Defoamers

TEGO® Foamex

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 Foam is a phenomenon which frequently • mechanical introduction of air during
occurs during the manufacture and appli- applications such as rolling, spraying,
What is foam?
cation of coatings and printing inks. The printing
formation of foam interrupts, for exam- • displacement of air when coating A stable dispersion of gas in a liquid is
ple, production processes, reduces the porous substrates called foam. If a stream of air is intro-
effective volumes in the production plant • chemical reaction such as the secondary duced into a liquid, the bubbles produced
and leads to unnecessary downtimes. reaction of isocyanates with water assume a spherical shape. Since they are
Foam also interferes with the application lighter than the liquid, the bubbles rise.
process. In printing, foam can cause the Stabilization of the liberated air to form A gas bubble, which has penetrated a sur-
ink reservoirs to overflow and impairs ink foam occurs as a result of surface-active factant-free liquid, has only limited stabil-
transfer from the printing cylinder to the substances (surfactants) present in coat- ity and bursts spontaneously. Air from the
substrate. Dried foam leaves surface ings and printing ink formulations where bubbles escapes and the liquid previously
defects in the paint film. they are essential for stabilizing, dispers- surrounding the air flows back. There-
ing and wetting the formulation. fore, stable foam does not form in pure,
The cause of foam is the introduction of surfactant-free liquids (fig. 1).
gas into the liquid material. The occurrence of foam must therefore
be considered as an undesirable but In liquids such as paints containing surfac-
This can occur by: unavoidable phenomenon in coatings tants, the gas bubbles are stabilized by the
• mechanical introduction of air during and printing inks. To prevent foam and surfactants. A surfactant film forms
manufacture by stirring and mixing destroy any foam present, defoamers around the gas bubble. If these bubbles
• displacement of air during wetting of have to be added to the formulation. reach the surface, which is also coated
pigments and fillers with surfactants, a surfactant-stabilized
double layer or duplex film is formed
(fig. 2).

macro-foam

micro-foam

Figure 1: Rise and bursting of air bubbles in surfactant-free liquids Figure 2: Rise and stabilization of air bubbles in a liquid containing surfactant

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 Once the macro-foam bubbles have
penetrated the surface, they initially
gas liquid gas
become spherical. In this phase, the vol-
~10 ... 100nm ume of the liquid in the foam is greater
foam lamella
than the volume of the air in the foam
macro-foam bubbles. Therefore, this foam is termed
wet foam. The foam bubbles are still
defoamer foam lamella
spherical and are stabilized by thick foam
lamellas. The bubbles from the liquid
cause a continuous rise in the foam head.
amphiphilic molecule
The liquid flows out of the foam lamella
gas liquid hydrophobic under gravity. During this so-called drain-
deaerator hydrophilic age process, the proportion of air in the
micro-foam foam increases. The spherical foam is now
forced to take on a more stable polyhedral
water with foam stabilising interfacial region ~ 1 nm shape. The polyhedral foam is termed dry
substances
foam because the volume content of
liquid is small. Polyhedral foam consists
Figure 3: Structure of foam and stabilization of the lamella by surfactants
of very thin (approx. 100 nm) but very
elastic foam lamellas, which are stabilized
by the surfactant molecules coating the
surface. The varying structure of foam is
Duplex films can occasionally be fractions summarized in fig. 3.
of a millimeter thick. Despite their very
small film thickness, they can form very
stable foams which are extremely difficult
to destroy. Foam stabilization
One can distinguish between two types Drainage would be expected to com-
of foam: macro- and micro-foam. Macro- pletely remove the water from foam
foam is the foam visible on the surface. lamellas which would then collapse on
Foam bubbles generally have a diameter their own accord. In practice, drainage
of more than 50 μm and are stabilized by comes to a halt when loss of liquid in the
a duplex film. Very fine foam bubbles, lamellas causes the surfactant concentra-
which are entrapped in the matrix of the tion to be so high that steric or electro-
coating film, are called micro-foam. To static repulsion forces between the sur-
eliminate macro-foam, defoamers are factant molecules prevent further
used; to eliminate micro-foam, deaerators retraction of the lamella walls. The foam
are used. (see “Technical Background lamella attains a thermodynamically stable
Deaerators“). state of equilibrium between drainage and

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 surfactant repulsion. Highly thinned foam deduce the requirements a compound or As already described, defoamers work
lamellas are therefore very stable and very formulation must meet to be effective as by penetrating and destroying the foam
elastic. The elasticity of the lamellas can be a defoamer. lamellas. It is a prerequisite that the
explained in terms of the Gibbs-Marangoni defoamer is in a position to penetrate the
elasticity. An increase in the lamella surface Requirements for defoamers: surface of the foam lamella. The first
caused by deformation of the foam lamella • insoluble in the formulation to be barrier to be overcome when penetrating
leads to a locally reduced concentration of defoamed is the pseudoemulsion film. This is a
surfactant and, with it, an increase in the • low surface tension thin liquid lamella between the rising
surface tension of the lamella. The resul- • positive penetration coefficient (E) defoamer droplet and the liquid surface.
tant imbalance results in strong restoring • positive spreading coefficient (S) or If the pseudoemulsion film is too stable, a
forces towards the energetically more positive bridging coefficient and defoamer droplet cannot penetrate the
favorable unstretched state of the foam dewetting characteristics surface and defoaming is not possible.
lamella (fig. 4).
Fundamentally, a defoamer must be insol- Once the defoamer droplet has overcome
uble in the formulation to be defoamed the pseudoemulsion film and penetrated
where it should be present in the form of the lamella, its further behavior can be
How do defoamers finely divided droplets. Furthermore, it is described using the penetration coeffi-
work? necessary for it to be sufficiently compati- cient which can be calculated from the
ble with the medium to be defoamed not interfacial tensions between the three
Whether defoamers or deaerators are to cause surface defects such as craters. phases: the liquid to be defoamed,
used depends on the type of foam, i.e The choice of defoamer is therefore always defoamer and air. It describes the force
macro- or micro-foam. To eliminate a compromise between defoaming perfor- equilibrium between the three phases.
macro-foam on the surface, prevent large mance and compatibility/insolubility.
air occlusions and for rapid foam collapse
in waterborne formulations, defoamers
are preferred. If finely dispersed air needs
to be removed from the system, deaerators
are preferred. In practice, it is usually not
possible to differentiate clearly between
defoamers and deaerators. Most defoam-
ers are also effective to some degree as Figure 4: Gibbs-Marangoni elasticity

deaerators and the reverse is true. The with surfactants to saturated interface
region to lower surface tension
mechanisms of deaeration are described Gibbs-Marangoni elasticity
in the section on deaerators.

Defoamers work by penetrating the foam

lamella, destabilizing it and making it
burst. Investigations using model systems retraction
have resulted in various mechanisms of
defoaming being discussed in the litera- elongation
ture. From the models, it is possible to

readjust power to equilibrate

surface tension

with surfactants to unsaturated interface

region to increased surface tension

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 Only if the penetration coefficient
remains positive, does the defoamer S = w/a– w/o – o/a = w/a– (w/o+ o/a)
remain permanently on the lamella
spreading coefficients formula
surface. If the penetration coefficient is
negative, the defoamer drop can migrate
back to the liquid phase.

are impaired and it may collapse. The Defoamers with insufficient spreading
E = w/a+ w/o – o/a spreading process leads to flow of the power may defoam through another
lamella liquid along the direction of mechanism called bridging. The basic
w/a = surface tension of the foaming spreading. This phenomenon, also known prerequisite is that the defoamer is
liquid as Marangoni flow, causes a local thinning capable of penetrating the foam lamella
w/o = interfacial tension between of the lamella at the location of the and has a positive penetration coefficient.
the defoamer and the foaming spreading defoamer droplet and leads to Defoaming by bridging requires that a
liquid further destabilization of the lamella. The defoamer droplet which has penetrated
o/a = surface tension of the defoamer penetration and spreading of a defoamer the lamella surface must also be capable
droplet is illustrated in fig. 5. of penetrating the opposite lamella side.
Frequently, this is only possible once
The spreading behavior can be described the lamella has been sufficiently thinned
If one assumes the interfacial tension of via the spreading coefficients as the equi- by continued drainage. In some cases,
the foaming medium w/a is constant, the librium of the surface tensions of the defoamer droplets become sufficiently
equation shows that a positive spreading three phases with each other. Only large by coalescing with other defoamer
coefficient can only be achieved if the defoamer droplets with positive spreading droplets for the bridging mechanism to
surface tension of the defoamer o/a is coefficients can spread on the surface of occur. If the defoamer droplet has pene-
sufficiently small. the medium to be defoamed. trated both sides of the lamella, a subse-
quent dewetting or stretching mechanism
The defoamer droplet may spread after The equation for spreading coefficients can lead to rupture of the lamella.
penetrating the lamella. If a defoamer can shows that defoamers can only spread
spread on the surface, it forms a defoamer if the sum of their interfacial tensions to
lens at the lamella surface and displaces air and to the medium to be defoamed is
the surfactants at this location. As a result, smaller than the surface tension of the
the stability and flexibility of the lamella foaming liquid.

Figure 5: Penetration and spreading of the active ingredient of the defoamer

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 B = (w/a)2 + (w/o)2 – (o/a)2
bridging coefficients formula

A basic condition for both mechanisms is If defoaming takes place via a stretching
for the bridging coefficient of the mechanism, the bridging defoamer drop-
defoamer to be positive. let marks the weakest point in the lamella.
If the lamella stretches, it ruptures at even
Calculation of the bridging coefficients very low stretching forces on the
involves the square of the interfacial ten- defoamer droplet (fig. 7).
sions. The bridging coefficient can only
be positive if the interfacial tension
between the defoamer and air is suffi-
ciently small.

In the case of the dewetting mechanism,

the foaming liquid is not capable of wet-
ting the surface of the defoamer droplet.
Consequently, dewetting of the defoamer
droplet occurs and the foam bubble col-
lapses. Solid defoaming agents can also
Figure 6: Film bridging during defoaming
act via a dewetting mechanism (fig. 6).

Figure 7: Dewetting during defoaming

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 individual coatings formulations. Polysi-
loxane defoamers have very high spread-
ing characteristics and are highly effec-
tive. They are used particularly frequently
in modern waterborne coatings and print-
ing inks where high demands are made
on defoaming characteristics and surface
finish. Applications include pigmented
and unpigmented wood, architectural and
industrial coatings and printing inks. They
do not impair gloss and are distinguished
by good compatibility. Modified poly-
siloxanes are synthesized by forming a
Si-O-C or a Si-C link between the
Which classes of substance have a defo- siloxane block and the organic modi-
aming effect in waterborne coatings? fication (fig. 8).

Typical active substances for formulating Silicone defoamers (polysiloxanes) Mineral oil defoamers
defoamers for waterborne coatings are:
polysiloxanes (silicones), mineral-, vege- Polysiloxanes and modified polysiloxanes Mineral oils, with their high spreading
table-oils and/or polymers. Particularly belong to the most widely used group of power and high incompatibility, have long
effective defoamers tailored to specific defoaming substances. An enormous been used as defoaming agents. Nowa-
applications can be formulated by com- range of defoaming agents is accessible days, aliphatic mineral oils are used in
bining the substances with each other and via modification with polyethers or other defoamer formulations. Aromatic oils are
also by adding fine-particle hydrophobic polymers. The compatibility and effec- increasingly rare because of environmen-
solids such as silicas. tiveness of these can be adjusted to suit tal and physiological considerations. Min-
eral oils are frequently used in the archi-
tectural paints and printing inks sectors.
When used in waterborne formulations,
where high demands are made on the
Figure 8: Typical polyether siloxane structures gloss of the finish, mineral oils frequently
ABA block copolymer comb-shaped copolymer reach their limits since they tend to impair
gloss or cause other surface defects.

branched
copolymer

A(BA)n block copolymer

n-1

Me
– Si – O – and similar hydrophobic polyether
Me

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 Vegetable oil-based defoamers
How are defoamers incorporated?
As renewable raw materials, vegetable
oils are increasingly important in the for- Choosing the method of incorporating a defoamer emulsions, the defoamer drop-
mulation of defoamers. They exhibit high defoamer is largely dependent on the lets which provide the defoaming effect
incompatibility and have very similar form in which it is supplied. Common in the finished coatings formulation must
properties to those of mineral oils. They forms are defoamer emulsions or concen- first be generated. This is typically done
are used mainly in architectural paints but trates. during incorporation of the concentrate
are increasingly important in other sec- by finely dispersing the defoamer in the
tors. In defoamer emulsions, the active sub- coating using sufficiently high shear
stance is already finely distributed in an forces. It is therefore recommended that
emulsified form. Defoamer emulsions can the defoamer concentrate be added to the
Polymer-based defoamers therefore be incorporated in the formula- millbase. The incorporation conditions
tion using low stirring intensity. They are can directly influence the effectiveness of
Examples of polymer-based defoamers also suitable for subsequent addition in the defoamer. Dispersing which is too
include modified fatty acids, polyethers the ready-to-use formulation. Typical weak results in defoamer droplets which
or modified amides. The polarity of the examples of Evonik’s defoamer emulsions are too large and causes surface defects.
defoamers can be adjusted via the com- for waterborne coatings and printing inks If the defoamer is too strongly dispersed,
position of the polymers. The effective- are TEGO® Foamex 805, 815 N, 822, the defoamer droplets are too small and
ness of polymeric defoamers is frequently 825 or 1488. cannot develop their full effectiveness
inferior to that of other substances. (fig. 9). Defoamer concentrates from the
However, the wide choice of polymeric Defoamer concentrates consist mainly of TEGO product range are TEGO® Foamex
defoamers enables the effectiveness and the active defoamer substance. They are 3062, 810, 883 and 8050.
compatibility of the defoamer to be pre- water- and solvent-free. In contrast to
cisely adjusted for very critical coatings
systems. Therefore, polymeric defoamers
are frequently used in formulations
where other defoamer technologies are
too incompatible.
Figure 9: Effectiveness as a function of droplet size

compatible optimum incompatible

good
defoaming efficiency

defoamer/
deaereator
bad

droplet size of defoamer

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 Which tests are recommended for evaluating defoamers?

Decisive criteria for choosing a defoamer ing characteristics are strongly influenced volume of a control sample without
are the formulation and application by the conditions during manufacturing defoamer is checked before and after
method. Different formulations require and application of the paint, it is recom- the stir test.
different defoamers. Important parame- mended that the test method permits
ters affecting the formulation include pig- evaluation under conditions close to
ment loading or the chemical nature of those in practice. The method should Flow test
the binder. The type of application also include an assessment of possible
method also affects the incorporation of surface defects that could be caused by In this test, air is stirred into the formula-
foam in the coating material and thus the the defoamer. tion with a fast running stirrer. The freshly
choice of defoamer. Defoamer recom- foamed sample is poured onto a surface.
mendations from Evonik take into account The activity of the defoamer can be
suitability for particular formulations and Stir tests assessed from the fresh pour-down. After
application methods. Nevertheless, it is the pour-down dries, the film can be visu-
recommended that defoamers are tested A frequently used method for low to ally assessed for foam and surface defects.
in the laboratory before using them in medium viscosity formulations is the stir The flow test frequently complements the
production. test in which air is stirred into the formu- stir test and is similarly suitable for low to
lation with a fast running stirrer. The medium viscosity paints.
When choosing a defoamer for a formula- effectiveness of different defoamers can
tion, its effectiveness should first be be compared via the volume of foamed
checked in the laboratory. Since defoam- material. It is recommended that the

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 Roller test

The roller test is used for testing paints

which are applied with rollers and simu-
lates real application conditions. The paint
is applied with a roller to a substrate and
foaming during application is assessed.
Surface defects caused by foam, incom-
patibilities or air occlusions in the coating
can be assessed on the dried paint film.

All procedures are shown in videos on our

homepage.

FAQs:
We use TEGO® Foamex 810 in a pig- indirectly via other raw materials for What types of pumps are suitable for
mented UV wood finish and sometimes which the defoamer is suited. Therefore, conveying defoamer emulsions?
have isolated craters on the application there cannot be a universal defoamer Defoamer emulsions should, in principle,
unit. Unfortunately, we cannot repro- which always functions in all formula- be conveyed with low-shear pumps.
duce this defect in the laboratory. What tions. However, empirical experience has Continuous stirring or pumping should
can we do? shown that certain defoamers are well be avoided as this can cause changes in or
One way of eliminating craters is by add- suited for individual areas of application. destabilization of the defoamer emulsion.
ing a wetting agent such as TEGO® Wet TEGO® Foamex 1488 or TEGO® Foamex
270 or TEGO® Twin 4100 in amounts of 855 or TEGO® Foamex K 8, for example,
0.1% to 0.4%. perform well over a wide spectrum in the
PVC range between 50 to 80% and in
We manufacture various interior paints. typical binders for this range of PVC
The PVC ranges from 50% to 80%. We such as styrene acrylic or vinyl acetate
also use various binders in these paints. copolymers.
At the moment, we are also using a vari-
ety of defoamers. Is there a defoamer Can defoamer emulsions be diluted with
which is effective in all paints? glycols to mix the defoamer into coatings
Foam formation and stabilization are without compatibility problems?
usually caused by a mix of emulsifiers and We basically recommend adding
stabilizers from the binder and other sur- defoamer emulsions in the form supplied.
face active substances added directly or Diluting with solvents can destabilize the
emulsion and cause it to break.

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