Current Opinion in Colloid & Interface Science 20 (2015) 81–91

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Current Opinion in Colloid & Interface Science

journal homepage: www.elsevier.com/locate/cocis

Defoaming: Antifoams and mechanical methods

Peter R. Garrett
School of Chemical Engineering and Analytical Science, University of Manchester, Oxford Road, Manchester M13 9PL, UK

a r t i c l e i n f o a b s t r a c t

Article history: Recent progress in both the mode of action of antifoams and mechanical defoaming is reviewed. New insights
Received 29 December 2014 concern the simulation of the orientation of particles in interfaces and films, the role of dynamic surface effects
Accepted 2 March 2015 in antifoam action, antifoam action under micro-gravity, deactivation of oil/particle antifoams and antifoam
Available online 10 March 2015
action in hydrocarbon media. Progress in mechanical defoaming is mainly confined to new insights concerning
the use of ultrasound.
Keywords:
Antifoam mechanism
© 2015 Elsevier Ltd. All rights reserved.
Particles
Deactivation of oil/particle antifoams
Dynamic effects
Ultrasound

1. Introduction in academic circles. A recent foam conference for example, included

Defoaming is a surprisingly ubiquitous requirement. In the oil
industry, for example, processes such as gas–crude oil separation and
desulphurization of natural gas by bubbling through alkanolamine
solutions usually require defoaming, which often involves the use of
chemical antifoams. Other industrial processes such as the jet dying of
textiles, radioactive waste treatment, the kraft pulp process and fer-
mentation using oxygen bubble columns are also beset by unwanted
foam. Again treatment with antifoams is often used but mechanical
means are sometimes employed in the case of bubble columns. The con-
trol of flotation froth in mineral processing can be adversely affected if
hydrophobed mineral particles too readily destabilize the froth. Forma-
tion of undesirable foam can also be an aspect of the use of certain for-
mulated products such as waterborne latex paints, and detergents for
use with machine washing of textiles and dishes. This problem usually
necessitates the addition of antifoams to the relevant formulations.
However some products, such as shampoos and hand dishwashing liq-
uids, are designed to produce copious amounts of foam during use.
These products must be formulated to minimize the antifoam effects
of the triglyceride soils which are intrinsic to their application. There
are even medical applications of defoaming. These include the use of an-
tifoams to treat gastrointestinal gas, to eliminate any foam obscuring
the view of colonoscopy cameras and in filters for removal of foam bub-
bles from the aspirated blood derived from surgery in order to permit
recirculation. Defoaming is therefore clearly widely relevant in many
contexts and does in fact present many interesting challenges to funda-
mental scientific understanding. This is however not always recognized
E-mail addresses: p.garrett@manchester.ac.uk, pgarcgar@btinternet.com.
only one paper explicitly concerning defoaming [1] out of a total of
over 100 oral and poster presentations.
Despite this seeming lack of recent interest much progress has been
made in understanding the mode of action of antifoams over the past
thirty years. A detailed account of that progress can be found in a recent
monograph [2⁎⁎] which is concerned with defoaming by both anti-
foams and mechanical means. Briefer accounts of defoaming by anti-
foams have also been published recently by Denkov et al. [3⁎] and
Karakashev and Grozdanova [4]. Another recent review by Owen [5] is
distinct in that it ignores much of the progress made over the past
twenty years. Earlier noteworthy reviews include those by Miller [6]
and Denkov [7⁎⁎].
Use of antifoams always implies contamination of the system to be
defoamed. Such contamination is, however, sometimes unacceptable.
Examples include preparation of pharmaceuticals by fermentation and
downstream processing in petrochemical plants where catalysts may
be poisoned by antifoam residues. In these situations recourse is some-
times made to defoaming by mechanical means, utilizing for example
either ultrasonic or various rotational devices. Progress in understand-
ing the mode of action of such devices has however been rather limited.
A complete review is to be found in the recent monograph [2⁎⁎].
Developments in the understanding of the mode of action of anti-
foams, which have been published over the past 5 years or so, are the
main concern of this review. Earlier work, however, is also cited in
order to provide relevant context. Antifoams are defined here as parti-
cles, oils or mixtures of oils and particles which reduce either the
foamability or foam stability of the liquid in which they are dispersed.
Some account of defoaming by mechanical means is also included
where however a dearth of recent relevant publications means a review
largely confined to ultrasonic defoaming.

http://dx.doi.org/10.1016/j.cocis.2015.03.007
1359-0294/© 2015 Elsevier Ltd. All rights reserved.
82 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
2. Defoaming by particles
2.1. Hydrophobic particles; theory
It is now well known that finely divided particles, which are suffi-
ciently hydrophobic, can produce antifoam effects when dispersed in
aqueous surfactant solution [2⁎⁎,3⁎,8]. Whether these effects are appar-
ent is dependent upon the contact angle and the shape of the particles.
In the case of spherical particles antifoam effects are only present if the
contact angle (measured through the aqueous phase), θAWN ~90° [2⁎⁎,
3⁎,8]. As the film drains the particles bridge the film, and dewet (now
often called the “bridging–dewetting mechanism” after Denkov [7⁎⁎])
leaving a hole in the foam film which subsequently expands to cause
film rupture. The essentials of this mechanism have been verified exper-
imentally in model experiments for spheres using high-speed cinema-
tography [8].
Joshi et al. [9⁎] present interesting observations concerning the anti-
foam mechanism of hydrophobic fatty alcohol particles in aqueous sur-
factant solution. The fatty alcohols consist of a blend of C14 –C30 chain
lengths. The particles appear to have a spherical or ellipsoidal geometry
and should therefore require contact angles N 90° in any given aqueous
medium for antifoam effect. However in the absence of surfactant the
particles possessed advancing and receding contact angles of 93° and
95° respectively and in the relevant aqueous surfactant solution 85°
and 71° respectively. The effect of these particles on the stability of the
film formed between two colliding bubbles was observed by video-
microscopy. In these experiments the fatty alcohol particles were dis-
persed in an aqueous concentrated ethoxylated alcohol solution con-
taining a thickener and preservative — the resultant concoction often
being described commercially as an aqueous or surfactant antifoam.
This concoction was then added to an aqueous solution of a second sur-
factant in order to achieve an antifoam effect for the latter. In this ar-
rangement one bubble was allowed to equilibrate with the antifoam
dispersion so that the fatty alcohol particles could attach to the relevant
air–water surface. The second bubble was then grown towards the first
to form a film between the two bubbles. The subsequent flow of liquid
from the film produced a surface tension gradient and effectively re-
moved the particles. However when that flow ceased, as the second
bubble closely approached the first, a reverse flow occurred because
the surface tension of the air–water surfaces in the film was now higher
than that on the remaining surface of the first bubble. The resulting
Marangoni effect dragged the antifoam particles back into the film
which then rapidly ruptured by a bridging mechanism. Joshi et al. [9⁎]
attribute the origin of the reverse flow to desorption of surfactant
from the fatty alcohol particles. However spreading from the shorter
chain length fatty acids in the blend used here could also contribute
(the equilibrium spreading pressure of, for example octadecanol – a
component of the blend used – will lower the surface tension of water
at the relevant temperature to some 20 mN m−1 below that of the solu-
tions of the second surfactant considered here [10]). Clearly a dynamic
process is occurring which probably means that dynamic contact angles
are relevant which could explain the apparent discrepancy between the
measured receding angles and the requirement that θAWN ~ 90°.
There are in fact two main difficulties with generalizing the condi-
tion θAWN ~ 90° to all foamability measurements. The first concerns
measurement of the contact angle under conditions directly relevant
for those actually existing during foam generation. As the work of
Joshi et al. [9⁎] suggests contact angle hysteresis and dynamic effects
due to the rate of surfactant transport relative to the rate of air–water
surface generation can conspire to produce antifoam effects even
though the receding contact angle b 90° [2⁎⁎]. However arguably a
more significant factor concerns particle geometry. The presence of
sharp edges and rugosities appears to confer antifoam effects at contact
angles significantly b 90° [2⁎⁎].
Orthorhombic particles have received particular recent interest in
this context following the work of Dippenaar [8] more than thirty
years ago. Dippenaar [8] investigated the rupture of single aqueous
films by orthorhombic hydrophobed galena particles using high-speed
cinematography. He attributed his finding that aqueous film rupture
by such particles occurs with contact angles of only (80 ± 8)° to the par-
ticle shape. He concluded that such particles could adopt two orienta-
tions at the air–water surface as that surface is pinned to edges as
shown in Fig. 1a and b. According to Dippenaar [8] only the diagonal
orientation can give rise to foam film rupture by a mechanism analo-
gous to that for a sphere but in this case, for a particle of a square
cross-section, contact angles must lie in the range 45° b θAW b 135°.
A problem with this argument concerns the assumption that only
two orientations of an orthorhombic particle at a planar air–water sur-
face are possible. That is strictly only true if the aspect ratio ≫ 1. In the
case of the diagonal orientation the air–water surface must satisfy the
contact angle against the two particle end surfaces perpendicular to
the plane of the paper as shown in Fig. 1c and d. If for example the
air–water surface remote from the particle is planar then the capillary
pressure across that surface must be zero. For equilibrium the capillary
pressure in the segment of air–water surface against the particle ends
must also be zero. That is only possible if it forms a catenoid element,
which must also contact everywhere the perpendicular surface of the
particle at the relevant contact angle. In the case of a particle with an as-
pect ratio close to unity the contribution of the surface energy of the two
particle end surfaces, including the catenoid elements, to the total work
of adhesion of the particle to the air–water surface must be significant.
This factor therefore greatly complicates calculation of the relative
work of adhesion and probabilities of the two orientations depicted in
Fig. 1a and b in the case of aspect ratios close to unity. It also suggests
the possibility that yet other orientations are possible.
Calculating the relative work of adhesion for orthorhombic particles
as a function of contact angles has been made tractable by use of an
iterative surface energy minimization technique described by Morris
et al. [11–13,14⁎⁎]. The technique makes use of the Surface Evolver soft-
ware developed by Brakke [15]. A more detailed description of the use
of this technique is given in the accompanying review by Morris et al.
[16]. It permits calculation of the (surface) energy profile of a particle
in an air–water surface or foam film as a function of the orientation, con-
tact angle and shape. The profile reveals the presence of energy minima,
consistent with stable orientations, where the depth of the minima
gives an indication of their relative probabilities. This analysis reveals,
for example, four possible orientations for an orthorhombic particle
bridging a foam film [14⁎⁎]. These are designated vertical, horizontal,
rotated and diagonal and are shown in Fig. 2. The relative stabilities of
these orientations are determined by both the contact angle and the
aspect ratio of the particle. This is exemplified in Table 1 for the aspect
ratios corresponding to the only direct experimental observations of
the rupture of aqueous films by orthorhombic particles.
Careful examination of the cinematographic film frames of Dippenaar
[8] reveals that the aspect ratio of the orthorhombic hydrophobed galena
particle is about 1.4. With a contact angle in the range of 72–88°
(i.e. 80 ± 8°) the results of Table 1 would suggest that either both hori-
zontal and diagonal orientations are likely to co-exist or that the diagonal
orientation alone is to be present. Dippenaar [8] suggests that his obser-
vations are in fact consistent with the former possibility. However the
relevant cinematographic frames do suggest a reconfiguration to a rotat-
ed orientation immediately prior to rupture of the aqueous film. Morris
and Cilliers [13] have recently repeated these observations of Dippenaar
[8] with a similar hydrophobed galena particle of contact angle in the
range of 70–90° (i.e. 80 ± 10°) but of aspect ratio unity. As expected
from the calculations summarized in Table 1 this particle adopted a
rotated orientation although with no apparent observations of either
horizontal or vertical orientations.
Morris et al. [11–13,14⁎⁎] have extended these surface energy min-
imization calculations to estimate the critical capillary pressure required
to rupture an aqueous film containing a bridging orthorhombic particle.
In particular Morris and Cilliers [13] have compared such calculations
 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91 83

air

water
film
thins

a horizontal orientation

air
water
film
thins

b diagonal orientation; aqueous phase peels

off particle to form a
hole

planar air-water
catenoid air- surface hinging on
water surface an edge

air

water

c d

Fig. 1. Orientation of an orthorhombic particle in a foam film. (a) and (b) Horizontal orientation stabilizes a draining foam film whereas a diagonal orientation leads to foam film rupture
provided θAW N θp = 45o according to Dippenaar [8] for the case of a particle with a square cross-section and an aspect ratio ≫ 1 (i.e. a 2D view). (c). Mechanical equilibrium requires that
the capillary pressure over the whole air–water surface be zero which must mean a catenoid profile over the end surfaces of a diagonally oriented particle which become progressively
more significant as the aspect ratio decreases. (d). Vertical slice through centre of particle where the contact angle is satisfied and the air–water surface is concave, the orthogonal radius
of curvature must then be convex if the surface is to form a catenoid as shown in (c).

with experimental observations which supposedly repeat those of
Dippenaar [8] but, as we have seen, using a hydrophobed galena particle
of aspect ratio unity rather than 1.4. The calculations indicate that the
particle, placed in a rotated orientation but bridging the film, maintains
that orientation as capillary pressure is increased and the film thins until
it ruptures. These calculations suggest that film rupture does not occur
as a result of the film liquid peeling off the particle surface as indicated
in Fig. 1b and apparently revealed for an orthorhombic particle by the
cinematographic observations of Dippenaar [8]. Morris and Cilliers
[13] rather suggest the particles induce rupture directly in foam films
where “its highly distorted shape around the particle is what forces
the opposite sides (of the film) together”. Unfortunately the experimen-
tal observations were not able to convincingly verify this conclusion.
Moreover strict comparison with Dippenaar [8] was not possible
because of selection of an aspect ratio of unity rather than 1.4.
The surface energy minimization technique used in these calcula-
tions of the critical capillary pressure is not able to account for the pos-
itive contribution to the disjoining forces, which will generally facilitate
stabilization aqueous films of solutions of surface active materials
against rupture. Application of this technique to the actual process of
film rupture by a bridging particle for comparison with the experiments
of Morris and Cilliers [13] and Dippenaar [8] is nevertheless justified be-
cause the aqueous films in that context consisted of pure water — no
surfactant at all was present and therefore a positive contribution to
the disjoining force was absent. However the presence of significant
positive disjoining forces due to the presence of surfactant is likely to
suppress the process of foam film rupture by the indirect influence of
a bridging particle on the neighbouring film. After all it is that property
of surfactants which justifies the addition of antifoams at all! It probably
means that in those circumstances foam film rupture would have to
occur by the mechanism originally suggested by Dippenaar [8] where
the film liquid peels off the particle until the two three phase contact
lines become coincident as shown in Fig. 1b. However as described by
Garrett [2⁎⁎] application of that mechanism to particles of complex ge-
ometry requires knowledge of their orientations at air–water surfaces
and in foam films. The surface energy minimization technique may
84 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91

a b

c d

Fig. 2. Possible stable orientations of an orthorhombic particle bridging a thin liquid film (of thickness ≪ dimensions of the particle). (a). Horizontal (H), (b). Diagonal (D), (c), Rotated (R),
(d). Vertical (V). Orientations calculated by a surface energy minimisation technique using the Surface Evolver software [14⁎⁎,15]. The catenoid surface suggested by Fig. 1c is clearly
revealed in the diagonal orientation (b).
Reprinted from Morris, G., Neethling, S.J., Cilliers, J.J. J. Colloid Interface Sci. 361, p373; copyright 2011, with permission from Elsevier.

therefore potentially yield valuable insights in that context especially [2⁎⁎]. Similarly addition of excess counterion to solutions of sodium do-
for particles of complex crystal habit. Such considerations are important decyl sulphate lowers the Krafft temperature to produce a crystalline
not only for rupture by particles of air–water–air foam films but also for precipitate. That precipitate also exhibits a finite contact angle [17]
the rupture by particles of oil–water–air pseudoemulsion films which against the saturated solution and appears to function by a bridging–
represents an important aspect of the mode of action of commercial an- dewetting mechanism as an antifoam [2⁎⁎,18].
tifoams for application in aqueous surfactant solution [2**]. In contrast to single chain surfactant molecules, exemplified by
carboxylate soaps and SDS, addition of counterions to double chain
2.2. Effect of precipitation of crystalline and mesophase particles on foam molecules tends to precipitate mesophase dispersions – often as
multi-walled vesicles of lamellar phase. The precipitates formed upon
Addition of counterions to aqueous solutions of anionic surfactants addition of Ca2 + ions to aqueous solutions of sodium alkyl benzene
can result in partial substitution of monomers or micelles by precipi- sulphonate [19,20] represent an example of this behaviour. Decreases
tates of either crystalline or mesophase particles. This change in physical in foamability of the solution accompany formation of the precipitate.
state of the relevant solution usually produces a marked reduction in The residual foam is however stable.
foamability. For example calcium soaps exhibit extremely low solubil- The defoaming effect accompanying addition of Ca2+ ions to solu-
ities so that they may be precipitated from aqueous mixed solutions of tions of sodium alkyl benzene sulphonate can find practical application
sodium soaps and other surfactants. The relevant precipitates are crys- in detergency by the elimination of residual foam during rinsing with
talline and can act as antifoams for solutions of the latter. Finite contact hard water. Removal of the lamellar phase precipitate by filtration
angles suggest that they function by a bridging–dewetting mechanism does not however restore the foamability [19,20] which means that
the precipitate does not function as an antifoam. This is probably a con-
Table 1 sequence of the structure of the multi-walled vesicles which are formed
Stable orientations of an orthorhombic particle in a thin aqueous film as a function of contact upon precipitation of lamellar phase. The outer layer of the vesicle
angle and aspect ratio calculated by surface energy minimization. H = Horizontal, D = formed in an aqueous environment has to be covered with surfactant
Diagonal, R = Rotated, and V = Vertical (see Fig. 2). From Morris et al. [14⁎⁎]. head groups if it is composed of bilayers. That surface is therefore hydro-
Aspect ratio Contact angle, θAW/degrees philic and is extremely unlikely to posses the contact angle of 90° re-
quired for antifoam action by a sphere — indeed it is likely to be near-
45 60 65 70 75 80 90
zero.
1.0 H/V H/V H/V H/R/V H/R/V R R Measurements of the dynamic surface tensions indicate that the
1.36 H/V H/V H/D/V H/D H/D D D
reduction of foamability simply accompanies replacement of labile
 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91 85

micelles with non-labile mesophase particles which are larger (with
smaller diffusion coefficients and slower breakdown kinetics) [2⁎⁎].
This is illustrated by a comparison of the effect of addition of Ca2 +
ions on the foam and dynamic surface tension behaviour of a micellar
solution of sodium dodecyl 4-phenyl sulphonate shown in Fig. 3. The
figure reveals a marked increase in dynamic surface tensions with the
onset of precipitation of the mesophase. In turn this suggests slow trans-
port of surfactant to air–water surfaces, which will contribute to low ad-
sorption levels, low positive contributions to disjoining forces and high
capillary pressures in Plateau borders. These factors will all conspire to
produce lower foam film stability during foam generation. However
after foam generation has ceased surfactant can slowly adsorb to ame-
liorate these factors ensuring the stability of any foam which survives
the process of generation.
All of this suggests the generalisation that precipitation of crystalline
or amorphous crystalline particles by addition of counterions to aque-
ous solutions of anionic surfactants may produce antifoam effects
whereas precipitation of mesophase is unlikely to do so. However pre-
cipitation in either case means that labile entities are replaced with
non-labile entities. In turn this means that the rate of transport of sur-
factant to the rapidly expanding surfaces present during foam formation
will be reduced. This factor will always contribute to diminished
foamabilities. In the case of crystalline precipitates it will even enhance
Clear micellar
region
Volume air in
foam/cm3
100
Lamellar phase
precipitate region
80
60
40
20
0 the bulk phase — so-called complete wetting [21]. In each of these three
-4 -3 -2
2+
Log10 ([Ca ]/M)
a
the likely antifoam effects. We should however emphasize that these
generalisations are drawn from relatively few examples. There is clearly
a need to extend these observations to other systems and include more
detailed characterization of the nature of the precipitates.
3. Antifoam effects by neat oils
3.1. Oil drops in aqueous foam films; definitions and theory
There is some confusion, even in recent literature, about the exact
criteria for effective defoaming action by liquid antifoams. Here we
give an abridged outline using an antifoam oil–water combination as
an example — with some important exceptions the same basic criteria
apply to other fluid–fluid systems. Full details are to be found elsewhere
(see for example reference [2⁎⁎]).
The first requirement for effective antifoam action is that the solubility
limit of the antifoam liquid in the foaming liquid should be exceeded
(there are however some exceptions to this generalisation — see for
example Section 3.3 and [2⁎⁎]). The second requirement is that the oil
be dispersed as drops, sufficiently small and numerous to ensure
presence in foam films. The third requirement is that the oil drops
spontaneously emerge into the air–water surface. This means that the
entry coefficient should be positive — a thermodynamic criterion.
However the aqueous “pseudoemulsion” film separating an oil drop
from the air is usually metastable and must first be ruptured by for
example, particles of a suitable wettability, if emergence of the drop is
to occur [2⁎⁎,3⁎].
Once the oil has emerged into the air–water surface there are
essentially three different phenomena which can occur. In the simplest
case the oil can form lenses without in any way contaminating the air–
water surface — so-called partial wetting (using the nomenclature of
Brochard-Wyatt et al. [21]). Alternatively the oil may spread to contami-
nate the air–water surface to form an unstable film which subsequently
breaks up to leave oil lenses in equilibrium with an air–water surface con-
taminated with oil — so-called pseudo-partial wetting [21]. Finally the oil
may spread to form a duplex film with no lenses. This film is so thick that
the oil–air and oil–water surface tensions of the film have the values of
cases the equilibrium spreading pressure, Se, must satisfy Eq. (1) where
we can only have [22]
e e
−2σ OW ≤ S ≤0 ð1Þ

Precipitation where σeOW is the oil–water surface tension. Eq. (1) means that (at equilib-
boundary rium) Se can only be either zero or negative. However in the case of both
pseudo-partial and complete wetting the oil must first spread over the
75 air–water surface before equilibrium is attained. In these cases a transient
“initial” positive spreading pressure prevails, defined by non-equilibrium
65 values of the relevant surface tensions.
An emerged oil drop, for which Eq. (1) is satisfied, may actually
55 bridge across both sides of an aqueous film. It was shown more than
thirty years ago [23] that if such an oil bridge forms in a plane parallel
45 foam film then it will be unstable if the angle θ* formed between the
air–water and oil–water surfaces is N π/2. That angle, θ*, is determined
35 by Neumann's triangle of surface forces so that we must have

25 
π=2 b θ ≤π ð2Þ
-4 -3.5 -3 -2.5 -2
Log10 ([Ca2+]/M)
b where θ* = π represents complete wetting of the aqueous film by a
duplex oil film. It follows from Neumann's triangle that we may rewrite
Fig. 3. Effect of precipitation of lamellar phase by addition of Ca2+ to a solution of 2 mM the Eq. (2) as
sodium 4-phenyl benzene sulphonate in 17 mM NaCl at 25 °C (a). Foamability by Bartsch
method (cylinder shaking by hand — see [2⁎⁎] for details). (b). Dynamic surface tensions e e
at surface ages; ▲, 0.1 s; ■, 1 s; ♦, 10 s. [19,20]. 0 b B ≤ 2σ OW σ AW ð3Þ
86 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
where B is the bridging coefficient defined by
e 2 e 2 e 2
B ¼ σ AW þ σ OW − σ AO
where σeAW and σeAO are respectively the equilibrium air–water and air–
oil surface tensions. Here we should note that if the oil exhibits a posi-
tive initial spreading coefficient, then mechanical equilibrium does not
exist between the three surface tensions while that transient condition
prevails and Neumann's triangle is violated. The bridging coefficient is
then meaningless with values higher than the upper limit of Eq. (3).
This restriction has not always been recognized [7⁎⁎,24–27].
There is much experimental evidence that the antifoam action of an
oil in an aqueous surfactant solution is largely confined to situations
where the bridging coefficient is positive [2⁎⁎,3⁎]. It should be stressed
also that Eqs. (2) and (3) account for antifoam effects by oils exhibiting
all types of possible wetting behaviour — complete wetting, pseudo-
partial wetting and partial wetting. Positive initial spreading coefficients
then simply imply a transient process of rapid supply of oil lenses or du-
plex film to foam films so that unstable liquid bridges can be formed.
Denkov et al. [3⁎,7⁎⁎] have proposed that unstable bridging drops
will lead to foam film rupture by either a bridging–stretching mechanism
or by a bridging–dewetting mechanism. In the bridging–stretching
mechanism the drop is stretched until the two oil–air surfaces touch
whereupon a hole forms and the drop is to torn apart to rupture the
film. By contrast the bridging–dewetting mechanism is supposed to
occur if the aqueous film peels off the drop in a manner similar to that
for a solid spherical hydrophobic particle [3⁎]. It would seem possible
that this mechanism could prevail if the viscosity of the oil is high
enough. Recently Denkov et al. [3⁎] claim to have observed bridging–
dewetting in the case of non-spreading mineral oils. The results are
however as yet unpublished.
Theoretical challenges here concern the exact nature of the process
by which a stretching oil drop ruptures a film — what are the conse-
quences for the drop, does it disproportionate into several smaller
drops as the foam film ruptures? What is the exact role, not only of cap-
illarity, but oil viscosity in the process and is the bridging–dewetting
mechanism likely to prevail at sufficiently high viscosities? There is
also some evidence that the magnitude of the bridging coefficient
(or θ*) can determine relative antifoam effectiveness even when the
Eq. (3) is satisfied [28] for which theory has no convincing explanation.
A recent study by Gao et al. [29] attempts to simulate the bridging–
stretching process in the case of an oil drop in a foam film formed from
an aqueous surfactant solution by recourse to a “steered molecular
dynamics” approach. Essentially this approach supplements classical
molecular dynamics with force probes to simulate processes which
are therefore only partially accounted for at a molecular level. In reality
the relevant forces are capillary and disjoining pressures which are
“mimicked” by arbitrary forces in this simulation, the molecular origins
of which are not revealed. In consequence it is not possible to link this
simulation to quantitative experimental observation. Also the simula-
tion produces only a two-dimensional view of the process little better
than the schematic diagrams to be found in the literature [2⁎⁎,3⁎].
None of the issues listed in the previous paragraph have therefore
been addressed (or even can be addressed by this kind of approach?).
Perhaps a more fruitful approach would be the use of the surface energy
minimization as exemplified by that described in Section 2.1 for the case
of solid particles at interfaces.
3.2. Comparison of the criteria for antifoam action by neat oils in aqueous
and non-aqueous liquids
Realization of antifoam effects in aqueous solutions of surface active
compounds by liquids which satisfy that Eq. (3) is inhibited by the
metastability of oil–water–air pseudoemulsion films. That metastability
largely derives from the electrostatic and steric contributions to the rel-
evant disjoining pressure isotherms due to adsorbed surfactant. It can
however be overcome in the case of drops trapped in Plateau borders
by the high capillary pressures attained as foam drains, producing
ð4Þ slow declines in the overall stability of foam [2⁎⁎]. Whether the resulting
foam film rupture, occurring in or at the edge of the Plateau border, is de-
termined by the bridging coefficient is however not yet established [2⁎⁎].
More commonly, however, rupture of pseudoemulsion films is achieved
in the case of commercial antifoams by adding hydrophobed particles
to the oil. Those particles supposedly rupture the pseudoemulsion
films by a bridging mechanism similar to that by which hydrophobic
particles rupture aqueous foam films (for full accounts of this see for
example [2⁎⁎,3⁎,7⁎⁎]). Other possibilities are sometimes claimed to
exist however. Shu et al. [27] for example show that addition of acid to
an aqueous solution of sodium oleate precipitates oleic acid drops and
causes reduction of foamability and foam stability. They claim that this
is due to a bridging antifoam effect by the oleic acid drops. The relevant
pseudoemulsion film is supposed intrinsically unstable at low pH due
to low levels of adsorption of charged species at the oleic acid–water in-
terface. The resulting absence of electrostatic effects would therefore
imply that particles are unnecessary in this case. However Shu et al.
[27] have not shown that removal of the oleic acid drops causes an in-
crease in foamability and therefore actual antifoam behaviour in this
case is not proven. The effect could be due entirely to transport effects
deriving from the change in concentration and nature of the remaining
dissolved surface active species after the addition of the acid. We should
note also that Shu et al. [27] present positive values of both spreading
and bridging coefficients in violation of Neumann's triangle so that the
quoted bridging coefficients are meaningless.
It has recently been shown that the defoaming of crude oil by
suitable neat liquid antifoams appears to involve a bridging mechanism
characterized by negative values of spreading coefficients and positive
values of bridging coefficients [30⁎]. Thus the available evidence
[30⁎] suggests that the criteria represented by Eqs. (1)–(3) are still
relevant for this non-aqueous system (making the substitutions of
σeGL for σeAW; σeDL for σeOW; σeGD for σeAO where σeGL, σeDL and σeGD are the
gas–crude oil, antifoam–crude oil and gas–antifoam surface tensions re-
spectively). We therefore have for the formation of unstable bridging
configurations by a neat antifoam liquid in this non-aqueous context
e e
0 b B ≤ 2σ DL σ GL : ð5Þ
However despite this overall similarity the differences in physical
properties between water and hydrocarbon liquids produce some im-
portant differences in the criteria for selection of antifoam liquids. The
dielectric constant of hydrocarbons is nearly two orders of magnitude
less than that of water which means that electrostatic effects derived
from charge separation of any solutes are essentially absent as shown
by Shearer & Akers [31] in the case of lubrication oils. Moreover adsorp-
tion of solutes at the air–hydrocarbon surface is expected to be small
[2⁎⁎,32]. In turn all this means that pseudoemulsion film stability is
likely to be low in this context and that therefore formulation of anti-
foams with particles is unnecessary, as revealed by normal commercial
practice. On the other hand the solubility of typical antifoam liquids
such as polydimethylsiloxanes and perfluoropolymers in hydrocarbons
is usually several orders of magnitude higher than in water (with poly-
dimethylsiloxane solubilities in crude oil of b10−3 g dm−3 and in water
of b10−6 g dm−3 [2⁎⁎]). Even polydimethylsiloxanes, when present at
concentrations below their solubility limit act as pro-foamers for
hydrocarbons [30⁎,31–33]. Effective foam control is then largely deter-
mined by solubility of such compounds. The study by Mansur and
coworkers [30⁎,33] of the antifoam behaviour of various alkoxylated
polydimethylsiloxanes in crude oil is illustrative. Here the solubilities
in the crude oil are reduced by incorporation of the alkoxy groups in
the polydimethylsiloxane chains. The most weight effective of these
molecules is the least soluble in the crude oil — differences in antifoam
effectiveness at equivalent concentrations above the solubility limits are
 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
not apparent with similar values of σeGD, positive values of bridging
coefficients and negative spreading coefficients [30⁎].
3.3. “Cloud point” antifoams
Ethoxylated and propoxylated nonionic surfactants and polymers
exhibit high solubilities in water at low temperatures and partial misci-
bility at higher temperatures. Above a critical temperature, micellar
solutions undergo a phase change to form two conjugate micellar
solutions — one dilute and the other relatively concentrated. This pro-
cess is accompanied by the onset of turbidity where the cloud point is
the temperature at which droplets of the concentrated conjugate
phase separate at a given overall surfactant concentration. Those drop-
lets readily act as antifoams for solutions of the dilute phase by a bridg-
ing mechanism apparently characterized by intrinsically unstable
pseudoemulsion films (see [2⁎⁎] for a review of this phenomenon).
Addition of ethoxylated and propoxylated nonionic compounds to
aqueous solutions of other surface active compounds can also produce
antifoam effects at temperatures above the cloud point. However the
cloud point may be increased or even eliminated in such systems as a
result of the formation of mixed micelles. Nevertheless compounds
such as polyethoxy–polypropoxy block copolymers are often described
as “cloud point” antifoams. Despite this nomenclature Nemeth et al. [34]
have shown that such compounds can exhibit antifoam effects when
added to aqueous solutions of a protein–bovine serum albumin at low
concentrations so that the cloud phase is absent. In such solutions the
polymers simply displace the protein from the air–water surface to pro-
duce low foamability much as would be the case in the absence of the
protein. Marinova et al. [35] recently report similar observations with
this type of polymer but with a different protein–sodium caseinate.
However these observations include some curious features. Firstly in-
creasing the concentration of two of the polymers studied, up to con-
centrations where cloud phase is present, is reported to actually
increase the foam height. Since the activity of the polymer will be at a
maximum at phase separation it is difficult to see how that could de-
crease any antifoam effect concerning displacement of protein from
the air–water surface. Another interesting feature concerns the effect
of addition of Ca2+ to the chosen system but with the polymer concen-
tration high enough for cloud phase drops to be present. This apparently
produces a precipitate of CaCO3, particles of which seem to be
hydrophobed so that they adhere to the cloud phase drops. The pres-
ence of such particles appears to be essential for the cloud point anti-
foam effect in this case because in the absence of Ca2 + there is
apparently little such effect. This then appears to represent an analogue
of the well-known oil-particle antifoam synergy. In turn this suggests
that the pseudoemulsion films present in these systems are intrinsically
relatively stable in contrast to those formed in the case of aqueous dis-
persions of cloud phase in the absence of any additional surface active
species. A detailed study of these issues would appear to be justified
in order to provide a firm basis for the optimisation of these cloud
point antifoams which find wide application in dish washing formula-
tion, sugar beet processing, and fermentation.
4. Mixed Oil-particle antifoams for aqueous solutions
4.1. Mode of action
It is now well-known that oils which exhibit positive bridging coef-
ficients in aqueous surfactant solutions are relatively ineffective as anti-
foams unless mixed with suitable hydrophobic particulate promoters
[2⁎⁎]. The role of the latter concerns reduction of the critical capillary
pressure required to overcome the disjoining forces in the oil–water–
air pseudoemulsion films to permit film rupture by bridging oil drops
[2⁎⁎,3⁎,7⁎⁎]. A detailed review of the present level of understanding is
given in reference [2⁎⁎]. However there remain serious challenges to
both experiment and theory, particularly concerning the role of particle
87
geometry, contact angle and even particle size. Here we should note
that even the orientation of particles of simple geometry at fluid–fluid
surfaces has been shown by surface energy minimization to be surpris-
ingly complex (see Section 2).
4.2. Transient dynamic effects
Another aspect of antifoam function concerns the likelihood that the
rate of surfactant transport to the rapidly expanding air–water surfaces
formed during foam generation is not fast enough to maintain equilibri-
um. This factor can give rise to high dynamic surface tensions during
foam generation and can therefore produce positive transient bridging
coefficients which become negative as surface tensions decline and
trend towards equilibrium values after foam generation ceases. Similar-
ly high dynamic surface tensions imply low dynamic adsorption levels
and therefore diminished contributions to the magnitude of disjoining
forces. In turn this could reduce entry barriers and facilitate emergence
of antifoam drops into the air–water surface. Approach to equilibrium
may subsequently lead to enhanced positive disjoining forces, failure
of drops to emerge into air–water surfaces and ineffective antifoam
action. Examples are known where the dynamic effect on the bridging
coefficient appears to dominate. Li Ran [20] for example has recently
reported negative bridging coefficients using equilibrium surface
tensions for a tristearin/triolein antifoam in sodium dodecyl 4-phenyl
sulphonate solutions – antifoam effects are only apparent under
dynamic conditions – the foam becomes stable after foam generation
ceases.
An obvious difficulty with these dynamic phenomenon concerns the
actual state of the air–water surfaces during foam generation. Calcula-
tion of bridging coefficients, for example, requires knowledge of the
air–water surface tension under dynamic conditions. Although dynamic
surface tensions can be readily measured as a function of surface age, in
general, we have no clear knowledge of the actual effective surface age
of the air–water surfaces during foam generation. Estimates have how-
ever been made, Garrett and Moore [28] have for example set the sur-
face age during foam generation by Ross Miles technique as 0.5–1 s.
Denkov et al. [3⁎] estimate that surface ages during typical foam gener-
ation as 0.1–1 s with a characteristic time for Ross Miles of 0.1–0.2 s.
Differences in characteristic time with different foam generation
techniques mean that antifoam effectiveness can even vary depending
upon the technique as shown by Marinova et al. [1]. It would seem
that enhanced dynamic antifoam effects are to be expected in decreas-
ing order; hand-shaking cylinders (the Bartsch method) N Ross-
Miles N bubble columns (see [2⁎⁎] for a description of these methodol-
ogies). The key challenge here is of course direct measurement of the
surface tension of the upper air–water surface of foam during genera-
tion for each of these techniques.
Transient antifoam effects accompanying foam generation have also
been shown to be apparent when foam is generated under micro-
gravity. This behaviour has been observed during a comparison of
foam behaviour under micro-gravity in the International Space Station
with that under earth gravity [36⁎]. This study included the effect of a
polydimethylsiloxane/silica antifoam on foam generation from aqueous
sodium dodecyl sulphate solutions using the Bartsch method [2⁎⁎].
Addition of this antifoam produced foam which totally collapsed in 2 s
under Earth gravity using the selected conditions. That any foam gener-
ated rapidly collapsed under gravity implies that this antifoam is effec-
tive under both dynamic and the near equilibrium conditions prevailing
after foam generation has ceased. In contrast significant amounts of
stable foam were generated under micro-gravity. Not surprisingly
Caps et al. [36⁎] attribute the presence of stable foam under micro-
gravity to the absence of gravity-driven drainage. Gas volume fractions
of this residual foam were so low that foam films would not exist
(i.e. with volume fractions of air ≤ ~ 0.72 [2⁎⁎]) — inter-bubble dis-
tances would be so thick that antifoam drops would not be able to
form bridging configurations leading to foam collapse. However the
88 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
total volume of foam generated in the presence of the antifoam was sig-
nificantly less than that generated under gravity in the absence of anti-
foam. Clearly some foam films must have been formed during shaking
of the relevant vessels to permit transient antifoam action to occur
under micro-gravity despite the absence of gravity driven drainage.
4.3. Antifoam deactivation
That polydimethylsiloxane (PDMS)/hydrophobed silica antifoams
gradually deactivate during the processes of foam generation (and
even during emulsification) is well-known [2⁎⁎]. It has been shown
by Denkov and co-workers [3⁎] that this deactivation appears to be
driven by disproportionation of antifoam oil drops containing parti-
cles into a population of inactive particle free drops and particle-
enriched drops and agglomerates, where the latter can assume
sizes of the order of mms. A detailed review of this issue is to be
found in [2⁎⁎].
It has been shown that the process of disproportionation cannot
simply concern a random distribution of particles across drops [2⁎⁎] –
that could in any case not account for the formation of large silica rich
agglomerates. Some process of coalescence is clearly implicated – in-
deed the presence of hydrophobed silica could facilitate that process
[2⁎⁎]. It has been suggested [2⁎⁎] that continuous drop splitting and co-
alescence could produce the disproportionation where the higher
viscosity of particle-rich drops inhibits splitting and facilitates coales-
cence. That drop splitting is also important is implied by overall de-
creasing rates of deactivation with increasing viscosity of the PDMS
[37]. Perhaps a rule-based simulation could be based on these observa-
tions to provide a clear explanation for the deactivation process.
An additional complication however concerns the behaviour of
other oil/particle antifoams. There is some evidence for example that
hydrocarbon/hydrophobed silica antifoams also show deactivation
when dispersions are subject to continuous aeration as do mixtures of
PDMS with ethylene distearamide [2⁎⁎]. On the other hand there is
that with (organic liquid/organic particle)-based antifoams deactivation
can be extremely slow (or even absent) [2⁎⁎]. For example antifoam
mixtures of triolein with tristearin particles reveal little or no deactiva-
tion after 2h of continuous aeration in solutions of sodium alkyl benzene
sulphonate [19].
If then all these various oil/particle antifoams are subject to the same
splitting and coalescence processes then we can have radically different
outcomes. It seems likely that those differences derive from the ease
with which intractable particle-rich entities can be formed. This in
turn may concern the viscosity of the oil, the rheology of the oil/particle
mixtures as a function of particle volume fraction and concentration, de-
gree of aggregation and even particle geometry. Systematic experimen-
tal studies of the behaviour of different antifoam types with respect to
rates of deactivation and characterized with respect to this list of vari-
ables would seem to have merit especially if combined with attempts
to develop a rule-based simulation of the deactivation process.
Experimental investigations of the effect of antifoam concentration
on the rate of deactivation are extremely rare. One such investigation
is reported by Pelton [38] for a PDMS/silica antifoam with foam gener-
ated by sparging. A theoretical treatment of deactivation which affords
comparison with these experiments has been published recently
[2⁎⁎]. Somewhat simplistically we can represent the deactivation pro-
cess as the sum of a first order splitting phenomenon and a second
order coalescing phenomenon so that the rate of loss, dc(t)/dt, of effec-
tive antifoam entities is given by
dcÞt 2 through a porous frit at 7 cm3 s−1. Antifoam concentrations, ■, 0.1 g dm−3; △,
− ¼ k1 cðt Þ þ k2 cðt Þ
dt
where k1 and k2 are rate constants and c(t) is the concentration of active
antifoam at time t. Integration of Eq. (6) yields c(t) as a function of time.
An empirical relationship between the known foam volume and
concentration may be used. Thus Garrett [2⁎⁎] has shown that a simple
exponential can represent the antifoam concentration dependence of
foam behaviour in the case of sparging in the presence of polydimethyl-
siloxane/silica antifoam at short times where deactivation is negligible
and concentration is therefore known. We can therefore write
Z
t
V F ðt Þ ¼ V G expðm  cðt ÞÞdt ð7Þ
0
where m is an empirical constant, VG is the volumetric gas flow rate and
VF(t) is the foam volume at time t in the presence of deactivating anti-
foam of residual antifoam concentration c(t). Integrating Eq. (6) and
substituting for c(t) in Eq. (7) produces an integral equation for the
time dependence of VF(t) containing three unknown constants — m, k1
and k2. This equation can be fitted to a plot of VF(t) against time for a
given initial antifoam concentration, c(t = 0), to obtain values of those
constants. The fit is shown in Fig. 4. A test of theory is then the predic-
tion of the time dependence of VF(t) for different initial antifoam con-
centrations which are also presented in the figure. Semi-quantitative
agreement is found — that agreement however represents a significant
improvement over earlier attempts [38] to interpret these results.
5. Mechanical defoaming
5.1. Ultrasonics
That ultrasound may represent a method of defoaming has been
known for more than sixty years. Initial demonstrations of defoaming
utilized sirens which proved impractical. Successful application re-
quired the development of piezoelectric ultrasonic generators in the
late 1970s. A review of the history of defoaming by ultrasound is to be
found in [2⁎⁎].
Some context is provided if we consider the general features of the
interaction of sound with foam in the usual case where the ultrasonic
generator is placed above the foam, separated by an air gap, as shown
in Fig. 5. Firstly we note that the velocity of sound in foam is significantly
less than that in either air or water [39] where we also remember that
the velocity of sound in water is more than three times faster than in
air. This means that the wavelength of the sound pressure wave de-
creases as it passes into foam from the air as shown in the figure.
Sound is also attenuated when passing through foam. Thus the rate of
3
Foam volume, V(t)/ cm
1000
900
calculated
800
700
600
500
400 fit
300
200
100
0
0 500 1000 1500 2000 2500
Time/s
Fig. 4. Deactivation of a hydrophobed silica/polydimethylsiloxane antifoam emulsion
dispersed in 5 g dm−3 of a dishwashing liquid [38]. Foam generated by passing nitrogen
ð6Þ 0.3 g dm−3; and ♦, 0.5 g dm−3. Fit to results at 0.5 g dm−3 yielded m = −9.65 g−1 dm3;
k1 = 1.3 × 10−6 s−1; k2 = 1.36 × 10−3 g−1 dm3 s−1 in Eqs. (6) and (7). These values
were used to calculate the plots shown for 0.1 and 0.3 g dm−3.
([2⁎⁎], © 2013 from The Science of Defoaming: Theory, Experiment and Applications by
P.R.Garrett. Reproduced by permission of Taylor and Francis Group, LLC, a division of
Informa plc).
 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
source
air
foam
liquid
Fig. 5. Schematic showing propagation of sound waves through foam in a bubble column.
Continuous lines represent progressive waves and broken lines represent reflected waves.
(after Komarov, S.V. et al. [43]. Originally published in ISIJ International).
delivery of acoustic energy per unit area, the acoustic intensity IH, after
passing through a foam layer of height H is given by [40]
IH
¼ expð−2αH Þ ð8Þ
IA
where IA is the acoustic intensity transmitted through the air–foam in-
terface and α is the attenuation coefficient. The attenuation coefficient
increases with increasing frequency [40]. The acoustic intensity is pro-
portional to the square of the amplitude of the pressure fluctuations
caused by the sound wave. The amplitude of that wave is therefore
shown in Fig. 5 to decline as it passes through the foam. However the
acoustic intensity arriving at a given interface is partially transmitted
and partially reflected at that interface. In general then [41]
IA 4Z 1 Z 2
¼ ð9Þ
Ii ðZ 1 þ Z 2 Þ2
where Ii is the incident intensity at the interface. Z1 and Z2 are the spe-
cific acoustic impendances of mediums 1 and 2 respectively where the
specific impedance of a medium is the product of the density and the
velocity of sound in that medium. Here we note that if Z1 = Z2 the trans-
mission is total but if there is a marked imbalance between the acoustic
impendances so that either Z1 ≫ Z2 or Z1 ≪ Z2 then transmission is min-
imal. In the case of foam of gas volume fraction 0.999 at the top of the
foam column, for example, the acoustic transmission is almost 94% at
the air–foam interface [2⁎⁎]. However in the case of a very wet foam,
with a gas volume fraction at the Kugelschaum limit of ~ 0.72 at the
89
top of the foam column [2⁎⁎], only about 10% of the acoustic energy is
transmitted into the foam. The imbalance is even more marked at the
water–foam interface. The high velocity of sound in water means that
essentially no acoustic energy will be transmitted across that interface
regardless of whether the transmission is from water to foam or foam
to water as shown in Fig. 5. Winterburn and Martin [42] have in fact
shown that placing the ultrasound generator in the aqueous phase is in-
effective in causing defoaming.
Although defoaming by ultrasound can be achieved there have ap-
parently been few attempts to understand or even optimize the process.
However some early insight is provided by the work of Komarov et al.
[43]. This study in part concerned the effect of low frequency sound
(using a loud speaker and therefore not in the ultrasound range) on
the steady state foam height obtained by sparging a solution of a surfac-
tant in aqueous mixtures of different proportions of glycerin and water.
For a given frequency defoaming became apparent only at a threshold
acoustic intensity (as measured by the acoustic pressure). Increase in
frequency however increased the threshold value of the acoustic inten-
sity. Increasing the viscosity of the solution decreased the threshold
slightly. All of this tends to suggest an optimal frequency where the
acoustic energy required for a given extent of defoaming is minimal.
Rodriguez et al. [44] have more recently made a study of the effect of
acoustic intensity on defoaming a fixed volume of foam sparged from an
aqueous solution of “soap”. This utilized only one ultrasonic frequency
of 25.8 kHz which was generated from a piezoelectric device. As found
by Komarov [43] there appears to be a threshold acoustic intensity
below which defoaming does not occur. Beyond the threshold
defoaming increases with increase in the total amount of acoustic ener-
gy — i.e. the higher the acoustic intensity and the longer it is applied
above the threshold the greater the volume of foam destroyed. Usefully
Rodriquez et al. [44] include gas volume fractions and estimates of bub-
ble sizes in their study. The wavelength of the ultrasound can be calcu-
lated from the frequency and knowledge of the velocity of sound as a
function of gas volume fraction in a foam (see for example Kann [39]).
We find then that in the case of foam with bubble diameters of
0.2–2 mm the acoustic wavelength was ~4 mm and in the case of bubble
diameters of 0.2–10 mm the wavelength was ~ 6 mm. These findings
hint at the possibility that defoaming by ultrasound concerns a
resonance with the mesostructure of the foam. The nature of any quan-
titative relationship between the bubble diameters and acoustic wave-
length would however require detailed knowledge of the bubble size
distributions so that at least mean bubble diameters can be calculated.
A recent paper by Ben Salem et al. [45⁎⁎] represents a significant de-
velopment in the understanding of the propagation of ultrasound in
aqueous foams. In this work the ultrasound frequency was again main-
tained constant but at acoustic intensities below the threshold for
defoaming. The bubble size of the foam was measured by image analysis
and allowed to vary by the process of diffusional disproportionation.
The change in amplitude of the ultrasound signal of constant incident
acoustic intensity across a sample of foam of known thickness was
used as a measure of the attenuation of acoustic intensity. The phase dif-
ference yielded the transit time across the foam and therefore the speed
of sound in that context. The relative amplitude varied as a function of
time as the bubble sizes increased due to diffusional disproportionation.
A plot of relative amplitude against time yielded a pronounced mini-
mum at a “transition time”, implying a maximum rate of energy absorp-
tion by the foam. A separate plot of the evolution of bubble size against
time meant that this transition time could be related to a “critical” bub-
ble size. Ben Salem et al. [45⁎⁎] used these techniques to compare the
transition times and critical bubble sizes of two radically different
foams — a shaving foam in air and a dilute SDS solution in C6F6. Despite
radically different extents of acoustic attenuation and rates of dispro-
portionation the critical bubble sizes of each of these foams were in
the same range, i.e. 50 ± 20 μm. Ben Salem et al. [45⁎⁎] then argue
that at the critical radius the “bubbles become resonant, hence they
pump a maximum of energy from the incident signal”. We should
90 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
however note that the critical bubble radius is about an order of magni-
tude less than the relevant acoustic wavelengths — this leaves open the
question of what energy absorption process could scale in such a man-
ner. Perhaps it concerns the number and size of foam films rather than
that of the bubbles [46]. Nevertheless it would appear surprising if the
critical bubble radius is not also some function of the acoustic frequency.
These findings of Ben Salem et al. [45⁎⁎] may be relevant for
defoaming by ultrasound where the latter may also involve resonance
but at higher incident acoustic intensities above the threshold leading
to foam film destruction of bubbles of the critical size. This could suggest
a possible speculative model for defoaming by ultrasound. Thus
defoaming becomes maximal if the bubble sizes are at the critical size
range for the resonant frequency. Increasing the intensity at that fre-
quency will produce progressively more effective defoaming. However
increasing the frequency above the resonant frequency for a foam of a
given bubble size will mean less efficient energy transfer into the
foam, needing higher threshold acoustic intensities for defoaming as
shown by Komarov [43]. If realistic all this could imply that optimal
defoaming requires multiple frequency generators tuned to the bubble
sizes in the polydisperse foams of practical interest. It does not however
address the nature of the actual process of foam collapse during the
application of ultrasound.
5.2. Use of rotary devices
Various rotary devices have been suggested for the control of foam,
especially in sparged unstirred and stirred bubble columns [2⁎⁎].
These devices are exemplified by spinning blades, rotor-stators,
turbines, and discs, placed at the top of these bubble columns. There
appears to be little consensus about the mode of action of such devices,
being variously attributed to either centrifugal or shear forces [2⁎⁎].
However the absence of any significant recent published literature on
this matter places the subject outside the scope of this review — an
account of earlier work is to be found in reference [2⁎⁎].
5.3. Orifice defoamer
Liu et al. [47] describe a defoaming device consisting of a collection
of perforated plates. Defoaming is induced by simply passing foam
through the orifices in the plates. However the orifices must have small-
er diameters than those of the bubbles in the foam. This arrangement
means that large deformations of bubbles occur as they pass through
the orifices. Foam films are thereby stretched until they rupture. This
in turn causes bubble coalescence and collapse, both of which contrib-
ute to defoaming. Observations of defoaming with this device were
however confined to aqueous submicellar sodium dodecyl sulphate
(SDS) solutions of concentrations ≤~3.5 × 10−3 M.
A measure of the resistance to stretching of a foam film is provided
by the Gibbs elasticity. Lucassen [48] has presented plots of Gibbs
elasticity, εG, for submicellar solutions of SDS which show a maximum
at ~ 2.5 × 10− 3 M for film thicknesses in the region of 1–2 μm. At
concentrations of SDS lower than that maximum the gradient of Gibbs
elasticity with respect to concentration, dεG/dc, is positive. This means
that if a foam film is stretched so that both the thickness and the
intra-lamellar surfactant concentration are reduced then the Gibbs elas-
ticity also decreases [2**,48]. Lucassen [48] argues that the film will then
be dynamically unstable. This conclusion appears to be consistent with
the observations of Liu et al. [47] who report decreasing defoaming ef-
fects with increasing SDS concentration up to ~3.5 × 10−3 M which is
close to the maximum experimental value quoted by Lucassen [48].
Any discrepancy could be due to the role of dynamic factors in the func-
tion of the device used by Liu et al. [47]. However if the apparent consis-
tency with the calculations of Lucassen [48] represents the reason for
the defoaming effect then increasing the surfactant concentration so
that dεG/dc b 0 (under the relevant dynamic conditions) will tend to
eliminate that effect.
6. Summarizing remarks
We conclude by summarizing the significant recent developments
and the remaining challenges in the study of defoaming. Use of surface
energy minimization clearly represents an example of such a develop-
ment, representing a useful technique for predicting the orientations
of particles at surfaces. It may also represent a means of simulating
other phenomena of importance in the study of defoaming such as the
bridging–stretching process and the effect of bridging drops in Plateau
borders. Limitations include exclusion of disjoining forces in thin films
and, of necessity, viscous dissipation.
Foam generation is a dynamic phenomenon where air–water sur-
faces may depart significantly from equilibrium if the rate of surfac-
tant transport to surfaces is slow relative to the rate of formation of
those surfaces. More evidence has been obtained to show that this
can lead to transient antifoam effects which only occur during foam
generation. In turn this can mean that the effectiveness of antifoams
can vary according the method of foam generation. A key and very
difficult challenge here is the characterization of the air–water
surface during actual foam generation. Such transient effects
concerning antifoam action are also apparent under micro-gravity
but are then due to low gas volume fractions and the absence of liq-
uid drainage after foam generation has ceased and do not concern
transport to air–water surfaces.
Precipitation of anionic surfactant from aqueous solution as
mesophase particles can be induced by the addition of, for example,
excess counterions. Such precipitation is accompanied by declines
in foamability due to the slow transport of the surfactant present in
the mesophase particles to the air–water surface. Similar behaviour
is apparent in the case of surfactants at temperatures below the rel-
evant Krafft temperature where the precipitate is then crystalline.
However the hydrophobic nature of such precipitates of surfactant
means that antifoam effects are likely to be superimposed upon the
transient effects due to slow surfactant transport to air–water sur-
faces. These generalisations are, however, based upon a relatively
small number of examples.
Extension of modern insights into the mode of action of antifoams
in aqueous systems to the study of non-aqueous systems has been
essentially absent until recently. In the case of a hydrocarbon based
liquid like crude oil it has recently been shown that antifoam action
by liquid alkoxylated polydimethylsiloxane antifoams occurs with
positive bridging coefficients and negative spreading coefficients.
The main differences with respect to aqueous systems concern
(1) the absence of factors which stabilize pseudoemulsion films so
that particles are not a necessary components of the antifoams and
(2) the relatively high solubility of these PDMS derivatives in the
foaming liquid (i.e. crude oil).
Mixtures of PDMS and hydrophobed silica are known to be effective
antifoams for aqueous systems. However these antifoams deactivate in
use. The process involves disproportionation of the dispersed antifoam
into inactive oil drops without particles and particle rich drops and ag-
glomerates. A simple theory based upon an assumption that this
process involves both first order drop splitting and second order coales-
cence is in semi-quantitative agreement with experimental observa-
tions of deactivation. However there is evidence that deactivation is
not a common feature of all types of oil/particle antifoams. There is a
need therefore to study this issue in order to improve overall under-
standing of deactivation so that more effective antifoams may be
developed.
Recent accounts of defoaming by mechanical means are largely con-
fined to the use of ultrasonics. There are indications that defoaming by
application of ultrasound is a resonant phenomenon where an optimum
frequency is tuned to a critical foam dimension which unsurprisingly
appears to be some function of bubble size. More effective application
of ultrasound in this context would appear to require detailed study of
this issue.
 P.R. Garrett / Current Opinion in Colloid & Interface Science 20 (2015) 81–91
Acknowledgement
The author is grateful to Dr. Gareth Morris (Imperial College) for
supplying the images shown in Fig. 2.
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