please provide the publisher location for source
references Drelich et al. (2002) and Hagel (2011).
AQ 34 Please confirm whether “υ” in υStokes could be changed
to “v.”
AQ 35 Please clarify “results in Stokes under . . . separation”
AQ 36 Should the formula include “× 100”? Please confirm.
AQ 37 Should the formula for “EI” be multiplied by 100, too,
in the figure? Please clarify.
AQ 38 I have changed “The two ways to overcome this are”
to “This can be overcome in two ways” and have
altered “accelerating storage by increasing . . . ” to
“by increasing … the droplets cream/settle to accelerate
storage.” Please confirm whether such changes preserve
the intended meaning of the sentence.
AQ 39 Please clarify “where they are forced into close
proximity”
AQ 40 Please check whether the inclusion of “cream” after
“a layer of” is okay.
AQ 41 Perhaps explain OSA here.
AQ 42 Please clarify the sense of the sentence “The bouncy
force on a droplet . . . ”
AQ 43 Please provide the publisher location for reference
Agriculture, U.S.D.O. (2014).
AQ 44 Please provide the editor name, page number,
publisher location for reference Dalgleish (2003).
AQ 45 Please provide the proceedings held date for reference
Davies (1957).
AQ 46 Please provide the congress held date for reference
Denkov et al. (2006).
AQ 47 Please provide the editor name and page numbers for
reference Drelich et al. (2002).
K16909_C003.indd 104 12/31/14 4:14 PM

AQ 48 Please clarify whether it should be “MSc Thesis” or
“MSc Dissertation” here.
AQ 49 Please provide publisher location for reference Hagel
(2011).
AQ 50 Please provide the organization name, year of
publication, article title and access date for URLs
“http://ndb.nal.usda.gov/ndb/foods” and http://www
.engineeringtoolbox.com/oil-melting-points-d_1088
.html.
AQ 51 Please provide the publisher location and page
numbers for reference Kasapis (2000).
AQ 52 Please provide the editor names, page number,
publisher and its location for reference Magnusson and
Nilsson (2013).
AQ 53 Please provide the editor names, page numbers for
reference McClements (2005a).
AQ 54 Please provide the chapter title and page numbers for
reference McClements (2005b).
AQ 55 Please provide publisher location for reference Walstra
(2005).
K16909_C003.indd 105 12/31/14 4:14 PM

Formulation of Emulsions: Marie Wahlgren, Björn Bergenståhl, Lars Nilsson, and Marilyn Rayner

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Formulation of Emulsions: Marie Wahlgren, Björn Bergenståhl, Lars Nilsson, and Marilyn Rayner

Uploaded by

Copyright:

Available Formats

3 Formulation of Emulsions

Marie Wahlgren, Björn Bergenståhl,

ABSTRACT In this chapter, we describe some of the main concerns when it

K16909_C003.indd 51 12/31/14 4:14 PM

1. Molecular (e.g., H2O, glucose, kappa casein, etc.)

Food manufacturers, product developers, and formulators are generally concerned

3.2 FunCtIonalIty that IngredIents

K16909_C003.indd 52 12/31/14 4:14 PM

The effectiveness of emulsions as vehicles for the delivery of individual nutritional

3.2.2 texture aNd Flavor

K16909_C003.indd 53 12/31/14 4:14 PM

3.2.3 SHelF-liFe Stability

3.2.3.1 emulsion stability

K16909_C003.indd 54 12/31/14 4:14 PM

K16909_C003.indd 55 12/31/14 4:14 PM

3.2.3.2 Chemical stability

K16909_C003.indd 56 12/31/14 4:14 PM

3.2.3.3 microbiological stability

K16909_C003.indd 57 12/31/14 4:14 PM

3.2.3.4 Freeze-thaw stability

K16909_C003.indd 58 12/31/14 4:14 PM

3.3 Issues to ConsIder when ChoosIng

K16909_C003.indd 59 12/31/14 4:14 PM

Solubility/ Water Oil Water Water Water Water Oil

Emulsion type O/W W/O O/W O/W O/W O/W W/O

3.4 Key IngredIents In emulsIons

K16909_C003.indd 62 12/31/14 4:14 PM

Hexagonal Orthorhombic Triclinic

3.4.2 low Molar MaSS eMulSiFierS

K16909_C003.indd 63 12/31/14 4:14 PM

CPP < 1/3 1/2 < CPP < 2 CPP > 2

V: volume of hydrophobic chain

K16909_C003.indd 65 12/31/14 4:14 PM

HLB = ∑ Hydrophilic group numbers − ∑ Hydrophobic group numbers + 7 (3.1)

Source: Davies, J.T., Proceedings of 2nd International Congress Surface Activity,

Butterworths, London, 1957.

K16909_C003.indd 66 12/31/14 4:14 PM

K16909_C003.indd 67 12/31/14 4:14 PM

Research, Academic Press, San Diego, CA 1989.

K16909_C003.indd 70 12/31/14 4:14 PM

K16909_C003.indd 71 12/31/14 4:14 PM

K16909_C003.indd 72 12/31/14 4:14 PM

and hydrophobically undergo melting, permitting granule swelling. This

3.4.5 ProteiN-PolySaccHaride coMPlexeS

1. A single homogenous phase is formed.

K16909_C003.indd 75 12/31/14 4:14 PM

Li 2013) or electrostatic complexes (Harnsilawat, Pongsawatmanit, and McClements

K16909_C003.indd 76 12/31/14 4:14 PM

K16909_C003.indd 77 12/31/14 4:14 PM

3.5 evaluatIon oF emulsIon FormulatIon

K16909_C003.indd 78 12/31/14 4:14 PM

AQ 31 and proteinsa oil–water interface. It is also good for measuring dynamic

d Sato, K., Chem. Eng. Sci., 56, 2255–2265, 2001.

g Nilsson, L., Food Hydrocolloids, 30, 1, 1–11, 2013.

i Harvey, D.J., Mass Spectrom. Rev., 30, 1:1–100, 2011.

we summarize some of the more important ingredient properties investigated and

3.5.1 eMulSiFicatioN caPacity

K16909_C003.indd 81 12/31/14 4:14 PM

Vcts (Cini − Cend ) (1 − φ) d32

K16909_C003.indd 82 12/31/14 4:14 PM

3.5.2 eMulSioN Stability iNdex

K16909_C003.indd 83 12/31/14 4:14 PM