Review

Received: 3 September 2012 Revised: 1 November 2012 Accepted article published: 26 November 2012 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jsfa.6013

Stabilising emulsion-based colloidal structures

with mixed food ingredients
Eric Dickinson∗

Abstract
The physical scientist views food as a complex form of soft matter. The complexity has its origin in the numerous ingredients
that are typically mixed together and the subtle variations in microstructure and texture induced by thermal and mechanical
processing. The colloid science approach to food product formulation is based on the assumption that the major product
attributes such as appearance, rheology and physical stability are determined by the spatial distribution and interactions of
a small number of generic structural entities (biopolymers, particles, droplets, bubbles, crystals) organised in various kinds
of structural arrangements (layers, complexes, aggregates, networks). This review describes some recent advances in this
field with reference to three discrete classes of dispersed systems: particle-stabilised emulsions, emulsion gels and aerated
emulsions. Particular attention is directed towards explaining the crucial role of the macromolecular ingredients (proteins
and polysaccharides) in controlling the formation and stabilisation of the colloidal structures. The ultimate objective of this
research is to provide the basic physicochemical insight required for the reliable manufacture of novel structured foods with
an appealing taste and texture, whilst incorporating a more healthy set of ingredients than those found in many existing
traditional products.

c 2012 Society of Chemical Industry

Keywords: emulsion droplets; Pickering stabilisation; air bubbles; nanoparticles; microparticles; starch granules; fat crystals

INTRODUCTION
Processed food products are multicomponent systems containing
many different kinds of ingredients. They are characterised by
structural complexity on many different length scales ranging from
the molecular to the macroscopic. The main structural building
blocks are food biopolymers – proteins and polysaccharides –
and various types of dispersed entities – emulsion droplets, gas
bubbles, fat crystals, starch granules, etc. The overall system
properties such as texture, rheology and physical stability are
determined by the nature and strength of interactions amongst
the different kinds of constituent polymers and dispersed entities,
as moderated by the influence of small molecules and ions (salts,
sugars, lipids, etc.). This conceptual description of food structure
is known as the colloid science approach.1 – 4
Food structure creation may be regarded as a sequence
of three stages of food processing:5 – 7 (I) destruction of the
natural biological structure of the raw food material; (II)
formation and deformation of new phases containing potential
structural building blocks resulting from thermal, mechanical and
biochemical treatments; (III) physicochemical stabilisation of some
final fabricated structure. Since stages I and II commonly involve
processing operations with intensive flow and heat/mass transfer,
they are typically handled using the methods and language of
chemical engineering.8 The type of non-equilibrium structural
state resulting from stage II is described by physicists as ‘strongly
driven soft matter’.9 By way of contrast, the essential features of
stage III can be more readily understood in terms of the principles
of statistical thermodynamics as applied to colloidal systems in a
state of effective thermodynamic equilibrium.10,11 In addition to
these three stages of food processing, there is, of course, a further
stage of structural change once the food product is eaten, as the
material first becomes broken down into fragments in the mouth,
then later into new colloidal entities and ultimately into individual
molecules as it makes its complicated journey through the human
digestive system.12 – 14
The epidemic of obesity in many developed societies is
presenting the food industry with the challenge of developing
new food structures with appealing taste and texture but without
the current strong reliance on conventional functional ingredients
such as fats, refined sugars and added salt.15 Consequently, there
is considerable research interest, for instance, in developing new
methods of replacing fat-based building blocks by gas bubbles
and biopolymer particles and in attempting to enhance the
consumer’s perceived in-mouth taste experience by the efficient
encapsulation of salts and other flavour compounds. In addition,
there is a requirement to develop new methods of encapsulation
technology for more effective incorporation of neutraceuticals
into functional foods.16 These bioactive compounds need to be
well protected within a colloid-based delivery system during
processing and storage, but once eaten they are required to
be rapidly released at an appropriate location within the human
gastrointestinal tract.13,17 – 19
This article describes ongoing research directed towards
creating new colloidal structures that may assist in the manufacture
of foods with enhanced taste, texture, nutritional quality and long-
term health benefits. While the main emphasis here is necessarily
∗
Correspondence to: Eric Dickinson, School of Food Science and Nutrition,
University of Leeds, Leeds LS2 9JT, UK. E-mail: e.dickinson@leeds.ac.uk
School of Food Science and Nutrition, University of Leeds, Leeds, LS2 9JT, UK

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on colloidal systems formulated with food-grade ingredients,
cursory mention is also made of some structured systems prepared
with non-food-grade components in order to illustrate specific
mechanisms and potential conceptual opportunities for the food
sector. The main body of the article is organised under three
headings: (i) particle-stabilised emulsions, (ii) emulsion gels; (iii)
aerated emulsions. However, before considering specific examples
of systems falling under these three headings, it seems worthwhile
to remind ourselves briefly of the key functional attributes of the
two main classes of food biopolymer ingredients – proteins and
polysaccharides.
FOOD BIOPOLYMER INGREDIENTS
Proteins
The chemical and structural diversity of food proteins makes them
especially well suited to act as versatile functional ingredients. The
soft solid-like textural characteristics of protein-based colloids arise
from the strong tendency of these biomacromolecules towards
self-assembly.20 Aggregation and gelation are readily induced
by heating and pH change. Heat treatment of globular proteins
causes unfolding and exposure of hydrophobic residues. (The
disordered protein casein is already largely unfolded in its native
state.) Acidification neutralises the net charge on the protein
molecules as the pH is lowered towards the isoelectric point. As
a consequence of the combined processes of protein unfolding,
denaturation and precipitation, the gelation of food proteins is
generally irreversible. (The reversible thermal gelation of gelatin
is a notable exception.) Proteins also possess ligand-binding
properties, so the formation of self-assembled protein aggregates
represents a powerful method of generating nanoscale delivery
vehicles for bioactive molecules.16,17 Moreover, protein-based
hydrogels comprise convenient matrix materials within which to
trap colloidal particles or emulsion droplets. Once formed, the gel
microstructure is sensitively influenced by the chemical structure
of the protein and by the aqueous solution conditions, i.e. pH, ionic
strength, calcium ions, etc. The food protein ingredients most often
utilised for texture control and encapsulation are casein, whey
proteins, gelatin, egg proteins, bovine serum albumin and some
plant proteins.21 Enhanced functionality of these food proteins
in the structuring of aqueous media is commonly achieved in
combination with polysaccharides.11
Most protein molecules have the ability to adsorb at oil–water
and air–water interfaces and to function effectively as stabilisers of
emulsions22 – 24 and foams.25 The primary thermodynamic driving
force for adsorption is the removal of the protein’s non-polar
side-chains away from the unfavourable environment of the
aqueous solution, leading to a lowering of the concentration
of water molecules in the interfacial region. A secondary driving
force is associated with the unfolding of the protein molecule
on adsorption. This causes a further change in the balance
of protein–protein and protein–water interactions. Once it is
adsorbed, the protein cannot normally be removed easily from
the interface. Therefore protein adsorption is often described as
‘irreversible’.
Depending on the protein molecular structure and the ionic
content of the aqueous medium, the stabilisation of dispersed
particles and droplets by adsorbed protein can be explained in
terms of a combination of polymeric (steric) and electrostatic
interactions.2,11 A disordered protein such as casein is an
excellent steric stabiliser.23 What this means is that, once
the protein has become adsorbed as a monolayer at the
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oil–water interface on a dispersed oil droplet, it generates a
strong repulsive barrier that prevents neighbouring casein-coated
droplets from close approach. An adsorbed layer of a globular
protein (e.g. whey protein) has a rather different interfacial
structure: it can be regarded as a two-dimensional close-packed
layer of compact particles.24 More complex interfacial structures
(i.e. heterogeneous layers and multilayers) can arise from the
adsorption of aggregated proteins or mixtures of proteins with
interacting polysaccharides.11 Differences in the structures of
adsorbed protein layers are sensitively reflected in their surface
shear rheological properties.11,24 Whereas an adsorbed layer of
casein is rather mobile and fluid-like, the more rigid globular
protein monolayer possesses the character of a two-dimensional
gel or glassy state. The mechanical properties of protein layers
(and mixed protein/polysaccharide layers) are relevant to the
food colloid scientist because they can be correlated with various
aspects of the stability behaviour of emulsions and (especially)
foams.11,24,25
Polysaccharides
Food polysaccharides are stiff polydisperse macromolecules with
a predominantly hydrophilic character. They are used in the food
industry for thickening and gelation of aqueous media under
the technical label of ‘hydrocolloids’.26 The physicochemical
mechanism underlying the rheological functionality of each
distinct hydrocolloid ingredient is determined by the molecular
structure of the constituent carbohydrate polymer.27 The most
commonly employed hydrocolloid thickeners in the food industry
are xanthan gum, modified celluloses and galactomannans (guar
and locust bean gum). Xanthan gum is well established as the
hydrocolloid of first choice for stabilising particulate suspensions
and emulsions because of its extremely high low-shear viscosity
in aqueous media of low polymer content (∼1 g kg−1 ). Dispersed
macroparticles or oil droplets become trapped and immobilised
in the xanthan polymer network, which exhibits an effective yield
stress that is more than sufficient to overcome the buoyancy forces
acting on the individual particles or droplets.
The gelation of a dilute solution of a non-starch polysaccharide
may be induced in one of three main ways:27 by the addition
of calcium ions (alginate, pectin), by lowering the temperature
(agar, carrageenan, gellan) or by raising the temperature (methyl
cellulose, hydroxypropylmethyl cellulose). In the case of starch,
the heat-induced gelatinisation of a concentrated dispersion of
granules produces an opaque thermoreversible gel on cooling. In
addition to their thickening/gelling functionality, some starch-
based ingredients (modified starches, maltodextrins) are also
used as ingredients for encapsulation under reduced moisture
conditions where it is required to achieve a high solids
concentration prior to drying.16 Amylose and cyclodextrins are
recognised as having potential as nano-sized delivery vehicles
through the formation of inclusion complexes with hydrophobic
bioactives and polyphenols.19 Also, in the context of colloidal
encapsulation technology, there is considerable current research
interest in the cationic polysaccharide chitosan – a soluble
deacetylated form of chitin – owing to its positive net charge
under acid conditions28 and its ability to complex electrostatically
with food proteins.29
Some polysaccharides adsorb at oil–water interfaces. Hence
they have the capacity to function as emulsifiers and emulsion
stabilisers by means of interfacial action.30,31 Hydrocolloids
that are commonly used as effective emulsifying agents in
food applications include gum arabic, modified starch/cellulose
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Stabilising emulsion-based colloidal structures with mixed food ingredients
and some types of pectin. Hydrocolloid surface activity has
its molecular origin in two alternative sources: the non-
polar character of certain chemical groups attached to the
hydrophilic polysaccharide backbone (hydrophobically modified
starch/cellulose) or the presence of a protein moiety linked
covalently to the carbohydrate polymer (gum arabic, sugar beet
pectin). Even a non-surface-active polysaccharide may contribute
to interfacial stabilisation of an oil-in-water emulsion if it can form
a secondary steric stabilising layer by electrostatic complexation
with pre-adsorbed protein.30 – 33 Furthermore, as an alternative
strategy to electrostatic protein–polysaccharide interaction, a
food polysaccharide ingredient may be induced to react covalently
with a protein to form a permanently bonded conjugate. In
practice, this is most conveniently achieved by means of dry
thermal processing (the Maillard reaction).31 The resulting surface-
active protein–polysaccharide conjugate can replace gum arabic
in certain food colloid applications.34
PARTICLE-STABILISED EMULSIONS
Over the past decade or so, there has been a growing interest
within the general colloid science community in the stabilisation
of emulsions by nanoparticles and microparticles.35 Much of this
research activity has so far been concerned with the study of
model colloidal systems containing inorganic (silica) particles with
surfaces chemically or physically modified to achieve optimum
wetting and adsorption properties. As a consequence of these
developments, novel opportunities for the stabilisation of food
emulsions by solid particles are becoming recognised.36,37
The mechanism whereby solid particles protect emulsion
droplets against coalescence by interfacial action is known as
Pickering stabilisation.35 In principle, the range of particle sizes
capable of exhibiting Pickering stabilisation extends from just
a few nanometres up to several micrometres. The effectiveness
of the mechanism relies on the fact that once a particle has
become attached to the oil–water interface it can be regarded as
being irreversibly adsorbed.36,37 So long as the particle packing
density at the droplet surface is sufficient to form a continuous
mechanical barrier, long-term steric stabilisation of dispersed
droplets is readily achieved. The protective effect of the mechanical
barrier is enhanced by particles that are preferentially wetted by
the emulsion’s continuous phase (Finkle’s rule). Hence it is found
that oil-in-water (O/W) emulsions are more effectively stabilised by
hydrophilic particles, and water-in-oil (W/O) emulsions by particles
that are predominantly hydrophobic. Some familiar foods are
stabilised (at least in part) by this mechanism, e.g. homogenised
or reconstituted milk (O/W emulsion stabilised by casein micelles)
and margarine and fatty spreads (W/O emulsion stabilised by fat
crystals).
Much recent understanding concerning the stabilisation of
Pickering emulsions has been based on experiments with systems
containing monodisperse polymer latex spheres or inorganic
particles.35 Polystyrene latices made by emulsion polymerisation
constitute well-defined model nanoparticles and microparticles
of variable surface charge density. Although the hydrophobic
character of the polystyrene core dominates their wettability
behaviour at the oil–water interface, the grafting of block
copolymers onto the polystyrene chains produces sterically
stabilised latex particles that are sufficiently hydrophilic to
stabilise O/W emulsions. In the case of synthetically prepared
solid nanoparticles of silica or alumina, the wettability of the
predominantly hydrophilic surface may be modified by the
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attachment of polymer chains or the adsorption of surfactants.
Nanoparticles of variable shape and surface charge are also
provided by natural clay minerals, e.g. Laponite silicate (negatively
charged disc-like particles) or boehmite alumina (positively
charged needle-like particles). Again the wettability of the bare
hydrophilic surface may be modified by the presence of adsorbed
surfactants, copolymers or proteins.
Pickering stabilisation conventionally requires the presence
of a complete monolayer coverage of closely packed particles,
as illustrated schematically in Fig. 1(a). In practice, however,
the concentration of particles available for adsorption during
emulsification may be limited, with the result that dispersed
droplets of reduced surface coverage are initially formed that are
unstable with respect to bridging flocculation and coalescence.36
Even if the bulk particle concentration is high enough and the
emulsification conditions are favourable, the idealised model of
stabilisation by a uniform particle monolayer is rarely achieved
in practice, because real colloidal particles are polydisperse in
size and shape and are often extensively aggregated. In fact,
colloidal particles having the requisite balance of hydrophilic
and hydrophobic character to adsorb optimally at the oil–water
interface during emulsification tend to exist in a state of weak
aggregation in the emulsion continuous phase. This has the
consequence that emulsion stability can be reached without
a fully saturated particle monolayer owing to the adsorbed
aggregates forming an interconnected steric barrier both around
and amongst the droplets (Fig. 1(b)). This aggregated particle
network functions to protect the emulsion not only against
droplet–droplet coalescence but also against gravity-induced
creaming/sedimentation and macroscopic phase separation.
In a Pickering O/W emulsion prepared with an oil phase having
a significant solubility in water (e.g. a flavour oil), the mechanical
rigidity of the adsorbed layer can prevent emulsion coarsening
arising from diffusive oil transport between droplets (Ostwald
ripening). This capability confers a functional advantage on the
use of solid particles instead of biopolymers as emulsifying agents
in food systems.36,37 The elastic character of the interfacial layer
under conditions of dense particle packing leads to a phenomenon
called ‘arrested coalescence’, whereby two (or more) unstable
droplets of intermediate surface coverage join together to form
a non-spherical composite droplet, as shown schematically in
Fig. 1(c). The arrested coalescence phenomenon is different from
the more well-known mechanism of ‘partial coalescence’ that
involves the formation of solid-like clumps of fat globules as a
consequence of the semicrystalline character of the fat phase in
dairy emulsions sheared at ambient temperature.38 Visualisation
of arrested coalescence has been convincingly demonstrated39 by
the application of a micromanipulation technique to individual
pairs of hydrocarbon droplets each with a controlled surface
coverage of silica microparticles. Evidence for the mechanism was
also recently observed40 in silica particle-stabilised O/W emulsions
of extremely high volume fraction. We may note that arrested
coalescence does not occur in emulsions prepared with surfactants
or proteins. In the surfactant case, this is because the adsorbed
molecules rapidly exchange with molecules in the bulk aqueous
phase as the surface area changes, whilst in the protein case the
viscoelastic adsorbed layer is not sufficiently rigid to resist the
Laplace pressure gradient driving liquid droplets into their normal
spherical shape.
A challenge for those working in the field of food colloids is
to identify microparticles and nanoparticles that are effective
as emulsion stabilisers and also acceptable for use in food
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(a)
STABLE UNSTABLE
(b)
(c)
Figure 1. Schematic representation of the stabilisation of emulsion droplets
by solid particles. (a) Pickering stabilisation requires close packing of
particles in the adsorbed monolayer at the droplet surface. (b) Aggregation
of particles confers stability by immobilisation of droplets in a gel-like
particle network. (c) Joining together of droplets of intermediate particle
surface coverage leads to stable non-spherical droplets by the mechanism
of arrested coalescence.
applications.36,37 The ubiquitous starch granule represents an
appealing first choice for consideration as a putative microparticle
stabiliser. While native starch is rather too hydrophilic to adsorb
at oil–water interfaces, it has been well demonstrated41 – 45 that,
by chemical treatment with octenyl succinic anhydride (OSA),
starch granules can be made to be sufficiently hydrophobic to
stabilise coarse O/W emulsions. Figure 2 is an optical micrograph
showing polydisperse starch granule fragments and aggregates in
an O/W emulsion prepared from 200 g kg−1 tetradecane and 30
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ADSORBED
STARCH SMALL OIL
PARTICLES DROPLETS
LARGE
OIL
DROPLET
STARCH
GRANULE
FRAGMENTS
Figure 2. Light micrograph of an O/W emulsion stabilised by hydrophobic
starch microparticles. The annotation highlights the presence of
polydisperse starch granule fragments and aggregates, both dispersed
in the bulk aqueous phase and adsorbed at the oil–water interface. Scale
bar = 200 µm. (Picture courtesy of BS Murray, University of Leeds.)
g kg−1 OSA-treated homogenised starch.41 Pickering stabilisation
of adsorbed polydisperse starch particles at the surface of the
largest oil droplet is visibly evident. Because of the large droplets,
the sample creamed rapidly under gravity, but it was found to
be extremely stable to coalescence, with no significant change
in droplet size distribution after several months.41 Exploiting the
substantial density differences amongst the main ingredients (i.e.
starch, oil and water), it has been suggested43 that it might be
feasible to adjust the composition of a starch particle-stabilised
emulsion so as to formulate a neutrally buoyant system exhibiting
no discernible creaming or settling.
Solid microparticles such as hydrophobically modified starch
granules, and also cellulose particles/fibres,46 – 48 do confer
impressive emulsion stabilisation properties once they have
become located at the oil–water interface. Unfortunately,
however, they are much less effective as emulsifying agents
than small-molecule surfactants or proteins. This is because of
the low diffusive mobility of the dispersed particles and the fact
that they produce negligible lowering of the interfacial tension
during emulsification. Consequently, a particle-stabilised emulsion
typically contains rather coarse droplets (∼10 µm diameter
or larger). In order to use high-pressure homogenisation to
make a particle-stabilised emulsion of mean droplet diameter
approaching that routinely achievable with milk protein or non-
ionic surfactant as emulsifying agent (i.e. ∼1 µm or less), it is
necessary to incorporate nanometre-sized particles.49
There have been several reports recently on the preparation
of Pickering O/W emulsions stabilised by nanoparticles of
biological origin: cellulose nanocrystals,50 chitin nanocrystals,51
flavonoid particles,52,53 starch nanospheres/nanocrystals,54,55 solid
lipid nanoparticles56 and corn protein (zein) particles.57 These
diverse materials really have little in common apart from their
insolubility and an ability to be dispersed in aqueous media. This
diversity shows the generic character of the Pickering mechanism
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as demonstrated in laboratory studies of model emulsions.

However, the situation is potentially more complicated for real
food products, because the behaviour of any particle-based
emulsifying agent/stabiliser will be affected by the presence of
other ingredients such as surface-active lipids and proteins. Indeed,
based on model system studies, it has been established that small-
molecule surfactants may adsorb on solid particle surfaces,58
may induce flocculation at the oil–water interface,59 may provide
synergistic stabilisation in combination with solid particles60 and
may competitively displace nanoparticles from the oil–water
interface.61 Synergistic effects have also been found in emulsion
systems containing mixtures of proteins and particles.42,62,63
Fat crystals are the main stabilising entities in edible
fatty spreads. The crystals derive their functionality from two
complementary mechanisms: adsorption at the surface of
dispersed water droplets (Pickering stabilisation) and formation of
a particle gel microstructure in the continuous phase of the W/O
emulsion (network stabilisation).64,65 A complicating mechanistic
factor in commercial products is the adsorption of small-molecule
emulsifiers (especially monoglycerides) at the triglyceride crystal
surface.66 This adsorption influences fat crystal morphology,
the mechanical strength of crystal–crystal interactions and the
wetting properties of crystals at the oil–water interface.67 The two
mechanisms of stabilisation are illustrated in Fig. 3. The model W/O
emulsions (800 g kg−1 canola oil) were made by high-pressure
homogenisation at elevated temperature (>70 ◦ C) followed by
rapid cooling to room temperature with continuous stirring to
allow small fat crystals to form.65 Glycerol monostearate (GMS) in
the oil phase was used to prepare Pickering emulsions (Fig. 3a).
Network-stabilised emulsions (Fig. 3b) were made by incorporating
fully hydrogenated canola oil (HCO) (mainly tristearin) into the oil
phase together with glycerol monooleate (GMO) as the primary
emulsifier. Emulsions prepared with either 40 g kg−1 GMS or
100 g kg−1 HCO + 40 g kg−1 GMO were composed of droplets
of average size ∼20 µm. The light microscopy image of Fig. 3a
reveals crystalline shells around the dispersed aqueous droplets
Figure 3. Illustration of the two mechanisms of W/O emulsion stabilisation
of the Pickering emulsion, whereas a continuous fat crystal matrix by fat crystals as observed by polarised light microscopy.65 (a) Pickering
is apparent in the network-stabilised emulsion (Fig. 3b). As a stabilisation by crystals of glycerol monostearate. (b) Network stabilisation
consequence of GMO adsorption at the solid tristearin surface, by crystals of tristearin in the continuous phase of a W/O emulsion prepared
some triglyceride crystals are attracted to the surface of the with glycerol monooleate (GMO) as emulsifying agent. Arrows indicate the
location of triglyceride crystals at the surface of GMO-stabilised water
dispersed aqueous droplets (as indicated by the arrows in Fig. 3b). droplets. Scale bars = 40 µm. (Reproduced from Ref. 65 with permission.
The two emulsion samples illustrated in Fig. 3 were stable towards Copyright 2011 American Chemical Society.)
coalescence and macroscopic phase separation over a period of
several days. However, on the basis of visual observations of phase
separation during extended quiescent storage, it was inferred65 particle-filled biopolymer gel whose mechanical properties are
that Pickering stabilisation by fat crystals is probably a more primarily determined by those of the bulk phase biopolymer
efficient mechanism than network stabilisation. Furthermore, it network. The structural state of a real food emulsion gel will most
could be observed65,68 that the Pickering emulsion was more likely exist as a composite network made up from a combination of
resilient to freeze–thaw temperature cycling than the emulsion aggregated emulsion droplets and crosslinked macromolecules.70
stabilised by the fat crystal network. The initial stage in emulsion gel formulation usually involves
making a stable protein-stabilised emulsion. The emulsifying agent
could be a single pure protein (e.g. β-lactoglobulin), a commercial
EMULSION GELS milk protein ingredient (whey protein isolate, sodium caseinate)
An emulsion gel is defined as an emulsion with a gel-like network or a non-dairy ingredient (egg yolk, soy protein).69 Under efficient
structure and solid-like mechanical properties.69 In the case of an emulsification conditions, and with a high enough protein/oil ratio,
O/W emulsion gel the colloidal structuring may be associated with the O/W emulsion can be prepared with fine droplets (diameter
the presence of (a) a network of flocculated oil droplets or (b) a <1 µm) and a narrow size distribution.71 Droplet aggregation
network of crosslinked biopolymer molecules in the continuous may occur, however, if the concentration of protein available
phase between the droplets. These alternative structuring schemes during emulsification is too low (bridging flocculation) or too high
are illustrated in Fig. 4. Structure (a) is a kind of aggregated particle (depletion flocculation).72 The formulation procedure may involve
gel whose mechanical and textural properties are determined by the incorporation of a hydrocolloid stabiliser during emulsification,
the interactions between oil droplets. Structure (b) is a kind of or extra ingredients (protein, polysaccharide, surfactant) may be

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Figure 4. Schematic presentation of idealised O/W emulsion gel structures:
(a) network of flocculated oil droplets; (b) oil droplets embedded in
biopolymer network.
added after emulsion formation, with further implications for
the state of flocculation.73 – 75 The liquid-like emulsion is then
converted into an emulsion gel either by aggregating the emulsion
droplets (Fig. 4(a)) or by gelling the continuous phase (Fig. 4(b)).
The transformation from liquid state to soft solid state is brought
about by some kind of processing step. For protein-based systems
the most widely employed methods are heating, acidification and
enzyme treatment.69,76
The mechanical properties of a particle-filled gel are determined,
inter alia, by the volume fraction of the filler particles and the
chemical nature of the filler–matrix interaction.77 For example,
incorporating whey protein-stabilised emulsion droplets into a
heat-set whey protein gel network leads to an enhancement in gel
rigidity as a result of matrix reinforcement by protein-coated
droplets functioning as active filler particles.78,79 In contrast,
dispersed oil droplets coated by non-ionic surfactant Tween
20 behave as inactive filler particles, thereby reducing the gel
rigidity.80 The matrix of the filled gel (Fig. 4(b)) consists of a network
of extensible biopolymer molecules, i.e. denatured protein or
linear carbohydrate chains. This network structure has some of
the features of a rubber-like material, insofar as the network
elasticity is dominated by entropic contributions from the flexible
chains between the crosslinks. On the other hand, the rheological
behaviour of an emulsion gel made from a protein-stabilised
emulsion of moderate or high volume fraction is more like that
of an aggregated particle gel (Fig. 4(a)). The essential difference
between the pure (entropic) polymer gel and the pure (enthalpic)
particle gel is that the former can be strained to high deformations
(over 100%) without fracturing, whereas the latter has a rather
small fracture strain (a few per cent).69
Acidification of a casein-based emulsion invariably leads to
irreversible aggregation followed by gelation.81 Indeed, this is the
destabilisation mechanism underlying the process of traditional
yoghurt making, whereby the action of lactic acid bacteria lowers
the pH of milk from around neutral to below 4.5. During this
slow acidification process, the native casein micelles become
partially dissociated and destabilised82 and the native milk fat
globules are trapped within the developing casein network as
inactive filler particles.83 In the case of homogenised milk, where
the native fat globule membrane has been mainly replaced by
micellar casein, the casein-coated droplets become incorporated
as active filler particles within the acid-induced casein network.83
In formulating a dairy emulsion product by acidification, a small
amount of polysaccharide (pectin, carrageenan, etc.) may be added
to enhance the gel texture and to control stability with respect
to phase separation and syneresis during long-term storage.
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Laboratory studies on model systems have demonstrated that the
microstructure and rheology of milk protein-stabilised emulsion
gels are sensitively dependent on the nature of the pH-dependent
protein–polysaccharide interactions.33,69,84 – 86
Protein adsorbs readily on the surface of colloidal particles.
Hence a mixed system of protein + Pickering particles provides
a potentially useful combination of functional ingredients for
the formulation of emulsion gels. A visual demonstration of
synergistic stabilisation with a mixture of protein (hydrophobin)
and inorganic colloidal particles (Laponite clay) is illustrated in
Fig. 5.62 Separate samples of concentrated O/W emulsions (oil
volume fraction 0.65) were prepared with protein alone (5 g
kg−1 ), colloidal particles alone (5 g kg−1 ) and a mixture of
protein + particles. It was observed62 that the emulsion stabilised
by the protein alone phase-separated into two distinct layers after
1 day of storage (Fig. 5(a)). The Pickering emulsion stabilised by
the Laponite particles also exhibited phase separation into three
regions (upper oily layer, middle emulsion layer and lower aqueous
layer) (Fig. 5(b)). However, the paste-like emulsion prepared with
the mixture of protein + particles possessed the homogeneous
appearance of a stable emulsion gel (Fig. 5(c)) with a large
elastic modulus and a high yield stress value. The gel character
of this mixed protein + particle system was attributed62 to the
elastic character of the particle–protein film surrounding the oil
droplets, leading to a self-supporting three-dimensional network,
as illustrated schematically in Fig. 5(d). A similar type of gel-like
emulsion structure could be prepared by the same researchers with
protein + boehmite clay particles.63 Whereas Laponite consists of
negatively charged disc-like particles (diameter 10–50 nm), the
needle-like boehmite particles (length 10–50 nm) carry an excess
positive surface charge. The hydrophobin was observed to adsorb
readily at the surfaces of both kinds of clay particles, and the ability
to form an emulsion gel was apparently unaffected by the surface
charge type or the particle shape.63
Colloidal aggregation and gelation may also come about from
the sticking together of oppositely charged particles.87,88 That is,
there is an opportunity for generating a gel-like emulsion through
the heteroaggregation of lipid droplets coated with oppositely
charged biopolymer layers. The resulting idealised microstructure
is illustrated schematically in Fig. 6. Proof of concept for this
structuring strategy was recently demonstrated89,90 for the case of
flocculated emulsions made by mixing together two different milk
protein-based emulsions – one made with β-lactoglobulin as the
sole emulsifier (isoelectric point pI ∼5) and the other made with
lactoferrin (pI ∼8). It was observed89 that microclusters of droplets
were formed under conditions where the protein-coated surfaces
possessed opposite net charges (5 < pH < 8). Depending on pH
and system composition, these mixed emulsions were found
to be characterised by large variations in microcluster size and
consequently by widely contrasting textures, from low-viscosity
liquids to gel-like soft solids. The same sort of heteroaggregation
strategy can also be used to generate gel-like emulsions from a
mixture of charged polysaccharide molecules (pectin) and protein-
coated droplets.91
AERATED EMULSIONS
Incorporating gas bubbles into a food material leads to a lighter
texture and a lower calorific density as well as to changes
in product appearance, microstructure and mouthfeel.92,93 This
general statement is well illustrated by the case of whipped dairy
cream. The incorporation of an equal volume of gas bubbles into
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Stabilising emulsion-based colloidal structures with mixed food ingredients
(a) (b) (c)
(d)
oil
BRIDGING
hydrophobin
Figure 5. Synergistic stabilising action of clay particles (Laponite) and
protein (hydrophobin) in O/W emulsions (silicone oil volume fraction 0.65)
prepared by high-pressure homogenisation.62 The three photographs
compare the visual appearances of 1-day-old emulsions prepared with (a)
hydrophobin (5 g kg−1 ), (b) Laponite (5 g kg−1 ) and (c) hydrophobin (5
g kg−1 ) + Laponite (5 g kg−1 ). Diagram (d) is a conceptual representation
of the three-dimensional network of hydrophobin-covered clay particles
located in the continuous phase between oil droplets. (Reproduced from
Ref. 62 with permission.)
dairy cream of relatively high fat content (>300 g kg−1 ) converts
the thick liquid-like O/W emulsion into a stiff solid-like structure
with a significant yield stress. The aerated emulsion structure is
stabilised by a network of partially coalesced fat globules (see
Fig. 7) formed under the influence of the localised shearing
forces generated during whipping.94 A crucial condition for the
successful shear-induced aeration of dairy cream is that the fat
phase should be semicrystalline. That is, there should be sufficient
liquid fat present to facilitate the efficient sticking together of the
globules via liquid fat bridges into a rigid crystal-based network,
but not so much liquid fat as to cause excessive clumping of
fat globules or incipient emulsion phase inversion (churning to
butter). Optimum processing is achieved by whipping the cream
to a maximum degree of stiffness at a temperature in the range
5–10 ◦ C. Overwhipping leads to large clumps of fat globules and a
loss of foam volume. The microscopic image in Fig. 7 shows some
evidence of overwhipping for this particular sample.94
There is growing research interest in designing novel ways
of incorporating air bubbles into conventional O/W emulsions
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Figure 6. Schematic representation of an emulsion gel structure made
by the heteroaggregation of two different kinds of biopolymer-coated oil
droplets.
FG
AIR
Figure 7. Scanning electron micrograph of the structure of traditional
whipped dairy cream showing the air cells stabilised by a network of
partially coalesced fat globules (FG).94 The presence of some large clumps
of aggregated globules (highlighted by arrows) indicates that this sample
was slightly overwhipped. Scale bar = 10 µm.
containing fully liquid droplets. While gas bubbles and liquid
oil droplets can in principle coexist in model systems without
destabilisation of the foam (or the emulsion),95 in order to confer
long-term stability, there usually has to be some kind of additional
structuring agent present within the continuous phase or at
the air–water interface.96 Researchers working on imaginative
methods of colloidal structuring in composite systems containing
bubbles and droplets have coined various descriptive terms such
as the ‘air-filled emulsion’,97 the ‘aerated emulsion gel’81 and the
‘foamulsion’.98 Some generic classes of structural arrangement are
illustrated schematically in Fig. 8.
In a system with air bubbles and oil droplets present together,
each individual spherical bubble is susceptible to a strong
buoyancy force because of its relatively large size and low
absolute density.96 For a total dispersed volume fraction that
is well below close packing (Fig. 8(a)), rapid destabilisation of the
system occurs owing to bubble creaming and phase separation.
Nevertheless, creaming can be restricted, and in principle stopped
altogether, by transforming the aqueous continuous phase into a
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(a) (b)
(c) (d)
Figure 8. Schematic representation of some putative stabilising structures
for aqueous systems containing both gas bubbles (large circles) and oil
droplets (small circles): (a) separately dispersed bubbles and droplets; (b)
bubbles surrounded by monolayers of emulsion droplets behaving as
Pickering particles; (c) bubbles trapped in a gel-like network of flocculated
droplets; (d) a binary gel-like network formed by heteroaggregation.
gel-like matrix93 or by increasing the total dispersed phase volume
fraction up to close packing. However, even for the case of a rather
concentrated O/W emulsion such as mayonnaise with 50% air
incorporated, bubble bouyancy is considered to be the primary
destabilising factor during long-term storage (∼1 month).99 Since
air has a significant solubility in the aqueous medium, the aerated
emulsion is susceptible to gas diffusion between bubbles (Ostwald
ripening) as well as gas loss to the external atmosphere.100 These
diffusive transport processes lead to time-dependent changes in
bubble size distribution (disproportionation) and a gradual loss of
total gas phase volume.101 What this all means is that long-term
prevention of the combination of instability processes (creaming,
coalescence, Ostwald ripening and loss of dispersed gas volume)
can only be achieved by converting the liquid-like continuous
phase into a solid matrix. In practice, this transformation may be
brought about by biopolymer gelation in the aqueous medium93
or by embedding the air bubbles in a densely packed dispersion
of rigid microparticles – for instance, the ice crystal network
of frozen ice-cream2 or the sugar particle network of fondant
confectionery.102
A viscoelastic layer of adsorbed protein at the air–water
interface can provide effective protection against bubble–bubble
coalescence, but it cannot prevent the relentless process of
bubble shrinkage due to gas diffusion. The reason for this
is that, although the protein monolayer may be substantially
elastic (solid-like) on short timescales (1 s), it is viscous (liquid-
like) on long timescales (1 s). In other words, the protein
monolayer does not have the mechanical strength to resist the
slow relentless change in interfacial area that accompanies bubble
disproportionation. The gradual compression of the surface layer
on a shrinking bubble causes partial protein desorption, and the
developing interfacial stresses induce wrinkling of the thickening
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E Dickinson
compressed film, leading to a final insoluble residue of denatured
protein.103
The situation described above applies to ‘normal’ food proteins.
However, there is a special group of proteins known collectively as
‘hydrophobin’ that is known to possess exceptional interfacial
and foam stabilisation properties.104,105 Interfacial layers of
hydrophobin are much more solid-like than those of casein or
whey protein. Moreover, in contrast to the behaviour of normal
food proteins, the adsorbed hydrophobin layer is capable of fully
inhibiting air loss from dispersed bubbles. Indeed, hydrophobin-
based foams have been observed105,106 to maintain stability with
respect to disproportionation for a period of several months or
even years.
Actually, there is a way to use ‘normal’ food proteins to make
protein-coated bubbles that are stable against disproportionation.
It involves the replacement of the familiar protein monolayer by
a mechanically strong capsule (thickness >10 nm) of thermally
crosslinked protein multilayers. Exploitation of this conceptual
approach has been used to demonstrate97,107,108 that air-filled
emulsions based on protein capsule shells made from crosslinked
cysteine-rich protein (bovine serum albumin or egg albumen)
can be made to exhibit long-term stability to match that of the
equivalent hydrophobin-based system.
Assembling a close-packed layer of emulsion droplets around
the surface of dispersed bubbles (Fig. 8(b)) provides another
potential mechanism for bubble stabilisation. This type of
structuring has recently been reported98 in ‘foamulsions’ made
by aeration of concentrated surfactant-based O/W emulsions. It
appears that the observed droplet layering acts to stabilise the
gas bubbles (and associated foam structures) through a Pickering-
type mechanism or a surface-jamming effect.109 Certainly, it has
been demonstrated110,111 that Pickering stabilisation of bubbles
by solid silica particles can provide outstanding long-term stability
with respect to bubble coarsening – even matching that found
with hydrophobin-stabilised bubbles.106 Also, indeed, it has been
proposed36 that the rigid hydrophobin protein molecule behaves
rather like an amphiphilic Pickering nanoparticle that is capable
of spontaneously self-assembling at the air–water interface into a
close-packed adsorbed layer. In the case of emulsion droplets
coated with a ‘normal’ food protein such as casein or β-
lactoglobulin, the droplet adsorption at the bubble surface is
considered not to be sufficiently strong to produce a long-lived
coherent droplet layer capable of preventing disproportionation.
On the other hand, the bubble coalescence stability can be
enhanced by the presence of neighbouring droplets functioning
as a partial steric barrier.112 Such structuring is involved in the
colloidal stabilisation of whipped homogenised cream.113,114
An effective method of structuring an aerated emulsion is
to encapsulate bubbles within a flocculated droplet network
(Fig. 8(c)). This concept has been exploited in the stabilisation
of an imitation whipped cream using the network structure of
an acid-induced protein-stabilised emulsion gel.115 A sodium
caseinate-stabilised O/W emulsion (vegetable oil volume fraction
0.35) was whipped at the same time as the emulsion aqueous
phase was steadily acidified with glucono-δ-lactone. The level
of air volume incorporation was observed to reach a maximum
at around pH 5.1 ± 0.1. This corresponds to the time when the
flocculated emulsion formed a weak gel,116 as indicated by the
cessation of dripping of liquid foam from the whisk beater. Aeration
under conditions of too little acidification, or alternatively too
much, was observed to be associated with a diminished bubble
stability and a lower foam volume.115 Supplementary functional
J Sci Food Agric (2012)
Stabilising emulsion-based colloidal structures with mixed food ingredients
ingredients such as a hydrocolloid (pectin) and small-molecule
emulsifiers (lactic acid esters of monoglycerides) were successfully
incorporated117,118 in order to improve the long-term stability of
the aerated emulsion and also to manipulate its rheology and
perceived texture to make it appear more like traditional whipped
dairy cream.
Other novel ways of producing composite structures from mixed
bubbles and droplets can be envisaged. One such conceptual
possibility, as illustrated in Fig. 8(d), is based on an extension of the
mechanism of heteroaggregation. In principle, this kind of gel-like
aerated emulsion could be fabricated from a heteroaggregated
mixture of dispersed bubbles and droplets with their air–water and
oil–water interfaces separately coated with oppositely charged
biopolymers (or protein–polysaccharide complexes). By exploiting
existing knowledge of the competitive and cooperative adsorption
of food biopolymers at fluid interfaces, there is the potential with
such a binary aerated emulsion system for separately fine-tuning
the nature of the colloidal interactions between biopolymer-
coated layers on droplets and bubbles.119
CONCLUSIONS AND OUTLOOK
This article has outlined some advances in the use of
mixed ingredients for the development of emulsion-based
food structures having improved colloid stability and textural
characteristics. The different types of structures have been
described under the three broad headings of particle-stabilised
emulsions, emulsion gels and aerated emulsions. For each of these
system types, and indeed some others not discussed here (e.g.
hydrogel microspheres120 or double emulsions121,122 ), a common
factor determining the microstructure and physical properties is
the nature of the interactions of the food biopolymers in the
bulk aqueous phase and at the various kinds of interfaces. We
recognise, of course, that the colloidal structures encountered in
practice are necessarily more complicated and messy than those
represented in the idealised schematic diagrams of this article.
Furthermore, while accessibility to advanced instrumentation
remains a key factor to progess in this field,4 the characterisation
of interfacial organisation on the nanoscale is by no means a
straightforward matter, despite the widespread availability of
powerful techniques such as X-ray/neutron scattering/reflectivity,
atomic force microscopy, confocal laser scanning microscopy,
Brewster angle microscopy, diffusing wave spectroscopy and
cryoscopic scanning electron microscopy.
In summary, the design principles involved in building these
different types of colloidal structures may be concisely expressed
in three words – layering, clustering and embedding.123 That is to
say, in essence, there are three main ways to build up the required
microstructure: (1) the biopolymer molecules or particles can be
made to become layered around the surface of droplets (and
bubbles); (2) the biopolymer-coated droplets and particles can be
made to cluster together into aggregates and networks; (3) the
droplets (and bubbles) can be made to become embedded within
gel networks formed from crosslinked biopolymers or aggregated
particles.
Looking further ahead, a considerable ongoing challenge is
to determine how these emulsion-based structures break down
during eating and digestion. This is a complex problem because,
once it is inside the human body, the evolving colloidal structure
becomes inaccessible to most of the conventional physical
techniques. Moreover, the original structure becomes disrupted
by a complex combination of (bio)chemical and mechanical
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processes triggered by the secretionary and motor responses
of the gastrointestinal tract.12,124
From the material science viewpoint, a useful tool for
deriving mechanistic understanding is numerical simulation and
modelling.9 The simulation methodology that is appropriate for
a particular problem depends on the length scale involved.
For instance, computational fluid dynamics has been used
to give insight into hydrodynamic flow conditions on the
macroscopic scale within the human digestive system;125,126
molecular dynamics has been used to simulate nanoparticle
adsorption and self-assembly at liquid–liquid interfaces;127 – 129
and Brownian dynamics simulations have been employed to
explore the effect of colloidal interactions on the formation and
shear-induced breakdown of model colloidal particle gels.130 – 132
These and other modelling approaches should provide a
general theoretical framework for understanding the structural
breakdown mechanisms of specific systems such as particle-
stabilised emulsions,133,134 mixed biopolymer gels135 – 138 and
emulsion gels,85,139 – 141 as studied under laboratory conditions
by the combined techniques of large-deformation rheology and
confocal microscopy.
The ultimate objective of these combined theoretical and
experimental studies is, of course, to determine the essential
physicochemical factors underlying the oral sensory perception of
food materials and the health-related aspects of food digestion.
Realistically speaking, though, it has to be emphasised that there
is still a long way to go before such in vitro laboratory models
and computer simulations can properly aspire to be considered as
reliable representations of what happens to the colloidal structure
of food within the human body.
ACKNOWLEDGEMENT
In attempting to understand some of the fundamental principles
underlying the science and technology of food systems, this
author has been greatly influenced by the inspiration and insight
of Professor Pieter Walstra, who sadly died in Wageningen on 29
May 2012 at the age of 81. His excellent textbook Physical Chemistry
of Food,142 written during an academically active retirement,
is a fitting testament to Pieter’s dedicated scholarship and his
undoubted commitment to the colloid science approach to food
structuring.
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