ISSN 2313–5891 (Online)
ISSN 2304–974X (Print)
Ukrainian
Food Journal
Volume 8, Issue 4
2019
Kyiv
2019
Kиїв
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Food dispersion systems process stabilization. A review.
Andrii Goralchuk, Olga Grinchenko, Olga Riabets, Оleg Kotlyar
Kharkiv State University of Food Technology and Trade, Kharkiv, Ukraine
Keywords:
Emulsion
Foam
Stabilization
Rheology
Layers
Article history:
Received 28.11.2018
Received in revised form
15.08.2019
Accepted 28.11.2019
Corresponding author:
Andrii Goralchuk
E-mail:
abgora@gmail.com
DOI: 10.24263/2304974X-2019-8-4-4
Abstract
Introduction. The overview is given to systematize
information on the indicators, affecting the production and
stabilization of foams and emulsions, for applying the
existing regularities for more complex dispersed
(polyphase) systems.
Materials and methods. Analytical studies of the
production and stabilization of foams and polyphase
dispersed systems published over the past 20 years. The
research focuses on the foams, emulsions, foam emulsion
systems and the systems, being simultaneously foam,
emulsion and suspension.
Results and discussion. Though foams and
emulsions have similarities and their production differs in
the dispersion rate, determined by the rate of surfactants
adsorption. Emulsifying is faster than foaming, therefore,
the production of foam emulsions can be sequential only.
Coalescence, as a destruction indicator, is typical of foams
and emulsions alike, and it is determined by the properties
of surfactants. Other indicators are determined by the
features of the dispersion medium. The study systematized
the factors, ensuring the stability of dispersion systems. The
structural mechanical factor is effective in stabilizing foams
and emulsions. It is implemented by the usage of proteins
only, or solids with partial soaking, or a combination of
proteins and low-molecular surfactants or a combination of
proteins and polysaccharides. The structural mechanical
factor for polyphase systems stabilization, in particular, for
foam emulsions, is based on selecting surfactants to
regulate rheological properties of interface adsorption
layers, the sequence of dispersion phases, which ensures
their spatial location in the food product.
Conclusions. The rheological properties of interface
adsorption layers, containing proteins, surfactants,
polysaccharides and high viscosity of the dispersion
medium play the vital part in ensuring the stability of food
dispersion systems.
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Introduction
Many culinary and confectionary products are characterized by the polyphase structure.
The phases may differ in content, aggregate state, ingredients, and the degree of dispersion.
Food dispersion systems are thermodynamically unstable. These systems require the
development of effective solutions to strengthen their process stability. In other words, it is
necessary to increase the time during which the food product will not be affected. Extensive
pure and applied studies have been discussing the production and stabilization of foams,
emulsions, suspensions, and foods. The fundamental research into the production and
stabilization of foams and emulsions, which unite the known evidence-based data,
determined by the system ingredients and the way of their production, is continuously
developing and scientifically expanding. However, fundamental papers that would ensure
polyphase foods (systems containing several different phases) production and stability are
nearly non-existent. Therefore, the development and intensification of process technologies
for heterogeneous polyphase foods are inhibited. Accordingly, it is necessary to analyze
scientific data on producing and stabilizing heterogeneous systems with a single continuous
phase – foams and emulsions and their further development for polyphase dispersed structure
foods.
Materials and methods
The analytical examination of the papers on the production and stabilization of
emulsions, foams and polyphase dispersed systems over the past 20 years.
The research focuses on the foams, emulsions, foam emulsion systems and the systems,
being simultaneously foam, emulsion and suspension. The study analyzes surfactants and
stabilizers, used to provide dispersion systems stability.
Results and Discussion
1. The production foams and emulsions, process differences and similarities
Foams are thermodynamically unstable systems, with a gaseous dispersed phase and a
liquid or solid dispersion. No clear size ranges of bubble have been reported in the literature.
It is noted that the gas bubble size fluctuates from several micrometers to several centimeters
[1]. Depending on the continuous phase content, bubbles have different shapes – from
spherical (provided low concentration phase) to dodecahedric (provided high concentration
phase). Foam stability is influenced by various factors, in particular: the nature and
concentration of the foaming agent, temperature, viscosity and рН of the dispersion medium,
the surface tension of solutions, the introduction of electrolytes into the liquid phase, different
foods as solid particles, fatty raw materials [2, 3]. However, their impact on the foam stability
has been studied insufficiently and further work is to be performed in this respect.
Foams are manufactured in two ways [1]. The first is in air dispersion via frothing,
intensive mixing or gas blowing through liquid. The other way is in gas or vapor liberation
in liquid as a result of liquid boiling due to fast heating or pressure drop. For this purpose,
gas is first dissolved in the liquid under high pressure. This approach is effectively
implemented in spray whipping cream.
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Emulsions belong to lyophobic colloids, they are also thermodynamically unstable
heterogeneous systems, which are two liquids that do not mix, but are distributed in each
other. The discontinuous (dispersed) phase size varies from 10 nm to 50 µm. Depending on
the discontinuous phase particle size emulsions are divided into nano-emulsions, microemulsions and emulsions (or macro emulsions). The specific feature of these emulsions is
that micro-emulsions, unlike the others, are formed by themselves due to the ultra-low
interfacial tension at about 0.1 mN/m, the discontinuous phase particle size ranging from 10
to 100 nm. Micro-emulsions are thermodynamically stable systems with high content of
surfactants. In nano-emulsions particle size varies from 50 to 500 nm. These emulsions are
kinetically stable, have low surface tension – 1–10 mN/m and the medium content of
surfactants. Emulsions are kinetically stable, have low interfacial tension and the dispersed
particle size from 500 nm to 50 µm [4, 5]. Nano-emulsions and emulsions have become
practically used in foods.
Emulsions are classified according to two criteria: discontinuous phase concentration –
diluted (С ≤ 0.1%), concentrated (0.1% ≤ С ≤ 74%) and highly concentrated (С > 74%);
dispersion medium polarity – direct (the dispersion medium is a polar liquid) and reverse (the
dispersion medium is a non-polar liquid) [6].
It is necessary to carry out thorough examination of the processes occurring while
forming and destroying foams and emulsions. The processes of forming and destroying
foams and emulsions are quite similar. The formation of the dispersed system of a foam
(Figure 1, а) or an emulsion (Figure 1, b) [6] is accompanied by three simultaneous processes:
– Discontinuous phase particles are deformed and broken;
– Srfactants are diffused in the newly created phase boundary surfaces and are adsorbed
on them;
– Discontinuous phase particles collide, which leads to coalescence or repulsion.
Emulsions are produced using the methods of dispersion in emulsifying machines,
rotary pulsers, homogenizers, ultrasound machines or via oil feeding through a network of
micro-channels [7]. Emulsifying features availability of two liquids, which are not dissolved
in each other, and the availability of surfactants, which ensure formation of the interface
adsorption layer. The way of energy supply is important to ensure emulsion dispersion [8, 9].
To produce a dispersed system, it is necessary to put efforts into forming a new phase
boundary surface, meaning that it is necessary to put efforts into destroying intermolecular
forces (cohesion forces). Thermodynamically, lower degree of dispersion corresponds to the
lower values of surface (in the foam) or interfacial (in emulsion) tension, which is ensured
by including surfactants [11, 12]. The breakup of drops, bubbles is counteracted by the
capillary pressure, which is proportionate to the surface (interfacial) tension and is turned
proportionate to the dispersion particle radius [11, 12]. The difference in the capillary
pressure of two adjacent bubbles triggers gas diffusion and leads to their coalescence.
Surfactants resist coalescence, due to the surface tension gradient [13, 14].
The foam and emulsion production processes are similar, but have certain differences.
An important difference between the formation of foams and emulsions is in the dispersion
rate. Emulsifying process is much faster than that of foam formation, which determines
different rates of adsorption on various phase boundary surfaces. The second difference is
the size of dispersion particles, which is normally lower in emulsion. In foams it is hard to
separate foam formation from stabilization, since the destruction processes start at the stage
of foam formation [15]. In emulsions (such as milk) fat particles can aggregate and coalesce
only under the homogenizing pressure of 8-10 MPa after cooling [16, 17].
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continuous phase
gaseous phase
Figure 1, а. Foam formation [1].
b)
Figure 1, b. Schematic representation of the various processes occurring during emulsion
formation. The drops are depicted by thin lines and the surfactant by heavy lines and dots [3].
2. Factors, affecting foam and emulsion destruction
The coalescence rate depends on many factors: the conditions of foam and emulsion
formation, size and homogeneity of continuous phase particles, the content of solid fat,
crystal shape and size, the content of continuous phase, the kind and content of surfactants,
the viscosity of dispersion medium [18, 19].
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The temperature impact on the stability of foams is rather complex due to numerous
simultaneous competing processes. If the temperature rises, the pressure inside bubbles rises,
too, as well as the surfactants solubility, the surface tension decreases, which improves foam
stability. However, if the temperature rises, thermal vibrations of adsorbed molecules
increase. That leads to the decrease in the mechanical strength of the surface layer, created
by surfactant molecules. Furthermore, solution viscosity decreases, which raises the rate of
liquid bleeding from the foam, and the conditions of surfactant polar group hydration change,
which causes foam stability loss. However, in some foams, received using high-molecular
substances (egg white), thermal treatment entails transition from the liquid dispersion
medium to solid. The resulting foam becomes stable. The examples of these foams are fruit
candy, marshmallow, sponge cake semi-finished product etc. Thus, the temperature effect on
the foam stability is to be analyzed on case-by-case basis [20].
Accordingly, the integrated process of forming and destroying dispersed systems
becomes obvious. In this respect, one of the main problems in producing dispersed systems
is that of their stability, which is in finding the conditions, necessary for long keeping of
homogeneously distributed continuous phase in the dispersion medium [21, 22]. The keeping
time is determined by process objectives in each case. Therefore, it is generally possible to
identify the factors of ensuring the process stability of dispersed systems.
Emulsion destabilization involves six processes: creaming, sedimentation, flocculation
(agglomeration), phase inversion, coalescence and Ostwald ripening [22] (Figure 2, a). Foam
destruction involves the following processes: syneresis and air bubble coalescence as well as
disproportionation (the appearance of much bigger bubbles due to the bubble coalescence
(merging)), the film rupture and thinning (Figure 2, b) [23, 24].
The surface tension gradient decreases the intensity of liquid bleeding from films [11,
13]. The motion of liquid in foam leads to the local changes in the liquid and gaseous phase
ratio and it occurs due to two forces – the local gradient of capillary pressure and gravity
force. It is expected that drainage phenomena are related to liquid bleeding from films, caused
by the capillary pressure change, which leads to the liquid flow to thicker areas with lower
pressure [26]. When the film thickness is below 10 nm, it loses its integrity. At the same time
gas bubbles merge (coalescence occurs), the bubbles volume increases, their quantity
decreases and, eventually, foam hardens [26]. Film ruptures near the foam boundary entail
the loss of the gaseous phase by the system [27]. Liquid from films gets in Plateau ribs. The
channels, formed by these ribs, build a complex network for the liquid to flow out of foam
due to the gravity force. The features of “wet foam” syneresis include the period of halfdecay – the time for the foam to half in volume [27].
Another important mechanism of foam destruction is disproportionation. Owing to
higher capillary pressure in foams a smaller bubble, compared to bugger one, undergoes gas
diffusion from the smaller to the bigger bubble through the dividing film [8, 28]. Eventually,
larger bubbles grow due to smaller ones. The higher the degree of polydispersion is, the
stronger the gas diffusion is. “Wet” foams with thick liquid layers firstly undergo liquid
bleeding, which entails film thinning followed by the gas diffusion and film rupture [29].
Emulsions destruction has both similarities and differences. Emulsion creaming is due
to the difference between the density between the continuous phase and medium, which leads
to bulk separation. In other words, creaming is characterized by continuous phase rise, as oil
density is lower than that of water.
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Sedimentation
Coalescence
Figure 2, а. Emulsion destruction [3].
film rupture
bubble
bubble
Liquid flow
p1
p2
p1 ˃ p2
gas diffusion
coalescence
merged
buble
A
B
C
Figure 2, b. Foams [25] Gravitational drainage (A), Coalescence (B), Ostwald ripening
(Disproportionation) (C).
Flocculation or agglomeration of the fat phase can occur in emulsion, provided van der
Waals energy values are higher than those of the repulsion forces energy. During flocculation
several oil droplets unite and form agglomeration, where each droplet stays intact, i.e. the
droplet content does not shift. The process of coalescence is generally similar, and the only
difference is that the droplet content unites, whereas the capillary pressure makes the
resulting drop spherically shaped. In existing food emulsions the above processes are
interrelated: creaming accelerates as the drop size increases through coalescence [30]. The
effect is explained by the fact [29] that the oil drop lift rate rises proportionately to its squared
radius. Flocculation and coalescence processes enlarge the radius of agglomerates or drops.
Studies also attend specifically to partial coalescence as a mechanism of emulsion
instability [31, 32]. This process is only between partially crystallized droplets, when a crystal
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of one droplet penetrates another. Liquid fat may flow out of the droplet, strengthen
molecular binding, and create a bridge between two droplets [33] the mechanical force of the
fat crystal binding is sufficient to stand capillary pressure, thus, protecting droplet shape and
preventing their merging [31, 32].
Thus, coalescence is inherent in foams and emulsions, which is determined by the
surface properties of surfactants. Such emulsion destruction processes as sedimentation,
separation, Ostwald ripening and foam destruction processes – syneresis and
disproportionation – are determined by the dispersion medium viscosity. The emulsion
flocculation and phase inversion is due to surfactants activity.
3. Factors, ensuring foam and emulsion stability
Following the processes, occurring in dispersed systems destruction, three kinds of
dispersion systems stability are singled out – aggregate, kinetic and phase. All of them are
supported by different factors (Figure 3). The aggregate stability is the ability to keep
unchanged size of dispersion particles over time, i.e. to resist coalescence. Kinetic stability
is the system ability to keep unchanged continuous phase particle distribution within the
system over time, i.e. to resist outflow or sedimentation of particles. Phase stability is the
ability to keep unchanged nature of interaction between dispersed particles over time, which
is important for the systems, where dispersed particles interact (flocculation) [34].
Dispersion system stability
Aggregate
stability
Kinetic
stability
– electrostatic;
Structural-mechanical
– adsorption-solvation; factor
– entropic factors
Phase
stability
Hydrodynamic
factor
- steric stabilization;
- Pickering stabilization
Figure 3. Factors, ensuring dispersion systems stability
The factors, ensuring the aggregate and kinetic stability of dispersed systems, include
thermodynamic and kinetic ones. These factors can emerge severally or jointly.
The thermodynamic stabilization factors are [35]:
–
Electrostatic;
–
Adsorption-solvation;
–
Entropic;
The electrostatic factor of stabilization is based on the theory, developed individually
by Derjaguin, Landau, Verwey and Overbeek (DLVO). According to this theory, a double
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electric layer of ions is formed on the surface of the continuous phase particles, which brings
about an electric power (energy) barrier (disjoining pressure). The latter prevents
approximation of like-charged particles to the distances with intensive molecular attraction
forces. It is not always possible to explain the stability of emulsions and foams, stabilized by
nonionic surfactants, using the electrostatic factor. Nevertheless, the application of disjoining
pressure models, under the DLVO theory, enables to unite several stabilization factors and
forecast system behavior [36, 37].
The adsorption-solvation factor consists in forming a dispersion medium or an adsorbed
molecule layer around the dispersed particle of solvation layers. When particles approach
each other, solvation (adsorption) layers prevent their coalescence [34].
The stabilization entropic factor is determined by the thermal motion and mutual
repulsion of flexible chains of surfactant macromolecules, partially bound to the dispersed
particles as a result of adsorbing some of their parts. This mechanism of stabilization is
definitely effective in low-concentration systems and in surfactant-containing systems with
long flexible chains, oriented on the dispersion medium [34].
Kinetic factors include hydrodynamic and the structurally mechanical factor. The
hydrodynamic factor is related to the speed of particles approximation and the speed of
medium layer bleeding between them. The slowdown in the destruction of these systems may
be achieved due to increasing the density and viscosity of the dispersion medium [34].
The structurally mechanical factor includes the steric stabilization factor and Pickering
stabilization. The steric stabilization factor is determined by the formation of protective
interface adsorption layers on the surface of dispersion particles, which prevent coagulation
of dispersion particles owing to high-molecular substances or low-molecular non-ionic
surfactants. Pickering stabilization of dispersion particles is due to the formation of a highdispersion solid particle protective barrier on their surface [37].
The study has established the effectiveness of stabilizing food dispersion systems
(foams and emulsions) with structural-mechanical stabilization factor varieties – steric
stabilization, provided the use of proteins, protein mixes [38], proteins with low-molecular
surfactants [39, 40], protein complexes with polysaccharides [41, 42], and Pickering
stabilization via using solid particles [43, 45], ethylcellulose [44], hydro dairy proteins, corn
[46], fat particles [47], mustard flour, ginger flour [48] (Figure 4). The stabilization of foams
and emulsions due to the structural-mechanical factor enables to significantly extend the shelf
life of these products.
The research into the joint impact of substances with various surface activity rates
allowed for emulsion stabilization with a combined emulsifier – protein and lecithin [51],
protein and polysaccharide [34, 50]. In this stabilization, provided a specific correlation of
two surfactants, the main stabilizer, though being partly replaced from the drop surface with
a more active surfactant, but insufficiently to damage mechanical strength of the shell. These
adsorption shells are mobile and easily self-restored.
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a
b
c
d
Figure 4. Schematic representation of relative thicknesses of thin films between closely
approaching oil droplets stabilized by (a) surfactants, (b) proteins, (c) hydrocolloids (complex
protein polysaccharides) and (d) colloidal particles (Pickering stabilization) [49]
Self-restoring emulsion properties are also typical of stabilizers thixotropic solutions,
which can create a spatial network in the dispersion medium or form complexes with proteins
and stabilize emulsions. The spatial network, on the one hand, binds a stabilizer with an
adsorption layer, on the other – with the dispersion medium. The spatial network can be
destroyed mechanically and easily restored upon the force loss [52, 53]. There are four kinds
of systems, containing two polymers and a solvent:
1. The solution containing two neutral polymers refers to the segregate systems (i.e.
formation of two solutions that do not mix).
2. A neutral polymer and a polyelectrolyte, that mix with each other with no creaming or
sedimentation, can form associates due to the hydrogen binding, and during the charge
neutralization the system may break into phases that do not mix [54].
3. Like-charged polyelectrolytes, thermodynamically incompatible, refer to segregate
systems.
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4. Oppositely charged polyelectrolytes. The electrostatic attraction between the oppositely
charged groups leads to the emergence of complexes with rather strong binding, i.e. these
systems refer to associative ones. They are widely spread in living systems and are
commonly used in practice. Polyelectrolyte complexes are formed owing to the
cooperative reactions of oppositely charged functional grouping. Cooperative reaction
implies the emergence of each inter-chain salt binding, facilitating the formation of
further bonds between polyelectrolyte complex chains, which makes is highly stable [55,
56].
The simplest way of producing polyelectrolyte complexes is mixing the solutions,
where one contains anionic, and the other – cationic polyelectrolyte. There are two types of
polyelectrolyte complexes – stoichiometrical and non-stoichiometrical. Stoichiometrical
complexes are normally water-insoluble and characterized by high hardness and
hydrophobicity. Non-stoichiometrical polyelectrolyte complexes are water-soluble as there
are chain segments that were not involved in complex formation. The formation of the
complexes features considerable viscosity increase, in some cases even gel formation. All
these processes are influenced by рН, solution ionic force and other factors [57]. The
production of polyelectrolyte complexes of milk proteins and low-etherified pectin on interphase surfaces enables not only to strengthen emulsion, but also to raise destruction resistance
under temperature rise [58].
It was found that if the рН value is above the isoelectric point, proteins and anionic
polysaccharides form soluble complexes, while if рН is below the isoelectric point, the
formed complexes are water-insoluble [59, 60]. Thus, provided the conditions of forming
soluble polyelectrolyte complexes between proteins and anionic polysaccharides, according
to the structural-mechanical stabilization factor theory, it is possible to produce stable foams
and emulsions.
Following the data analysis of the indicators, ensuring the stability of dispersion
systems, structural mechanical stabilization factor varieties show high performance.
4. Factors in foam and emulsion stabilization
Food emulsion stabilization frequently involves the increase of dispersion medium
viscosity. It was found that the inclusion of k-carrageenan polysaccharide in aqueous phase
at 0.4% slightly raised the concentrated drop average size (30% soy oil) in sodium caseinate
emulsions [61]. If the k-carrageenan content is below 0.2% there is fast coagulation of oil
drops. Under high polysaccharide concentrations emulsion creaming decreases due to the
formation of the mesh structure of flocculating drops. Emulsions viscosity rises along with
the increase of the k-carrageenan content. The stability of emulsions, their structure and
rheological properties directly relate to the quantity of the polysaccharide added to the
aqueous phase.
Sodium caseinate-stabilized emulsions with k-carrageenan feature pseudo-plastic
behavior, showing the reverse flocculation of oil drops. Similar properties are typical of whey
protein isolate emulsions [62]. It was also identified that if pH is <6.0, and, mainly under low
shear rates, the emulsion effective viscosity rose, which stabilized emulsions against
creaming. This effect referred to creating oil-droplet bridges due to electrostatic interaction
between whey protein isolate and k-carrageenan on the drop surface and formation of a
netlike framework.
When studying the impact of k-carrageenan on the bovine-serum-albumin-stabilized
(BSA) emulsion properties, it was found [63] that under the aqueous phase pH of 6.0 and
certain polysaccharide limit concentration there emerges the so-called “binding”
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flocculation, which leads to the formation of an oil-drop netlike framework. Provided the
above pH value, experimental data on surface tension under the low ionic force show strong
electrostatic BSA and k-carrageenan interaction.
It was established that adding low-molecular surfactants or polysaccharides to a proteincontaining system causes emulsion flocculation and form destruction [64, 65]. To this end,
the examination of the visco-elastic properties of sodium caseinate stabilized 1Bromohexadecane-in-water emulsions confirmed [65] that under low xantan gum content,
the region of emulsions linear visco-elasticity reduces, which, according to the authors,
shows drop flocculation. In other words, the stabilizer acts as a flotation agent, which may
be caused by charge neutralization on the surface of dispersed particles or by simultaneous
adsorption of polysaccharide on different particles, thus intensifying their flotation. However,
the rise of polysaccharide concentration is accompanied by the increase of visco-elastic
properties – the elasticity module and complex viscosity values grow. As xantan content rises
in the emulsion flow curves, there emerges a Newtonian region in the flow. Therewith, the
value of the highest Newtonian viscosity grows along with the rise of the polysaccharide
content in the system. That points to the formation of a spatial structure, which hinders the
emulsion drops motion, and to the lower flocculation of emulsion drops. When analyzing
emulsion relaxation properties it was shown that the higher xantan concentration in the
stabilizing mix, the longer relaxation is required [65], which also indicates protection against
emulsion drops flocculation when polysaccharide is added. The obtained data are quite
comparable with findings in [66].
Studies were carried out on the stability of n-tetradecane aqueous emulsions [67, 68],
stabilized by sodium caseinate and non-ionic surfactant Tween-20 (Polyethylene glycol
sorbitan monolaurate) at 21 °С. In the emulsions with a stable surfactant content, the
replacement of Tween-20 with caseinate leads to higher emulsifying, which, in turn,
increases protein content. In addition, under lower caseinate concentrations in emulsions,
their rheological parameters gradually change from visco-elastic to Newtonian – non-ionic
surfactants Tween-20 weakly interact with proteins and reduce sodium caseinate emulsion
viscosity. This is determined by the ability of the non-ionic surfactant, in case of adsorption,
to replace protein macromolecules from the drop surface.
It was noted in [69] that despite new studies in the rheology of emulsions and interface
layers, the data related to the correlation between the rheological properties of protein
adsorption layers and protein-surfactant mixes and emulsion stability based on these systems
are insufficient due to the missing indicator or quantitative ration between rheological
interface properties and emulsion stability. It is noted that without the data on the ingredients,
structure of sodium caseinate-surfactant associates and mixed interface adsorption layers it
is impossible to identify the emulsion stabilization mechanism.
Thus, the joint use of proteins and polysaccharides or proteins and surfactants enables
to regulate the stability of emulsions and foams. However, the mechanisms ensuring the
stability (as shown in analyzed literature) may vary even in the systems with identical
surfactants, but with different proportions. The situation becomes more complicated provided
a polyphase system.
5. The perception and stabilization of foam emulsions
The availability and kind of oil differently influence the process of foaming and foam
stability, which depends on the oil content, fat globule size and its aggregate condition [67,
70]. The production of foam emulsion systems using hard oils improves foaming ability and
foam stability. This is the way to stabilize ice cream structure [71]. This process is related to
foam stabilization due to adhesion of solid fat particles on air bubbles [72] (Figure 5).
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Serum
Liquid oil
Air
Air
Air
Serum
Fat crystal linking
adjoining particles
Figure 5. Adhesion of fat particles on air bubbles
as a factor of foam emulsion stabilization [73]
The addition of liquid oils to foamy protein-based systems leads to lower foaming
capacity and foam stability, which is related to the foam destruction and is in its ability to
intensively replace protein from phase boundaries and entail the rupture of interface
adsorption layers. Vice versa, the addition of hard oils raises the foaming capacity and
mechanical strength of foam emulsion systems [74]. The addition of liquid oils is an effective
antifoam [75], which is used in antifoaming technologies. The antifoam mechanism is in the
fact that due to the adhesion of oil drops on air bubbles they, depending on the size of the
surface tension, either spread on the surface of the bubble, or form a fat bridge between two
adjacent bubbles (foam is destroyed anyway) Figure 6.
a
b
c
d
Figure 6. Schematic presentation Bridging-stretching mechanism of foam film rupture.
(a-b) Bridging of the foam film surfaces by antifoam globule leads to an oil bridge with nonbalanced capillary pressures at the oil-water and air-water interfaces.
(c-d) The bridge stretches with time until a thin, unstable oil film is formed in the bridge center.
The rupture of this oil film leads to destruction of the entire foam lamella [76].
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However, in case of forming a fat bridge the destruction becomes more effective. To
describe these processes a theoretical model was developed. Therewith, it involved Dupre
equation and the equation of defining Harkinson spreading parameter, which the authors call
the input and the spread ratios, respectively. This model describes the foam destruction
process. It is noted that provided an input barrier, at the bubble interface foam destruction
becomes less effective, which requires inputting non-spherical hydrophobic particles into oil
[76, 77]. The input barrier may be created by colloidal surfactants, proteins. If there is an
adsorption layer on fat particles and air bubbles, the stability of systems is determined by the
behavior of pseudo-emulsion film, surface, interfacial tension and film tension, which create
the Neumann’s triangle [78].
When studying the impact of oil mixes with different content of liquid triglycerides, it
was found that the higher the liquid triglycerides content is, the lower the volume of foam is.
That is the result of the oil spreading on the air/water interface [79] Figure 7.
a
b
c
Figure 7. Schematic presentation of the “spreading-wave generation” mechanism, (a, b) Entry
of an oil drop in the region of the Plateau channel leads to oil spreading on the surfaces of the
neighboring foam films (b, c).
The higher the fat phase content in foam emulsion systems is, the higher the air
dispersion general volume becomes, which indirectly points to the fat globules involvement
in the air bubble stabilization [80]. There is also a shift of the foaming maximum towards a
later whipping stage, which is, probably, related to the increase in the system viscosity. The
impact of other factors on the air dispersion volume appears related to the fat dispersion
destabilization. Lower destabilization and higher whipping temperature reduce foam volume.
Higher destabilization of emulsions due to longer storage of cooled fat-containing emulsion
products and higher acidity result in higher foam volume [81].
The air of foam emulsion structured products undergoes considerable changes while
being whipped. These changes are cause by mechanical impact of mixing. The average
diameter of air bubbles, which is 100–150 µm during the first five minutes, gradually reduces
to 50…70 µm by about the mid of the process and further it increases by 20 µm on average
till foam destruction [81].
When emulsion products are whipped, individual fat particles aggregate. This process
of fat particles aggregation is both on the water/air interface and thoughout the volume of the
systems. The initial stage of aggregation is the involvement of hydrophobic fat globules
interfaces (flotation). The fat particles aggregation in the volume phase is not normally
caused by simple collisions of single particles, but when air bubbles are actively introduced
and then used to float fat globules [72].
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The conditions of dispersed particles flotation include the creation a non-zero contact
angle of the continuous phase and a dispersed particle, low viscosity of dispersion medium,
no “protective barrier”, which can be formed by high-molecular compounds [82, 83],
significant shift rates (a turbulent flow), which raise the probability of air bubbles collision
with dispersed particles [84, 85]. Higher hydrophobization (destabilization) of the fat phase
raises the contact angle.
The process of fat particles aggregation in the aqueous phase comprises two successive
stages: flocculation of fat globules with preserved, though somewhat changed shells and the
aggregation of glyceride nuclei of fat globules to form emulsion gels [86, 87]. The
aggregation of fat particles and forming emulsions gels might occur due to building the
binding hydrophobic or salt bridges between proteins on different fat particles [88] or due to
the hydrophobic binding between fat crystals or liquid oil [89, 90]. The value of the
structural-mechanic barrier to be overcome by the fat globules aggregation is determined by
the degree of shell native structure destruction during the whipping process or another
mechanical impact. The first stage of the fat bubbles aggregation at the water/air interface is
their flotation by air bubbles. The main pre-condition of this process is the hydrophobicity of
the fat particles surface. The hydropobization of fat globules surfaces is ongoing throughout
the emulsion production, during products preparation for whipping and while whipping; it is
related to the shell loss of the most hydrophilic elements. As they are removed, the shell
surface (fat globule surface) grows hydrophobic. Consequently, the shell surface becomes
mosaic. Hydrophobic and hydrophilic regions are unstable, and they differently interact with
the molecules of the aqueous medium [81, 86]. Accordingly, emulsion whipping process
depends on the original size of the fat globules and the enlargement of fat particles while
whipping [91, 92].
The foaming capacity and stability of foams in foam emulsion systems depends on the
functional process properties of surfactants, namely, on the interface activities between
surfactants and proteins, carbohydrates, and fats, which form rheological properties of
foodstuffs [93, 94]. Depending on the specifications and texture characteristics it is necessary
to regulate spatial distribution of fat particles in the aerated product, which requires different
process solutions and recipes. For instance, in creams fat particles need to be distributed on
the surface of air bubbles (Figure 8, а) thus providing plastic texture properties. In oil,
chocolate and nut sponge cakes and aerated nut semi-finished products they are to be
distributed throughout these products (Figure 8, b), since during the thermal treatment fat
particles on the bubble surface will destroy and reduce the volume of the foam.
Surfactants in foam emulsion systems can destabilize emulsion, caused by mechanical
impact, and lead to fat agglomeration. While whipping, agglomerates form a strong structure
around air bubbles and among them, thus stabilizing the foam. To achieve required indicators
of foaming capacity, foam stability and finished product texture, the functional and process
properties of surfactants are to be considered, as they ensure destabilization and
agglomeration of fat particles in foam emulsion systems. The fat phase agglomeration raises
foaming capacity and foam stability in foam emulsion systems, though the mechanisms
underlying the foaming capacity rise have not been fully clarified [95, 96].
It was found in [97] that the entry of saturated mono-glycerides in the emulsion fat
phase enables to form foam emulsion systems with high foaming capacity, high air phase
dispersion, dense texture, whereas the use of unsaturated mono-glycerides leads to forming
soft foam emulsion systems with few large air bubbles, which sediment faster while being
stored.
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Air bubble
Polysaccharides
Proteins
Solid fat with
surfactants
Air bubble
a
Air bubble
Complex protein
polysaccharides
Solid fat or liquid oil with
surfactants
Air bubble
b
Figure 8. The diagram of foam emulsions with fat particles on air bubbles (а) and throughout
the system (b)
The studies in [98, 99] made it evident that during the reconstitution and whipping of
fat-containing mix powders, surfactants play an important part in destabilizing the emulsion,
while protein is necessary to create the initial emulsion stability. Reconstituted whipped
systems are mainly stabilized providing crystal fat at water/air interface [99, 100]. It was
proven in [98] that a part of the fat in spray-dried mix powers is overcooled. During the
reconstitution of these mix powders at low temperatures by adding water, there are significant
changes that determine whipping properties and foam structure. The emulsion becomes
unstable due to the rapid recrystallization of overcooled fat [101, 102]. The emulsion
destabilization promotes protein desorption from the water-oil surface [103, 104].
Therefore, foam emulsion systems are stabilized due to surfactant properties at various
interfaces. It is necessary to consider the interaction of different surfactants in foam
emulsions. The sequence of dispersion phase production in foam emulsions specifies their
spatial location and different texture properties. Thus, it becomes possible to make products
with different textures but identical system ingredients.
6. Interface protein and low molecular surfactant interactions
Interface protein and low molecular surfactant interactions at the water-fat interface
play an important role for the emulsion stability, destabilization level control, and for the
formation of foam emulsion system texture. Surfactants influence fat crystallization,
preventing their recrystallization, which leads to defects in fat-based foodstuffs [95, 106].
Functional and process properties of food surfactants are determined by their chemical
composition, which is due to the hydrophilic and hydrophobic properties of molecules [107,
108]. The surfactants that have distinct hydrophilic properties, in particular, anionic
surfactants or non-ionic ones with high hydrophilic-lipophilic balance, can disperse in water
[109, 110]. These surfactants are adsorbed on the water-oil interface or interact on other phase
interfaces with other foodstuff components, e.g. with proteins [111, 112].
In the systems containing several surfactants three kinds of adsorption are singled out:
competitive, associative and layered. Schematically, the adsorption kinds are shown in Figure
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WPI
beet pectin
WPI beet pectin conjugate
а – Associative [114]
whey protein
casein
lecithin
b – Competitive [115]
c – Layered [116]
Figure 9. The diagram of adsorption in the systems with several surfactants:
a – Associative; b – Competitive; c – Layered
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Dairy and many other products, containing proteins, interface adsorption layers are a
mix of proteins and surfactants. The actual composition of interface adsorption layers
depends on the chemical structure and relative concentrations of proteins and surfactants.
During the adsorption of the chaotic protein, e.g. β-casein, rather thick interface adsorption
layers with long hydrophilic ends are formed. They exude at phase interfaces, while the
molecules of β-lactoglobulin are densely located near the phase interface, forming thinner
interface adsorption layers [113]. The availability of surfactants impacts adsorbed proteins,
in many cases replacing them from the phase interfaces, which promotes protein foaming in
emulsion systems.
Non-ionic surfactants with high hydrophilic-lipophilic balance most effectively replace
proteins from the interface at 15–25 ºС compared to non-ionic surfactants with low
hydrophilic-lipophilic balance, for example, with mono-glycerides [117, 118]. The impact
on the adsorbed protein depends on the surfactant concentration. Providing the concentration
is low, the surfactant has nearly no effect on the level of protein, adsorbed on the surface,
whereas higher concentration enables almost total replacement of protein from the interface,
which significantly destabilizes the emulsion.
Lipophilic surfactants are less effective in replacing the protein from the phase interface.
The combined use of lipophilic and hydrophilic surfactants leads to the synergy in the protein
replacement [117, 118].
The effectiveness of protein replacement from the phase interface with a specific
surfactant is considerably dependent on the closeness of the surfactant to the phase interface.
For many lipid surfactants this process depends on temperature. Low-polarity surfactants
(mono-glycerides), in small quantities, at high temperature (above 70 °С) increase the content
of protein, adsorbed on the surface. Protein adsorption decrease occurs at higher
concentrations. Diglycerides (Е471) do not affect the adsorption or replacement of proteins
[93]. At 10–40 °С saturated and unsaturated mono-glycerides (Е471) decrease the interfacial
tension more intensively than protein [119]. This is due to the formation of mixed interface
surfactant-protein adsorption layers. Provided the temperature is below 10 °С, there appears
a distinction between saturated and unsaturated mono-glycerides: saturated ones, unlike the
unsaturated, determine significant decrease in the interfacial tension. The difference in the
impact of saturated and unsaturated mono-glycerides on the interfacial tension at low
temperatures is explained by the surfactant crystallization – saturated mono-glycerides
feature higher Krafft point temperatures than the unsaturated ones.
Surfactants with stronger hydrophobic properties (saturated mono- and diglycerides,
lecithin and polysorbates) more intensively reduce the interfacial tension owing to their
hydrophobicity. Furthermore, their impact on the interfacial tension is less temperature
dependent. A more significant decrease of the surface tension is determined by higher
adsorption of the surfactant on the phase interface, thus replacing more protein. However, in
food emulsions with high protein concentrations, its total replacement is not observed [120,
121].
Similarly to protein and surfactant interaction in simple emulsions, complex food
emulsions involve interaction of different proteins. The proteins that are more surface-active
may replace less surface-active proteins, for instance, β-casein is more likely to replace αcasein than vice versa. It was also proven that casein is added into a gelatin-stabilized
emulsion, the added protein can replace gelatin [122, 123].
Under certain circumstances, the fat phase destabilization, important for foam emulsion
systems (creams, ice cream etc.), may be achieved by adding differently polarized
surfactants. The destabilization includes several physical changes, occurring in the emulsion,
in particular, partial desorption of the interface protein and fat phase crystallization. Both
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processes decrease emulsion stability during a mechanical impact. It is known that fat
crystallization is required to achieve partial coalescence [124]. The addition of different
surfactants can affect the degree of the fat crystallization and the shape of the created fat
crystals. With water available, saturated and unsaturated surfactants promote the formation
of different fat crystals. In model systems as well as in food foam emulsion ones the use of
unsaturated mono-glycerides leads to forming large, multi-faceted fat crystals, while
saturated mono-glycerides encourage forming smaller but more evenly structured fat crystals
[125, 126].
During the emulsion whipping, protein is partially desorbed. For the beginning of fat
globules flocculation protein replacement from the fat globule surface is not required [127].
Thus, for the partial destabilization of the emulsion, which is necessary to produce foam
emulsion systems, the impact of surfactants on rheological properties of interface adsorption
layers may be more important than their ability to replace protein. It was found that
unsaturated mono-glycerides facilitate destabilization more than the unsaturated ones [119].
The control of the interaction among proteins, surfactants and fat particles on the surface of
the water-air interface in foam emulsion systems can be considered as the process of air
bubbles stabilization [128, 129].
Therefore, the process of forming and stabilizing foam emulsion systems is influenced
by a number of factors, which eventually determine not only the stability of these systems
but also their rheological properties [130]. However, rheological properties of food foam
emulsion systems have been studied insufficiently, and the rheological behavior of these
dispersion systems are frequently characterized qualitatively. Despite the fact that the
properties of the interacting phases and components of foam emulsion systems during their
formation and stabilization are essential factors for their diversity, their relation to the
foaming capacity and foam stability has not been fully identified, which is determined by a
wide composition of food dispersion systems and the conditions of their production.
The analysis of the above information enables to state controversial as to the
stabilization of foam emulsion systems. Obviously, the stability of foam emulsion systems is
achieved by raising the viscosity of dispersion medium – adding a stabilizer, higher content
of the dispersion phase, ensuring conditions for fat particles agglomeration and forming a
three-dimensional grid, the formation of strong interface adsorption layers on the surface of
dispersion particles. As to the controversial data, it is necessary to specify the conditions and
the need of fat particles flotation by regulating their contact, which, in turn, leads to the need
of identifying the conditions of forming interface adsorption layers using proteins, surfactants
or their mixes. To ensure flotation, it is necessary to identify the rational dispersion capacity
of fat particles. It becomes evident that the key role belongs to the interface adsorption layer
formation and the identification of regularities in their control, as well as the mechanisms,
underlying their formation and destruction. It is clearly specified what conditions are required
for the fat particles to agglomerate, float and adhere to air bubbles and the conditions, under
which fat particles can provide process stability to the systems with a polyphaser dispersed
structure.
The study allowed us to specify the concentrations of proteins and surfactants as well
as the parameters of homogenization and whipping under which there emerge processes of
emulsion destabilization, fat particle agglomeration and flotation to produce a foam emulsion
system [131]. The role of proteins and surfactants was identified and NaCMC in resistance
to fat particle flotation and make the structure of the aerated nut semi-finished product [132].
The process flow parameters and the content of proteins and surfactants in dry fat mixes to
produce a foam emulsion system based on them [133].
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Thus, interface adsorption layers play an essential role in stabilizing foams, emulsions
and dispersion polyphaser systems.
7. The role of interface adsorption layers in process stability of food heterogeneous
systems
The structural mechanical barrier is expressed in inhibiting coalescence and is among
universal factors of dispersion system stabilization owing to its high viscosity, elasticity and
mechanical strength of the interface adsorption layers. The best known interface adsorption
layers are based on proteins; they can form quasi-crystal or gel-like structures. The data on
the protein adsorption show [34, 134] that the effective stabilization is ensured only provided
protein on the phase interface. This ensures the formation of a monomolecular layer. These
interface adsorption layers determine dispersion system stability. Structured interface
adsorption layers of proteins form 10–100 nm thick layers, which are sometimes are
considered as a separate phase, where the protein content in this interface adsorption layer
may be 20…40% [34, 35]. The role of the structural mechanical barrier in the stability of
direct emulsions, stabilized by high molecular substances, was proven [135, 136].
To enforce the structural mechanical stabilization factor it is important to:
– provide decrease of the surplus free energy at the phase interface [137, 138];
– ensure the Hamaker constant, especially on the outer part of the stabilizing layer,
which lowers energy and the force of dispersion particles interaction [139, 140];
– provide high shear stress, elasticity module, the viscosity of an interface adsorption
layer (elastoplastic body) [141, 142];
– confirm the need to overcome a high activation barrier to destroy the interface
adsorption layer (according to Zhurkov’s theory) [136].
The structural mechanical barrier includes thermodynamic (elasticity modules) and
kinetic (viscosity) factors, which may guarantee stability of dispersion systems in case of
drop interaction [143, 144]. The stabilization of dispersion systems with high molecular
substances is usually considered within the steric stabilization model [145, 146]. The steric
stabilization can be regarded as a special case of the structural mechanical barrier effect
[147].
The study of the structural mechanical barrier role in the stability of foams and
emulsions includes the assessment of rheological parameters and the structure of stabilizing
layers as well as the study of the peculiarities of losing aggregate stability of bubbles and
drops when interacting with each other [34].
Today it is possible to consider a new science – rheology of interface adsorption layers,
which emerged at the boundary of biological disciplines (molecular biology, biophysics and
cytology), physical chemistry, physical-chemical mechanics of dispersion systems and
rheology [148].
To describe the kinetics of pattern structuring in the interface adsorption layers the study
in [148] offers a quantitative method, based on the parameter of structure strength growth in
the interface layers of polyelectrolytes and their mixes with surfactants. The time of reaching
the permanent shear stress Рs (maximum number of contacts) in the layer and the balanced
surface tension is measured in hours.
The process of forming adsorption layers by proteins is divided into three stages. At the
first stage there is diffusion to the phase interface, at the second – a contact with a phase,
resulting in destroying the force balance, stabilizing the globule, and, accordingly, there occur
conformation changes, i.e. orientation processes, at the third stage, there is a process of
saturating the surface layer and the reduction of surface energy [149].
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Adsorbed molecules hamper further adsorption. Depending on the redistribution of
components among phases and on the king of protein there are two types of interface
adsorption layers: gel-like and quasi-crystal [147, 150]. During the multilayer adsorption the
protein-oil binding is replaced by the protein-protein binding, and this adsorption becomes
reverse [151, 152]. It is known that proteins with flexible chains (beta-casein) are more
surface active that globular proteins (lysozyme, beta-lactoglobulin, alpha-casein) or hard rodlike proteins, which becomes, inter alia, evident when studying the time of forming
adsorption layers.
The rheological properties of the interface adsorption layers of high molecular
surfactants on the flexible phase boundaries have been studied thoroughly [153, 154]. It was
shown that the adsorption layers are characterized by the shear stress, modules of plasticity
and elasticity.
As the concentration of the high molecular surfactant in the aqueous solution increases,
it is possible to observe the transition from the liquid state of the layer with a low quantity of
contacts, which shows Newtonian behavior, to the solid-like, strong low-defect elastoplastic
structures.
Significant scope of accumulated data on interface adsorption layers rheological
properties enabled to summarize the information and develop models, underlying the
interface adsorption layer formation. For example, the models of gel-like and quasi-crystal
interface adsorption layers correspond to the structures with coagulation and crystalcondensate contacts [147, 151]. The models of interface adsorption layers formation were
developed and their quantification was carried out in the conditions of the combined use of
proteins and polysaccharides [155, 156], the combined use of proteins and low-molecular
surfactants [159], and the combined use of several proteins [160, 161]. However, there is
scarce data on the properties of the interface adsorption layers, formed by proteins and solids
[162]. However, the developed models refer to foams or emulsions. As to the models of
dispersion system stabilization with two or more phases, these studies are limited, and discuss
only foam emulsion systems [79, 90] and creams [73, 163]. These models are based on the
principle of surface and interfacial tension and their values, which enables to substantiate the
principles of stabilization. Nevertheless, following the values of the surface and interfacial
tension it is impossible to explain the processes, occurring when whipping emulsions, and,
probably, it is necessary to consider rheological properties of interface adsorption layers [79].
The stability of foams and emulsions greatly depends on the properties of interface adsorption
layers [137, 164]. The knowledge limited by the value of surface or interfacial tension is
insufficient to understand and forecast their behavior; rheological properties are more useful
and informative to assess the behavior of these systems. Rheological properties of interface
adsorption layers correlate to the rheological properties of foams [165] and the stability of
foams and emulsions [166] as well as theoretical models [167]. Using the rheological
properties of interface adsorption layers, theoretical models were developed on the foodstuff
patterns with steric-stabilized polyphase dispersion structures [132], foam stabilization with
fat particles [131] and their combination [133].
The analysis of literature in the field has confirmed the need to use rheological methods
to do research into interface adsorption layers.
8. Methods of studying rheological properties of interface adsorption layers
The overview papers [156, 158] provide the list and features of rheological methods of
studying interface adsorption layers. In addition to the torsion viscosimeter with various disk
shapes, other devices are applied, but it is remarked that the torsion viscosimeter is the most
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universal tool in researching interface adsorption layers with proteins. It was found that
depending on the selected theoretical model of interface adsorption layers, different methods
are used to study rheological properties of interface adsorption layers [157].
Surface rheological properties measurement results, obtained using the torsion surface
viscosimeter [34], brought to the conclusion that there is perfect analogy of surface and
volume rheology provided that measurements of surface layer rheological properties are
carried out on flat faces and liquid phase interfaces. Thus, the mathematical tools, developed
to describe rheological properties of three-dimensional systems, may be applied to studying
rheological properties of interface adsorption layers.
To describe the interface adsorption layer behavior, it is possible to use methods with
different mechanical impact on the interface adsorption layer (under permanent deformation,
continuous stress, waved stress) and thus it is possible to specify such indicators as the yield
shear stress [34, 169], viscosity [170], modules of plasticity and elasticity [171, 172]. To
assess emulsion stability the Boussinesq number as the correlation of the interface adsorption
layer viscosity to the medium viscosity [168]. In case the Boussinesq number is considerably
higher than one, the system is stable, and vice versa – if it is below one – stability is low. A
dilatational elasticity module is used as the ability of interface adsorption layers to resist
external forces and restore interface adsorption layers to the original state after the external
force termination [173, 174]. The viscosity and dilatational elasticity module are used in the
systems with low protein content (up to 0.5%) or in the systems, containing low molecular
substances. For the systems with high protein content (over 0.5%) in the systems, containing
proteins and polysaccharides the yield shear stress of interface adsorption layers is found, as
well as the elasticity module [33, 34].
Considering the known data and interface adsorption layer models, it is necessary to
analyze the main approaches to regulating rheological properties of protein interface
adsorption layers, using low molecular surfactants and polysaccharides. As mentioned above,
surfactants can either raise or lower the stability of emulsions and foams.
9. Regulation of rheological properties of interface adsorption layers
The research into the rheological properties of gelatin interface adsorption layers
showed that the layers feature visco-elastic properties [178]. A model of an interface
multilayer pattern was suggested. According to it, the gelatin adsorption layer at the waterair boundary consists of one irreversibly adsorbed monomolecular layer and several
reversible adsorbed secondary layers.
The yield shear stress of interface adsorption layers rises along with the protein content
rise in the system, reaching the maximum, typical of gelatin для желатини, ovalbumin and
casein [34]. It is due to the fact that the maximum shear stress corresponds to the
monomolecular layer and strongest binding (cohesion force) of protein-protein. The
maximum yield shear stress of protein interface adsorption layers meets all requirements to
their coagulation, i.e. under the environment рН value that corresponds to the protein
isoelectric point, ovalbumin thermal coagulation temperature (55 °С) the strength of the
interface adsorption layer at the water-air interface rises 10 times. The regulation of the
solution ionic force and the addition of substances, suppressing the formation of hydrogen
bonds, enabled to define that bond formation in interface adsorption layers is due to the
hydrogen, electrostatic and hydrophobic interactions. It was found out that regardless of the
protein in the yield shear stress of interface adsorption layers at the phase interface with a
non-polar solvent is 6–10 times higher compared to the interface adsorption layers at the
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phase interface with air. Thus, this opens a way to regulate the yield shear stress of protein
interface adsorption layers either with process factors or with addition of substances [34].
The formation of protein-polysaccharide complexes is widely used in dispersion system
stabilization [179, 180]. Therewith, electrostatic or chelate coordination compound is used
(formation of salt bridges between proteins and polysaccharides [181]. These complexes are
characterized by quite a strong binding. Polyelectrolyte complexes are created as a result of
cooperative reactions of uniting oppositely charged functional groups. The cooperative
nature of reactions implies the emergence of each inter-chain salt bond, facilitating the
formation of other bonds between chains of the polyelectrolyte complex, which makes it
highly stable. There are two types of polyelectrolyte complexes – stoichiometrical and nonstoichiometrical [182, 183]. Stoichiometrical complexes are normally not water-soluble and
feature high hardness and hydrophobic level. Non-stoichiometrical polyelectrolyte
complexes are water-soluble, which is determined by the presence of chain segments, which
were not involved in complex formation [55, 56]. Being formed, these complexes have high
viscosity, in some cases gels are formed, which is influenced by the рН value, solution ionic
force and other factors. The complexes can be formed throughout the volume and further
adsorbed, or be built directly at the phase interface [58, 184].
The rheological parameters of interface layers, e.g. their viscosity, elasticity module,
and shear stress can be controlled, using surfactant mixes. The strength of mixed interface
adsorption layers in the considered systems is always higher than in the conditions, when
proteins and surfactants are taken separately, which is determined by the formation of
additional hydrogen and hydrophobic bonds between polar groups of both surfactants [142,
144].
The best and systematically known surface properties of protein-surfactants binary
systems, as well as their role in forming the structure and ensuring the stability of colloidal
systems are those of emulsions or foam. At the same time a special focus is on searching a
possible synergetic interaction of proteins and surfactants. The combination of hydrophilic
and hydrophobic segments enables the protein to form complexes with ionic and non-ionic
surfactants, which is due to different physical-chemical mechanisms. In particular, owing to
the electrostatic attraction between oppositely charged functional groups of ionic surfactants
and proteins, or owing to the interaction between hydrophobic spots on the protein surface
and non-ionic surfactants [165, 174]. Depending on the concentration, surfactants can interact
with protein as individual molecules or as micelle-like aggregates. However, joining the
protein, molecules of the surfactants can either stabilize or destabilize the protein structure,
while acceleration or inhibiting self-association of protein molecules depending on the type
of surfactants (hydrophilic-lipophilic balance, availability of charge), its concentration and
environmental conditions (temperature, pH, ionic force) [185, 186].
It was established that the addition of phospholipids results in the protein interface
layers losing their hardness [187], lower shear stress value [188, 189]. On the other hand, it
is possible to strengthen interface layers by forming at the phase interface of inter-polymer
associates, using gelatin and water-soluble surfactants (with a high hydrophilic-lipophilic
balance) [189] as well as oil-soluble surfactants (with a low hydrophilic-lipophilic balance)
[190].
It was stated that proteins, being adsorbed on the fat phase surface, form separate sites
covered with protein [191, 192]. At low concentration of surfactants, mixed interface
adsorption layers are formed. They comprise adsorbed surfactants and proteins. Surfactants
can be adsorbed, being built in between the hydrophobic parts of protein molecules. That
explains low correlation of surfactants: a protein does not entail protein desorption.
Moreover, low concentrations of mono-glycerides can intensify protein adsorption at phase
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interfaces. Adsorbed surfactants create a rather high surface pressure, interface adsorption
layers aggregate, which leads to protein layer thickening. Then the regions of interface
adsorption layers are finally removed into the aqueous phase as protein aggregates [193].
Rheological properties of emulsions, containing β-lactoglobulin and anionic surfactants
sodium dodecylbenzenesulfonate (SDS) (at 30 °С), are defined by the molar surfactantprotein ratio [194]. A ratio, which enables emulsion elasticity modules to reach maximum
values, was found. At the low and high SDS concentration the boundary of emulsion fluidity
decreases compared to protein emulsions without surfactants. The results are explained by
the specifics of the associated surfactant structures and the interactions between protein and
SDS at the phase interface. The addition of SDS to sodium caseinate emulsions [195] raises
the stability and viscosity of emulsions, which is explained by binding SDS with protein
throughout the aqueous phase and by forming layers with surfactant complexes. The milk
protein and iota-carrageenan correlation, under which the shear stress of the interface
adsorption layers at the water-air and water-oil phases interface increases, was found [196].
Further, the sodium caseinate and k-carrageenan correlation was identified, too [133]. In both
cases the increase of the maximum shear stress of interface adsorption layers is due to the
formation of milk protein-carrageenans complexes.
Combined availability of a certain quantitative ration of proteins and surfactants can
lead to the formation of mixed adsorption layers or to the competitive replacement of a less
surface active component from the adsorption layer [67, 197].
There may emerge thermodynamic incompatibility between proteins and surfactants
when exceeding the critical micelle concentration at the phase interface, thus allowing for
replacement of one component with another [198, 199]. In addition, two more mechanisms
were suggested to replace proteins from the surfactants phase interface [200]. The first is the
mechanism of solubilization meaning the increase of the protein water solubility as a result
of forming a more hydrophilic protein-surfactant complex and adding water-soluble
surfactants; the other is the replacement mechanism, under which, the surfactant is stronger
bound to the surface of the phase interface compared to protein (or a protein-surfactant
complex) and replaces the latter.
The stability of foams, based on protein-surfactant mixes, depends on the kind of phase
interface of proteins and surfactants under competitive or associative adsorption [201, 202].
In the first case, the protein interface adsorption layer is destroyed (i.e. foam stability falls),
while in the other case rheological properties of interface adsorption layers strengthen (foam
stability rises). For instance, the addition of Tween 20 led to the destruction of foams based
on β-lactoglobulin and α-lactoalbumin [203].
The addition of non-ionic surfactants (e.g. Tween-80) to protein aqueous solutions leads
to the weak interaction among components [66, 204]. The formation of complexes between
bovine serum albumin (BSA) and Tween-80, is due to hydrogen bonds [205]. It was marked
that the surface activity of the created complexes, is nearly 5 times higher than protein surface
activity and twice as high as the Tween-80 surface activity.
The interaction between proteins was considered: β-casein, β-lactoglobulin, BSA,
human serum albumin (HSA) and ionic and non-ionic surfactants throughout the aqueous
phase [186]. The models of protein-ionic surfactant complexes were offered. They are formed
under low concentrations of surfactants, and under electrostatic interaction between the
protein and surfactants, resulting in a hydrophobic complex (associate). The complex has
much lower solubility than protein, but higher surface activity. As the surfactant
concentration rises throughout the aqueous phase, electrostatic interactions are
complemented by hydrophobic ones. Thus, the complex becomes hydrophilic, and,
accordingly, more water-soluble, and loses its surface activity.
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Summing up, it is to be noted that the analysis of the literature on rheological properties
shows their important role in ensuring the stability of dispersion systems. It was found that
the additional entry of polysaccharides or surfactants with different hydrophilic-lipophilic
balance values to protein solutions enables to regulate adsorption of proteins and surfactants
in the system, change the surface activity by forming protein-polysaccharide or proteinsurfactants complexes. It was established that in the literary sources most results are related
to the use of non-food surfactants (sodium dodecylbenzenesulfonate) or those, restricted in
their application – Tween-20, Tween-80, and also proteins as separate fractions. This
approach allows for précising molecular interactions. However, to transfer them into
foodstuffs, even to model systems requires some systematic experimental research.
Conclusion
1. The differences in the production of foams and emulsions are in the speed of
dispersion. Emulsifying is faster than that of foaming, and the size of fat particles is
smaller than that of air bubbles. Therefore, the production of foam emulsions food
products, where emulsifying and foaming are simultaneous is impossible
thermodynamically. The production must be performed sequentially.
2. The work systematized the factors, determining foam and emulsion destruction. The
destruction factors are due to the properties and viscosity of the dispersion medium.
Providing food products include both airy and fat phases, destruction will run faster.
3. The study systematized the factors, ensuring the stability of foams and emulsions.
Multi-component food systems may feature several factors. The most considerable
includes the varieties of the structural mechanical stabilization factor. It is
implemented by the formation of a protection barrier on the dispersion particles via
using only proteins, or solids with partial soaking (according to the Pickering
stabilization), or combined use of proteins with low-molecular surfactants or the
combined use of proteins and polysaccharides.
4. The production and stabilization of foam emulsions is to be based on the required
spatial location of phases in the system, which is decisive for the foods textural
properties. It is necessary to consider that this system contains phase boundaries of
water-air and water-oil with varied difference of polarity. Thus, when selecting the
kind and concentration of surfactants it is required to comply with the rheological
properties of interface adsorption layers.
5. Interface properties of proteins and low-molecular surfactants specify rheological
properties of interface adsorption layers, due to their kinds of adsorption (competitive,
associative or layered), and their temperature-dependent surface activity. The
rheological properties of interface adsorption layers play the leading role in the
stability of foam emulsions, and foam emulsion suspensions.
6. The paper analyzed the methods of studying the rheological properties of interface
adsorption layers. The values of viscosity, yield stress shear, and the elasticity
modules correlate with the stability of foams and emulsions, and can be effectively
used to forecast the stability of polyphase dispersion systems.
7. The rheological properties of interface adsorption layers are regulated by the addition
of low-molecular surfactants with different hydrophilic-lipophilic балансу to the
protein-containing systems, thus regulating adsorption, and the addition of
polysaccharides, forming complexes throughout or at the boundaries of phases.
722
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