CHAPTER 8

Foam Breaking in Aqueous Systems

Robert J. Pugh
Institute for Surface Chemistry, Stockholm, Sweden

1 Introduction 143 2.6 Droplets and oil lenses 148

1.1 Background 143 2.7 Superspreaders 149
1.2 Commercial chemical 2.8 Elimination of the surface tension
antifoamers 145 gradients 150
2 Types of Antifoamers and Mechanisms . . . 147 2.9 Particles 150
2.1 Liquids (inhibitors) which may 2.10 Mixtures of particles and oils 151
lower the viscosity and increase 2.11 Emulsion and pseudo-emulsion
drainage 147 films 152
2.2 Surfactant-precipitation antifoamers . 147 2.12 Electrolytes 154
2.3 Solubilized chemicals 147 3 Ageing Effects with Chemical
2.4 Defoamering caused by changes in Defoamers 154
stability of the micellar 4 Physical Methods of Defoaming 155
aggregates 148 4.1 Ultrasonics 155
2.5 Cloud-point defoamers 148 5 References 156

1 INTRODUCTION added to eliminate an existing foam. However, today this

distinction is confusing since many chemical additives
1.1 Background appear to cover both roles.
There are at least sixty defoamer suppliers listed
Antifoamers or defoamers are a group of important spe- and many of these companies provide both technical
cialized chemicals which are used throughout a range and sales services. The market is over 150000 metric
of industrial processes where foaming causes problems, tons per year in North America for the paper industry
e.g. in the production of paper, pharmaceuticals, materi- alone, which is about the same as for the rest of the
als and coatings, etc., and in oil recovery. In many indus- world. Defoamer economics are usually measured as
trial plants and sites (distillation columns, pipes, boilers, the cost per unit of product manufactured, e.g., the
water discharges, etc.) foams can reduce the process cost per litre of paint, the cost per ton of paper or the
efficiency and cause environmental problems in waste cost per batch of chemical produced. In many cases,
discharge. Antifoamers are also used as formulation this results in the use of relatively small amounts of
additives in the preparation of commercial products such expensive defoamer, which thus gives a lower cost per
as detergents, paints, foodstuffs, beer, tomato juice, etc. unit product. However, although expensive antifoamers
Early definitions of antifoamers referred to the chemicals may be more efficient, the wastage may be high, so that
which were added to the aqueous phase, prior to foam it is often cheaper to use an inexpensive defoamer. In
formation, which act to prevent foam formation (foam many industries, special equipment has been developed
inhibitors), while defoamers were referred to chemicals to control the minimum defoamer consumption.

Handbook of Applied Surface and Colloid Chemistry. Edited by Krister Holmberg

ISBN 0471 490830 © 2001 John Wiley & Sons, Ltd
 At present, the most effective and versatile chemical liquids, oils, gels, hydrophobic particles, emulsions and
antifoamers are mixtures. In fact, modern commercial microemulsions. A typical list of single-system chemi-
formulations often contain mixtures of silicone oils, sil- cal antifoamers might include tributyl phosphate (TBP),
icone surfactants or silica gels, with possibly two or polydimethylsiloxane (PDMS), alkyl amines, amides,
more types of dispersed hydrophobic aggregates (with thioethers, mineral and vegetable oils, waxes, silicone
sizes around 1 micron, specific gravity 1.0-1.3, with fluids, fatty acid esters ("Span 20"), alcohols (octanol),
rough fractal shapes). These mixed-type antifoamers are fatty acids and their derivatives (tall oil, aluminium
very effective at low concentrations (10-1000 ppm) and stearate, and the calcium, aluminium and zinc salts of
are widely used. The (hydrophobic) particles may be fatty acids) and many other different types of parti-
hydrophobized silica or glass and are often referred cles. The different types of chemicals and the phys-
to as the activator, with the hydrocarbon or poly- ical methods used in defoaming are summarized in
dimethylsiloxane (PDMS) liquid or oil being referred to Figure 8.1.
as the carrier. However, less expensive single-system It is important to note that antifoaming occurs
antifoamers are commonly used, and these exist in by a range of both physical and chemical mecha-
many different forms such as soluble liquids, insoluble nisms. Many of these will be discussed in detail in

Re-engineering of pipe work and Use of high-pressure Use of Paddles or

tanks to reduce turbulence in flow, water sprayed on propellors to break foam
or to decrease the pressure surface, vapour or
on pumping stream of air, heat,etc. Use of cyclonic devices,
or flow through a narrow
Rough hydrophobic gap to separate gases
particles (PTFE, from liquids, or to remove
hydrophobized silica etc.); particles
size and degree of
hydrophobicity critical Ultrasonics Vapours (low MW
alcohols or ketones),
Smooth hydrophobic benzene, hexane,
spherical particles heptane, octane
(powders) and dodecane

Emulsions (contain 5-35%

actives); upper temperature
limit of fatty acid esters, waxei Metal cations, such
Foam as Ca2+ or Mg2+ to
fatty alcohols, PEG esters of destroyed
di-fatty acids, ethanolamides, precipitate anionic
by.... soaps (fatty acids,
alkylamides, etc.
xanthates, etc.)

Formulated microemulsions
Tributyl phosphate, (ethyleneoxide condensates)
methylisobutyl carbinol,
fatty acid esters and alkyl
phosphates k
Hydrophobic particles
Gels, pastes and dispersed in an oil or silicone-
bricks (silicones) oil-based liquid; synergistic
Soluble liquids effects (hydrophobized silica
(silicones) of high in polydimethylsiloxane).
viscosity; must be Cloud-point defoamers; Specific gravity and surface
pumpable. Precipation block copolymers; tension of oil are important
may occur at increased "Pluronics", "Poloxamers"
processing temperatures (PEO-PPO, PPO-PEO-PPO, Insoluble oil-foaming droplets, animal fats,
PEO-PPO-PEO, silicone-based soya oil, mineral seal oil, diesel oil,
copolymers, silicone polyethers) corn oil, etc.

Figure 8.1. Chemical and physical methods of foam breaking; the latter, which are usually of low efficiency, are indicated in
italic script
 Coating-bubble spots formed Bubbles breaking on fibre web
leaves behind solids (fibres,
fines, pigments, pitch, etc.)

Drainage efficiency
of paper machine is Reduced effectiveness of pumps
reduced by channelling and tanks (cavitation causes
problems in metering accurately)

Difficult to blend Problems

caused by Reduced output and
liquid from foams cut down on residence
into bulk of stock foams
time in refiners, mixing
and bleaching towers

Foam on surface of effluent; BOD of effluent reduced Overflow, loss of material, "mess"
causes environmental problems (reducing O2 uptake) and safely hazards. Other solid
particles, fines, fillers, etc.,
concentrated in foam

Figure 8.2. Problems caused by foams in the pulp and paper industry

the following sections. In addition, the most important and with a lower density than water and lubricating
use of antifoamers is in the pulp and paper indus- oils. Other special polymers such as perfluorinated
try, where foams are produced at various stages in hydrocarbons are also involatile and have low surface
the processing. Foaming causes many different types of tensions.
problems, which must be eliminated by the use of effec- However, in cases where the surface tension of the
tive antifoaming agents. Some of these problems are substrate is no more than about 20 mN/m less than that
outlined in Figure 8.2. Modern paper mills need easy- of water, it is then not necessary to use silicone or
to-pump, easy-to-mix, stable-on-storage, cost-effective perfluorinated hydrocarbon foam inhibitors (with such
antifoamers. extreme surface tensions) and cheaper chemicals can be
employed, such as glyceryl esters in the form of "pork",
fat or butter. If fats prove ineffective, then synthetic
1.2 Commercial chemical antifoamers esters of polyhydric alcohols can be used.
Since such a wide range of antifoaming chemicals
The patent literature contains a large range of chemicals are employed, it is therefore not altogether surprising
which have been recommended as antifoamers, ranging that so many alternative mechanisms have been pro-
from simple compounds, such as octyl alcohol, to posed to explain their action. Recently, many extensive
more sophisticated mixtures of antifoamers, which are experimental studies dealing with the basic mechanisms
sometimes required in special applications. From a of antifoam action have been reported. It also appears
universal viewpoint, polydimethylsiloxanes are probably that there may be several different mechanisms occur-
the most expensive, yet the most effective materials ring concurrently in some systems. Over the years, this
for inhibiting foam. Such compounds are involatile and has caused many different theories to be put forward,
have extremely low surface tensions and low interfacial depending on the type of antifoaming agent being used.
tensions against water. The surface tensions of liquid However, overall it has been generally concluded that
hydrocarbons are usually between 25 and 30 mN/m the mode of action of oil droplets, hydrophobic parti-
and since the silicones have lower surface tensions, cles and mixtures of hydrophobic particles/oils must first
they then can easily enter the hydrocarbon substrate. In involve the emergence of this phase from bulk solution
addition, they are chemically inert, insoluble in water, into the air/water interface. This first stage of the process
 Drop entry
Small barrier

Monolayer
spreading S might be Bridging
Bridging
negative

Duplex film
(bulk spreading) De-wetting Stretching

Figure 8.3. Mechanisms for foam film rupture by antifoam particle (a) spreading-fluid entrapment; (b) bridging de-wetting;
(c) stretching bridging. In all of the mechanisms, the first step is the particle entry, which requires a positive entry coefficient
and a small force barrier, thus enabling thinning of the thin film to occur. The spreading (a) leads to a Marangoni-driven flow of
water, so causing local thinning. Alternatively, de-wetting (b) or stretching (c) could also lead to a rupture of the foam lamella
(adapted from ref. (2)), reprinted with permission from American Chemical Society

is characterized by an entry coefficient (E) which must (i) Why do antifoamers become less efficient with
have a value > 0. This aspect will be discussed later in time?
this review. (ii) What is the effect of the particle size, shape,
The entry step is followed by a fluid entrainment interfacial properties, specific gravity and concen-
or bridging process, which involves the antifoam oil tration on the performance?
spreading rapidly over the lamella surfaces, which may (iii) What is the influence of the antifoamer viscos-
cause a Marangoni (1) driven flow of liquid in the ity?
foam film (fluid entrainment). The enhanced drainage (iv) What is the influence of surface tension and
is due to capillary effects and this can lead to film specific gravity of the oil?
rupture, by bridging the aqueous films by a de-wetting (v) What is the effect of the adsorption of surfactant
mechanism. A bridging/stretching mechanisms have also on the antifoamer additive?
been recently suggested (2). These different types of (vi) To what extent is there a synergistic effect
mechanisms are outlined in Figure 8.3. For mixtures between the particle and liquid, and can this be
of hydrophobic particles and oils, the particles must enhanced?
rupture the oil/water pseudo-emulsion film to facilitate
(vii) What is the influence of the size, fractal charac-
the process of the emergence of the oil droplets into
teristics and hydrophobicity of the particles in the
the air/water interface. This is a necessary precursor
mixed antifoamer?
step in the formation of an unstable bridging-oil-drop
(viii) What is the concentration of hydrophobic particles
configuration.
in the oil which gives the most effective perfor-
The above description presents a broad generalization
of the theoretical mechanisms that have been proposed, mance?
although and there are many important problems which
still require more intensive studies, in order to improve In the following sections, some of these problems are
the efficiency of antifoamers. These are based on the discussed, together with a more detailed review of the
following questions: theoretical mechanisms that are involved.
2 TYPES OF ANTIFOAMERS AND 2.2 Surfactant-precipitation antifoamers
MECHANISMS
Foam films stabilized by anionic surfactants can be
2.1 Liquids (inhibitors) which may lower destroyed by the addition of an oppositely charged inor-
the viscosity and increase drainage ganic species or near-stoichiomeric concentrations of
metallic ions to form insoluble salts. For example, fatty
acids and their derivatives (tall oil, stearate, etc.) can
Chemicals, which are dispersed in the liquid, will
be precipitated by the addition of calcium, aluminium
emerge at the thin film interface as a lens and can cause a
and zinc salts (forming insoluble salts of the acids).
lowering of the viscosity and an increase in the drainage,
There have been several attempts to relate the defoam-
which generally leads to a decrease in stability. In this
ing action to the solubility product of the particles. A
group, we include chemicals which may (a) reduce the
typical series of results for metal oleates are shown in
bulk viscosity and increase the drainage, or (b) reduce
Figure 8.4. The influence of hydrophobic calcium fatty
the surface viscosity and elasticity. For the latter case,
acid soaps on foaming, and quantification of the data
the surface elasticity is eliminated by a swamping
in terms of the solubility product of the calcium and
of the surface layer with an excess of a compound
sodium fatty acids have also been reported. Cationic
with a lower viscosity. If the compound is soluble,
surfactants added to foam stabilized by anionic surfac-
then a sufficient amount must be added to exceed
tants could also destroy the foam. Unfortunately, due
the solubility limit. The insoluble monolayer cannot
to the formation of solid contaminants and the adverse
provide any elasticity, while the soluble monolayer in
consumption of chemicals, precipitation antifoamers are
equilibrium with the dissolved form can do this. One of
used infrequently in industry.
the more general theories suggests that the spreading
film of antifoam may simply displace the stabilizing
surfactant monolayers. As the oil lens spreads and
expands on the surface, the tension will gradually reach 2.3 Solubilized chemicals
a reduced uniform value. This may cause elimination
of both the stabilizing surface tension gradient and the As discussed earlier, many of the basic theories assumed
surface elasticity. that for effective antifoam action to occur, the antifoam-
There are several other different mechanisms for ing agent must be in the form of insoluble or undissolved
reducing the surface viscosity, depending on the con- particles or droplets, which transfer to the interface.
ditions in the surface layers. For example, many low- However, this is not necessarily the case since there
molecular-weight bulky surfactants, such as tributyl is some evidence that some solubilized antifoamers,
phosphate, can be used to reduce the coherence of the such as tributyl phosphate and methylisobutyl carbinol
layer. Alternatively, small amounts of nonionic sur- (MIBC), can reduce the stability of sodium dodecyl sul-
factants can be effective in disrupting the coherent fate (SDS) and sodium oleate foam systems. However,
layer, with such effects depending on the molecular in some cases, the oils may exceed the solubility limit,
structure of the additive. Other materials may not be
surface-active, but may act as a cosolvent and thus
reduce the concentration of surfactant in the surface
Froth air volume (ml)

layer. Unfortunately, fairly large quantities (e.g. 10% Metal oleates

ethanol or methanol) would be needed in many cases.
This may be reduced for low-molecular-weight (short-
lasting) antifoamers by spraying the solution, which
is a more economical approach. In addition, although
small amounts of solubilized dodecanol may increase
the foam stability of an anionic surfactant in water, a
like quantity of solubilized octanol will have a con- (solubility product)
trary effect. The octanol rapidly diffuses to the sur-
face, and will reduce the dynamic surface tension more Figure 8.4. The importance of the solubility product of the
rapidly, and thus allows less time for a Marangoni particles in defoaming, as shown by a plot of the froth air
volume versus the solubility product of various metal oleates
effect (1) to function. This will be discussed further (2 x 10~5 M in a 10 mg dm~ 3 commercial frother solution,
below. (from ref. (3))
and the emulsifier droplets of oil may then have an influ-
ence on the antifoam action. In addition, it has been
claimed that oil solubilized in the surfactant micelle can
also cause a weak defoaming action. Mixed micelle for-
mation with extremely low concentrations of surfactant
may explain the actions of insoluble fatty acid esters,
alkyl phosphates (esters) and alkyl amines. At present, Labile micelle Stable micelle Labile micelle
there appears to be no complete explanation. While
Increasing antifoaming agent concentration
there are many cases which demonstrate that solubilized
antifoams may reduce the foam stability in micellar solu- SDS
tions, there are also examples where dissolved antifoams
can give enhanced foaming. Antifoaming agent

Figure 8.5. Schematic of the microstructure changes for SDS

micelles on the addition of an antifoaming agent (from ref. (4),
2.4 Defoamering caused by changes in reprinted with permission from American Chemical Society
stability of the micellar aggregates
2.5 Cloud-point defoamers
It is well known that certain antifoams, such as methyl Block polymers of poly(ethylene oxide) (PEO) and
or ethyl alcohol, when added to the foaming solution poly(propylene oxide) (PPO) adsorb at interfaces in
may change the CMC or solubility of the surfactant and aqueous solution and can form organized micellar struc-
thus indirectly affect the adsorbed layer. In fact, detailed tures. The polarity of these copolymers depends on the
studies by Jha and co-workers (4) clearly emphasized ratio of the PEO (hydrophilic) and PPO (hydropholic)
the relationship between the stability of a surfactant components. Aqueous solutions of these polymers show
micelle and the stability of the foams. From experi- a cloud point (CP) at increasing temperatures due to
ments carried out with foam stabilized by SDS, it was dehydration of the hydrophilic (PEO) units, and the gen-
shown that several chemicals, such as 2-ethylhexanol eral view is that they act as antifoamers in the region
(EH), tributyl phosphate (TBP) and tetrabutylammonium of the cloud point (due to the formation of this hetero-
chloride (TBAC), can change the stability of the micel- geneous phase). Triblock copolymers (PEO-PPO-PEO
lar aggregates, thus leading to changes in the stability or PPO-PEO-PPO types, "Pluronics" and poloxam-
of the foam systems. In these studies, the stability of ers) are interesting systems since the CP varies with
micelles was determined from the micellar relaxation the PEO/PPO ratio. Such polymers have a wide range
times, as measured by pressure jumps. As the antifoam of applications (in textiles, dishwashing, etc.) since
concentration increases, the micellar relaxation time also they show effective spreading, adsorption and foaming
increases (indicating increasing micellar stability), until behaviour at lower temperatures. They display defoam-
a critical concentration was reached. Further increases ing characteristics at elevated temperatures (above the
in antifoamer lead to a decrease in the micellar relax- CP), while at lower temperatures they remain soluble
ation time (indicating a decrease in micellar stability). in the aqueous phase. Siloxane-based copolymers (sil-
The initial increase was attributed to a stabilization icone poly ethers) are PEO-PPO-modified antifoamers,
of the micelle by the added chemicals, which mini- and again the CP changes by changing the PEO/PPO
mized the repulsion between the head-groups of the SDS ratio. With these surfactant solutions, mixed micelles
molecules at the micellar surface or at the interface. Two are formed and the foam breaks up a few degrees below
opposing effects were therefore reported to be occur- the CP (5). Other commercial surfactants, such as Triton
XlOO, OP-IO and DC-IO, behave in a similar manner,
ring, depending on the concentrations of antifoamer.
with liquid drops being observed in solutions above
The antifoaming agents can stabilize the SDS micelle at
the CP.
lower concentrations and in turn act as a foam inhibitor.
However, beyond a critical concentration, the antifoam-
ing agents destabilize the micelle, which then begins to 2.6 Droplets and oil lenses
improve the formability of the SDS. The microstruc-
ture changes for SDS micelles on the addition of an Many antifoamers cause undissolved oil droplets to
antifoaming agent is shown in Figure 8.5. be formed on the surface of the film and this can
successfully leads to film rupture. Chemicals such as direction, and such liquid movement induces a thinning
alkyl phosphates, alcohol, fatty acid esters and poly- which increases the probability of rupture. The possible
dimethylsiloxanes are included in this group. Several mechanisms involved are illustrated above in Figure 8.3.
possible mechanisms for foam film rupture by antifoam- Although equations (8.1) and (8.2) are useful in that they
ing droplets or oil lenses have been suggested. give a rough guide to antifoaming action, they are often
As briefly discussed earlier, a widely accepted mech- inadequate since they do not consider the geometry of
anism for antifoaming action is that first the oil drop the system or the interactions of thin film forces, and
enters the air/water interface, and in a secondary step, hence their application is severely limited.
begins to spread over the foam film, so causing rup- Another possible explanation for the unreliability of
ture. An entering coefficient (E) and a spreading coef- these spreading equations ((8.1) and (8.2)) is that there
ficient (S) have been defined in terms of the change in is a difference in magnitude between the initial entry
free energy when the oil droplet enters the interface or coefficient (where the components are pure) and the
spreads at the surface. These are defined as follows: equilibrium values (where contamination often occurs).
In some cases, it may be that the operative entry
E = KW/A + yw/o — Yo/A (8.1) coefficient lies between an initial (E) and final (Ee)
value. In addition, it may be useful to define both an
S = KW/A — yw/o — Yo/A (8.2)
initial and a final spreading coefficient (i.e. S and Se).
where /W/A> YO/A and Yw/o a r ^ the macroscopic inter- Garrett (3) has stressed the importance of the formation
facial tensions of the aqueous phase and oil phase, and of the oil lens (but not necessarily the spreading) in the
the interfacial tension of the oil/water interface, respec- mechanism of antifoaming. It was suggested that the oil
tively. lens could break the foam by a bridging mechanism.
It was originally suggested that for efficient defoam- The oil drop first enters one surface and forms a lens,
ing, the oil drop after entering the air/water interface followed by thinning, until it enters the other surface
must spread as a duplex film on each side of the original to form an oil bridge. The stability of oil bridges in
film. This acts to drive out the original liquid film and the bridging - de-wetting mechanism was quantified in
leaves an oil film, which is unstable and easily breaks terms of the oil/water contact angle and the bridging
up. Clearly, two important steps need to be considered, coefficient B, as defined by the following:
since the mechanism is only feasible under certain crit-
ical conditions. These can be defined by E > 0, where B = YW/A + Kw/o2 " KO2/A (8.3)
the oil enters the air/water interface, and S > 0, where
From a theoretical analysis, it was shown that positive
the oil spreads on the duplex film on each side of the
values of B correspond to bridge de-wetting. However,
original film. This situation is illustrated in Figure 8.6,
although values of E,S and B can be determined from
where the balance between the relevant surface tension
measurements of the interfacial tension, these models
and spreading coefficient is shown.
do not account for the rupture barrier of asymmet-
It was assumed that it was the purely mechanical rical oil-water-air films which appear when the oil
action of the spreading liquid which ruptures the aque- approaches the foam film surface.
ous foam film. As the lens slips over the underlying
liquid, the lateral stress to the liquid below communi-
cates a shearing stress to a depth of several microns.
This causes the adjacent liquid to move in the same
2.7 Superspreaders
Several studies suggest that effective defoaming is
Air related to polymolecular spreading or other types of
spreading which involve the acceleration or transfor-
Air
mation of non-stable polymolecular films into lenses.
Aqueous solution The spreading of defoamers is rather complex and non-
Oil GIfI
ionic trisiloxane surfactants have been reported to show
drop superior wetting properties, particularly on hydrophobic
Drop moves toward surfaces. This is the so-called superspreading concept.
surface and enters These surfactants not only have low surface tensions
but also a tendency to form bilayers, which aggre-
Figure 8.6. (a) Entry of oil droplet into air/solution interface;
E = yw/A 4- yw/o — Yo/A > 0. (b) Spreading of oil droplet: gate (into vesicles, lamellar phases, etc.), in aque-
S = Xw/A — Yw/o — Yo/A > 0 ous solution (6). Based on molecular packing, there
is a fundamental difference in behaviour at the inter-

Volume of foam destroyed (ml)

face of a micelle-forming surfactant and of a vesi-
cle-forming surfactant. Models for spreading have been
suggested from experiments of the spreading kinetics of
ethoxylated and propoxylated trisiloxane surfactants on
a polypropylene substrate.

2.8 Elimination of the surface tension

gradients Contact angle, 0aw (degree)

It has also been reported that antifoaming action may Figure 8.7. Antifoam effect of polytetrafluorethylene particles
lead to the elimination of the surface tension gradient in (~ 5 jxm) as a function of the receding contact angle (from
ref. (3))
foam films by reducing the Marangoni effect (1). Since
the spreading is driven by a surface tension gradient
between the spreading front and the leading edge, then PTFE particles as the antifoam material. A correlation
thinning and foam rupture can occur by this gradient between the foam volume destroyed and the receding
acting as a shear force, thus dragging the underlying contact angle was found from this study (Figure 8.7).
liquid away from the source. It has been suggested The antifoam action for these spherical particles was
that three different types of antifoam materials may related to the wettability, contact angle and the bridging
function by this mechanism, i.e. (a) solids or liquids characteristics for this particular system.
containing surfactants other than those stabilizing the However, for particles with rough edges, the situa-
foam, (b) liquids which contain foam stabilizers at tion then becomes somewhat more complex. Johansson
higher concentrations than that which is present in the and Pugh (7) have studied the stability of foams in the
foam, and (c) the vapours of surface-active liquids. presence of finely ground quartz particles of different
size fractions. In this work, the surfaces of the dif-
ferent particles were methylated to produce a range of
2.9 Particles hydrophobicities. Both the dynamic and static froth sta-
bilities were then determined in a froth column. From
Solid particles, which have some degree of hydropho- this, the concept of "maximum enhanced foam stability",
bicity (e.g. coal dust, sulfur, non-wetting quartz, etc.) which corresponded to a critical surface hydrophobicity
usually exhibit a finite contact angle when adhering shape and size, was developed.
to an aqueous interface, and may cause destabilization The mechanism of film collapse by single spherical
of froths. Many practical examples of such behaviour particles has been studied in cinematographic experi-
can be found in mineralised foams. In addition, the ments carried out by Dippennar (8, 9), and the results
mechanism may not necessary involve wetting, since obtained generally confirmed Garrett's de-wetting mech-
hydrophobic silica can deplete the stabilizing surfactant anism. In fact, Dippennar (9) emphasized the dynamic
(through rapid adsorption) and can result in weak spots contact angle, rather than the equilibrium situation. This
in the film. is particularly relevant since foam generation is a non-
In earlier studies, there was a tendency to try and equilibrium process in which the air-water interface is
emphasize the importance of wetting by showing that expanding rapidly. This study appeared to indicate that
an increase in contact angle can cause an increase in with large particles and high contact angles, the film
defoaming action. However, much experimental data are easily becomes destabilized. Further experiments carried
erroneous due to the difficulties of measuring contact out with galena (cubic shaped particles) also showed
angles and the influence of the shape and roughness that with contact angles < 90°, the froth was destabi-
of the particles in the foaming action. Other studies lized and this was explained by the ease of movement
have been reported in which foaming was related to of the three phase boundaries across the smooth regular
the degree of wetting of the inert particles and this surface. (Figure 8.8). All of these studies more or less
leads to the idea of a particle bridging mechanism (a confirm the importance of the size, the shape, and the
similar mechanism as for the oil droplets), leading to hydrophobicity of the particle on the foam stability. In
rupturing of the thin film. Garrett (3) carried out a series fact, the particles characteristics can govern the degree
of shake-test experiments with finely divided (~ 5 urn) of penetration into the individual foam films and also
 to liquid, the antifoaming effect has been reported to be
Time (ms) Air much less effective. This behaviour has been explained
Water Solid by the solid particles having a more irregular shape, with
sharp and rough edges and apexes, thus producing finite
Horizontal orientation contact angles under dynamic conditions. As the wax
melts, the edges are removed and the particles become
more symmetrical. Under such circumstances, it would
appear that a bridging mechanism comes into play.
Frye and Berg (10) carried out a hydrodynamic
Air analysis of the mode of action of smooth-shaped, inert,
Solid
Water solid hydrophobic particles (spheres, discs, rods and
Diagonal orientation ellipsoids) on thin films. It was concluded that for de-
wetting and rupture to occur, the receding contact angle
must be > 90°, while to achieve rapid film rupture and
high breakdown rates, then an extra 5° or 10° over
this critical angle was required. However, in "foamy"
solutions, these values were difficult to achieve and it
was suggested that it was then preferential to use rough-
shaped particles, which gave sharp angles.
Figure 8.8. (a) Sequence taken from high-speed photography
experiments showing the interaction of cubic galena particles
with a thinning film, thus demonstrating the importance of
the contact angle on the film rupture. The latter can occur as 2.10 Mixtures of particles and oils
the bubble can bridge both surfaces of the film, whatever the
contact angle. With cleaved surfaces, the contact angle gives
The synergistic antifoaming effect of mixtures of insol-
only a rough guide to stability, (b) Orientation of the cleavage
uble hydrophobic particles and hydrophobic oils (filled
plane can occur in, or diagonally to, the surface. Stable films
antifoams) when dispersed in aqueous media has been
will interface and thus allow easy movement of the three-phase
contact (from ref. (8)), with permission from Elsevier Science
well established in the patent literature since the early
1950s. Some examples taken from various industrial
the movement of the three-phase boundary along the patents, which indicate the complex nature of the chem-
surface. In addition, Dippennar (9) demonstrated that in istry involved, are shown in Table 8.1. The effect
addition to size, the number of particles in the froth appears to be quite general and even precipitates of
could also be related to the stability (thus proving the polyvalent metal ions with long-chain alkyl phosphates
particles were of uniform hydrophobicity and shape). A and carboxylates may be combined with mineral oil or
simple relationship for the rate of thinning was derived PDMS to produce an synergistic antifoaming effect. The
as followed: sizes of the particles are within the range 0.001-1 urn,
ax = stability constant (8.4) with the solid content of the mixture being 1-20 wt%.
One possible idea for the role of the hydrophobic par-
where x is the number of particles and a is the particle ticles in the synergistic effect is that the spreading coef-
radius. ficient of the (PDMS) oil is modified by the addition of
In an attempt to study the difference between the the hydrophobic particle. In late studies, Garett (3) sug-
solid and the emulsified liquid states in defoaming, sev- gested that oil-particle mixtures form composite entities
eral thermal (melting) investigations have been carried where the particles can adhere to the oil-water sur-
out by using hydrocarbon particles. Triglycerides and face. The particles alone only show a weak antifoaming
long-chain fatty acids with melting points < 1000C have action (probably involving de-wetting and bridging in
been frequently used. Dispersions of the hydrocarbon foam films to form holes in a manner similar to that
particles were prepared by first emulsifying the molten caused by the PTFE particles). However, the behaviour
material and then cooling below the melting point. Sev- of the particles in adhering to the oil-water interface
eral experiments have shown a sharp deterioration in the may facilitate the emergence of oil droplets into the
antifoaming effect in the region of the melting points for air-water interface to form lenses, thus causing ruptur-
paraffin waxes in sodium alkylbenzene sulfonate solution ing of the oil-water-air films. This mechanism is simi-
(i.e. where a sharp melting point transition occurs). At lar to that of oil droplets forming mechanically unstable
higher temperatures, where all of the solid is converted bridging lenses in foam films, where the configuration
Table 8.1. Some examples, taken from the patent literature, of the synergistic antifoaming effect of various mixtures of
hydrophobic mineral particles and silicone oils (from ref. (3))
Oils claimed to be effective Particles claimed Actual examples Preferred concentration
to be effective given of particles (wt%)
Partially oxidized Silica aerogel, presumably As claimed 7.5
methylsiloxane polymer. rendered hydrophobic by
May be diluted with reaction in situ with the
dimethyl siloxane polymer siloxane
and dispersed in benzene
Methyl polysiloxane Finely divided silica, Silica + methyl polysiloxane 2-10
presumably rendered + emulsifiers
hydrophobic by reaction in
situ with the siloxane
Silicone oils (product may be Aluminium oxides, titanium (1) Dimethyl polysiloxane + 1-30
diluted by hydrocarbons, dioxides, plus various silicas. silica + aerogel + AICI3
ethers, ketones or These react with silicone oil diluted by toluene.
chlorohydrocarbons, although in situ, with the reaction (2) Dimethyl polysiloxane +
this does not, however, being catalyzed by an alumina + SnCL* diluted by
appear as a specific claim) acid-condensation reagent toluene.
(3) Dimethyl polysiloxane +
precipitated silica +
phosphorous nitrile chloride
+ poly(ethylene glycol)
stearate
Silicone oils Pyrogenic or precipitated As claimed 2-8
silicas, hydrophobized with (preferably 5)
"chemically bound methyl
groups"0. Special reference
is made to the relative
ineffectiveness of the oil
alone
a
probably silanized.

requires the rupture of oil-water-air films by particles, (a) (b) Pseudo-emulsion film
although the contact angle for rupture is less severe than Air J ^ Entering
that required for symmetrical air-water-oil films.
/6iT\ ~* (^) ~~
2.11 Emulsion and pseudo-emulsion films Aqueous solution Aqueous solution

Lobo and co-workers (11) investigated the influence of (c) Thin oil film (d)
(monolayer) Spread oil layer
oil (in the micellar environment) on the stability of
A i r
s ^--^ / /
foam. Two different types of emulsified oil systems were = < b i l lens/=^ • - '
studied, i.e. (a) a microemulsion (solubilized within Aqueous solution Aqueous solution
the micelle), and (b) a macroemulsion system. It was
found that in each case, the foam stability was affected Figure 8.9. A macroemulsified oil system, showing the con-
by a completely different mechanism. In the case of figurations of the oil at the gas/aqueous interface: (a) oil
(a), where the foam films containing oil is solubilized drop inside the solution; (b) oil drop at the surface sep-
within the micelle to form a microemulsion, the normal arated from the gas phase by a pseudo-emulsion film;
(c) oil lens; (d) spread oil layer at the solution surface. The
micellar interactions are changed. It had been earlier
pseudo-emulsion film is unstable, thus enabling the oil to
demonstrated that micellar structuring causes a step-wise spread on the surface (from ref. (12)), reproduced by permis-
thinning due to layer-by-layer expulsion of the micelles sion of Academic Press
and such as effect was found to inhibit drainage and thus
increase the foam stability.
In the case of the macroemulsified oil system, approaching oil droplet) on the stability of the aque-
the important role of the so-called "pseudo-emulsion" ous foaming system was emphasized (Figure 8.9).
film (formed between the air/water interface and an Clearly, the entering and spreading coefficients are
thermodynamic properties, which determine whether the Koczo and co-workers (12) also considered the role
particular configuration of the oil droplet is energetically of the pseudo-emulsion film in the breaking of foam
favourable, although they cannot predict the fate of the by using both hydrophobic particles and heterogeneous
oil droplet under dynamic conditions, which exist within antifoamers (hydrophobic particles and oil). The rup-
the draining film. ture of the pseudo-emulsion film was again considered
Under these circumstances, two distinct cases were to be the primary step for heterogenous (particle/oil)
considered, i.e. (a) where the pseudo-emulsion film is antifoaming, which eventually leads to a bridging mech-
unstable and the oil spreads, and (b) where the pseudo- anism and finally rupture of the foam film Figure 8.11.
emulsion film is stable and the oil drops do not enter Models for the role of the pseudo-emulsion film in
the air/water interface. These workers again found that mixed-type antifoamers (containing oil droplets and par-
the classical entering and spreading coefficients cannot ticles) were also developed.
predict the configuration of oil at the air-water surface, Wasan and coworkers (13) have discussed a
and thus cannot predict the effect of the oil on the foam antifoaming mechanism for hydrophobic particles in
stability (i.e. even in the case of E > 0, the oil droplet insoluble liquids which involves the oil droplet
will not necessary enter the air/water interface if this containing the particle moving to the plateau border
film is stable and its stability is controlled by drainage). of the draining foam and becoming trapped during the
In fact, the classical theories generally do not consider thinning process. The droplets enter the air/solution
the excess pseudo-emulsion film energy. In addition, the interface, so forming a lens because the particles
drainage of the pseudo-emulsion film is extremely com- destabilize the pseudo-emulsion film, and on further
plex and may be controlled by several parameters, either drainage the trapped lens enters another surface of the
singly or in combination. These factors include surface plateau border, thus forming a bridge and hence leading
gradients at the interface and the surface viscosity of to rupture.
the film, as well as thermodynamic quantities such as More recent studies, based on fluorescence labelling
the disjoining pressure and film stratification. In addi- and microscopy, by Wang et al. (14), were carried out
tion, the emulsified oil droplets may also accumulate with hydrophobic particles in mineral-based defoamers.
within the plateau borders of the draining foam films, In this work, it was clearly shown that the hydrophobic
thus inhibiting the drainage (Figure 8.10). silica particles concentrate in the oil/water interface near
the three-phase contact angle line. The sequence of

Bubble Pseudo-emulsion
film Lens
Oil drops
Bubble Oil drops Plateau
with particles border
Bubble
Foam film
Drainage

Pseudo-emulsion film
Bridge
Foam film (lamella)

Plateau border
Gas phase
(bubble) Emulsion film
Aqueous

Figure 8.11. The suggested antifoaming mechanism for a

Figure 8.10. Schematic of a macroemulsified oil system. The mixed-type antifoamer: (a) oil drops (containing solid particles)
drainage of the film may be reduced due to accumulation collect in the Plateau border; (b) the drops become trapped in
of emulsified oil droplets within the plateau borders. The the thinning border; (c) the pseudo-emulsion film breaks and a
formation of both the emulsion and pseudo-emulsion films is drop enters and forms a solid plus oil lens; (d) the lens becomes
indicated. The factors effecting the foam stability were found trapped during thinning; (e) the lens bridges the film at the
to be the oil volume fraction, drop size and oil phase density plateau border and the bridge (from ref. (12)), reproduced by
(from ref. (12)) permission of Academic Press
 Defoamer
lenses
Air

Air Defoamer
droplet

After t= O s After t= 5 s

After t= 9 s After t= 10 s

Figure 8.12. A sequence of captured video frames showing the migration progress of the defoamer lens into the film between
two air bubbles, thus causing coalescence (from (ref. 14)), reprinted with permission from American Chemical Society

events shown in Figure 8.12 illustrates the migration are outlined in Figure 8.13. For example, decomposi-
process of the defoamer lens between two air bubbles tion due to chemical oxidation of a fatty acid containing
which leads to coalescence. unsaturated groups, or the hydrolysis of certain silicones
under acidic or basic conditions, may occur with time.
This could lead to changes in the surface tension of
2.12 Electrolytes the materials, thus causing differences in the entering,
Schick and Schmolka (15) have summarized the influ- spreading and bridging characteristics of the antifoamer.
ence of electrolytes on the foam film thickness and In addition, the size of the antifoaming droplet may
stability for nonionic surfactant systems. Specific effects change. Droplets may become emulsified under shear,
of such anions on the film "blackening" times have been and when the size falls below 5 urn thermal energy will
reported. The order of the magnitude of the effect fol- dominate over gravity. There is also the possibility that
lows the lyotropic series, where SCN~ and Cl~ act as the globules will remain in solution and will no longer
inhibitors while PO 4 2 ", SO 4 2 ", CO 3 2 ", F " and OH~ act be buoyant and capable of entering the air/water inter-
as promoters of the black film formation, thus promot- face. By predicting the balance between the buoyancy
ing foam stability. It has been suggested that the effect forces and the thermal forces, Bergeron (16) derived an
is related to the dehydration of the nonionic surfactant equation for the critical radius, which corresponded to
molecules. the optimum antifoamer performance. Drop size reduc-
tion may be achieved by increasing the drop viscos-
ity and the interfacial tension. A patent from Diamond
3 AGEING EFFECTS WITH
Shamrock describes a microemulsion defoamer, com-
CHEMICAL DEFOAMERS
posed of an oil in water colloidal dispersion, which
There are many explanations available for the decrease is prepared by mixing an ethylene oxide condensate,
in antifoamer performance with time. Some of these a coupling agent, water and an anti-gelling agent (17).
 Chemical oxidation of
unsaturated fatty acids, oil
droplets or the hydrolysis of
silicone organics at low or
high pH levels
Adsorption of surfactant Decrease in globule size to
on hydrophobic particles, 1-2 |Ltm, due to shear forces
resulting in the latter preventing the droplets settling
becoming hydrophilic and attaching themselves to the
in nature interface

Reduction in
Precipitation of metallic efficiency of Emulsification of oil
cations, leading to antifoaming film during the spreading
adsorption of the action caused process
antifoamer by
Bacterial degradation Volatization
of oil droplets

Segregation of oil and Disappearance of spread oil

silica into two distinct layer from the solution surface
populations of antifoam (due to the settling of silica)
globules (silica-free and and oil emulsification
silica-enriched) during
storage

Figure 8.13. Some of the ageing effects of antifoamers

This composition is claimed to be more stable than the technique has been reported to be only partially
conventional defoamer systems and also has a lower successful.
viscosity. Several attempts have also been made to destroy
high-viscosity foams in the food industry (e.g. sugar and
molasses), but unfortunately with these highly stabilized
systems, the success rate is much lower. However, for
4 PHYSICAL METHODS OF
the case of particle-stabilized foams (i.e. in the mineral
DEFOAMING
industry, e.g. clays and carbonates) some degree of
success has been achieved. Preliminary studies carried
4.1 Ultrasonics out by Sandor and Stein (18) clearly indicate that
ultrasonic vibrations can both prevent the formation of
The use of "breaking chemicals" or inhibitors may foams and destroy foams stabilized with SDS surfactant
contaminate the required product and cause additional and that those vibrators, which give the higher power
pollution. A possible solution to this problem is to consumption are more effective. It was also shown that
use weak shock waves to destroy the foam. The idea the power consumption could be greatly enhanced when
of utilizing such shock waves to simulate thickness a broader tip was used.
fluctuations in foam films, so leading to accelerated In the brewing industry, there is no ideal foam-
drainage and film rupture, is not altogether novel. In control method currently in use, although ultrasonics
fact, there are several industrial patents describing the have been tested to suppress foaming in fermenting ves-
application of low frequency vibrations (20-20000 Hz) sels. The ultrasound generated by ceramic piezoelectric
to destroy certain types of detergent foams. In addition, transducers has the unusual property that when an elec-
a considerable amount of success has been achieved in tric voltage is applied across their crystalline ceramic
breaking low viscosity foams produced in the textile structure, deformation occurs, so that an alternating cur-
and dairy industries. For medium-viscosity foams, which rent thus produces a sinusoidal vibration. The resonance
are produced from poly(vinyl chloride)-based adhesives, frequency depends on the physical dimensions of the
 Radial Thickness
Directional
beam

Focused
beam
Electrode
Piezoelectric
ceramic

Head-space
Easily
broken
Secondary Harder
Primary
focus to break
focus
Foam Very hard
to break

Wort

Figure 8.14. Ultrasonic foam breaking: (a) equipment; (b) ultrasonic fields from the radiation plate; (c) effect of reflection around
the vessel head-space; (d) the effect of foam position on ultrasonic foam breakage (from ref. (19))

transducer and its surroundings. By using such a system, 2. Denkov, N. D., Cooper, P. and Martin, J.-Y., Mechanism
it is possible to focus the ultrasonic power on to a small of action of mixed solid/liquid antifoamers 1. Dynamics of
volume of the surface foam. foam film rupture, Langmuir, 15, 8514-8529 (1999).
Furtherwork on the use of ultrasound was carried 3. Garrett, P. R., The mode of action of antifoams, in
out at the Guinness Brewing Worldwide Pilot Brewery Defoaming, Garett, P. R. (Ed.), Surfactant Science Series,
in London (19). It was found that the older foams at the Vol. 45, Marcel Dekker, New York, 1993, pp. 1-118.
top of the foam layer are more susceptible to breakage 4. Jha, B. K., Patist, A. and Shah, D. 0., Effect of antifoamer
with ultrafoam and there was an effect over the entire on the micellar stability and foamability of SDS solution,
foam surface. This was explained by reflection around Langmuir, 15, 3042-3044 (1999).
the head-space of the vessel, where the ultrasound can be 5. Zemeth, Z., Racz, G. and Koezo, K., Foam control by sil-
reflected off the vessel walls and the liquid surfaces. The icone polyethers - mechanism of cloud point antifoamers,
equipment, plus schematics of the ultrasonic fields from J. Colloid Interface ScL, 207, 386-394 (1998).
the radiation plate and the influence of the position of 6. Venzer, J. and Wilkowski, S. P., Trisiloxane surfac-
the foam on the effectiveness of the breakage, are shown tants - mechanism of spreading and wetting, in Pesticide
in Figure 8.14. It was also shown that a wide beam of Formulations and Applications Systems, Vol. 18, ASTM
ultrasonic radiation was less effective than a focused Special Technical Publication, STP 1347, American Soci-
beam. From these pilot-scale studies, it was shown that ety for Testing and Materials, West Conshohocken, PA,
a fermented foam could prove useful in controlling a 1998, pp. 140-151.
high-foaming wort. 7. Johansson, G. and Pugh, R. J., The influence of particle
Other non-chemical methods for foam breaking size and hydrophobicity on the stability of mineralized
include projecting air-streams, horizontal rotating discs, froths, Int. J. Min. Process, 34, 1-22 (1992).
paddle wheels, forcing foam through a wire stream, heat 8. Dippennar, A., The destruction of froths by solids, 1.
(hot wires above the rising foam), sparks, etc. Mechanism of film rupture, Int. J. Min. Process, 9, 1-14,
(1982).
9. Dippennar, A., The destruction of froths by solids, 2. The
5 REFERENCES rate determining step, Int. J. Min. Process, 9, 15-22
(1982).
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225-238 (1994). Bremen, Germany, 1999, pp. 41-47.
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