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7 The Stability/instability of Bubbles and Foams

1. The stability of foams can be classified into four categories based on their lifetime: unstable foams that last seconds, metastable foams that last hours to days, high stability foams that last weeks to months, and ultra-stable foams that can last 6 months or more. 2. Foam stability is influenced by many factors including drainage, disproportionation, external vibrations, evaporation, and temperature gradients. Different mechanisms like capillary pressure, shear viscosity, disjoining pressure, and surface elasticity can contribute to foam stabilization at different stages. 3. The document discusses various destabilization and stabilization mechanisms for foams and how they relate to foam properties like film thickness, bubble size

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101 views49 pages

7 The Stability/instability of Bubbles and Foams

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7 The stability/instability of bubbles

and foams

The paradox is easily explained. Proﬁt-seeking people will take more ﬁnancial risk when they
believe the coast is clear. By taking bigger chances, however, they unwittingly make the world
unsafe all over again.
Hyman Minsky, US Economist, Paying the Price for the Fed’s Success, The
New York Times, www.nytimes.com/200801/27/opinion/27grant.html

7.1 Overview

All foams are thermodynamically unstable due to their high interfacial free energy, the
decrease of which causes foam decay. It is well known that there are several different
types of mechanisms involved in the stabilization and decay of foams, which has
caused a considerable amount of confusion. In the literature there are many conﬂicting
explanations frequently caused by experimental anomalies and the incomplete inter-
pretation of foaming experiments. Another aspect to consider is that the lifetime of
a foam can pass through several different stages, and each stage may involve
a different type of mechanism. To explain the overall stability in terms of one
mechanism is almost impossible, and the interplay of different mechanisms needs to
be taken into consideration. During generation, bubbles expand and contract and are
subjected to severe vibrations and dynamic disturbances causing distortion of
the adsorption layer. During this process, the liquid ﬁlms separating the bubbles are
relatively thick and subject to stretching, and viscous elastic forces play a crucial role.
Possibly the most important mechanisms for the survival of a wet foam during this
stage involves the surface elasticity theories of Gibbs and Marangoni. Gravitational
forces also cause fairly rapid drainage to occur during this preliminary stage, but this
can be retarded by a high bulk viscosity. On entering a secondary stage, capillary
forces come into play causing suction and thinning of the lamellae, and this occurs
at a lower rate. In addition, disproportionation may occur causing the diffusion of
gas between bubbles. As all these processes occur under dynamic conditions, the
equilibrium adsorption coverage is rarely reached.
The process of gas diffusion owes its origins to the difference in pressure, surface
tension and curvature of the bubbles, but the gas diffusion to the atmosphere also needs
to be considered. In addition to diffusive disproportionation theories to explain the
changes in size distribution in bubbles, alternate processes have been considered

Downloaded from https://www.cambridge.org/core. CERN Library, on 11 Jan 2021 at 19:52:30, subject to the Cambridge Core terms of use, available at
https://www.cambridge.org/core/terms. https://doi.org/10.1017/CBO9781316106938.008
7.1 Overview 221

which involve the effect of interfacial rheology on the shrinkage of bubbles. As the
smaller bubbles are further reduced in size, the adsorption layer becomes compressed
during shrinkage, causing an increase in the surface excess (Γ) and a decrease in surface
tension. This process would act to counteract shrinking. Under these circumstances, the
driving force for disproportionation will also be influenced by the surface dilational
modulus of the film. However, bubble shrinkage is usually a fairly slow process, so that
the dilational modulus may have sufficient time to relax. At the moment, the role of the
surface rheological parameters on diffusive disproportionation remains controversial.
At the same time, evaporation, external vibration and shock may occur at the surface of
the foam. However, provided the thick films survive drainage, the foam can proceed
toward the final state of stability described by the dry foam state. In this final stage, an
equilibrium is reached in the formation of the thin lamella films, stabilized by the
“disjoining pressure” theories, as discussed in Chapter 3. For well-drained quasi-static
foam films (< 100 nm), intermolecular forces become dominant and stability must be
discussed in terms of common black films (CBFs) and Newton black films (NBFs).
In this chapter the main stabilization mechanisms are reviewed, and these are summar-
ized in Table 7.1. More recently, other stabilizing theories involving partial hydrophobic
particles have been under intense study and are discussed in Chapter 8.

Table 7.1 Foam Destabilization/Stabilization Mechanisms

Destabilization mechanisms Stabilization mechanisms Stabilization aids

1. Drainage Capillary pressure High viscosity bulk fluids.

Fairly Polymeric viscosity enhances (water soluble
thick high m.w polymers; polyacrylamides, EHEC).
Shear viscosity Coherent mixed surfactant films, proteins.
films
Monodispersed latex or nanoparticles
Stratification Thin films High concentrations of surfactants > CMC
Liquid crystals, gels, particle/polymer and
Flow of liquid through Junctions of particle/surfactant mixtures.
Blockage (clogging) interconnecting
foam under gravity Steric and electrostatic repulsion (polymers
channels and charged surfactants).
+ + +
Disjoining pressure Thin lamella Specific ion effects (Na , K , Cs and pH control).

2. External vibrations Gibbs Marangoni High surfactant concentrations > CMC

Shock waves (healing of film) Condensed shells (diglycerols / PE glycols)
Hydrophobic, nanopattering agents
Visco-elasticity (glycose syrups)
surface dilational

3. Disproportionation Low solubility gases (low gas diffusion) Bubble soluble gas through perfluorohexane
(Oswald’s ripening) Air, N2 > O2 > CO2 type vapours or use surfactant to control type
Gas diffusion through of film.
liquid phase (Common black or Newton black films)
High Low
press pressure

4. Evaporation, temperature Temperature and humidity control Well packed coherent dense
gradients, humidity packed molecular films

7.2 Classiﬁcation of the stability of foams

Clearly, there is a sharp distinction between the rates of decay of different types of
foams and, for convenience, the instability can be classiﬁed into the following different
types: (I) unstable or transient foams with lifetimes of seconds or even less; (II)
metastable foams with lifetimes of hours or even days; (III) high stability foams
which exhibit stability of the order of weeks or a few months; (IV) ultra-stable foams
which are stable for at least 6 months and in some cases for years. There is an industrial
demand for high-stability foams, particularly in the manufacture of polymers, materials
and metal foams.

7.2.1 Unstable (transient) foams

Champagne is a classic example of an unstable foam (Fig. 7.1(a)). Some sea foams also
last for only a few seconds, whereas foams produced in turbulent rivers and streams can
persist a little longer. Transient foams are also generated in solutions of inorganic
electrolytes such as NaCl. Mild surfactants such as short-chain alcohols (ethyl, propyl,
isobutyl, etc.) aniline, phenol, pine oil and short-chain undissociated fatty acids (formic,
propionic) belong to this group and are considered to be weak foaming agents. These
compounds are usually sparingly soluble in water and generate a low degree of surface
elasticity and rupture fairly easily. The lifetime of these unstable foams is sensitive to the
concentration of the surfactant, and a maximum stability tends to occur at some critical
concentration. The foamability of transient foams can be explained by weak surface
tension gradients and the Gibbs–Marangoni effect, which will be discussed in a later
section of this chapter.

(a) (b)

Fig. 7.1 Transient foams (champagne) are dynamic, with lifetimes in seconds, whereas static foams
such as beer have lifetimes of hours. Drainage and disproportionation occur in both systems,
but the beer foams are stabilized by proteins which induce steric disjoining pressure interactions
between the lamellae.

7.2.2 Metastable foams

These foams are capable of withstanding ordinary disturbances, such as thermal or
Brownian fluctuations, but they usually collapse in an irregular manner due to abnor-
mal disturbances such as evaporation and temperature gradients. Many surfactant
systems produce metastable foams at fairly high concentrations (near or above the
CMC). Generally, the lifetimes increase exponentially with concentration of surfac-
tant, and a plot of foam lifetime versus concentration often produces an S-shaped
profile. This plot becomes steep beyond a critical concentration, and usually
a maximum stability is reached which corresponds to the Plateau region on the
curve. In these systems, the thin film drainage times are relatively short (compared
to the total foam lifetimes), and the stability is controlled by the balance of interfacial
forces, which equilibrate after film drainage has been completed.

7.2.3 High-stability foams

High-stability foams can be prepared from detergents, mixtures of oppositely
charged surfactants (anionic and cationic surfactants), surfactant/particle mixtures,
etc. In other cases, the systems are stabilized by high molecular weight polymers or
water-soluble proteins. In these systems, steric interfacial forces play an important
role in preventing thin ﬁlm rupture. Beer foams are essentially polypeptide foams,
and a “Guinness” foam (Fig. 7.1(b)) is a typical example of a thermodynamically
(sterically) stabilized system where disproportionation and coalescence occur
slowly.

7.2.4 Ultrastable foams

These foams are extremely stable and may be produced from xanthate gums, proteins
(hydrophobins), partially hydrophobic particles, mixtures of silica nanoparticles and
short-chain surfactants. Usually, these types of surfactant systems produce bulk
aggregates, soft or crystalline entities which compact in the Plateau borders and arrest
drainage. The foams are fully stable against disproportionation and coalescence. Also,
gel formation of solids play an important role in these systems, particularly in
surfactant/nanoparticle mixtures that arrest drainage and gas diffusion.

7.3 Reversing the stability of foams

In certain industrial processes, the stability of the foam needs to be tuned for speciﬁc
performance requirements. For example, there is an initial requirement for
a surfactant with strong foaming action, but, at a later stage in the process, the
foam needs to be reduced or suppressed without the use of defoaming agents. This is
the case in the cleaning of radioactive vessels, where a good foaming agent can be
applied to remove particles from the walls of the vessel, but then the foam needs to

(a) (b)
60 100 Maximum hydrophobicity
Maximum hydrophobicity
Foamability (%)

50 75

Stability (%)
40 50

30 Hydrophilic charged surface 25 Hydrophilic charged surface

20 0
2 4 6 8 10 2 4 6 8 10
pH pH
Fig. 7.2 Foamability (determined by the maximum foam volume after 10 s of gas ﬂow at a constant ﬂow
rate of 5 ml/s) versus pH and (b) foam stability (after 300 s standing) versus pH. From ref (2).

be destroyed releasing a small volume of contaminated liquid. Reversibility or

regeneration can be achieved by applying a simple trigger mechanism, which can
involve a change in pH, temperature, UV radiation or changes in the aggregated state
of the foaming agent.

7.3.1 pH-responsive foams

A pH-responsive foam often involves a change in stability with change in pH region.
In 2007, Binks and coworkers (1) developed a pH-responsive foam system using
colloidal polystyrene latex particles stabilized by polyacrylic acid. These particles had
an isoelectric point (pHiep) of 3.5. The particles were found to strongly adsorb on the
bubbles, enabling stable foams to be easily generated at low pH (< 3.5) where the
surfaces are partially hydrophobic with only a slight positive charge. At high pH, where
the particles were negatively charged (hydrophilic surfaces), no foaming was observed,
but by decreasing the pH and suppressing the charge, foams could be regenerated.
Alternatively, protein surfactants can be used, and in 2012, Engelhardt and coworkers
(2) carried out experiments with a bovine serum albumin (BSA) protein. The adsorption
was related to the pHiep of the protein (which had a value of about pH 6) and the foaming
performance is shown in Fig 7.2.
In this study, vibrational sum frequency generation (SFG) was used to provide
speciﬁc information on the composition and orientation of the protein molecules
adsorbed at the bubble interface, and ellipsometry enabled complementary informa-
tion on the thickness of adsorbed layer to be obtained. Maximum foamability
and foam stability were found to occur in the region of the pHiep and it was suggested
that the strongly adsorbed ﬁlm was partially hydrophobic and consisted of a thick
amorphous aggregated network that stabilized the bubbles against disproportiona-
tion, and retarded the drainage. Above or below the pHiep, the particles were less

HO CH3
OH

12-hydroxy stearic acid

NH2 NH2
HO HO

ethanolamine hexanolamine
Fig. 7.3 Fatty acid system 12-hydroxyl stearic acid (12-HAS) surfactant which was dispersed in water
with an organic counterion (such as ethanolamine or hexanolamine). From ref (4).

hydrophobic, which reduced both foamability and foam stability. In 2011,

Middelberg and coworkers (3) found that good foaming occurred in the alkaline
pH range for a green biosurfactant protein designated DAMPA4, and a suppression in
foaming was achieved through a small pH shift (one unit, from 8.5 to 7.5). The
response was found to be reversible.

7.3.2 Temperature-responsive foams

A temperature-responsive aqueous foaming system was developed by Fameau
and coworkers (4) in 2011 based on a fatty acid: 12 hydroxyl stearic acid,
designated 12-HAS. This was dissolved in water with an organic counterion (etha-
nolamine or hexanolamine). The chemical structure of these molecules is shown
in Fig. 7.3.
At low temperatures, after handshaking, this surfactant was found to give foams
which were stable over weeks and even months. This behavior was explained by the
formation of a self-assembly consisting of multi-tubes (10 µm length and 600 nm
diameter) which strongly adsorbed at the bubble interface, producing strongly visco-
elastic ﬁlms. Confocal microscopy and SANS analysis indicated that the structural
network of tubes restricts the drainage within the lamellae. However, it was also
shown that these tubes melt into micelles at higher temperatures, which caused the
complete destruction of foam in the presence of both ethanolamine and hexanolamine
fatty acid salts. Lowering the temperature caused the tubes to be reformed, and this
reversed the foam stability. In a further step, the thermo-responsive 12-HAS tube
structures were combined with carbon black particles to create photo-responsive
foams (5). On exposure to UV illumination, the carbon black particles in the foam
absorb light radiation and act as a photothermal heat converter. This causes the

(a)
1000
CO2 N2 CO2 N2

800
Foam volume (mm)

600

400

200

0
0 100 200 300 400 500 600 700
Time (s)

(b) Me Me
CO2 + H2O
R R HCO3–
N NMe2 N2 N + NMe2
H

R = C12H25, C14H29, C16H33

Fig. 7.4 (a) Foam control by diffusing different types of gases through foaming solution. (a) The
transformation from stable to unstable foam by changing the type of gas. Two cycles of treatment
with CO2 followed by N2 are shown. (b) The change in surfactant structure. Bubbling with
CO2 results in the conversion of imidazoline (HEAIs) type surfactant (non-foaming) to
the 2-alkyl-1-hydroxylethylimidazolinium carbonate cationic (HEAIBs) type surfactant.
From ref (6).

temperature inside the foam to increase, resulting in the transition of tubes into micelles
and leading to rapid destabilization. The approach was extended to magnetic particles,
producing the ﬁrst foam to exhibit a thermo-photo-magneto-tunable response.

7.3.3 Gas-responsive foams

It was also found possible to trigger foams generated from a 2-alkyl-1-hydroxy-
lethylimidazolinium carbonate cationic surfactant (HEAIB) by alternatively bub-
bling CO2 and N2 through the solution (6). The experiments were carried out in
sealed vessels. Interestingly, the foaming behavior was shown to be cyclic (Fig. 7.4
(a)). Initially, on bubbling CO2 through the solution, the foam volume is shown to
sharply increase, reaching a maximum after about 2 minutes and then, after
a further 2 minutes, N2 was bubbled through the solution to remove the CO2,
which suppressed the foaming. It was suggested that the mechanism involved
the conversion of the imidazoline HEAI, which is a low foaming surfactant
to imidazolium bicarbonates cationic HEAIBs (which is a good foamer).
The mechanism is illustrated in Fig. 7.4(b).

The results indicate a lower volume fraction in the second cycles, possibly because
this conversion process was not 100% efﬁcient. This type of triggering mechanism was
thought to be useful for generating and breaking foams in gas wells, but these foam
systems had a disadvantage in that they became unstable at higher temperatures.

7.4 Gibbs–Marangoni effect

Surface tension gradients are essential for a freshly produced foam to survive.
However, the main deficiency in the early studies on Gibbs elasticity (as discussed
in Chapter 1) was that it applies to thin films, and the rate of diffusion of surfactant
from bulk solution to the bubble was neglected. In fact, the Gibbs theory only applies
to a hypothetical equilibrium state (i.e. it is assumed that there is insufficient
surfactant in the film to diffuse to the surface and lower the surface tension). For
thick lamellae, under dynamic conditions, the Marangoni effect becomes important
and operates on both expanding and contracting films. The Marangoni effect tends to
oppose any rapid expansion or contraction of the surface and may provide
a temporary restoring or stabilizing force to thin films, which are susceptible to
rupture. In fact, the Marangoni effect is superimposed on the Gibbs elasticity, so
that the effective restoring force is a function of the rate of extension, as well as the
thickness. The Gibbs–Marangoni effect can also explain the maximum foaming
behavior which occurs at a critical surfactant concentration in transient foams, as
explained schematically in Fig. 7.5.
If the solution is too dilute, then the greatest possible differential surface tension will
only be relatively small and little foaming will occur (Fig. 7.5(a)). In the case of the
solution being too concentrated, the differential tension relaxes too rapidly because of
the supply of surfactant which diffuses to the surface. This causes the restoring force to
have time to counteract the disturbing forces and produce a thinner film (Fig. 7.5(c)),
resulting in poor foaming. It is in the intermediate surfactant concentration range that
maximum foaming occurs (Fig. 7.5(b)). As yet, there is no clear-cut technique to
measure the magnitude of the Marangoni effect, and the theoretical treatment is incom-
plete. The damping of waves (without changing the wavelength of the ripples) in dilute
pure surfactant is believed to be caused by the Marangoni effect, since the surfactant
may not impart any significant surface viscosities.

7.5 Interfacial rheology

Although the reduction in surface tension is the main driving force for the genera-
tion of foam, it is the rheological properties that impact the stability. During foam
generation, it is the expansion and contraction of the air/solution interface under
strongly dynamic conditions that prevail, while during drainage, it is the compres-
sion, coalescence and disproportionation which are the most important factors.
During these processes, the initial equilibrium state becomes distorted, causing the

(a) (b) (c)

Original state of thin film

Local mechanism Higher local

caused a thin section surface tension developed

Low surfactant Action of elasticity pulls back Surfactant molecules

TIME

concentration gradient surfactant molecules into diffuse from bulk

(no elasticity) thinned section solution to surface
dg dg

Returning surfactant Surfactant concentration

molecules drag back gradient in surface
underlaying layers removed
of liquid with them

Film thinned and Surface film repaired Film thinned and

easily ruptured by surface transport easily ruptured
mechanism
Fig. 7.5 Gibbs–Marangoni mechanism of dynamic foam stability. Reaction of a liquid film to a surface
disturbance. (a) Low surfactant concentration gives only low differential tension in film and low
foaming. (b) Intermediate surfactant concentration. Strong Gibbs–Marangoni effect restores film
to original thickness and stabilizes foam. (c) High surfactant concentration (> CMC) differential
tension relaxes too rapidly due to diffusion of surfactant. Thinner film formed which can easily
rupture.

amphiphiles to dissolve in the bulk solution or adsorb at the interface to restore the
equilibrium coverage. Several models were developed for understanding adsorption
of surfactant at the surface of bubbles, and two extreme cases were taken into
consideration: (a) rapid deformation of the interface so that a non-equilibrium
adsorption predominates and (b) slow deformation of the interface such that the
adsorption is in equilibrium. In considering the rheology of the interface, different
types of deformation occur. The main ones have been classiﬁed by (a) the dilational
shearing modulus, where the deformation involves an increase or decrease in area of

(a)

Dilation deformation (expansion / compression)

(b) a da

Shear deformation
Fig. 7.6 Examples of a 2D dilational and shear deformation (measured upon expansion/compression)
of an interface. From ref (7).

the liquid surface whereas the shape of the area remains the same, and by (b) the
shearing deformation, where the shape of the liquid interface is changed while the
interface area is kept constant. These processes are illustrated in Fig. 7.6.
External perturbations can cause internal relaxation of the adsorbed surfactant ﬁlm,
and this behavior can give useful information on the dynamics of adsorption layers
and the stability of the foam. The drop shape and the capillary pressure tensiometer are
suitable methods to measure the dilational rheology of the interfacial layers which
deﬁne the key properties for understanding the behavior of foams. Dilational elasticity
and viscosity are nominated as the important parameters for understanding the
dynamic behavior of the interfacial layers. Dilational elasticity of the adsorbed
surfactant can be better understood by introducing an intrinsic compressibility of
the surface layer. Surface shear rheology provides important information on the
structure of the interfacial layer.

7.5.1 Dilational surface viscoelasticity

Although E as presented in Chapter 1 describes the ﬁlm elasticity in the Gibbs
equation, it is a purely thermodynamic quantity, and the experimentally measurable
parameters which are needed to characterize the mechanical-dynamical monolayers
are the viscoelastic properties (the surface elasticity and surface viscosity). These
parameters are coupled and deﬁned by the dilational surface viscoelasticity E* (also
called the interfacial viscoelastic modulus), resulting from the derivation of the

interfacial tension over adsorption (E* = dγ/dln Γ), which also corresponds to the
derivation of interfacial tension over bulk concentration (E* = dγ/dlnc). E* is then
dependent on both thermodynamic and kinetic characteristics of the foam systems
and may be considered as a dilational or compression modulus (surface stiffness or
resistance to deformation) that relates the dilational change in surface area and the
resulting change in surface tension. Essentially, surface viscosity reflects the speed of
the relaxation processes that restore the equilibrium in the system after imposing
stress on it. It is also a measure of the energy dissipation in the surface layer.
In contrast, the surface elasticity is a measure of the energy stored in the surface
layer as a result of an external stress. However, it is generally difficult to distinguish
between the effects on surface viscosity and the surface elasticity, although the steric
factors which effect the packing of the mixed film presumably control the rheological
behavior of the viscous mixed layers. Isolating the interfacial viscosity is also
difficult since the interface is connected to the substrate so that interfacial viscosity
is coupled to the bulk viscosity.
In addition to diffusion from the bulk phase, other kinetic processes play a role inside
the adsorbed layer, such as orientation, aggregation and compression, and cause rear-
rangements of the molecular structure. These factors affect E* and the magnitude of the
forces stabilizing the foam films, and, overall, it is difficult to achieve a complete
understanding of the surface rheology of soluble and insoluble layers at the interface
without knowledge of the shear viscosity, shear elasticity, dilational elasticity, dilational
viscosity and transport effects. In 2005, Ivanov (8) carried out a detailed analysis of the
range of aspects of interfacial viscoelasticity and concluded that it was impossible to
present the exact definition of the surface dilational viscosity. In many cases, the
experimentally determined values depended on the interpretation of results and char-
acteristics of the model. At sufficiently high deformation frequencies, E* may reach
a limiting value, which corresponds to a state of equilibrium adsorption where the
molecular exchange is suppressed and the adsorption layer will behave as an insoluble
monolayer (no diffusion exchange). At much lower frequencies, there is no resistance
against area change and the surface remains in equilibrium.
In general, the most interesting region is within intermediate frequency range, which
for soluble surfactants is about 1–500 Hz, where relaxation processes take place in and
near the interface (e.g. diffusion exchange). This causes viscoelastic surface behavior
and, therefore, the viscoelastic modulus E* has both elastic and viscous components.
In the case of sinusoidal deformation in which adsorption and surface tension oscillate
around their equilibrium values, the surface dilational modulus is a complex function of
frequency. At high surfactant concentrations, the interfacial tension follows the area
change with a certain delay due to the various relaxation processes within the interfacial
layer and between the interface and bulk solution. In this more general case, the surface
behavior is complex and E* has both elastic and viscous components. In the case of
soluble surfactants, the magnitude of the elasticity modulus E is a strong function of
frequency of external disturbances. For a more complete understanding of the surface
behavior, the complex surface dilational modulus E* (or visco-elastic modulus) has been
expressed in the form of

0
E ¼ E þ iE″ ð7:1Þ
0
where E is called the storage modulus (dilational elasticity) which is obtained as the
pure dilational elasticity and E″ is loss modulus and is proportionate to the viscous
contribution where

E″ ¼ ωηd ð7:2Þ

and ηd is the surface dilational viscosity and ω the circular or angular frequency. E*
is a complex function, and the molecular interpretation of the dissipative process
that gives rise to the imaginary part of the modulus is subject to some controversy.
Also, E* = dγ(t) /dlnA(t) where dγ(t) and dlnA(t) are incremental changes in surface
tension and area, respectively, and ɳd is determined by the changes from the phase
angle between the generated surface area changes and the response (changes in
surface tension). For pure elastic interfaces (insoluble monolayers), the dynamic
interfacial tension response γ(t) follows the area change A (t) without any phase
difference, ηd → 0 and E* = E̍ .
Bos (9) also stressed the importance of the process kinetics and interfacial rheology
in the generation and breakdown of foams. During the generation of foams, new
interfaces are produced in a millisecond or less, and time scales with rapid expansion
and compression and shear viscosity would probably be more relevant under these
conditions. However, high interfacial shear viscosity would probably make
a contribution to long-term foam stability. In conditions where bubble break-up
occurs, large deformations and high strain rates need to be considered, and since
these processes involve large deformations in area (mainly dilational), dilational
elasticity and dilational viscosity play important roles. However, the coalescence
process is not completely dependent on rheology since activation energies, bending
energies and the bulk rheological properties (particularly in high volume fraction and
high collision frequencies) play an important role. Under more quiescent conditions,
such as when the foam is standing, lower strain rates would be involved. During
drainage, several different types of deformation processes may occur. For example,
liquid ﬂowing downward due to gravity from the top of the bubble droplet would be
subjected initially to dilatation forces, whereas on reaching the bottom will be com-
pressed. In the middle of the droplet, where the distance between bubbles is the
narrowest, the interface is subjected to shear deformation. This situation is illustrated
in Fig. 7.7. In these circumstances, the overﬂow cylinder method and the maximum
bubble pressure method would possibly be relevant methods of measuring the inter-
facial elasticity.

7.5.2 Theories and models

Early theories relating to surface elasticity of oscillating systems were developed by
Lucassen (7) in 1968 and van den Temple/Hansen (10) in 1965 for a monolayer of
surfactant in which the surface elasticity as a function of the surfactant concentration

(a) (b)
x-y plane x-z plane

Dilation

Gas Gas
cell cell Shear Shear

Compression

Liquid flows Liquid expands or is

downwards compressed at base of cells
Fig. 7.7 Drainage of a liquid ﬁlm between two droplets (gas cells); (b) ﬂow types in the
droplet (gas cell) interface. From ref (9).

was related to the frequency of the perturbation. This approach led to the establishment
of the Lucassen van Temple Hansen (LvdT) model. This was successful in accounting
for many surface elastic systems but failed to completely account for the viscoelastic
properties of the monolayer. The theory was modiﬁed by Wantke and coworkers (11)
where a sub-layer was built into the model, and it was assumed that the surface
viscoelasticity was associated with a delayed exchange process between the sub-
surface and the monolayer. It was also assumed that this exchange process was relatively
rapid compared to the deformation rate in surface elastic systems, and this model was
found to be useful in describing the data obtained from measurements of surface
elasticity and surface viscoelasticity of foam systems. Over recent years, several other
models were developed to include underlying dissipative processes such as surfactant
re-orientation, surface compression, phase transitions or surface reaction in the surfac-
tant monolayer (12).

7.5.3 Experimental techniques for measurement of elasticity and surface viscosity

Many different methods have been used to investigate the expansion and compression of
the air/water interface. These techniques include capillary waves, longitudinal waves,
oscillating barriers and oscillating bubbles and can be used at a wide range of different
frequencies. They were originally reviewed by Bos (9) but, over recent years, several of
these methods have been improved to operate at even higher frequencies. The relevance
of the surface dynamic and surface viscosity characteristics were considered with
respect to the time of restoring the liquid interface. It was concluded that the former
played the more important role close to equilibrium conditions, while the latter was
relevant under conditions which were far from equilibrium. These techniques have
enabled values of E″ to be determined, and many of these studies have been directed
toward studying the inﬂuence of the kinetic exchange processes on the dilational

elasticity and the physical interaction between the adsorbed molecules on the surface
viscosity.
Surface laser scattering techniques have proved particularly useful for determining
the viscoelastic properties of monolayers, and this technique is very sensitive to the
behavior at the air/solution interface. When transversal ripples occur, periodic dilation
and compression of the adsorbed layer occur which can be studied. This enables
the viscoelastic behavior of equilibrium and non-equilibrium monolayers at an air/
water interface to be characterized without disturbing the original state of the mono-
layer. Surface elasticity values were obtained from surface dilational modulus mea-
surements determined at different angular frequencies for ﬁlms of speciﬁc thickness.
It is important to consider the thickness and adsorption behavior since these para-
meters are also inter-related with elasticity. More recently, Derkash and coworkers
(13) gave an extended review of the more recent methods of measuring the rheological
properties of interfacial layers. Magnetic needle viscometers and rods have also
been developed which enable sensitive measurements of the interfacial stress to be
achieved (14, 15).

7.5.4 Oscillating bubble methods

Oscillating bubble methods based on the measurement of the variation in surface
tension as a response to harmonic compression/expansion of the surface area of
a bubble (via variations of the volume) have been well developed and are widely
used to measure the surface dilational elasticity. The accuracy of the methods has
considerably improved in recent years due to the advancement in high-speed videos
and data processing. The oscillating bubble technique was first developed to measure
surface dilational elasticity by Kretzschmar and Lunkenheimer (16) working at the
Max Planck Institute for Colloids and Interfaces, Potsdam, Germany. This test was
originally carried out in the low frequency range from about 10−3 to 0.2 Hz. In 2001,
Wankte and coworkers (17) modified the method to operate in the 1–300 Hz frequency
range. In this method, a small bubble is formed at the end of a capillary tip in a cell and
the bubble is subjected to sinusoidal oscillations which are generated from a piezo-
element. This causes compressions and expansions of the bubble surface. Changes in
bubble radius and surface area produce sinusoidal changes of the pressure in the
measuring chamber, and the pressure change is measured by a pressure transducer.
As an alternative, the capillary pressure tensiometer measures the capillary pressure
directly at higher frequency of 0.1–100 Hz even up to 500 Hz or higher. Both
measuring techniques are highly sensitive to the surfactant present at surface and
can be used to quantitatively characterize the surface layers. A commercially available
instrument known as the bubble profile analysis tensiometer (PAT) has been widely
used, and the basic set up together with the profile of the pulsing bubble is shown in
Fig. 7.8.
Based on analysis of the oscillations of the bubble shape, values of the dilational
interfacial elasticity and information of the surfactant exchange process can be obtained.
In Fig. 7.9, the harmonic oscillations of the interfacial surface tension and the drop area

(a) (b)

CCD & objective

Capillary

Oscillating bubble

Light
Liquid
Piezo Compression

Equilibrium
Pressure
Computer
transducer
Manual Dilatation
dosing

Interface
Fig. 7.8 (a) The measuring cell in which the change in surface tension is monitored by capillary pressure
measurements and (b) proﬁle of the pulsing bubble showing the adsorption kinetics of the
surfactant. Fast oscillation up 100 Hz can be easily achieved.

~
A = A0 + Asin (2 P vt)
D
~
dA/A γ = γ0 + γ (2 P vt + D)

A ~
A
Elastic
surface
dγ

γ
~
γ

Amplitude is a
Visocoelastic surface measure of elasticity

Time
Fig. 7.9 The response to the interfacial tension (γ) and interfacial area (A) to the sinusoidal perturbations of
a pendant drop as a function of the component of frequency. For the viscoelastic surfaces the
interface storage shear modulus and the interface loss shear modulus can be obtained from the
phase difference between the two signals.

obtained at a ﬁxed frequency are shown. In Fig. 7.10, a typical set of results are shown
for a surfactant which was measured at three different concentrations.
For a low amplitude harmonic perturbation, the complex dilational viscoelastic
modulus or the dilational viscoelasticity E can be expressed by the equation:

(a) (b)
dA/A Amplitude is a measure of elasticity
C1 65
60
C1
C2
50
55 d γ/γ
C3 C2
A 40 γ
Phase log is a measure
30 of the dilational viscosity 45
C3
20 Area

10 35
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Time Time
Fig. 7.10 Harmonic oscillations of the interfacial surface tension and the drop area at three different
concentrations of surfactant as represented by C1, C2 and C3.

Δγ
E¼ πr2 ð7:3Þ
ΔA=A0

The complex surface dilational modulus can be obtained from analysis of the
amplitude and relative phase shift between the change of area of the bubble image and
the change of interfacial tension as a function of time. More in-depth discussions of these
techniques are given by Ravera and coworkers (18) in 2010, by Miller and Liggieri (19)
in 2005, and Liggieri and coworkers (20). This oscillating bubble instrument has
been successfully used at fairly high frequencies, enabling interesting data to be
collected on the relaxation mechanisms occurring between the surface layer and
adjacent bulk phase within the surface layer. This technique has proved useful in
understanding the composition of the interfacial layer and strength of the inter-
action between adsorbed species. The pulsating bubble module has also been used
to investigate the inﬂuence of the surfactant concentration above and below the
CMC on E*. Studies have been reported on a wide range of different types of
surfactant systems, including blends of surfactants, polymers and surfactant/poly-
mer mixtures (20).

7.5.5 Experimental studies of elasticity and surface viscosity

Although the oscillating bubble method is probably the most widely used technique
today, many earlier attempts have been made to try to establish a relationship between
the surface rheology and the generation and stability of foams using other methods. This
has met with some success, although it appeared to depend on the type of foam and
measuring methods. However, it is important to note that the surface rheological
measurements are almost always carried out on macroscopic surfaces, and this is often
not compatible to the stress and strain in practical foams where turbulence and non-
equilibrium conditions can prevail. Early light scattering measurements of the capillary

wave motion of aqueous surfaces covered with fatty acid and lecithin monolayers
were reported by Hard and Neuman (21) in 1981. Quantitative determinations of the
ﬁlm dilational elasticity and ﬁlm dilational viscosity were reported. Viscosity mea-
surements by light scattering were comparable in magnitude to surface viscosities
obtained by mechanical (shear) viscometers. Colegate and Bain (22) carried out
ellipsometry studies on a liquid jet with a micellar solution of a nonionic surfactant
(C14EO8). The results were discussed in terms of the diffusion of micelles to the
interface, the adsorption step and the immediate breakdown of the micelles into
monomer species. These observations contradicted standard micellar models since
it was suggested that the micelles may break down into monomers not only in bulk
solution but also in the sublayer before adsorption.
In 2003, Wantke and coworkers (23) measured the surface dilatational properties
of aqueous solutions of sodium dodecyl sulfate (SDS) and n-dodecanol in the
frequency range 1–500 Hz using the oscillating bubble method. It was found that
pure dodecanol solution exhibited an elastic surface without viscous effect, whereas
the surface of an SDS solution without added dodecanol exhibits a strong viscoe-
lastic behavior. Mixtures showed a graduated transition from elastic to viscoelastic
behavior and it was suggested that the dodecanol molecules drive the SDS mole-
cules slowly out of the surface. This study established that a one-component model
describing the surface dilatational modulus can be used also for these mixtures.
Surface dilational modulus measurements carried out in the mid-frequency range
were reported by Anderson and coworkers (24) in 2006. The dynamic state of the
surface layer was monitored using a pressure sensor and surface second-harmonic
generation (SHG) recorded. The pressure sensor measures the real and imaginary
part of the modulus while SHG monitored independently the surface composition
(the concentration of soluble surfactant) under dynamic conditions. Two aqueous
solutions were studied, a surface elastic and surface viscoelastic solution.
The results could be explained by the LvH model, which included a molecular
exchange process and provided evidence for a non-equilibrium state within the
surface phase.
Recent trends have led to the combination of the oscillating bubble method with
other advanced surface analysis techniques. Possible future studies could involve
coupling the surface rheology with more precise measurements of the adsorption
kinetics, adsorbed amount and surface layer composition. The combination of shear
rheometry, ellipsometry and Brewster angle microscope might give more advanced
insight into the different mechanisms involved in foaming processes.

7.6 Stability control agents

The stability of foams can be controlled by using single surfactant systems and
controlling the aqueous environment by adjustment of pH or by adding inorganic
electrolytes to produce speciﬁc ion effects. There is also the possibility of adding
a second surface-active agent such as a low molecule long straight-chain unbranched

(a) (b)
Cohesive interactions
Air
Air

Solution Solution

Air Air

Surfactant (mixed film) Polymer

Solution Solution

Air Air
Particle where θ > 90º
Polymer / Surfactant (mixed film)
(low degree of wetting)
Fig. 7.11 High packing densities result from certain types of mixed surfactant species which can cause
strong cohesive interactions similar to polymer or particle ﬁlms. For example: (a) mixed
surfactants system, (b) polymers (c) polymer/surfactant (d) particles with high contact angle
attached to the air-solution interface.

hydrocarbon to a polymer or using particles in combination with these chemicals.

There are many examples in the literature where mixed surfactant systems such as
surfactant/polymers, particles/polymers, etc., have been shown to provide enhanced
foam stability, but the complete mechanism for many of these systems has not been
completely resolved. Some of these mixed films compared to single component films
are shown in Fig. 7.11. However, it has been well known for several decades that these
mixtures form coherent surface layers (with high packing densities) which act as an
elastic membrane or skin that can stretch and relax. Essentially, the primary effect is
thought to be caused by an increase in surface viscosity and elasticity which acts to
protect the film against lateral forces produced by disturbances such as thermal
fluctuations, evaporation, temperature gradients and external vibrations. Cohesive
films are also formed by adding relatively high molar mass polymers, proteins,
polysaccharides or certain types of particle. Many food foams are stabilized by protein
polymers adsorbed at the air/water interface. However, in recent years it was found
that the high mechanical viscoelastic properties associated with coherent films may
also reduce thin film drainage.

7.6.1 Single surfactant systems, pH, electrolyte and speciﬁc ion effects
As discussed in Chapter 2, the foaming of long straight-chain hydrocarbon ionic
surfactant reaches a maximum value around the CMC, but the addition of inorganic
electrolytes to the surfactant solution decreases the CMC, enhancing the foaming.
Generally, at low electrolyte concentrations, speciﬁc adsorption effects change the

magnitude of interfacial charge and electrostatic interactions. This mainly inﬂuences

the charging of the film, but at high salt concentrations screening of electrostatic
repulsion becomes an important mechanism with regard to the stability. It is also
important to consider the fact that the type of counterion can affect the degree
of dissociation of the surfactant. It has also been well established that the type of
counterions and co-ions of the electrolyte has a strong influence on the thickness
of foam films and can be used to tune the stability. For example, Schelero and
coworkers (25) in 2010 determined the influence of monovalent ions Li+, Na+, Cs+
on the dodecyl salt of SDS. As the size of the cation increased, the adsorption
increased, producing thinner and less stable films. In the case of anions, thicker and
more stable films are produced which increased the foaming.

7.6.2 Mixtures of surfactants, foam builders/boosters

The formation of coherent films from densely packed layers of adsorbed unbranched
surfactant molecules containing long straight-chain hydrocarbons and small terminal
polar groups is a basic requirement to obtain stable equilibrium films. For example, it
is well known that the mixtures of SDS with dodecylalcohol, and dodecylbenzene
sulfonate with lauryl isopropanolamide show improved foaming compared with the
single components. Some common impurities present in alkyl sulfates, such as free
fatty acid, can act to enhance foam stability, and the mechanism may involve inter-
facial rheology. Many types of surfactants can be added to enhance the foaminess of
weakly foaming systems and they have been designated as foam boosters. This may
cause an increase in foamability or an increase in stability or both. In industries foam
boosters are often evaluated on an empirical trial-and-error basis, and many different
types of surfactants have been screened but only a few have become widely
acceptable.
Although nonionic surfactants produce only low or moderate foam volumes
when used alone, they can act as excellent foam boosters for many anionic systems.
It was postulated that stabilizers penetrate the surfactant surface film giving
a coherently packed surface film, and straight-chain surfactants give more foam
promotion than branched chain surfactants. According to early studies by Schick
and Schmolka (26), the order of susceptibility to foam promotion follows the
order of decreasing van der Waals forces between the straight-chain hydrophobe
of the stabilizer and the hydrophobe of the adjacent surfactant. This order may be
expressed as
primary alkyl sulfates > 2-n-alkane sulfonates, secondary alkyl sulfates> alkyl
benzene sulfates > branched-chain alkyl sulfonates.
Foam boosters at fairly high concentrations may also increase the bulk viscosity and
possibly the foam liquid network and may be associated with formation of liquid
crystals. On the other hand, additives which defer or destroy liquid crystalline structures,
such as short or branched alcohols, promote drainage and decrease stability.

Table 7.2 Correlation between foam stability and CMC lowering by additives for sodium
2-n-dodecylbenzene sulfonate solutions. From ref (25).

Foam stability
Decrease in CMC Foam volume (ml)
Additive CMC (g/L) (%) after 20 min.

None 0.59 18
Lauryl glycerol ether 0.29 51 32
Laurylethanolamide 0.31 48 50
n-Decyl glycerol ether 0.33 44 34
Laurylsulfolanylamide 0.35 41 40
n-Decyl-3-sulfolanyl ether 0.35 41 28
n-Octyl glycerol ether 0.36 39 32
n-Decyl alcohol 0.41 31 26
N-(3-Sulfolanyl)oleylamide 0.48 19 23
Caprylamide 0.50 15 17
Lauryl chlorohydrin glycerol ether 0.57 3 22
Tetradecanol-2 0.60 0 12

Further, a correlation between CMC lowering and foam stability indicates that the
more effective stabilizers are those which cause the greatest lowering of the CMC.
An early systematic study by Schick and Fowkes (27) with a series of different
detergents, showed the importance of different additives on reducing the CMC. From
this work it can be concluded that the additives which had the greater influence in
reducing the CMC were the most effective foam stability boosters. The additives with
unbranched paraffin chains (which were equal in length to the detergent molecule) and
that had highly hydrophilic nonionic polar groups at one end were the most effective.
This can be illustrated by the effect of different types of surfactants on the stability of
sodium 2-n-dodecylbenzene sulfonate, are shown in Table 7.2.
Other effective foam enhancers or boosters include alkanolamide-type surfac-
tants. Sanders and Knaggs (28) reported that these types of additives were extre-
mely effective in practical systems. Early studies suggested that extremely closely
packed layers are formed in the mixed surfactant films containing alkanolamides
due to the formation of multiple hydrogen bonds, which improves the rheological
properties. Rodriguez and coworkers (29) carried out an extensive phase study and
small-angle X-ray scattering with an alkanolamide-type foam booster, dodecanoyl
N-methyl ethanolamide (NMEA-12). The structure of the surfactant is shown in
Fig. 7.12.
This surfactant was reported to have a lower melting point (compared to other
alkanolamides) and formed a lyotropic liquid crystalline phase at room temperature
which was attributed to an attached methyl group. This increases the fluidity of the
molecule. In SDS/NMEA-12 system, wide hexagonal and lamellar liquid crystalline
regions were detected at relatively low surfactant concentrations. For both the SDS and
the C12EO8 surfactants, the addition of NMEA-12 caused the effective area per molecule

Fig. 7.12 Chemical structure of dodecanoyl N-methyl ethanolamide.

to shrink, producing a tightly compact layer which correlated with the foam booster
characteristics.
Foam boosters are needed in detergent, body-care shampoos and hair-conditioner
formulations which are mainly stabilized by anionic surfactants. In these systems, oil
droplets from grease from the body or hair become dispersed in solution and act as
antifoamers. It is often necessary to add an amphoteric and nonionic cosurfactant to
suppress the antifoam effects of oil. Basheva and coworkers (30) evaluated a series of
surfactants as potential as a foam boosters in the presence of a model detergent system
containing silica oil. The surfactants included lauryl amide propyl betaine (LAPB),
lauryl acid diethanol amide (LADA), lauryl alcohol (LA) and a glycerine-based
nonionic. The weakly foaming solutions contained a commercial anionic surfactant
(sodium dodecyl polyoxyethylene-3-sulfate (SPD 3S)), and the silicon oil droplets
were dispersed in foaming solution as micrometer-sized droplets. From thin lamellae
film experiments, it was shown that the enhanced foam stability in the presence of
LAPB and LA correlated with the energetics required to overcome the entry of the oil
drop into the air/water interface. It was also shown that the size of the silicone droplet
had a significant effect on foam stability and that droplets above about 5 microns
caused foam destruction. The mechanism involved the compression of the droplets by
walls of the Plateau channels. This resulted in a reduction in film thickness during
drainage.

7.6.3 Polymer/surfactant mixtures

The interactions between surfactants and polymers have been extensively covered in
a book entitled Polymers and Surfactants in Aqueous Solution edited by Holmberg and
coworkers (31). Numerous experiments have been reported with different systems, but,
due to the wide diversity of the components in these mixtures, it has been difﬁcult to
buildup a complete explanation of the relevant mechanisms involved in their application
as foam stabilizers. On mixing a surfactant with polymer, frequently the onset of
binding or the start of the attachment of the premicellar aggregates on the polymer
chain occurs at a critical concentration. This has been designated “the critical aggregate
concentration” (CAC) and the value of the CAC is at a signiﬁcantly lower concentration
than the CMC of the pure surfactant. It is also independent of the polymer concentration
and, as the polymer concentration decreases, the CAC approaches the CMC of the
surfactant. Many studies have been made with mixtures of an ionic surfactant and
a nonionic polymer leading to complex formation, and other types of interactions have

Fig. 7.13 Mixed polyelectrolyte/surfactant ﬁlm with (a) adsorbed polymer on the surface (b) via formation
of surfactant/polymer complexes or (b) via hydrophobic attraction and (c) mesoscopic structured
poylectrolytes chains in the ﬁlm bulk. The distance Δh between the neighboring branches is
independent of the kind of surfactant but differs with the kind of polyelectrolyte. From ref (32).

been shown to be involved (31). These have been shown to include (a) the redistribution
of the surfactant between the bulk solution and the coil regions, with the surfactant
molecules bound individually along the chain, (b) surfactant molecules clustered around
hydrophobic sites on the polymer and (c) polymer molecules wrapped around surfactant
micelles in such a way that the polymer segments partially penetrate and wrap around the
polar headgroup regions of the micelles. It has also been suggested that electrostatic
interactions are important in these systems, and the adsorption of these types of complex
species at the interface has an important influence on the foaming.
Klitzing and Muller (32) reviewed the different parameters involved in stabilizing
binary polymer/surfactant films under dynamic and static conditions. The importance of
intermolecular interactions, including DLVO and steric forces, was considered for
relatively low and high molecular weight amphiphilic mixtures. The influence of
the complex architecture of the polymers in the case of block copolymers and
tri-copolymers was discussed in terms of electrostatic screening effects and coiling of
the grafted chains. These factors were particularly important under high ionic strength
conditions. Fig. 7.13 indicates the different types of interaction which may occur within
a thin foam film.
It has also been well established that surface complexes formed below and above the
CAC can cause a synergistic lowering of surface tension in these systems. In some cases
above the CAC, the stability becomes even higher due to the formation of gel-like
structures in the thin film. An overview documenting the different interactions involving
combinations of polyelectrolytes and surfactant with different charges was published
by Langevin and coworkers (33) in 2001. It is well known that with mixtures of cationic
and anionic polyelectrolytes, the thin film stability can be enhanced, particularly if
one species is only slightly charged. However, in addition to electrostatic interactions,
hydrophobic interactions and hydrogen bonding can also play a role in complex
formation. With polymer/surfactant interactions, an increase in polymer concentration
above CAC may cause desorption of complexes from the interface which will

destabilize the film and reduce the foaming stability. For many industrial applications,
cellulose polymers are used in mixed formulation with low molecular weight surfac-
tants, and it is often necessary to optimize the formulation in order to prevent foaming.
Guerrini and coworkers (34) studied the interactions of an amino-alkyl carbonyl
cellulose derivative with SDS and reported that maximum foaming occurred in the region
where the charge of the polymer/surfactant complex was neutralized. Precipitation was
also reported to occur in this concentration range. For mixtures of a SDS surfactant and an
ethyl hydroxyl cellulose (EHEC) polymer, Djuve and coworkers (35) showed that the
formation and adsorption of complex polymer/surfactant aggregates at the interface had
a pronounced effect on foam stability in aqueous solution. The driving force of the
interaction has been discussed in terms of the hydrophobic interactions and the electro-
static interactions between polar SDS and the EHEC polymer. In these systems,
a synergism in foaming was established. This behavior was explained by the adsorption
of aggregates at the air/water lamellae interface leading to the formation of a coherent
gelatinous layer which reduced drainage.
In 2011, Langevin and coworkers (36) reviewed the stability and drainage of free
suspended film stabilized by surfactant/polymer mixtures, and in this paper, parti-
cular attention was paid to protein systems. Proteins alone are known to form brittle
monolayers at the air/water interface that can easily break and leave unprotected
areas. However, for mixed surfactant/protein films, the hydrophilic sections and
neutral hydrophobic segments can produce compact aggregates which may also
partially unfold at interface. In the case of a mixed monolayers produced from
surfactants and rigid polyelectrolytes of opposite signs, the surfactants may trans-
form the rigid proteins layer into more flexible and mobile entities that might be
capable of responding to applied stress without rupturing. This may be the reason
why protein/surfactant film mixtures are more stable than surfactants alone. There is
also a possibility that at high surfactant concentration, the proteins may be displaced
toward the film interior. From optical observations of the thin films containing
proteins, it could be suggested that the inhomogeneous films consisted of gel-like
aggregates, and interferometry showed different colors indicating a wide variation of
the film thickness. The adsorption of the aggregated proteins also corrugated and
deformed the surface, and their confinement in the film possibly provides a gel-like
jamming behavior. This prevented measurements of the disjoining pressure between
the interfaces of the thin films, but it has been shown by Bergeron and coworkers (37)
that it was possible to relate visually the surface characteristics of its the film to the
stability. Gel-like structures were observed within critical concentration levels in thin
film produced from polyelectrolytes with opposite charge. For example, the thin
film images produced from the PAMPS and DTAB systems are shown in Fig. 7.14.
These were reported to be extremely stable and near to the precipitation limit of the
complex.
Gel-like structures have also been observed in films produced from sodium caseinate
(Fig. 7.15). It was reported that the inhomogeneities in such films are mobile at
low concentration but become more strongly attached and static at higher

Fig. 7.14 Image of a ﬁlm made from PAMPS and DTAB at a concentration near the precipitation
boundary (top and bottom: Schematic illustration of the ﬁlm structure). From ref (37).

(a) (b) (c)

Fig. 7.15 Top view of casein thin ﬁlms for three different casein bulk concentrations (a) c = 0.05 g/l, (b)
c = 0.3 g/l and (c) c = 0.83 g/l and showing heterogeneous thickness and the presence of
aggregates. The ﬁlms become stable as soon as the aggregates percolate. From ref (37, 38).

concentrations (> 0.1 g/l, which corresponds to the stability threshold of foams gener-
ated with these solutions).
In industries, frequently mixtures of oppositely charged surface-active agents
(anionic and cationic surfactants and surfactant mixtures) are used in foaming for-
mulations; for example, mixtures produced from xanthane-gums, proteins, mixtures
of partially hydrophobic silica nanoparticles and short-chain amine surfactants.
These mixtures are sometimes referred to as catanionics. Usually these types of
mixtures produce bulk aggregates or soft entities which compact in the Plateau
borders of the foam preventing drainage.
Many basic research experiments using self-supporting foam films have been used to
study these systems. Schelero and von Klitzing (39) prepared foam films with a mixture
of a cationic surfactant (alkyl trimethyl ammonium bromide, CnTAB) and variable
amounts of anionic surfactants. Three different types of anionic surfactants with head
groups of different size and charge (sodium decanoate, sodium sulfate and sodium
styrene sulfate) were investigated. From these studies it was observed that with increas-
ing concentration of the anionic surfactant the film thickness and stability decreased to

a minimum value that was dependent on the type of head group interaction, as well as the
hydrophilic/hydrophobic balance of molecules. Stronger interactions, due to hydropho-
bic interactions and the head groups, appeared to dominate the synergism. From the
study it could be suggested that the amount and type of anionic surfactant could be
adjusted to tailor the stability of the foam. Also, surface tension was conﬁrmed as
a useful technique to study these systems.

7.6.4 Condensed shells

In 2008, Shen and coworkers (40) reported that it was possible to stabilize microbubbles
with a mixture of saturated long-chain mono and diglyceride; sodium stearoyl-2-lacty-
late (SSL-2) in combination with polyethylene glycol (PEG-40 stearate). Langmuir
trough studies on monolayers and ﬂuorescence microscopy were combined; this enabled
the surface tension, interfacial elasticity modulus, phase behavior and microstructure of
the monolayer shells coating microbubbles to be characterized. It was suggested the
components were squeezed out to form compact, collapsed aggregates which resulted in
the formation of a microbubble shell surrounding the bubbles. The compacted shell was
reported to be composed of a condensed phase of low surface tension mono- and
diglycerides mixtures with some of the PEG40S and SSL2 remaining trapped between
the condensed phase domains.

7.6.5 Nanopatterning
In 2008, extremely stable microbubbles (stable for over 1 year) were prepared by
Dressaire and coworkers (41) from a solution of sodium stearate which was dispersed
and sheared in a highly viscous glucose syrup phase. The enhanced stability has been
explained by the formation of an elastic condensed surfactant phase with hexagonal
domains buckled outward from the bubble covered surface. It was suggested that it was
the elastic response of the interface which prevented the shrinkage of the bubbles.
The systems were found to have a wide bubble size distribution (ranging
from hundreds of nanometers to tens of microns). From cro-SEM and TEM imaging it
was shown that a self-assembled surfactant film coated the air/water interface.
Thermodynamic and molecular models based on the energetic competition between
the bending elasticity of the interface and the formation of domain boundaries were used
to describe the pattern geometry. It was suggested that these features of the nano-scaling
could be modified by changing the chemical composition of the film. Controlling the
nature of the surfactant self-assembly could prove to be a useful tool in designing
complex coatings to stabilize bubbles and foams. The structure of a neatly formed
hexagonal surface pattern has been clearly demonstrated (41).

7.6.6 Hydrophobins
Biomolecules such as hydrophobins can outperform synthetic molecules in many
applications, and there has been a growing interest in utilizing these natural polymers

in stabilizing bubbles and foams. These molecules are part of a class of small cysteine-
rich surface-active proteins composed of amino acids, and they are commonly found in
button mushroom. The structures contain distinctive hydrophobic and hydrophilic
amino acid residues in the protein sequence and can be considered to have similar
features to Janus particles. They form self-assemblies that are strong and irreversibly
adsorb at the air/water interfaces, and they have been described as the most surface-
active protein, known and produce surface tension reductions as low as 27 mN/m.
In 2009, Cox and coworkers (42) showed that bubbles could be stabilized for long
periods (for at least 4 months) and even up to several years in some cases.
The unique properties of hydrophobins have been reviewed by Linder (43) in 2009.
Hydrophobins have also been evaluated as bubble stabilization agents in aerated foods
such as ice cream, and early studies enabled them to be classiﬁed into two distinct
groups: class I and II. In class I, aggregates form in water which are highly insoluble,
whereas class II aggregates which are more soluble. On dispersion in water, class II
produce oligomers which dissociate into aggregates and membranes that disintegrate
when subject to shear deformation and transform into a viscoelastic layer similar to
a highly elastic membrane. It is interesting to note that macroscopic bubbles formed in
HFB II solution have been shown by Basheva and coworkers (44) to preserve the
irregular non-spherical shape they had at the moment of solidiﬁcation, as shown in
Fig. 7.16.
There has been a considerable effort to understand the relationship between the
functionality and the molecular rearrangements of the hydrophobin fragments, which

Fig. 7.16 Photograph of millimeter-sized bubbles resting below the surface of a 0.005 w% HFB class II
solution containing added CaCl2 (25 mM). From ref (44).

are produced under shear. Emphasis has been directed toward determining the size
and geometry of the hydrophobic and hydrophilic head groups and the packing
density at the interface. Basheva and coworkers (44) also carried out monolayer
compression experiments and foam film studies which indicated that more mechan-
ical, stiffer films were formed with hydrophobins than with more common proteins
such as β-casein and β-lactoglobulin. These molecules appear to have sufficient
hydrophobic and also hydrophilic moieties to form compact films with high packing
densities, strongly attach to the bubble interface and reduce gas diffusion. They show
periodic wrinkles (ripples) with well-defined bending elasticity. It has also been
suggested that the protein monolayers of HFB II exhibited high mechanical strength
compared to typical amphiphlic proteins. From free foam film studies, it was found
that the interface was electrostatically stabilized, but near the pHiep, aggregates were
produced from dimers and tetramers that tended to adhere to each and to the air/water
interface. Generally, these large aggregates in water could be considered to exhibit
behavior similar to sticky particles, and this to some extent explains the compact
adsorption layers. Also, it was suggested that expanding monolayers vulnerable to
rupture could be repaired by the molecules filling the voids.
Adsorbed layers of hydrophobin HFB II with added β-casein were studied by
Radulova and coworkers (45) using a rotational surface shear rheometer. Experiments
were carried out at different shear rates and at different concentrations of added β-casein.
High values of the surface shear elasticity were explained by the formation of an
interfacial bilayer, with the layer from the more hydrophobic HFB II facing the air
phase. With increase in shear rate, the layers were found to fluidize, and the addition of
casein gave more rigid adsorption layers with faster fluidization. It was also possible to
study the different processes that occur in the viscoelastic adsorption layer in different
flow regimes which involve the breakage and restoration of intermolecular bonds and
solidification of the adsorption layers. In Fig. 7.17, the results from surface rheological
studies are shown together with a model illustrating the interfacial bilayer formed from
the casein/HFB II aggregate.

7.6.7 Control of gas diffusion

Coherent interfacial films not only increase the surface elasticity but also have a major
effect on the diffusion of gas across the aqueous films separating the bubbles. It is the
structure of the thin film (the packing density, film type, the nature and concentration of
the surfactant, molecular weight, the type of head group, electrolyte type and concentra-
tion, etc.) that plays a key role in defining the permeability of the barrier. In the case of
polymers, thick layers are often adsorbed, but they are often porous due to the irregular
alignments at the interface; however, they can become more effective when they become
cross-linked after adsorption. Many proteins unfold at the interface, producing
cross-linked layers, and some sucrose-based surfactants form crystallized defect-free
dense films around the bubble. Although many studies have been carried out with
proteins, the properties and composition of the adsorbed layers can change with aging,
and also batch-to-batch variation occurs on storage, making it difficult to collect

(a) (b)
Decreasing angular velocity
HFBII
40 adsorption
layer
Torque, τ (mN.m)

30
Adsorbed
HFBII tetramers
20
β–casein
10
HFBII +
0
β–casein
0 10 100 1000
Time, t (s)
Fig. 7.17 Surface shear rheology studies on hydrophobin II: (a) plot of the torque versus time at six different
angular velocities. The data indicate an increasing ﬂuidization with rise in shear rate. (b) Top: HFB
II dimers and tetramers can adhere to the ﬁlm due to attractive interactions between hydrophilic
parts of HFB II molecules. Bottom: With β-casein, an interfacial bilayer consisting of more
hydrophobic HFB II facing the water phase and a layer of more hydrophobic casein that faces the
water phase is formed. From ref (45).

reproducible experimental data on these systems. Particles can also jam on the bubble
surface and become irreversibly adsorbed, and these layers can form effective barriers
which decrease and even arrest the rate of bubble coarsening.

7.6.7.1 Gas type and foam type

The type of gas plays a key role in disproportionation since the permeation rate of the gas
is proportionate to the gas solubility and the molecular size. For example, CO2 gas is
readily soluble in water (e.g. in soft drinks) and has 50 times greater solubility than N2;
this leads to less stable foams since the CO2 is rapidly transported across the aqueous
film. Gregorian and coworkers (46) generated foams for use in the textile industry with
six different types of gases and found that the redistribution of bubble sizes for the
different gases caused by disproportionation led to different rates of bubble growth and
a decrease in foam bulk viscosity. Measuring the change in foam viscosity as a function
of time enabled the stability of the foams to be estimated and the data are consistent with
the hypothesis that the gas flow through the bubble walls occurs by an activated diffusion
process.
A small fraction of relatively insoluble gas can effectively inhibit foam evolution and
a binary gas mixture in which one of the gases is relatively insoluble can therefore be
used to improve stability. In these systems, the disproportionation behavior becomes
particularly interesting and as the gas composition of the bubble changes during
shrinkage, the smaller bubbles become enriched by the lower solubility gas while the
larger ones become enriched by the higher solubility gas. This effect is of practical
importance in the brewing industry, where the addition of a low percent of N2 to the CO2
in beer is sufficient to stabilize the head of beer for some time after it has been drawn into
a glass. Below a certain critical concentration of the insoluble gas, an inhomogeneous

(a) (b)

Liquid retained in the foam (%)

100 100

80 80

60 60

40 40
CO2 / PFH
N2 / Water
20 0.42%, 0.83%, 3.75%
20 N2 / PFH
0.29% CO2 / Water
0.20%
0% 0.091%
0 0
0 100 200 300 400 500 600 0 250 500 750 1000
Time (sec) Time (sec)

Fig. 7.18 (a) Drainage rates of foams produced from mixtures of CO2 gas containing different
concentrations of Perﬂuoro vapor. In this experiment FC104 vapor was selected. Solution contains
1 g/l of Pluronic F68. Initial volume of solution = 50 ml, temperature 25°C and rate of foam
formation = 0.22 cm/s). (b) Comparison between two gases, CO2 and N2, with and without PFH
solution. 1 g/l of Pluronic F68. V0 = 50 ml, temperature 30°C and rate of foam formation =
0.22 cm/s. From ref (48).

structure is formed. This concept can be generally used to inhibit coarsening. For
example, by bubbling a soluble gas through a small amount of liquid such as perfluor-
ohexane (PFH), a small amount of insoluble vapor is introduced into the liquid causing
the lifetime of a foam to be extended from only a few hours to several days.
The theoretical background to this behavior has been presented by Weaire and cow-
orkers (47) and is based on the differences in mixing entropies of the gas molecules
which cause a counteractive driving force for gas diffusion.
The effectiveness of this method of stabilizing foams was evaluated in some detail
in experiments by Gandolfo and Rosano (48) in which foams were generated in
a column using a milk protein surfactant. Two systems were studied in which the
stability of the foams (generated by N2 and O2) was measured from the changes in the
drainage rates. Further experiments were made in which small concentrations of
insoluble secondary gases (vapors) were introduced into these gases. Experiments
were carried out with several different types of insoluble gases: Pluronic (F67: a block
copolymer of ethylene oxide and propylene oxide condensate), a PFH and other types
of commercial fluoro-inert (linear perfluoro molecules) designated FC 77, FC 104, FC
40 and FC 70. Fig. 7.18(a) shows a typical set of data of the drainage rates for foams
generated by CO2 containing increasing levels of the perfluoro vapor, compared to
foams generated by bubbling CO2 alone through the aqueous solution. The foams
were generated at a fixed flow rate, and the gas supply was switched-off after the foam
reached a pre-determined height.
These results show that an increase in the level of FC 104 in the gas mixture to above
0.42% caused the drainage curves to be reduced, and they finally level off. Also, in
Fig. 7.18(b), the drainage results for CO2 and N2 are shown, and it can be seen that
without the PFH vapor, the CO2 causes a large increase in drainage rate compared with
N2, as expected. Nevertheless, it can be seen that by using gas mixtures containing PFH,
the drainage can be substantially reduced for both gases.

(a) (b)
C12TAB C12TAB
Permeability coeff (cm/s)

Permeability coeff (cm/s)

0.6 0.6

SDS
0.4 0.4

0.2 0.2 SDS AOS

C12G2 C12G2

0.0 0.0
Air
N2
Ar
O2

Air
N2
Ar
O2
Air
N2
Ar
O2

Air
N2
Ar
O2

Air
N2
Ar
O2
Air
N2
Ar
O2
Air
Xe
Fig. 7.19 Comparison of (a) gas permeability of CBF stabilized by β–C12G2, C12TAB, SDS to different
gases and (b) gas permeability of NBF stabilized by β – C12G2, C12TAB, SDS and AOS to
different gases. From ref (49).

Farajzdah and coworkers (49) measured the permeability rates (diffusion rates) of
foam films prepared with anionic, cationic and nonionic surfactant solutions with several
different types of gases which included argon, oxygen, nitrogen, air and in one case
xenon. All the surfactant solutions were above the CMC, and the electrolyte concentra-
tions were adjusted so that the film type could be changed. In the lower electrolyte
concentrations, CBFs were formed with the ionic surfactants with typical equilibrium
thicknesses of 10–15 nm, but at high electrolyte concentrations, NBFs were formed with
thicknesses about 5 nm at 0.5 M electrolyte. The results of the gas diffusion experiments
are summarized in Fig. 7.19 (a) and (b) for the two different film types, and this enables
a comparison to be made between different surfactants, gases and types of film.
The results from this study indicate that the gas permeability of the CBFs were
generally higher than that of the thinner NBFs, but this effect was mostly more
pronounced for films stabilized by SDS surfactants. It is difficult to give a complete
explanation of this behavior, but it is possible that the gas permeability is governed not
only by the film thicknesses but also by the nature of the interacting surfactant mono-
layers, which would be dependent on the surfactant adsorption densities.

7.7 Interfacial rheology and gas permeability

There has been considerable debate on the influence of the surface elasticity on
disproportionation. It has been thought that during this process, as small bubbles
shrink, the film compacts and after a time the compression forces reach a sufficient
magnitude to retard the shrinkage. However, it is possible that the adsorbed surfactant
layers may collapse upon increasing compaction and form multilayers. A further
possibility is that the molecules desorb from the surface. In 2008, Tcholakova and
coworkers (50, 51) carried out a series of fundamental experiments using a mixed
surfactant system in order to study the influence of gas permeability on interfacial
rheology and drainage. Initially, a surfactant system was prepared by adding low

2.8

SLES+CAPB
2.6

2.2
(Rt /R0)

SLES+CAPB+LAc

1.8

1.4 SLES+CAPB+MAc

1.0
0 1000 2000 3000
Time (seconds)
Fig. 7.20 Change of mean bubble radius R with time as a result of Oswald ripening. The bubbles are
observed at the foam contact with a glass plate (the size of the ﬁrst layer of bubbles was measured).
From ref (50).

concentrations of a co-surfactant that was a medium-chain fatty acid, mystic acid

(MAc) or lauric acid (LAc), to a mixture consisting of sodium lauryl–dioxyethylene
sulfate (SLES) and a zwitterionic surfactant, cocamidopropyl betaine (CAPB) (50).
Addition of the fatty acid surfactant to this mixture caused a substantial increase in
dilational modulus which was explained by the formation of a surface-condensed
phase of fatty acid molecules in the surface adsorption layer.
The permeability results obtained using the diminishing bubble experiments (which
related the change in bubble size to time) are shown in Fig. 7.20, and these plots enable
a comparison to be made of the different systems with and without the addition of the
two fatty acids MAc and LAc.
These results indicate that the rate of diffusion was substantially reduced in the
presence of the fatty acids, which exhibited a higher surface modulus, and the greater
reduction occurred for the MAc. However, it was difficult to confirm that the rheological
properties were playing a key role in retarding the gas diffusion, since the adsorbed fatty
acid structured film alone would act as a barrier and reduce gas flow.
These initial studies were extended by Tcholakova and coworkers (51) using aminon
L-02 Bis(2-hydroxyethyl)-lauramide as the added co-surfactants, instead of the fatty
acids in order to give a low surface modulus. The permeability data again determined
using both bulk foam experiments and the diminishing bubble method, and the results
from the two methods gave good agreement. The results of the bubble shrinking process
for the different systems indicated that the systems with high surface modulus tend to
give slower rates of diffusion. However, Langmuir trough experiments indicated the
surface tension of the shrinking and expanding bubble was low; this tended to suggest
that interfacial elasticity did not play a major influence on the diffusion rate.
An alternative mechanism was suggested to explain the decrease in gas diffusion
which considered the formation of a surface-condensed phase (solid rather than fluid
molecular packing) on the bubble surface, as illustrated in Fig. 7.21. This acted as
a resistance to the diffusion of gas molecules across the film.

(a) Solid adsorption layer (b) Fluid adsorption layer

GAS GAS

P1 P2 P1 P2

JGAS JGAS

Fig. 7.21 Presentation of flux of dissolved gas across a foam film stabilized by surfactant with (a) high
surface modulus and (b) low surface modulus. The formation of surface-condensed phase of
surfactant molecules by myristic acid leads to a very low solubility and diffusivity of the dissolved
gas molecules in the condensed adsorption layers on the foam film surface. From ref (51).

200
WPI = (whey protein isolate)

150
Rb (μm)

Soy β-lacto
100
glycinin globulin

Oval-
50 WPI bumin Gelatin
Sodium
caseinate
0
0 50 100 150 200 250
r (min)
Fig. 7.22 Plot of bubble radius versus time for isolated bubbles near a planar air/water interface. Stabilized
by different proteins at pH 7. From ref (52).

Dickenson and coworkers (52) concluded that irreversibly adsorbed globular

proteins such as ovalbumin, which form highly viscoelastic ﬁlms at the air/water
interface, were capable of slowing down bubble shrinkage/expansion but not pre-
venting it altogether. In this study, the rate of shrinkage of air bubbles beneath
a planar air/water interface stabilized by four different types of proteins (whey
protein isolate, sodium caseinate, gelatin, β-lactoglobulin) was measured, and it
was found that fairly fast shrinkage of bubbles occurred in all cases, as shown in
Fig. 7.22. Within one hour the bubble size was reduced to about 1 µm with no
signiﬁcant difference in rates. From the data, dilational modulus values were calcu-
lated for the proteins, and values ranged from 2.3 for gelatin to 12.5 mNm−1 for
ovalbumin.

7.8 Stability by increase in bulk viscosity

Information on foam drainage rates is important in the design of many processes,

particularly in the beverage and food industry and, as a general rule, the drainage rate
of foams may be decreased by increasing the bulk viscosity of the liquid from which the
foam is prepared. Overall, the more viscous the liquid, the slower is the downward ﬂow
of liquid between the bubbles. This may be achieved in aqueous systems by simply
adding a solute such as glycerol, liquid parafﬁn or polyoxyethylene (high molecular
weight (MW)) to the aqueous phase. Alternatively, the phase of the aqueous surfactant
solution can be changed by adding electrolyte, thus producing a gel network. For many
practical systems, such as food foams, the drainage can be easily halted by hydrous gel
formation and the lamella stabilized at relatively large thicknesses (≈ 1 µm).

7.9 Stability control in aerated food systems

Although the basic framework for studying gas diffusion to the atmosphere from single
bubbles is fairly well understood, there has been only limited work carried out to
understand the gas diffusion in real aerated food systems. These usually consist of well-
dispersed, high gas fraction systems with a large number of bubbles. In 2004, Dutta and
coworkers (53) generated two aerated food products by whipping mesophase mixed
dispersions (containing 33% sugar 65% water) with a 2% surfactant blend consisting of
sucrose stearate together with either propylene glycol stearate (PPGS) or triglycerol
stearate (TGS). The foams were allowed to stand, and the disproportionation process
was evaluated by measuring the change in bubble size using video frames and micro-
scopy. In addition, overrun, which was the decrease in the volume fraction of air in the
foam, was measured. This could be considered as the difference in the degree of air lost
to the atmosphere between the two systems due to the difference in diffusion rate in the
two systems. The results are shown in Fig. 7.23(a) for the TGS-sucrose stearate system

(a) (b)
20 30
Volume fraction

Volume fraction

After 1 week 1 week After 1 week 1 week

of system (%)

15 25°C 25°C
whipping 10°C 20 whipping 10°C

10
10
5

0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 80
Bubble diameter (microns) Bubble diameter (microns)
Fig. 7.23 The long-term stability of (a) triglycerol stearate surfactant system and (b) propylene glycol
stearate surfactant system. From ref (53).

and in Fig. 7.23(b) for the PPGS-sucrose stearate system. These samples were prepared
immediately after whipping and after a period of one week.
For the TGS system, the volume fraction did not change drastically after a week,
whereas the PPGS was found to be more unstable. Also, the temperature of storage did
not affect the size distribution to a great extent. The decrease in the overrun was
explained by the diffusion of air from the bubbles to the atmosphere and was found to
be higher at higher temperatures.
Two different types of models were developed to account for this behavior. The first
model described the gas diffusion in terms of an inter-bubble diffusion occurring
between bubbles of different sizes and driven by the difference in capillary pressure.
The second model described the diffusion process in terms of the gas flowing from the
larger bubbles to the atmosphere. Interestingly, the experimental results obtained from
this study did not agree with the prediction of either models and it was necessary to
construct a new gas diffusion model based on the combination of both models, which
assumed that both processes occurred simultaneously. This combined diffusion model
was found to give the most satisfactory fit to the experimental data.

7.10 Stratiﬁcation

Johnnott (54) in 2006 and Perrin (55) in 1918 initially demonstrated that at surfactant
concentrations beyond the CMC, organized molecular structures can be formed within
thin films. This caused thinning of the film through a stepwise drainage mechanism
known as stratification. It has been well established over the past 50 years that stratifica-
tion can occur in dispersions of surfactant micelles, silica particles, microemulsions,
globular proteins polymeric macromolecules and colloidal nanoparticles. Extended
lifetimes have been observed for stratificating of liquid films, resulting in higher shelf-
stability of foams. On thinning of the film, the particulates are forced into the restricted
volume of the film which delays the drainage process and stabilises foam lamellae.
The different steps in the drainage of the thin film containing a surfactant (above the
CMC) are shown in Fig. 7.24(a) and for films containing low levels of surfactant in
Fig. 7.24(b).
Organized structures can be formed from micelles produced from both ionic
and nonionic surfactants in the aqueous solution and these provide an additional con-
tribution to the disjoining pressure. These micelle layers flow out of the film to the
Plateau borders, thus causing stepwise thinning, with each step corresponding to
specific black spot concentrations (Cb). The phenomenon was earlier summarized by
Ivan and Dimitrov (57), and several early experiments by Wasan and coworkers (58, 59,
60) showed that the ordering was caused by the interaction (via repulsive forces)
of surfactant micelles or colloidal particles with narrow size distributions which were
forced into the restricted volume of the film. These workers clearly showed that the
ordered microstructure could play an important role in stabilizing foam lamellae.
They suggested that the driving force for the stepwise thinning of the film was
caused by the gradient of the chemical potential of the micelles at the film’s periphery.

(a) Films with micelles (b) Films without micelles

n=5 701 Å

n=4 592 Å

Thinning Thinning
n=3 483 Å

n=2 374 Å

n=1 261 Å

n=0 162 Å

Interferogram Interferogram
Stepwise thinning First or
common black
Film thickness

Film thickness

10 nm
Second or
micellar Newton black
diameter

Time Time
Fig. 7.24 (a) Stratiﬁcation of thinning mechanism at high surfactant concentration (> CMC) and the
main stages in the evolution of a thin ﬁlm and (b) thinning at low surfactant concentrations
(< CMC). From ref (56).

Both the experimental and theoretical aspects of these studies were summarized in 2007
by Wasan and Nikolov (61).
In 1992, Bergeron and Radke (62, 63) determined disjoining pressure isotherms for
single isolated foam films stabilized by SDS at concentrations greater than the CMC.
They reported that the oscillating component extended out to film thicknesses as large as
50 nm and that the discrete change in film thickness for each black film transition ranged
from 6 to 10 nm and depended on the ionic strength and surfactant concentration. Studies
of the oscillatory form of the disjoining pressure permitted quantitative interpretation of
the stepwise thinning behavior.

7.10.1 Hole formation and the diffusion osmotic mechanism

In the stratiﬁed thinning process, the formation of a black spot in the ﬁlm was considered
to be associated with the dynamic removal of a layer of micellar species, which was
considered to be initiated by the formation of a hole and subsequent sheeting of a hole
which occurs at each step. Bergeron and coworkers (64) developed a nonlinear
hydrodynamic stability analysis that modeled the dynamics of the hole formation and

Fig. 7.25 The layer-by-layer thinning of the micellar films is triggered by the formation of black spots
inside the film. One can distinguish up to five stratified layers shown by photocurrent
time plot. From ref (65).

sheeting by taking into account an equilibrium oscillating structured component of the

disjoining pressure. They attributed the initiation of a hole in the film to the nonlinear
growth of hydrodynamic instability that occurred under the action of a constant capillary
pressure and oscillating disjoining pressure. The subsequent growth of the hole was
explained by the outward fluid flow within the inhomogeneous thin film as radial
pressure gradients developed from curvature variations and viscous resistance to flow.
In the final stage, a small black spot appears in the film which contained only one layer of
particles and continues to expand until the film ruptures. The black spot expands because
the particles leave the films and the expansion rate can be used as a measure of exodus
from film. The complete thinning process that occurs through stepwise transitions is
summarized in Fig. 7.25.
The black spot expansion during the last transition was found to be dependent on film
size and it was found that the area of black spot expanded linearly with time. A vacancy
diffusion osmotic (DO) mechanism of film thinning was proposed by Kralchevsky and
coworkers (59). In this theory, the thickness transformation from hn to hn-1, where n is
the number of micellar layers, occurs due to the decrease in free energy, and it was
assumed the film thickness transition was in a metastable state. The process of the
micelles leaving the film at each step resulted from the osmotic pressure gradient and
involves the provision of vacancies by a condensation mechanism controlled by the film
size for a fixed micellar concentration. However, although this theory has been used to
account for the stratification of SDS and CTAB micellar solutions and also for charged

Fig. 7.26 Interdroplet interactions and resulting oscillating structural forces within the thin liquid ﬁlm
separating the bubbles. Both attraction depletion forces and structural barriers occur between
bubbles. From ref (69).

particles, it does not fit the nonionics where the transition is a reversible process. In fact,
for the nonionics, the energy of both stable states must be almost identical.
Several theoretical models have been developed over the years by Wasan and co-
workers (66, 67, 68, 69, 70, 71) during the period 2001–2004 to rationalize the experi-
mental results. Generally, the oscillation component comprised an attractive depletion
component opposing the repulsive structural energy barrier inside the film. In the case of
very thin intervening film when the thickness is less than the micellar size, the micelles
became excluded from the film, and osmotic pressure inside the film is reduced. This
causes an attractive depletion force (i.e. Asakura–Osawa depletion attraction). However,
when the film thickness is of the order of several micellar diameters, the micelles are
ordered in the confines of the film surfaces, thereby resulting in a structural energy
barrier separating (stabilizing) the bubbles (Fig. 7.26).
Further studies were carried out based on statistical mechanics, and numerical
Monte Carlo simulations have been performed using an effective one-component
fluid potential model that incorporated particle hard-core repulsion. Both the
screened Coulombic electrostatic interaction and the entropic contribution due to
the discrete nature of the solvent and the finite size of the electrolyte ions were
included in these models. Concise formalism was developed based on the general-
ization of Ornstein–Zernike equations for fluid mixtures, and it was found that in
hard-sphere colloidal suspension, comprised of larger entities, the solvent molecules

enhance the structural forces both among the larger particles themselves and between
them and the ﬁlm interfaces (68, 69, 70).

7.10.2 Reversible stratiﬁcation behavior in nonionic surfactants

Stratification is well known to be an important mechanism for many nonionic foams.
Niskolov and Wasan and coworkers (69) carried out stratification experiments using
curved and flat films which were stabilized by nonionic ethoxylated alcohols (containing
15–16 n-carbons chain length and 13 ethylene oxide groups). Experiments were carried
out at three concentrations: 2, 4 and 8% corresponding to 3.25, 6.50 and 13.00 times
CMC. The capillary force balance apparatus was used in conjunction with combined
differential and common interferometric methods, and this enabled the film curvature,
film radius, capillary pressure and film thickness to be monitored simultaneously.
In addition, the effect of film size on the lamella thickness transition was investigated.
In Fig. 7.27(a) and (b), the stratification is shown for micellar film made from surfactant
concentration at 3.25 CMC, with two films of different sizes.
With the smaller film (diameter 17.5 micron and surface area 2.6 × 10−4 cm2) as
shown in Fig. 7.27(a), two stepwise thickness transitions were observed, one at
a thicknesses of 42.7 nm and one at a thickness of 33.2 nm; the amplitude of
thickness transition is about 9 nm which is equal to an effective micelle diameter.
After these two thickness transitions, the film remains stable at 25 nm with one
micellar layer inside it. However, at the greater film diameter (250 microns
with area of 5.9 × 10−4 cm2 and a capillary pressure of 38.5 Pa) as shown in
Fig. 7.27(b), one more stepwise thickness is observed. It was also observed that as
the film thickness decreases, the time for the next thickness stepwise transition to
occur increases and also that the stepwise transition occurs more rapidly for the

(a) (b)
Film area: S = 2.6 10–4 cm2 Film area: S = 5.9 10–4 cm2
Capillary pressure: 40.7 Pa Capillary pressure: 38.5 Pa
Photocurrent (film thickness)
Photocurrent (film thickness)

42.7 nm
42.7 nm
33.2 nm
33.2 nm
25.0 nm 25.0 nm

17.0 nm

Time (min) Time (min)

Fig. 7.27 Photocurrent versus interferogram of the thinning of a curved foam film at a surfactant
concentration of 2% (3.25 × CMC) depecting the effect of film size on film stepwise thinning. Film
areas (a) 2.6 x 10–4 and (b) 5.9 x 10–4 cm2. From ref (67, 69).

larger film. In addition, it was observed that when the thickness is reduced from 250
to 175 microns, the film slowly increases in thickness from 17 back to 25 nm (from
one micellar layer to two micellar layers), indicating that micellar lamellar layer
thinning occurred as a reversible process. This unusual thinning behavior of micellar
nonionic films could not be explained by the previously proposed diffusive-osmotic
mechanism which had been successfully applied to anionic or cationic micellar
films. For charged ionic surfactants, the formation of black spots in micellar films
was based on a micellar vacancy diffusive-osmotic mechanism, which assumed that
the film at each stepwise transition is in a metastable state. In fact, for the nonionics,
the energy of both stable states must be almost same.
Generally, it was concluded from these studies that the stability of the micellar films is
governed by the film size (the bubble size), and the capillary pressure but the concept of
disjoining pressure isotherm alone cannot predict film thickness stability. Experiments
show that film stability depends more on the lamella or film size and micelle concentra-
tion and less on the capillary pressure.

7.10.3 Stratiﬁcation in charged surfactant systems

In the case of foam films formed from micellar solutions of nonionic surfactants
(uncharged micelles), the height of the stratification layer (h1 – h2 = Δh) was
considered to be equal to the diameter of a hard sphere but slightly decreasing
with the rise of the particle volume fraction. However, with ionic micelles, the step
height is greater than the micelle hydrodynamic diameter, and it is accepted that
another double-layer thickness counterion atmosphere needs to be considered in
estimating the thickness. Electrostatic interaction between charged micelles plays
a key role during the thinning process.
Although this is a physically correct interpretation, a more detailed model was
developed by Danev and coworkers (72) for charged surfactant systems in which the
step height and final thickness of the film was related to the micelle size. Initially, these
workers carried out stepwise stratification experiments using a Schedudko Exerowa
cell (see Chapter 3) for an anionic and two cationic surfactant systems (SDS CTAB and
cetyl pyridinium chloride (CPC)) at concentrations above the CMC. From the results,
both values of step height and final thickness of the films could be related to the bulk
surfactant concentrations for the three systems. The step heights were found to be
equal: h3 – h2 = h1 – h0 = Δh which enabled data to be collected in which Δh and h0
could be related to the surfactant concentration. Theoretical models could then be
constructed to interpret this dependency. Two approaches were considered; first an
energy approach where the step height was identified with the effective diameter of
charged micelle. The charge on films and micelles was calculated using a charge
regulation model. Also, a second approach was attempted based on osmotic pressure
in which the step height was dependent on the number density of the micelles in bulk
solution.
With regard to the distribution of micelles in the systems, three models were tested:
a Poisson–Boltzmann model, a Jellium approximation (JA), which assumes a uniform

charge distribution, and a cell model. The JA model assumes that micelle concentration
was uniformly distributed, despite the field of electric double layers. It was found that the
JA gave the best agreement between theory and experiment. In fact, two theoretical
approaches which were based on energy and osmotic pressure were found to give
reasonable agreement. The experimental data providing the suspension of charged
micelles was represented as Jellium. This model proved to be useful for determining
the aggregate number of ionic surfactant micelle from the experimental heights of the
steps. It was also concluded from theory (based on the dispersion of charged particles
behaving as jellium) and experiment that the thinnest stable films (h0) experimentally
observed were thick enough to contain micelles (at very low concentration) to ensure the
osmotic balance between the film and bulk solution.

7.10.4 Stratiﬁcation in polydispersed systems

In many practical industrial systems, the particles are rarely monodispersed, and Wasan
and coworkers (65, 73) have shown from experiments and calculations that the poly-
dispersity has a pronounced effect on stratification and film stability and can cause
a weakening effect on the particle layering (structural barrier) and a reduction of
foaminess. Stratification experiments were carried out with bidispersed mixtures pre-
pared from of mono-dispersed particles (8% v/v of 8 nm sized hydrophilic colloidal
silica particles with an addition of 2% v/v of 100 nm particles). The effective volume
fraction of particles was about 0.35. Initially, stratification experiments were carried out
using films of different sizes (diameters 133 and 105 µm) for these bidispersed systems,
and the change in size of the black spot expansion rate of the last transition was recorded
(Fig. 7.28). These plots show that black spot expansion rate and area expand linearly

Film diameter = 105 μm

3500
Film diameter = 133 μm Slope = 1907 μm2/s
Slope = 3069 μm2/s

2500
Area (mm2)

1500

500

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Time (s)
Fig 7.28 Black spot expansion bidispersed mixtures at different ﬁlm sizes. From ref (63).

Film diameter = 135 μm

3500 8 nm + 100 nm (bidispersed)

Slope = 3069 μm2/s

2500
Area (μm2)

1500 8 nm (monodispersed)
Slope = 356 μm2/s

500

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

Time (s)
Fig. 7.29 Black spot expansion for monodispersed and bidispersed cases at comparable ﬁlm
sizes. From ref (63).

with time for both systems, but rate of expansion of the bidispersed systems was the
greatest for the large film sizes.
In a second series of experiments, the spot expansion rate for monodispersed system
was compared with a bidispersed system for films of about the same diameter (135
microns), and the results are shown in Fig. 7.29. In this case, it can be seen that the
monodispersed particles and the bidispersed particles left the film more rapidly.
Generally, it was concluded from these studies that the rate of particle movement from
the film to the bulk was the lowest for the monodispersed system, intermediate for the
polydispersed (prepared by mixing three different sized particles) and the highest for the
bidispersed system, and in general, monodispersed particles exhibit slower expulsion
and more stable films. However, in case of the experiments in curved and plain films, an
increased particle efflux from the film to the meniscus was reported for the polydispersed
systems. It was also found that the black spot area expands linearly with time and the
larger films exhibit faster rates of spot expansion which was explained by the DO model.
The influence of polydispersity on the structure barrier oscillation and oscillation forces
was discussed by Wasan and coworkers (65), and a representative picture of the inter-
action is shown in Fig. 7.30.
It was stressed that confined in-layer structures in films were essential for retarding
thinning and that polydispersity leads to the weakening of particle laying (decreasing in
the structural barrier) and film stability. But, in addition, it is the degree of polydispersity
that plays an important role in the height of the energy barrier. The interactions between
two approaching bubbles in a polydispersed system are shown in Fig. 7.30(a),
where initially a weak barrier (Us) is encountered but on further thinning smaller
particles are ejected from the film (Fig. 7.30(b)). This results in a reduction in poly-
dispersity and an improvement in layer structuring which causes the height of the
structural barrier to increase. However, on reaching a critical thickness the particles
are finally ejected and a depletion well is encountered. In Fig. 7.30(c), the relationship

(a) (b)
Attraction Repulsive structural

between two large particles

depletion barrier stabilizer

Potential of mean force

Us well

(d)
40
0.2

0
Height of structural barrier
U / kT

40 V% monodispersed 0.1
–40 40 V% with 30 V% polydispersity
[Polydispersity = (std. deviation)(mean size)]

–80
0 1 2 3 4 5 6 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Film thickness,
Polydispersity
scaled by particle diameter
Fig. 7.30 Effect of particle polydispersity on the height of the structural barrier between ﬁlm
surfaces. From ref (63).

between film thickness and the disjoining pressure is illustrated for a monodispersed
and polydispersed system. In both cases, the oscillating disjoining pressure is
increased as the film thickness is reduced for both systems. The height of the
barrier is a measure of the film stabilizing effect, and in Fig. 7.30(d), it is related
to the degree of polydispersity.

7.11 Stabilization by liquid crystals

It is well known that liquid crystals can adsorb at the bubble interface and stabilize
both aqueous and non-aqueous foam systems. At higher surfactant concentrations,
the liquid crystalline surface phase is often in equilibrium with a bulk isotropic
phase. The stability in non-aqueous systems is covered in Chapter 9. Frequently,
liquid crystals have been formed in aqueous mixed surfactant systems, for exam-
ple, by the addition of small amounts of a nonionic surfactant to an anionic
surfactant, which can lead to enhanced foam stability. In addition, there are several
possible explanations to account for the increase in foam stability caused by the
precipitation or formation of crystalline or structural aggregates in the solution.
For example, they may cause a reduction in hydrodynamic drainage or retardation
in interfacial drainage caused by viscous layers or an increase in the mechanical

Time (min)
0 50 100 150 200 250 300 350

C12EO9 C12EO7
Drainage volume (mL)

2 C12EO5 C12EO3

0 1000 2000 3000 4000 5000 6000 7000

Time (min)
Fig. 7.31 Liquid drainage from foams stabilized solely by C12 En type surfactant (30wt%). From ref (77).

strength of a liquid film, which may increase the resistance between bubbles. Also,
the accumulation of the liquid crystal phase in the lamellae film may reduce the
diffusion rate of entrapped gas. In addition, there is a possibility that accumulation
in Plateau borders can distort the radius of curvature which may influence the
Laplace pressure. Although the liquid crystals may act as a reservoir of surfactant,
they are unlikely to enhance the Gibbs–Marangoni elasticity since early studies
have indicated that the dispersed liquid crystalline phase, rather than micelles,
exhibits the diminished rates of transport to the bubble interface. This would
suggest that relatively low levels of dynamic adsorption would lead to
a lowering of foamability (74).
Novales and coworkers (75) in 2010 carried out foaming studies on fatty
acid–lysine salts in aqueous solution. The alkyl chain length was varied from
dodecyl to stearic and an attempt was made to relate the foamability to the phase
behavior. Extremely stable foams were obtained with palmitic acid/lysine salts, but
for other chain alkyl length poor foams or no foaming was reported. It was found
that the structural aggregates played an important role in foaming, and quantitative
information on the aggregate structure could be obtained using a transmission
electron microscope, differential scanning calorimetry, solid state NMR and small-
angle neutron scattering. In aqueous solution, the lysine salt of the dodecyl chain
gave an isotropic micellar solution, whereas for longer alkyl chains, the fatty acid
vesicles were embedded in a lamellar arrangement that passes from gel to fluid state
on aging or upon heating. At low concentration no significant structure has been
detected.
Shrestha and coworkers (76) in 2006 studied the foaming characteristics of
penta-glycerol monostearate (C18G5) and penta-glycerol monoleate (C18:1G5) in
dilute aqueous solution. Both surfactants showed an increase in foaming with

concentration and foams prepared from C18:1G5 shown to be less stable than foam
prepared from C18G5. Also, dispersions of ɑ particles and Lɑ phase could be
detected in the water-rich regions for both systems but, it was not possible to
explain this difference in foaming, and no correlation between dynamic interfacial
properties and foaming could be established. Chen and coworkers (77) showed
that the stability of foams produced from the series of low molecular weight
polyoxyethylene-type nonionic surfactants (C12EOn) could also be explained by
the formation of liquid crystals. In these experiments, the foam stability was
evaluated from the drainage profiles (the volume of liquid drained plotted as
a function of time). A wide range of profiles was detected, and the stability
initially increased with increments of concentration for each nonionic. It was
found that maximum foamability occurred at 10 w% except for C12EOn which
occurred at 1 wt%. In Fig. 7.31, the drainage volumes of foams stabilized by the
different nonionic surfactants in the series C12En are shown corresponding to 30 w%
surfactant concentration. “S”-shaped profiles are shown and three stages in the drainage
curves were identified: an initial stable stage, followed by a rapid gravity-driven liquid
drainage region which accounted for removal of 90% of the liquid and the final
thinning of the foam films.
The viscosities and microstructures were also explored; for C12EO3 and C12EO5 the
maximum stability occurred at 30 wt% structures, which was explained by the presence
of high concentrations of lamellar liquid crystals adsorbed at the interface. These were
clearly visible between bubbles, and the foams and were stable for about 20 hours. In the
case of C12EO7 and C12EO9 the stability was considerably lower; it was only for
10 minutes and no liquid crystals were detected.

7.12 Stabilization by emulsion and pseudo-emulsion ﬁlms

Wasan and coworkers (78) investigated the influence of oil (in the micellar envir-
onment) on the stability of foam. Two different types of emulsified oil systems were
studied which consisted of (a) a microemulsion (solubilized within the micelle) and
(b) a macroemulsion. It was found that in each case the foam stability was affected
by a completely different mechanism. In the first case, where the foam film contain-
ing oil, it solubilized within the micelle to form a microemulsion and the normal
micellar interactions are changed. It had been earlier demonstrated that micellar
structuring causes stepwise thinning due to layer-by-layer expulsion of micelles and
that this effect was found to inhibit drainage and increase the foam stability.
Generally, this stratification phenomenon was found to be inhibited by the oil
solubilized within the micelle, which decreased the micelle volume (representing
a decrease in the repulsion between the micelles). In the case of the macroemulsified
oil system, the important role of the so-called pseudo-emulsion film (formed
between the air/water interface and an approaching oil droplet) in the stability of
the aqueous foaming system was emphasized (Fig. 7.32).

Pseudo-emulsion film

Oil drops

Plateau
border

Emulsion film
Air bubble
Fig. 7.32 Illustration of a macroemulsified oil system. The drainage of the film may be reduced due to
accumulation of emulsified oil droplets within the Plateau borders. The formation of the emulsion
film and pseudo-emulsion film are indicated. Factors affecting the foam stability were found to be
oil volume fraction, drop size and oil phase density.

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