TECHNICAL BACKGROUND / DEFOAMERS

44

Defoamers

TEGO® Foamex
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It is almost impossible to imagine indus-

try today without surfactants. Their use
is required in the most diverse processes
to obtain a broad range of effects. Emul-
sifiers, for example, facilitate the incor-
poration of water-insoluble binders in
waterborne paints. Other examples in-
clude additives which improve substrate
wetting (see “Technical Background Sub-
strate Wetting Additives“) and dispersion
of pigments (see “Technical Background
Wetting and Dispersing Additives“). Figure 1:
Rise and bursting of
air bubbles in a
The most important property of these surfactant-free liquid
surfactants is their tendency to concen-
trate at interfaces such as the air/water
boundary where they orientate accord-
ing to their chemical structure.

Surfactants have an amphiphilic molec- than that of the liquid, they rise. When In liquids containing surfactants, the
ular structure. The hydrophilic area of the individual bubbles reach and pass unstable bubbles give rise to stable
the molecule penetrates into the polar through a surfactant-free liquid, they foam consisting of spherical bubbles. A
liquid and the hydrophobic part into the burst. Air from the bubbles dissipates surfactant film forms around the gas
gas phase. Consequently, the surfactant and the liquid previously surrounding bubbles. If these bubbles reach the sur-
lowers the surface tension and stabilizes them flows back. Pure, surfactant-free face, which is also coated with surfac-
the system. However, undesirable side liquids do not foam (fig. 1). tants, a lamella or double layer stabi-
effects also occur: surfactants stabilize lized by the surfactant is formed (fig. 2).
air, incorporated during manufacture or
application of the coating in the form of
foam, particularly in the case of water-
borne formulations.

What is foam?
Foam can be defined as a stable disper-
sion of gas bubbles in a liquid and is
therefore a colloidally dispersed system.
In a paint formulation, the binder is the
continuous phase. The dispersed phase
consists of air or gas-filled bubbles.
Figure 2:
If a stream of air is introduced into a liq- Rise and stabilization
of air bubbles in a
uid, the bubbles produced assume a liquid containing
spherical shape. As their density is less surfactant
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46

Foam formation
Foam is produced during manufacture
and application of waterborne coatings.
Foam crown heads lengthen production
times and reduce the effective volumes
of production plants. Foam also inter-
feres with the application process since
it leaves various surface defects after
drying. In printing, for example, foam
impairs ink transfer and can also cause
the ink reservoirs to overflow.

How can foam be stabilized?

The following effects are involved:

• electrostatic repulsion of the treated

surfaces
Figure 3: Detailed view on the liquid/air interface • steric effects
• surface effects such as the Gibbs-
Marangoni effect which counteract
As such double layer surface films can the volume content of the liquid is stronger drainage of the lamella
be several microns thick, this fine foam greater than that of the air, this foam is • the Gibbs-Marangoni elasticity of the
is very stable and extremely difficult to termed “wet foam”. The subsequent bub- foam lamella
disrupt. The rising bubbles generally bles cause a continuous rise in the foam
have a diameter greater than 50 µm and head. The Gibbs-Marangoni elasticity stabi-
give rise to macro-foam. Foam bubbles, lizes foam because it increases the
which are so small that they rise only As the liquid flows out of the double surface area when the foam lamella de-
slowly, if at all, and cannot escape from layer under gravitational effects, the forms. Consequently, the concentration
the system, are termed micro-foam. The spherical foam is forced to take on an- of surfactant per unit area decreases
viscosity of the system plays a decisive other stable form: polyhedral foam. and the surface tension increases pro-
role (see “Technical Background Deaera- Polyhedral foam is called “dry foam” be- portionately which is energetically
tors”). cause it contains only a small amount of unfavorable. In trying to achieve the
liquid. Because of the low film thickness lowest possible surface tension, the
The macro-foam bubbles, which have of the lamella (approx. 100 nm), this foam stretched film contracts like an elastic
reached the liquid/air interface, retain is often relatively easily disrupted. The skin. The foam bubble remains intact
their spherical shape as long as the air surfactant properties can lead to some- (fig. 4).
content is lower than that corresponding what more stable foams. fig. 3 shows
to maximum sphere packing density. the described phenomena.
Since in this phase of foam formation,
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How do defoamers work? To develop its effect, the defoamer,

emulsified into fine droplets, must pen-
Current terminology distinguishes be- A defoamer must exhibit a range of pro- etrate into the foam lamella. Before the
tween defoamers and deaerators. In wa- perties: defoamer droplet can fully develop its
terborne formulations, defoamers de- positive penetration coefficient, the so-
stroy the macro-foam on the surface • insoluble in the formulation to be de- called pseudoemulsion film must be
and prevent large air entrapments. foamed broken. This is formed as the defoamer
Deaerators evacuate the finely dispersed • low surface tension droplets approach the foam surface
air out of the paint film as quickly as • positive penetration coefficient E with the formation of an asymmetric
possible during application. In practice • positive spreading coefficient S three phase film (oil/water/air).
differentiation is not usually so clear • dewetting mechanism
cut. Thus defoamers are also effective to The mathematical formula for the pene-
some extent against micro-foam. Both On the one hand, the active ingredient tration coefficient shows that the re-
additives are active at the surfactant- in the defoamer must be almost insolu- quired low surface tension of the active
stabilized air/liquid interface. ble in the coating. On the other no de- ingredient phase of the defoamer results
fects such as craters should be gener- in a positive penetration coefficient.
There is no single defoamer theory. ated. The defoamer must therefore be

E = w/a + w/o – o/a

Some explanations and prerequisites for sufficiently compatible with the binder.
effective defoamers are however known. Thus every defoamer is on a tightrope
Combating foam in waterborne coatings between compatibility and targeted in- w/a = surface tension of the
is described below. compatibility. foaming liquid
w/o = interfacial tension between
the defoamer and the foa-
ming liquid
o/a = surface tension of the
defoamer

At the foam surface the defoamer

droplets penetrate the surfactant film
which stabilizes the lamella.

Because of its high spreading tendency,

the defoamer droplet expands into a
lens at the liquid/air interface. The
spreading coefficient of the defoamer
must be positive for this phenomenon to
take place:

S = w/a – w/o – o/a

Figure 4: Gibbs-Marangoni elasticity
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48

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

pseudoemulsion film

w/a high; w/o o/a low Penetration coefficient E Destabilization of the foam lamella additional viscosity resistance of the
E = w/a+ w/o – o/a > 0 spreading coefficient S liquid
S = w/a– w/o – o/a > 0

The progressive spreading process re- Dewetting: traditionally used as active spreading
duces the thickness of the lens, the The hydrophobic solid aids piercing of substances. Aromatic oils were used but
shape of which is altered by movements the pseudoemulsion film. The surfactant entail physiological and ecological risks.
in the foam. Stresses occur until the lens film which stabilizes the foam lamella Aliphatic oils are less toxic but their lack
breaks and the foam lamella ruptures. cannot wet the hydrophobic solid and of compatibility in aqueous media often
The resultant film is considerably less “shrinks back”. An unstable area results causes a serious reduction in the gloss
elastic than the surfactant film which where the lamella is able to break (fig. 7). of emulsion paints.
previously stabilized the lamella. This
destabilization facilitates rupture of the Which classes of substances have A highly effective class of defoamers is
lamella (fig. 5). a defoaming effect in waterborne obtained by combining dimethylpoly-
coatings? siloxanes with hydrophobic and partially
The following mechanism is possible: Of the numerous defoaming formula- hydrophilic polyethers. This results in
The foam lamella thins through drainage tions for waterborne coatings, those defoamers with very active spreading
(fig. 6a), so that the defoamer droplet defoamers based on mineral oil and sili- characteristics which are highly suited
can penetrate one side of the lamella cones are of greatest importance. Aro- for use in modern waterborne coatings
(fig. 6b and 6c). Further drainage of the matic or aliphatic mineral oils have been and printing inks. They do not impair
lamella liquid enables the defoamer
droplet to then penetrate the other side
of the lamella (fig. 6d). This process is
termed film bridge forming (fig. 6e).
Once this stage is reached, the foam
lamella ruptures. The defoamer droplet
is released and can become active again
(fig. 6f).

The addition of finely divided hydropho-

bic particles, such as hydrophobic silica,
increases the effect of defoaming sub-
stances. The reasons for this is as fol-
lows.
Figure 6: Film bridging during defoaming
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are particularly popular in printing inks

and industrial coatings. This defoamer is
highly effective in hybrid systems and
resin solutions even after lengthy stor-
age of the ink or coating.

How are defoamers incorporated?

The dosage rate and effectiveness of a
defoamer depend on the coating formu-
lation, particularly the type of polymer
dispersion, pH-value, degree of pigmen-
tation, binder, etc. and the chemical
Figure 7:
Dewetting during
structure of the additives used. Manu-
defoaming facturing and application processes also
affect the type and amount of defoamer
gloss and are highly compatible. Poly- without hydrophobic solids. TEGO® required.
ethersiloxanes are synthesized using Foamex 805 and TEGO® Foamex 7447
SiOC- or Si-C linkages between poly- are therefore supplied free of solids. When considering incorporation, a dis-
ether and siloxane blocks resulting in TEGO® Foamex 845 has been developed tinction should be made between de-
various possible structures (fig. 8). specifically for hybrid systems (aqueous foamer emulsions and 100 % active prod-
resin solution/emulsion blends) which ucts. Emulsions such as TEGO® Foamex
Interfacial activity stems from the silicone 800, 815 N, 822 and 825 do not pose a
block while the degree of compatibility is Figure 8: Typical polyethersiloxane structures problem here as the ideal particle size
controlled largely by the polyether block. distribution is specified. They can be
The choice of active ingredients is mainly added to the mill-base and require only
dependent on the composition of the homogeneous mixing in. Solids-free
medium in which the defoamer must emulsions such as TEGO® Foamex 805
work. However, the complexity of paint and 7447 can even be stirred into the
formulations makes it difficult to ex- finished paint.
plain clearly the relationships between
the defoamer’s structure and its prop- With defoamer concentrates such as
erty profile. Since very different require- TEGO® Foamex 3062, 810 and 8050 the
ments must be met, only general advice defoaming effect is largely determined
can be given; no universal solutions to by the method of incorporation, since it
these foam problems can be expected. is at this stage that the particle size dis-
tribution, which governs effectiveness,
TEGO® Foamex 815 N, TEGO® Foamex is achieved. If the defoamer droplets are
825 and TEGO® Foamex 855 are partic- too small, insufficient mass is present to
ularly effective in pure acrylic and enable a lens consisting of active ingre-
styrene-acrylic systems. TEGO® Foamex dient to be generated. Defoamer drops
800, TEGO® Foamex 805 and TEGO® which are too large cannot penetrate
Foamex 822 are suited mainly for use in the foam lamella and poor wetting re-
PU and PU/acrylic systems. Because of sults in the paint film (fig. 9).
their high spreading force, some poly-
ethersiloxanes are good defoamers even
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50

Concentrates are therefore often used Which practical tests The procedure of both tests is shown in
to defoam mill-bases. The defoamer is the Video “Defoamer test for polymer
incorporated using high shear. Care
are meaningful? emulsions” on the enclosed CD-ROM.
must be taken that this is not excessive. Defoamer performance must first be
The effect of the defoamer may be im- determined in the laboratory. Often it is Another stir test is used to determine
paired by extreme shear forces or long not possible to transfer laboratory re- the amount of macro-foam. Air is stirred
stirring. The effectiveness of the de- sults to production scale without further into the medium to be defoamed under
foamer is reduced, because too small testing. We are constantly striving to defined conditions and the resulting
droplets develop. develop test methods which permit total volume including the foam head
evaluation of the efficacy of defoamers determined in a measuring cylinder
Low shear during addition may provide under production and application con- (video “Defoamer test for printing inks
good results but often the defoamer ditions. The choice of test and any nec- and varnishes (stir test)”). This test pro-
shows incompatibility in the paint sys- essary modifications depend on the ap- vides information on the optimum oper-
tem. Thus bad wetting or irregular areas plication method (brushing, spraying, ation of the mixing vessels if a ready
occur in the application. dipping, printing, etc). made paint is used instead of a disper-
sion.
Tego defoamers are designed to be used Many defoamers cause surface defects
as supplied. If shear forces are inadequate such as cratering which are just as un- Roller test
during processing, then prior dilution of desirable as the problems caused by Because of the differing porosity and sur-
the 100 % products (TEGO® Foamex foam bubbles. These side effects must face texture of the substrate (e.g. stone,
3062, TEGO® Foamex 810 and TEGO® also be investigated using suitable tests. wood, metal), foam development varies
Foamex 8050) with film forming aids or in intensity. On strongly textured sur-
alcohol is recommended. Dilution in the Stir tests faces, the amount of defoamer gauged as
range 1: 1 to 1: 9 facilitates incorpora- One of the methods used is a stir test optimum by the stir test is not always
tion into the batch and accelerates which shows how much air is contained sufficient to destroy foam occurring dur-
distribution in the formulation resulting in the formulation as spherical bubbles. ing application. The amount of defoamer
in improved defoaming and a reduced needs to be adjusted to the application
tendency to cratering. The storage sta- Flow test conditions.
bility of prediluted solid-containing de- The flow test permits evaluation of the
foamers is generally limited and should effect and compatibility of a defoamer The roller test reproduces real applica-
be checked. in a coatings formulation. tion conditions relatively closely so that
it is possible to assess suitable concen-
trations of different foamers (see video
“Defoamer test for emulsion paints“ on
the enclosed CD-ROM).

The above tests enable the most suitable

defoamer and dosage to be ascertained
for a given formulation, area of and con-
ditions of application.

Figure 9:
Effectiveness as a
function of drop size
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paints stabilize the foam and their huge

variety is one of the reasons why there
can be no universal defoamer.

TEGO® Foamex 855, however, exhibits a

broad spectrum of activity. We have
achieved good to very good results in
various binders, such as styrene-acry-
lates or terpolymers and at various PVCs.
Of course different amounts are re-
quired for different applications.

Can defoamer emulsions be diluted with

glycols such as butyl glycol to mix the
defoamer into a parquet varnish without
compatibility problems?
FAQ: No. You should not dilute with solvents
such as glycols as they would destabilize
We use TEGO® Foamex 810 in a pig- the emulsion and certainly result in
mented UV wood finish and sometimes compatibility problems. Moreover, the
have isolated craters in the product. We defoamer droplets would be destroyed
are unable to reproduce this defect in the and the excellent defoaming action
laboratory. What can we do? would no longer occur.
We recommend diluting the defoamer
with butyl glycol in a ratio of 1:1 (this How long does an aqueous dilution of a
does not apply to emulsions) or another defoamer remain stable and how long
glycolether before adding to the coat- can one use these diluted products?
ing. Another possibility is to add one of Diluted defoamer emulsions should be
our wetting agents. TEGO® Wet 270 in used within two days if they contain a
amounts of 0.1 to 0.4 % has proved very solid (usually silica). Silica-free products
effective in such cases. such as TEGO® Foamex 805 can still be
used even after storing for seven days.
We manufacture various interior paints. The diluted products should not be pre-
The PVC ranges from 50 % to 80 %. We pared with a solids content < 5 %.
also use various binders in these paints.
At the moment we are also using various What types of pumps are suitable for
defoamers but should like to use just one. conveying defoamer emulsions?
Is there a defoamer which is effective in Defoamer emulsions should, in principle,
all paints? be conveyed with low-shear pumps, e.g.
No, even we have not found a universal centrifugal pumps.
defoamer. Emulsifiers and stabilizers
used in the manufacture of emulsion