Article No : a11_465

Foams and Foam Control

FER, Henkel KGaA, D
RAINER HO usseldorf, Federal Republic of Germany
FRANZ JOST, Henkel KGaA, Dusseldorf, Federal Republic of Germany
MILAN J. SCHWUGER, Henkel KGaA, Dusseldorf, Federal Republic of Germany
ROLF SCHARF, Henkel KGaA, Dusseldorf, Federal Republic of Germany
JURGEN GEKE, Henkel KGaA, Dusseldorf, Federal Republic of Germany
JOSEF KRESSE, Henkel KGaA, Dusseldorf, Federal Republic of Germany
HERBERT LINGMANN, Henkel KGaA, Dusseldorf, Federal Republic of Germany
RUDOLF VEITENHANSL, Henkel KGaA, Dusseldorf, Federal Republic of Germany
WERNER ERWIED, Henkel KGaA, Dusseldorf, Federal Republic of Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . 572 5.2.2. Food Processing . . . . . . . . . . . . . . . . . . . 583

2. Theory of Foam and Foam Control . . . . 572 5.2.2.1. Sugar . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
2.1. Characteristic Properties of Foam . . . . . 572 5.2.2.2. Yeast . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
2.2. Foam Formation . . . . . . . . . . . . . . . . . . 572 5.2.2.3. Potatoes . . . . . . . . . . . . . . . . . . . . . . . . . 584
2.2.1. Surface Activity of Adsorbed Surfactants . 572 5.3. Metal Treatment . . . . . . . . . . . . . . . . . . 584
2.2.2. Methods of Foam Generation . . . . . . . . . . 573 5.3.1. Foam Problems Associated with Cooling
2.3. Foam Stability . . . . . . . . . . . . . . . . . . . . 574 Lubricants . . . . . . . . . . . . . . . . . . . . . . . . 584
2.3.1. Gibbs Film Elasticity and Marangoni Effect 574 5.3.2. Foam in Alkaline Cleansing Solutions . . . 585
2.3.2. Rheological Aspects of Foam Stability . . . 575 5.3.3. Foam Control in Neutral Cleansers. . . . . . 586
2.3.3. Electrostatic Foam Stabilization . . . . . . . . 576 5.4. Polymer Industry. . . . . . . . . . . . . . . . . . 586
2.3.4. Mechanism of Lamellar Rupture . . . . . . . 577 5.5. Paint and Coating Industry . . . . . . . . . . 587
2.4. Foam Inhibition and Destruction. . . . . . 577 5.6. Construction Industry . . . . . . . . . . . . . . 589
2.4.1. Chemical Foam Inhibition and Destruction 578 5.7. Adhesives Industry . . . . . . . . . . . . . . . . 589
2.4.2. Mechanical Defoaming . . . . . . . . . . . . . . 579 5.8. Textile Industry . . . . . . . . . . . . . . . . . . . 589
3. Antifoaming Agent Composition . . . . . . 579 5.8.1. Pretreatment . . . . . . . . . . . . . . . . . . . . . . 590
3.1. Carrier Oils . . . . . . . . . . . . . . . . . . . . . . 579 5.8.2. Dyeing . . . . . . . . . . . . . . . . . . . . . . . . . . 590
3.2. Silicone Oils and Silicone Foam Inhibitors 579 5.8.3. Foam Application of Textile Auxiliaries . . 590
3.3. Hydrophobic Silica . . . . . . . . . . . . . . . . 580 5.9. Leather Industry . . . . . . . . . . . . . . . . . . 591
3.4. Hydrophobic Fat Derivatives and Waxes 580 5.10. Pulp and Paper Industry . . . . . . . . . . . . 591
3.5. Water-Insoluble Polymers . . . . . . . . . . . 580 5.10.1. Pulping . . . . . . . . . . . . . . . . . . . . . . . . . . 591
3.6. Amphiphilic Components. . . . . . . . . . . . 581 5.10.2. Pulping Liquor Disposal . . . . . . . . . . . . . 591
3.7. Emulsifiers . . . . . . . . . . . . . . . . . . . . . . . 581 5.10.3. Air Content of Pulp Suspensions . . . . . . . 592
3.8. Coupling Agents . . . . . . . . . . . . . . . . . . 581 5.10.4. Conversion to Paper . . . . . . . . . . . . . . . . 592
4. Mechanical Means of Combating Foam. 581 5.10.5. Paper Coating . . . . . . . . . . . . . . . . . . . . . 592
5. Foam Problems in Specific Applications 582 5.10.6. Waste Paper Deinking . . . . . . . . . . . . . . . 592
5.1. Detergents . . . . . . . . . . . . . . . . . . . . . . . 582 5.11. Phosphoric Acid Manufacture . . . . . . . . 592
5.2. Food and Beverage Industries . . . . . . . . 582 5.12. Wastewater Treatment . . . . . . . . . . . . . 593
5.2.1. Cleansing and Disinfecting . . . . . . . . . . . 582 6. Testing Methods . . . . . . . . . . . . . . . . . . 593
5.2.1.1. Tank Cleansing Based on the Cleaning-in- 7. Legal Aspects. . . . . . . . . . . . . . . . . . . . . 594
Place (CIP) Method . . . . . . . . . . . . . . . . . 582 8. Economic Aspects . . . . . . . . . . . . . . . . . 594
5.2.1.2. Cleansing of Returnable Bottles . . . . . . . . 583 References . . . . . . . . . . . . . . . . . . . . . . . 595

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a11_465
572 Foams and Foam Control Vol. 15

1. Introduction
In a number of contexts, foaming is considered a
desirable phenomenon. The food and beverage
industries are well aware of the wholesome
connotations associated with the foamy head on
a glass of beer or such foams as whipped cream
and meringue. Generations of housewives have
assumed that foam is evidence of a detergents
cleaning power. Meerschaum provides another
interesting example. It is a form of sepiolite
[61180-58-3] prized as a decorative basis for Figure 1. Schematic representations of the major types of
pipes, and its common name means sea foam foam [9]
in German. Other solid foams are important for A) Spherical-bubble foam; B) Polyhedral foam
their use as insulating or lightweight construction
materials (! Foamed Plastics). [9], [11]. The physicochemical aspects of foam
Nevertheless, foam is often very undesirable: stabilization can be examined by preparing well-
it can severely hinder the filling of a container, defined, isolated lamellae [10]. Nevertheless, a
reduce the efficiency of many high-speed opera- sound theoretical understanding of the various
tions, and cause surface defects in coating opera- stabilization mechanisms has not yet been
tions. Various terms such as foam inhibitor, achieved.
antifoaming agent, foam controller, and defoa-
mer are applied to substances designed to prevent
or control foaming, but the distinctions are some- 2.2. Foam Formation
what vague and a given material often serves
both preventive and control functions. 2.2.1. Surface Activity of Adsorbed
Surfactants

2. Theory of Foam and Foam Control The introduction and dispersion of a gaseous
material under the surface of a foaming liquid
2.1. Characteristic Properties of Foam (e.g., when air is brought into an aqueous surfac-
tant solution) leads to the formation of rising
A foam consists of gas dispersed within a liquid. bubbles. In the process, dissolved surfactant
Pure liquids are incapable of foaming; soluble molecules diffuse out of the bulk phase toward
surfactants or impurities [8] are required to sta- the gas liquid interfaces, to form reversibly
bilize a foam by retarding the otherwise extreme- adsorbed monolayers. Polar groups in the surfac-
ly rapid coalescence of gas bubbles. tant molecules remain directed toward the water,
Foams are thermodynamically unstable. A while hydrophobic chains extend into the air
freshly prepared wet foam dissipates rapidly. [12].
Such a foam is of the spherical-bubble type [9] The spreading pressure p of an adsorbed
(Fig. 1 A), with individual bubbles having little surfactant increases to a limiting value as the
influence upon one another. As a foam is dehy- surface concentration increases; this reduces the
drated, the distance between bubbles progres- opposing surface tension of the initially pure
sively diminishes, leading ultimately to a dry liquid (g 0) to a new value g.
polyhedral agglomerate of bubbles (Fig. 1 B). A
metastable state can be established if equilibrium p g 0
g 1
is reached among the various forces contributing
to foam stabilization and destabilization [10]. The spreading pressure can be determined ten-
Exceptionally regular polyhedral foam struc- siometrically by the Wilhelmy method [13].
tures with a lifetime of several hours can be Because dp
dg, the spreading pressure
prepared if an appropriate system is thermostated characterizes the surface activity of a given
and carefully protected from external influences surfactant or surfactant mixture at a particular
Vol. 15 Foams and Foam Control 573

concentration. At constant temperature, a dy- Table 1. Critical micelle concentration cM of surfactants at 25  C

namic equilibrium is established between the Surfactant cM, mol/L
surfactant dissolved in the bulk phase and the
surfactant adsorbed at the boundary surface. C9H19OSO3Na 5910
3
C12H25OSO3Na 8.010
3
Surface-active agents are repelled by the bulk C16H33OSO3Na 0.3810
3 (35  C)
phase because the van der Waals forces between C18H37OSO3Na 0.1710
3 (50  C)
water and the hydrophobic chains of the surfac- C12H25(OCH2CH2)4OH 4.310
5
tant molecules are weaker than those between C12H25(OCH2CH2)8OH 1.010
4
C12H25(OCH2CH2)12OH 1.410
4
water molecules. At low concentrations, the C12H25N(CH3)3Cl 1.810
2
amount of adsorbed surfactant G (surface con- C14H29N(CH3)3Cl 5.010
3
centration in moles per unit area) increases with C18H37N(CH3)3Cl 3.510
4
increasing concentration c [14]. Simultaneously,
the increasing spreading pressure p reduces
the surface tension g, as shown by Equation (1). face tension minima are commonly observed
For a nondissociating amphiphilic substance with commercial surfactants, but such minima
(m 1), the following equation applies [15]: appear to be caused by impurities. The time
required to establish diffusion-controlled equi-
1 dg librium increases markedly as the concentration
G  2
mRT d lnc differs from cM [18] (Fig. 3).

Modified forms of this equation have been sug-

gested [16] for ionic substances in which 2.2.2. Methods of Foam Generation
1 < m  2. Equation (2) is known as the Gibbs
adsorption equation; it describes an equilibrium Many techniques have been described for pro-
situation and facilitates estimation of the surface ducing a foam [9], [19], but they fall into two
area requirement per adsorbed molecule. Only at main mechanistic categories.
very low surface concentrations do hydrophobic
groups lie flat on the surface, where they are free Dispersion Methods. Mechanical action
to rotate about their hydrophilic partners. A greatly increases the surface area that separates
relatively low surfactant concentration often suf- a liquid from a gas. The continuous phase may
fices to induce the formation of densely packed undergo extreme fragmentation, thereby estab-
aggregates in which the hydrophobic chains are lishing a foam with maximum homogeneity.
held erect. Good results are often simply achieved in a
Once the maximum spreading pressure has long tube by establishing flow velocities in the
been reached, the adsorption capacity of the
surface is fully utilized, so that the number of
adsorbed molecules remains constant despite
further increase in overall surfactant concentra-
tion. At this point, the two-dimensional structure
is fully ordered. The critical micelle concentra-
tion (cM), the concentration at which micelles
begin to form, may be viewed as a measure of
surface activity; above this value, the spreading
pressure of a given pure surfactant is constant.
Table 1 contains a selection of typical cM values;
these vary significantly as a function of the
molecular structure of the surfactant. The effect
of changes in the size of the hydrophobic group is
illustrated in Figure 2. Nonionic ethoxylates with
limited water solubility reach their maximum Figure 2. Influence of surfactant structure on surface activity
[17]
spreading pressure at extremely low volume Surface tension g of aqueous sodium n-alkyl sulfate solutions
concentrations. Concentration-dependent sur- as a function of concentration c at 25  C
574 Foams and Foam Control
Figure 3. Influence of surfactant concentration on adsorption
rate [18]
Surface tension vs. time curves for various concentrations of
octylphenol dodecaglycol ether at 25  C
turbulent range. In a commonly used procedure,
the two phases are forced through a column
tightly packed with glass beads or other appro-
priate material. Thin films of liquid form in the
resulting narrow gaps, and these films are blown
into bubbles by the passing gases. Foam gen-
erators and dispersion turbines operate in a simi-
lar fashion.
Condensation Methods. Foam generation
methods based on condensation rely on sponta-
neous degassing of supersaturated, continuous
liquid phases. The degassing may result from
either pressure reduction or temperature increase.
The most familiar example is the carbon dioxide
foam that develops at the surface of carbonated
soft drinks, beer, and sparkling wine. Although
this method entails a minimum expenditure of
effort, the associated costs often greatly exceed
those of mechanical (dispersion) methods.
2.3. Foam Stability
The economic impact of practical foam problems
is evident from the number of experimental and
theoretical studies devoted to this subject [8],
[20]. Unfortunately, most of the usual physico-
chemical measurement techniques are unsuitable
for the direct study of such complicated agglom-
erates of draining gas bubbles in a moving,
foaming liquid. More limited theories attempt
to correlate foam stability with changes in a
single dominant parameter. Several fundamental
issues related to foam stability have been clari-
Vol. 15
fied by studies conducted on isolated foam la-
mellae. This is a legitimate approach, because
foam degradation is a mechanical process con-
sisting of the rupture of large numbers of indi-
vidual lamellae [10].
2.3.1. Gibbs Film Elasticity and Marangoni
Effect
Except in the case of pure liquids, foam bubbles
and lamellae are stabilized relative to small
changes in bubble size and lamellar thickness
by two closely related mechanisms, the Gibbs
film elasticity and the Marangoni effect.
Gibbs Film Elasticity E applies to extended
lamellae with thicknesses several orders of mag-
nitude smaller than their surface dimensions
[21]. Film elasticity is defined as the quotient
obtained by dividing an increment in the surface
tension (2 dg) by the corresponding increase in
relative surface area of the film (dA/A):
dg dp
E 2A
2A 3
dA dA
Extension of a lamella results in a corresponding
reduction in the equilibrium surface concentra-
tion of adsorbed surfactant molecules and thus in
an increase in the surface tension g, which acts as
a restoring force (Fig. 4).
An additional stabilizing restorative force that
diminishes with time also exists, this is known as
the Marangoni mechanism. The time required for
establishing the Gibbs adsorption equilibrium is
determined by the diffusion-controlled transport
of surfactant molecules out of the bulk phase.
The rapidly expanding, but still relatively
thick lamellae characteristic of a low-viscosity,
aqueous, spherical-bubble foam often exhibit
surface depressions. These are caused by local-
ized expansion and corresponding reductions in
the spreading pressure. Adsorbed monolayers in
undisturbed regions spread spontaneously into
such depressions and compensate for the low
surface concentration [22], [23]. Furthermore,
solvated hydrophilic groups of spreading sur-
face-active agents aid in the transport of inter-
lamellar liquid from nearby layers, which helps
compensate for the destabilizing effect of local
dilution [24]. Both mechanisms are depicted
schematically in Figure 4.
Vol. 15
Figure 4. Schematic representation of the Gibbs and Marangoni foam-stabilization mechanisms
2.3.2. Rheological Aspects of Foam
Stability
Foams tend to lose their interlamellar liquid
under the influence of gravitational forces. As
the foam lamellae become thinner, their fragility
increases. Thus, any factor causing resistance to
flow should contribute to stabilization. Addition-
ally, low-viscosity foams often exhibit yield
points with important consequences from the
standpoint of applications, as in the case of
shaving cream [11].
Viscosity of the Interlamellar Liquid. An
increase in viscosity diminishes the rate of escape
of interlamellar liquid, thereby increasing foam
stability and height [9], [18]. At the same time,
however, high viscosity can also inhibit the
process of foam formation.
Surface Shear Viscosity. Whereas three-
dimensional rheology is the factor defining the
dynamic viscosity of a bulk phase, the two-dimen-
sional surface viscosity g s is responsible for the
velocity gradient between parallel linear elements
at a sheared surface [25]. Experimental determina-
tion of this parameter presents certain difficulties.
Foams and Foam Control 575
A modified couette system [26] is normally
employed for measurements on non-Newtonian
systems. The sample is placed in a rotating cup.
An inverted bowl-shaped sensor is allowed to
make concentric contact with the rotating liquid
surface, thereby permitting accurate determina-
tion of the corresponding torque.
Absolute values can be determined even at
elevated temperature, but their significance re-
mains uncertain. Relative values are of more
interest, particularly for surfactant mixtures, as
are the significant increases in surface viscosity
commonly observed with higher alcohols and
other water-insoluble substances [27]. The ex-
pected proportionality between surface shear
viscosity and foam stability has been confirmed
to only a limited extent. Solutions of surface-
active substances with a high surface shear vis-
cosity do indeed exhibit significant foam stabili-
ty, and foams in low-viscosity media subside
rather rapidly; however, solutions with interme-
diate surface shear viscosities fail to yield satis-
factory correlations.
Surface Dilatation Viscosity. Dilatation
[28] and compression are modes of deformation
that accompany pure shearing in certain types of
576 Foams and Foam Control
flow. The surface dilatation viscosity K is deter-
mined with the aid of a modified film balance [29]
by using the relationship
1 dA
Dg K  4 are generally several micrometers thick. Liquid
A dt
The total surface of the surfactant solution under
investigation is confined between two movable
barriers whose position is varied such that the
relative rate of expansion d ln A/dt remains con-
stant. The resulting increase in surface tension Dg
in the stationary zone between the barriers is
measured tensiometrically by the Wilhelmy
method [13].
Studies of the mechanism of lamellar ruptur-
ing suggest parallels between the stability of thin
films and the corresponding surface dilatation
viscosity [30].
2.3.3. Electrostatic Foam Stabilization
A fresh foam is a thermodynamically unstable
system. However, thin lamellae can be trans-
formed into a metastable state by electrostatic
repulsion.
True Foam Lamellae. A solution that is
supersaturated with a gas generally produces a
spherical-bubble foam (see Fig. 1) [9], [11] con-
taining considerable amounts of liquid. Progres-
sive draining leads to rapid transformation of the
spherical foam into a symmetrical polyhedral
foam.
The lamellae within a polyhedral foam are
separated from one another by surface regions
exhibiting concave deformation as well as in-
creased strength. These plateau regions [9], [32]. Thus, for a given disjoining pressure, the
[10] have a destabilizing suction effect on the
interlamellar liquid. An ideal unit cell of a uni-
form polyhedral foam resembles a regular pen-
tagonal dodecahedron. However, true foams are
ill-suited to the study of the opposing forces
involved in progressive draining because of their
instability.
Single Lamellae. Single lamellae can be
withdrawn easily from a liquid with the aid of
a glass frame [9], [10]. Unlike foams, they can be
subjected to intensive investigation as long as
they are protected from the effects of dust, evap-
oration, temperature change, and vibration. Lines
Vol. 15
of contact with the frame are characterized by
plateau regions analogous to those encountered
between the lamellae of a true foam.
Freshly drawn, vertically oriented lamellae
flows out of the center of such a lamella under the
combined influence of gravity and the suction
effect of plateau regions. A lamella stretched to a
thickness between roughly 1000 and 100 nm
displays a characteristic pattern of interference
colors [9]. As soon as the lamellar thickness falls
significantly below the wavelength of visible
light, a black film results; which is so desig-
nated because of complete interference between
incident and reflected light. Depending on a
variety of factors, including the composition of
the solution, lamellar shrinkage ceases at a thick-
ness between 60 and 10 nm. The existence of
such metastable black films implies that mechan-
ical equilibrium is achieved between attractive
and repulsive forces.
A potential energy curve [10] can be used to
illustrate the combined effects of repulsion
caused by identically charged diffuse double
layers adsorbed on the two faces of a surfactant
film and the concurrent attraction due to van der
Waals forces. Such a curve generally displays
two minima (Fig. 5). Differentiation of the curve
with respect to distance yields the disjoining
pressure per unit area, a force which compen-
sates in the metastable state (at equilibrium
thickness d0) for the destructive effect of suction.
The lamellar thickness corresponding to a
black film represents the shallow secondary min-
imum on the potential energy curve. Conclusions
derived from theoretical considerations can be
largely confirmed at low salt concentrations [31],
thickness of a metastable film decreases with
increasing concentration of electrolytes (Fig. 6).
At higher electrolyte concentration, film
thicknesses approach a limiting value of ca.
12 nm, a result which is essentially independent
of the suction effect and may be due to additional
separating forces of steric origin.
Metastable lamellae often transform them-
selves into type II black films with a thickness
of only ca. 5 nm [10], [33]. These extremely thin
sandwich structures probably consist of two
surfactant films separated by a thin layer of water
of hydration. They are thought to occupy the
primary minimum in the potential energy diagram.
Vol. 15
Figure 5. Force equilibria resulting in metastable lamellae
[10]
A) Potential energy curves showing van der Waals attraction
VA, charge repulsion VR, and the resultant energy V as a
function of thickness d of the lamella
B) Disjoining pressure p
dv/dd
Figure 6. Disjoining pressure in a solution of sodium oleate
(10
3 mol/L) at various sodium chloride concentrations
Foams and Foam Control 577
2.3.4. Mechanism of Lamellar Rupture
The surfaces of foam lamellae are under constant
stress due to surface tension, a spontaneous force
that tends to minimize surface extension. How-
ever, no direct relationship has ever been dem-
onstrated between surface tension and foam sta-
bility. Rupture of the lamellae cannot, therefore,
be regarded as a simple matter of overcoming
some critical tear resistance; rather, it appears to
be due to statistical fluctuations in lamellar
thickness [34]. Reducing the thickness below a
certain critical value ensures that the energy
criteria for destabilization are met. Countless
local instabilities can be expected to arise under
practical working conditions as a result of vibra-
tion, temperature gradients, evaporation, and
dust. Small particles of hydrophobic solids and
liquids are particularly disruptive.
Lamellae containing relatively weak surface-
active agents (alcohols or short-chain fatty acids)
tend to decompose at an early stage of solvent
exclusion and, therefore, never profit from the
stabilization associated with thin black films.
Instead, the concentration-dependent maxima
observed for low-stability foams are attributed
to the stabilizing effect of the Gibbs film elastic-
ity (see Section 2.3.1) [35]. Lamellae associated
with powerful surfactants rarely show such con-
centration-dependent maxima. Although the
Gibbs stabilizing mechanism is inoperative, pro-
gressive thinning of the lamellae often termi-
nates in a metastable black film rather than film
rupture.
Many water-soluble polymers (e.g., gelatin
and cellulose ethers) show very limited surface
activity but nevertheless possess significant
foam stabilization power. The reasons for this
are of rheological and especially steric origin.
The most familiar example is the stabilization of
beer foam by adsorbed protein polysaccharide
complexes.
2.4. Foam Inhibition and Destruction
A variety of chemical, biological, and technical
processes are severely hindered by foam forma-
tion. Foams are controlled by chemical (Section
2.4.1), thermal, or mechanical (Section 2.4.2)
means. In practical applications, foam inhibition,
which aims to inhibit foam formation in liquids,
578 Foams and Foam Control
is distinguished from destruction of foams that
have already formed. Thermal foam destruction
primarily promotes bursting of enlarged gas
bubbles and accelerates the destabilizing drain-
age of interlamellar liquids. However, this ap-
proach is often rather ineffective, and undesir-
able deterioration of the product is usually
unavoidable.
2.4.1. Chemical Foam Inhibition and
Destruction
Effective foam inhibitors and defoaming agents
often spread spontaneously over liquid surfaces.
Earlier studies [36] assumed the existence of a
causal relationship between this characteristic
and foam destruction, but more recent findings
[37] demonstrate frequent deviations from any
such correlation. A foam inhibitor may be in-
troduced in either dispersed (e.g., oils or pig-
ments) or molecular form. The principal mech-
anism of action of oils appears to involve local
displacement of the adsorption film containing
the foaming agent. Thus, spontaneous spreading
is not a precondition for effectiveness. What
matters is that the surface-active component in
the foaming agent should not be adsorptively
incorporated into the oil water boundary sur-
face. The stabilizing film is, therefore, perfor-
ated; the lamellae become seriously deformed;
and the interfacial surface energy of the moist-
ened portion of the oil droplet approaches a
maximum. Intensive investigation of pure sodi-
um dodecyl sulfate and a range of purified liquid
foam inhibitors provides support for this mech-
anism [37].
Another approach attempts to explain the
mechanisms and energetics of foam destruction
as consequences of two consecutive spreading
phenomena. Thus, if drifting oil particles within
the bulk phase are to be effective on the surface of
a foaming liquid, two fundamental energy crite-
ria must be fulfilled [8]:
1. Hydrophobic materials, rising because of
their buoyancy, must spontaneously penetrate
the liquid surface and form droplets. In the
process, an aqueous film is replaced by an
oil gas surface. This step is characterized
by a negative spreading coefficient S1, which
implies a positive entering coefficient.
Vol. 15
2. Floating oil droplets must then distribute
themselves spontaneously over the lamellae
that are to be destroyed (S2> 0). This second
condition is best fulfilled by foam inhibitors
whose surface and interfacial tensions are
both low.
However, hydrophobic agents characterized
by these two criteria (i.e., S1< 0 and S2> 0) often
prove to be rather poor foam inhibitors or com-
batants. In particular, silicone oils are ineffective
unless they have been activated with highly
dispersed particles of hydrophobic solids [38].
Particles of hydrophobic silica alone have a
destructive effect on polyhedral foams, although
they show no tendency to inhibit the formation of
wet spherical-bubble foams [38]. On the basis of
numerous investigations [39], this activity is now
assumed to be a consequence of the free hydro-
phobic surfaces becoming hydrophilic due to
adsorbed surfactants. Silicone oils spread in most
media and protect the surface of hydrophobic
silica particles, thus they transport active silica to
the breaking foam bubbles.
The converse of the Marangoni effect also has
a destabilizing effect [10], [24] because it leads to
the removal of interlamellar liquid (Fig. 7).
The foam-destroying properties of dispersed,
hydrophobic solid particles (e.g., Teflon, sila-
nized silica, solidified paraffins, or sulfur) can
also be explained in another way [40]: as the
Figure 7. Effect of a spontaneously spreading oil on lamellar
thickness (Marangoni mechanism)
Vol. 15
particles penetrate an expanding liquid lamella,
they contribute to its rupture by markedly in-
creasing the interfacial tension. This phenome-
non can be viewed as a displacement of the
aqueous phase resulting from a dewetting tension
(cf. the condition S1< 0 in [8]).
Soap mixtures with a broad range of chain
lengths (C12
22) are often used in detergents
based on alkylbenzenesulfonates and fatty alco-
hol polyglycol ethers [41], [42]. The foam-in-
hibiting action is due to calcium salts formed in
situ (see Section 3.6). Therefore, builders must
not completely remove the calcium ions.
2.4.2. Mechanical Defoaming
Mechanical defoaming is used when chemical
foam inhibitors or defoamers might impair pro-
cess or product quality [43]. Foam lamellae can
be subjected to high shear forces with the aid of
centrifuges, injectors and ejectors, and especial-
ly, rotating disks. The dominant foam-breaking
mechanism here involves the rupture of individ-
ual lamellae, which becomes possible above a
specific minimum shear velocity [44]. Optimiza-
tion of this approach is complex [4345].
3. Antifoaming Agent Composition
Traditionally, antifoaming agents were often
single-component liquid systems or homoge-
neous solutions derived from vegetable oils or
their constituent glyceride oils and fatty acids.
Other useful materials included mineral oils and
their derivatives [46], [47]. However, more com-
plex formulations were also known, including
aqueous sols derived from plant phosphatides
[48], as well as other water-soluble or water-
emulsifiable preparations [49].
Modern antifoaming agents (also called de-
foamers) are formulated to meet more diverse
demands, including optimal effectiveness, easy
application in an industrial context, convenient
dosage, low volatility, and safety from both
toxicological and ecological standpoints.
Most defoamers are composites rather than sim-
ple substances. Several groups can be distinguished:
1. Liquid single-component systems or homo-
geneous solutions
Foams and Foam Control 579
2. Dispersions of hydrophobic solids in a carrier
oil
3. Aqueous or water-containing emulsions or
suspension
4. Solid defoamer formulations
The functional components of a foam inhibi-
tor can be divided into four categories:
1. Carrier oils
2. Active ingredients
3. Amphiphilic substances
4. Coupling and stabilizing agents
Foam-inhibiting emulsions contain water,
which serves as the continuous phase [50]. Solid
foam inhibitors are free-flowing powders in which
the foam-inhibiting ingredients, as well as any
emulsifying or dispersing agents, are bound ad-
sorptively to an inorganic sorbent such as calcium
silicate [51] or sodium triphosphate [52], or to a
polymeric organic matrix such as methyl cellulose
[53]. Particulate solid antifoaming ingredients suit-
able for incorporation into detergent powder com-
positions comprise a core that consists of an oily,
solid, or gel-like carrier material. The core supports
the antifoaming substances and is surrounded by a
coating which is disrupted on contact with water to
release the antifoaming substances [54].
3.1. Carrier Oils
The most important carrier oils are water-insol-
uble paraffinic and naphthenic mineral oils, to-
gether with vegetable oils such as tall oil [8000-
26-4], castor oil [8001-79-4], soybean oil [8001-
22-7], or peanut oil [8002-03-7]. These oils
themselves have foam-control capability. Useful
agents for prolonging antifoam effectiveness,
which to some extent also show synergistic ac-
tivity, include residues from the oxo alcohol
synthesis, alkylbenzenes, and crude oils from
the low-temperature carbonization of brown coal
or other bituminous materials.
3.2. Silicone Oils and Silicone Foam
Inhibitors
Silicone oils are particularly effective antifoam-
ing agents because of their low surface tension,
580 Foams and Foam Control
thermal stability, chemical inertness, and total
water insolubility [55], [56]. One of the largest
applications for silicone oils is their use as anti-
foaming agents in the petroleum industry, par-
ticularly in gas oil separation [57]. By far the
most important silicone oils are the dimethylpo-
lysiloxanes [63148-62-9], in which chain ends
are saturated with trimethylsilyl groups. The
number of siloxane units present ranges typically
from 2 to 2000.
Dimethylpolysiloxanes by themselves show
little foam-inhibiting activity with respect to
aqueous surfactant solutions. Most silicone de-
foamers are in fact not pure silicone oils, but
rather silicone formulations supplemented with
finely divided hydrophobic solid particles. These
particles presumably confer the actual foam-in-
hibiting properties, while the silicone oil acts as a
hydrophobic carrier oil that offers unusually
good spreading properties [58].
Silicone foam inhibitors are supplied in the
form of anhydrous dispersions of pyrogenic or
hydrophobized silica [7631-86-9] in silicone oil.
Such mixtures are oily and cloudy. In some cases
they have the consistency of a paste, but the most
commonly used foam inhibitors for aqueous sys-
tems are 5 50 % emulsions. Silicone antifoam-
ing agent are directed toward suppressing undesir-
able side effects silicone antifoaming agents such
as the formation of fish eyes in surface coatings,
investigators have studied the effect of introducing
organic residues into the polymeric siloxane matrix
[5961]. Other goals have included the develop-
ment of foam inhibitors containing only traces of
silicone oil, as well as silicone antifoams based on
hydrocarbon oils [62]. Certain polyether modifica-
tions of poly(methylsiloxanes) have achieved im-
portance as foam stabilizers and cell regulators in
polyether urethane foams (! Polyurethanes).
3.3. Hydrophobic Silica
The development of hydrophobic silica [63] can
be regarded as one of the most important innova-
tions in the field of foam-control agents. Several
methods have been perfected for conferring hy-
drophobic properties on this normally hydrophil-
ic material [64], the most important of which are
1. spraying the silica with silicone oil and tem-
pering at 250 350  C,
Vol. 15
2. treatment with organosilicon halide vapors in
an autoclave, and
3. dispersing the silica in a silicone oil at elevat-
ed temperature and recovery of the solid by
centrifugation.
Hydrophobic silica can also be produced by
reacting silicia hydrogel with alcohol [65], [66],
fatty amines, or wax. Amorphous, precipitated
silica (particle size 1 2 mm) is the most suitable
starting material for foam-inhibiting agents from
the standpoint of both cost and performance.
3.4. Hydrophobic Fat Derivatives and
Waxes
Hydrophobic fats and waxes include the follow-
ing materials:
1. fatty acid esters of monofunctional and poly-
functional alcohols;
2. fatty acid amides and sulfonamides;
3. paraffinic hydrocarbon waxes [8002-74-2],
ozokerite [8001-75-0], and montan wax
[8002-53-7];
4. phosphoric acid mono-, di-, and triesters of
short- and long-chain fatty alcohols (for the
triesters, even tributyl phosphate [126-73-8]
and tributoxyethyl phosphate [78-51-3] have
foam-inhibiting properties [67]);
5. short- and long-chain natural or synthetic
fatty alcohols [68], [69];
6. water-insoluble soaps of long-chain fatty
acids, including aluminum stearate [637-12-
7], calcium stearate [1592-23-0], and calcium
behenate [3578-72-1] [70];
7. perfluorinated fatty alcohols [71].
3.5. Water-Insoluble Polymers
A number of polymeric substances have been
reported to have antifoaming properties, includ-
ing low molecular mass, fatty acid modified
alkyd resins; low molecular mass novolaks; co-
polymers of vinyl acetate and long-chain maleic
and fumaric acid diesters; and methyl methacry-
late vinylpyrrolidone copolymers. Other rele-
vant polymeric materials include poly(propylene
glycols) and high molecular mass propylene
oxide adducts to glycerol [56-81-5], trimethylol-
Vol. 15
propane (1,1,1-tris(hydroxymethyl)propane)
[77-99-6], pentaerythritol [115-77-5], triethano-
lamine [102-71-6], dipentaerythritol [126-58-9],
or polyglycerol [25618-55-7] [7274].
Addition products of butylene oxide or
long-chain a-epoxides with polyvalent alcohols
show the same effects as propylene oxide
polymers [75], [76].
3.6. Amphiphilic Components
The category of amphiphilic compounds in-
cludes antifoam components with varying water
solubility whose foam-inhibiting effects are due
to a variety of mechanisms. Examples include
sodium oleate [143-19-1] and the hardened fish
fatty acid soaps used as foam regulators in de-
tergents [41], [42]. The activity of the latter
depends on in situ formation of calcium salts,
which restricts their application to water that has
not been demineralized.
Some amphiphilic substances are water soluble
at low temperature but flocculate upon warming
beyond a particular point called the cloud point.
Above the cloud point, these surface-active mate-
rials act as foam inhibitors. Their foam-breaking
effectiveness reaches an optimum at the cloud
point itself. Examples of this type are nonionic
surfactants such as modestly ethoxylated fatty
alcohols, fatty acids, rosin acids, fatty amines, and
alkylphenol derivatives with HLB (hydrophilic
lipophilic balance) values < 10. (For further ex-
planation of HLB values, see ! Emulsions.)
However, the effectiveness of this group of am-
phiphilic substances can be increased markedly if
the free, primary hydroxyl groups of the polyglycol
ether portions are blocked through esterification or
ether formation with a hydrophobic residue.
Silicone surfactants can also be classified as
amphiphilic substances. Silicone surfactants are
silicone oils to which polyether groups have been
chemically bonded. Introduction of polyether re-
sidues increases the hydrophilic character of a
siloxane; as a result, it is no longer totally water
insoluble and, instead, possesses a cloud point [77].
3.7. Emulsifiers
Emulsifiers assure rapid distribution of active
ingredients throughout an aqueous phase
Foams and Foam Control 581
(! Emulsions). Those surfactants already
enumerated in the amphiphilic category fulfill
this role to some extent, although more strongly
hydrophilic, nonionic surfactants with an HLB
value > 10 are also employed (e.g., ethoxylated
sorbitan esters).
3.8. Coupling Agents
Coupling agents increase the mutual tolerance of
the various components of a foam inhibitor and
prevent gel formation or sedimentation during
long-term storage at fluctuating temperatures.
Most of these materials are glycols, low molecu-
lar mass alcohols, or other ingredients known as
solubilizers such as naphthalenesulfonate [1321-
69-3] or p-toluenesulfonate [657-84-1].
4. Mechanical Means of Combating
Foam
Foam problems can often be prevented or at least
minimized by proper design of production facili-
ties and careful adjustment of operating condi-
tions. Examples include reduction of stirring
rates, avoidance of vigorous boiling or sudden
evacuation, and elimination of rough surfaces.
Foam formation can also be reduced by careful
control of venting operations, and by diminishing
surface areas and the corresponding potential for
uptake of air (e.g., by selecting tall vessels of
limited diameter). The proper arrangement of
heating devices can also have a beneficial effect,
as can the choice of reactor construction materi-
als. Thus, the presence of highly conductive
materials in the region above the fill level of a
reactor vessel can result in more rapid dissipation
of foams with low stability.
Foam can sometimes be countered by spray-
ing with finely divided water [78], introducing air
(perhaps supplemented by carbon dioxide), use
of a spark discharge [79] or balancing electrical
charge [80]. Other mechanical approaches to
dealing with foam include the removal of gases
or gas-laden liquids by means of a porous filter.
This method is particularly applicable to fermen-
tation processes and, under appropriate condi-
tions, to the monomer-stripping operation of
vinyl chloride used in the manufacture of poly
(vinyl chloride) [81]. Modern computer technol-
582 Foams and Foam Control
ogy has created new means of optimizing the rate
at which the defoamer is supplied to the proces-
sing vessel [82].
5. Foam Problems in Specific
Applications
5.1. Detergents
See ! Laundry Detergents, 1. Introduction and
[83].
5.2. Food and Beverage Industries
5.2.1. Cleansing and Disinfecting
Any surface that comes in contact with food or
beverages during their manufacture, processing,
or transport must be cleaned and disinfected at
regular intervals. Because the affected indus-
tries (e.g., breweries, soft drink manufacturers,
dairies, meat packers, the sugar and preserves
industries) are confronted with very different
problems of residue removal, a wide range of
processes, cleansing agents, and disinfectants is
required.
The ever-increasing role of mechanization
and automation in industry has focused increased
attention on potential foam problems. In particu-
lar, inconvenient foam formation must be antici-
pated in all of the following activities:
1. CIP (cleaning in place) cleansing and dis-
infecting of tanks, if the active solutions are to
be recovered and stored for reuse;
Figure 8. Cleaning-in-place (CIP) system for cleansing and disinfecting tanks
a) Soiled tank; b) Recycle water; c) Alkaline wash solution; d) Acid; e) Disinfectant; f) Fresh water; g) Alkaline solution pump
(precleaning); h) Pressure pump
Vol. 15
2. cleansing and disinfecting drums, containers,
milk collectors, and other vessels if active
solution is sprayed over the contaminated
surfaces;
3. cleansing of returnable bottles, regardless of
whether the automatic bottle-cleaning assem-
bly utilizes immersion or spray technology;
and
4. lubrication of bottle transport lines.
5.2.1.1. Tank Cleansing Based on the
Cleaning-in-Place (CIP) Method
The CIP technique involves application of a
recirculating cleansing or disinfecting solution
onto the walls of a soiled tank by means of spray
heads or targeted nozzles. Generally, the process
is conducted at low pressure. Recovered cleans-
ing solution is led into storage tanks to permit its
reuse (Fig. 8).
Foam may cause air to be drawn into the
circulating pumps, leave residues that are diffi-
cult to remove, or result in solution losses due to
reservoir overflow. Residues that can produce
foaming in the tanks include
1. proteins and fats (dairy industry);
2. proteins, polysaccharides, tannin or polyphe-
nols, hop resins, and bittering agents (brew-
eries); and
3. pectin, cell components, ethereal oils, and
polysaccharides (vegetable and fruit juice
processors).
Components of the cleansing or disinfecting
agent itself may also present problems. These
Vol. 15 Foams and Foam Control 583

include nonionic, anionic, and cationic surfac-
tants (e.g., quaternary ammonium compounds).
5.2.1.2. Cleansing of Returnable Bottles
A distinction is generally made between two
fundamental types of bottle washers: those that
utilize separate soakers (soaking baths) and those
that combine soaking with spraying (Fig. 9).
Machines of the latter type are subject to foam
problems both when the bottles are initially
flooded with cleansing solution and later during
spray cleaning. Foam arises as a result of the
following contaminants.
1. soaps and surfactants originating in lubricants
applied to the conveyor belt;
2. cellulose, sizing, surfactants, dyes, and pig-
ments derived from bottle labels;
3. dextrin, casein, and vegetable gum, as well as
synthetic glue, again from bottle labels; and
4. sugar, protein, and fat residues from the orig-
inal beverages.
Intensive foaming in a bottle-cleaning line can
result in overflow of the cleansing baths and can
hinder the discharge of bottle labels. The labels
tend to float in or on the foam. They gradually
disintegrate and may eventually clog the spray
nozzles. Foam also causes the recirculating
pumps to draw a mixture of detergent solution
and air, which in turn reduces the effectiveness of
the bottle-flooding operation. Label fragments
carried into the rinse baths can cause further
clogging, and bottles may exit the machine con-
taminated with cleansing solution.
The most important characteristic of a foam
inhibitor intended for use in a bottle-washing
system is that it be stable to alkali. In some
countries, including the Federal Republic of
Germany, such agents must also be biodegrad-
able (to the extent of 80 %, according to the
German surfactant law). The latter requirement
has been addressed in 1987 by the introduction of
nonionic surfactants bearing specially designed
protective end groups [84].
5.2.2. Food Processing
5.2.2.1. Sugar
Modern methods for processing sugar beets are
fully mechanized and automated (! Sugar).
The raw beets are first washed and chopped.
The sugar is then extracted with hot water in
extracting towers. The crude extract, which also
contains nonsugar components of the beets, is
treated first with limewater and then with carbon
dioxide. The lime sludge includes most of the
nonsugar components and is removed by filt-
ration. The filtrate is subjected to multistage

Figure 9. Automatic bottle-washing unit employing a combination soaking spray system (Riwella-RK, Seitz Enzinger Noll
Maschinenbau, FRG)
a) Preheating stage 1; b) Preheating stage 2; c) Preheating stage 3; d) Caustic 1 submersion soaking bath; e) Immersion flooding;
f) Label removal assembly; g) Above-surface flushing; h) Wash IIinterior (moving) and exterior spray; i) Warm-water
intermediate spray, internal and external (internal synchronized); j) Warm-water spray, internal and external (internal
synchronized); h) Cold-water spray, internal and external (internal synchronized); l) Fresh-water spray, internal synchronized;
m) Fresh-water spray curtain; n) Guided vapor removal system; o) Bottle feed; p) Bottle discharge
584 Foams and Foam Control
evaporation ultimately under vacuum leaving
a supersaturated crystalline broth, the masse-
cuite. Sugar is finally separated by centrifugation
from the residual syrup, known as molasses.
More or less intensive foam formation is
observed in each of the above steps [125]. The
foam is attributed to the numerous nonsugar
materials present, such as cellulose, lignin, pro-
tein, vegetable bases (betaine and choline), and
especially, saponin.
Foam controllers employed in the beet-wash-
ing process are likely to appear in wastewater;
therefore, biodegradability is an important pre-
requisite. Because sugar is intended for human
consumption and trace amounts of antifoaming
agents may be present in the finished product,
various legal and health issues are involved (see
Chap. 7) [126]. Furthermore, steam-volatile
components must be avoided during the evapo-
ration and boiling steps, as must any material
that might leave deposits which would diminish
the effectiveness of the heat exchangers. Foam-
control agents must also not inhibit the ion-
exchange resins commonly employed to remove
residual hardness from the dilute syrup. Finally,
antifoaming agents must not affect subsequent
use of the molasses in yeast production (see
below).
5.2.2.2. Yeast
Bakers yeast is prepared commercially in mas-
sive (up to 200 000-L) fermentation tanks. The
most commonly employed nutrient is the molas-
ses obtained as a byproduct of sugar refining.
A large amount of air is required to ensure
rapid multiplication of yeast cells; it is generally
introduced through a series of tiny nozzles. After
12 14 h, the yeast is ready for harvesting. It is
removed from the exhausted growth medium,
reduced to the proper moisture content by means
of a rotary filter, and pressed into tablets for final
distribution.
The initial stage of yeast culture is an anaero-
bic process that is rarely subject to disruptive
foam formation; by contrast, fermentation is
aerobic, and is generally accompanied by exten-
sive foaming. Foam suppressants are necessary
to prevent overflow from the fermentor [127].
This heavy foaming is due mainly to residual
nonsugar beet constituents that accompany the
raw molasses (see Section 5.2.2.1).
Vol. 15
In modern yeast production facilities, foam
suppressants are introduced by means of auto-
matic electrode-activated devices. The chemical
defoaming preparation chosen must not interfere
with the transport of oxygen because yeast
growth would then suffer [128, 129]. In addition,
the absence of detrimental effects on the final
yeast cubes, such as premature softening or
liquefaction must be ensured [130].
5.2.2.3. Potatoes
Whether the product is potato chips, French fries,
mashed potatoes, or potato starch, potato proces-
sing is always beset by foam formation. A wash
bath is always employed, and foaming can lead to
serious processing difficulties. Starch manufac-
ture, in particular, is plagued by intensive foam-
ing in the potato juice, the starch slurry, and the
processing water, caused by proteins and other
nitrogenous compounds found in potatoes.
Starch foam is very stable and difficult to counter.
Mechanical methods of foam control have such
limited effectiveness that the addition of foam-
control agents may be regarded as the most
practical and universally applicable solution
[131].
5.3. Metal Treatment
5.3.1. Foam Problems Associated with
Cooling Lubricants
Cooling lubricants mixed with water are used
frequently in the metal-working industry in con-
junction with operations that involve the removal
of shavings or turnings (e.g., drilling, turning,
milling, or grinding) as well as in such processes
as wire drawing, rolling, and deep drawing.
Cooling lubricants are concentrates based on
mineral oils and emulsifiers. The user dilutes
these with water to the desired concentration.
Certain applications require the use of oil-free,
transparent solutions. Both emulsifiers and corro-
sion inhibitors can induce foam formation, which
in turn diminishes the filterability and cooling
capacity of the lubricant and may lead to over-
flow. Foam behavior is, therefore, an important
consideration in the selection of emulsifiers and
other components for a cooling lubricant concen-
trate. However, considerations related to
Vol. 15
emulsion stability often so limit the choice that the
only way of avoiding foam problems is to incor-
porate additional foam inhibiting agents.
A widely accepted approach utilizes calcium
soaps as foam inhibitors. These are formed when
the soaps present in the cooling lubricant con-
centrate react with hardening agents in the water
used to dilute the concentrate. The calcium soaps
are produced as a finely divided suspension of
insoluble particles. The amount and type of soap
must be adjusted to ensure an appropriate amount
of residue and the correct particle size and to
avoid disruptive buildup of sediment.
Cooling lubricants normally have a working
lifetime of weeks or even months. As a result,
external influences can alter their foam behavior
and may require the addition of other foam
inhibitors based on wax dispersions or silicone
oil. However, these materials cling to metal
surfaces, which can lead to irregularities in sub-
sequent surface treatment. Their application
must therefore be kept to a minimum and should
preferably be continuous rather than on an as-
needed basis.
5.3.2. Foam in Alkaline Cleansing
Solutions
Alkaline cleansing agents are used primarily for
difficult industrial cleaning tasks such as the
removal of large amounts of oil, fat, or pigments.
They are also employed in the final preparation of
metallic surfaces prior to finishing. The com-
bined action of the builders, the surfactants, and
various additives removes pigments, metal shav-
ings, metallic soaps, graphite, fats, and oils and
helps in dispersing and emulsifying soil particles
in the wash liquor. Such agents are widely em-
ployed in repair shops, enameling, galvanizing,
electroplating, and sheet steel manufacture.
The major constituents of alkaline cleansing
agents used in the metals industry are builders
and surfactants. Builders are generally hydro-
xides or inorganic salts, such as silicates, phos-
phates, borates, or carbonates of sodium or
potassium. The surfactants include anionic
materials such as alkylbenzenesulfonates, and/
or nonionic substances. Such products are
often supplemented with other substances (e.g.,
chelating agents, corrosion inhibitors) in order to
meet the needs of a particular application.
Foams and Foam Control 585
In many cases, foaming can be controlled by
cloud point adjustment. The cloud point is de-
fined as that temperature at which a second phase,
enriched in wetting agent, forms; it is recognized
by the onset of cloudiness. The foaming tendency
decreases rapidly above the cloud point, but
cleaning capacity also diminishes. For this rea-
son, the cloud point should be set slightly below
the expected application temperature. However,
the fact that the cloud point decreases with
increasing salt concentration and thus with in-
creasing total concentration of the cleansing
agent must also be taken into consideration.
Careful choice of nonionic surfactants with vari-
ous HLB values, perhaps in combination with
appropriate concentrations of one or more anion-
ic surfactants, ensures that a specific cloud point
will be obtained at the dilution employed. If
properly employed, cleansing solutions whose
cloud point has been correctly set, are free of
foaming problems even when large amounts of
air are introduced, as in spray applications.
If the surfactant concentration is not constant,
e.g., due to contamination by extraneous surface-
active substances, foam control by cloud point
adjustment is no longer possible.
Extraneous surface-active substances may be
introduced into a cleansing bath directly in the
form of soil on the objects being washed or
indirectly as a result of chemical reactions with
the alkaline solution. Relevant soils include non-
ionic emulsifiers as well as fatty acids and other
long-chain carboxylic acids present either as
anionic emulsifiers or because of their effective
lubricating properties. Carboxylic acid esters,
which are often included in lubricating agents
as high pressure (HP) additives, are saponified in
the alkaline cleansing solution to alcohols and
high-foaming soaps. The rate of hydrolysis in-
creases with increasing alkalinity, temperature,
and concentration of cleansing agent as well as
with rising emulsification potential. An example
of the problem is the cleansing with orthosilicate
solution of cold-rolled black plate contaminated
with palm oil.
In this case, introduction of specific foam-
control agents on an as-needed basis may be
advantageous. Foams due to soap can be con-
trolled by soluble calcium salts, perhaps in the
form of hard water added to make up for evapo-
rative losses. Substances belonging to the cate-
gory of ethylene oxide propylene oxide block
586 Foams and Foam Control
polymers [9003-11-6] are also commonly em-
ployed. Silicone oils are inappropriate for appli-
cations involving the cleaning of metals because
they are likely to interfere with subsequent sur-
face treatments.
5.3.3. Foam Control in Neutral Cleansers
Neutral cleansers are liquid industrial cleansers
that provide temporary corrosion protection.
Their basic chemical constituents are nonionic
and cationic surfactants, as well as organic cor-
rosion inhibitors. Neutral cleansers are used
preferably in automatic spray washers at tem-
peratures between 5 and 90  C to clean iron or
steel, aluminum, nonferrous metal, and plastic
parts after cutting or noncutting working [85].
The aqueous solutions have a pH of ca. 9. Foam
produced by vigorous mechanical action during
spraying can be controlled by cloud point adjust-
ment (see Section 5.3.2) of the nonionic surfac-
tants; foam-controlling nonionics based on
mixed ethers are now preferred for both ecologi-
cal and toxicological reasons [84]. The cationic
surfactants present in neutral cleansers also in-
hibit the formation of foams caused by extrane-
ous anionic surfactants during spraying and thus
permit recycling of the cleansing solution [86],
[87].
5.4. Polymer Industry
Foam problems are common in the production of
plastics, synthetic rubber, and polymer disper-
sions. Foaming may accompany not only the
actual polymerization step but also the recovery
of unreacted monomer and the packaging, trans-
fer, and transport of aqueous dispersions or
latices.
Foam problems during polymerization are
particularly common when heat generated by the
reaction is removed by refluxing low-boiling
monomers, e.g., in the preparation of poly(vinyl
acetate) or poly(vinyl chloride).
Emulsion (E) polymerizations have a greater
tendency to foam than suspension or dispersion
polymerizations. Weakly foaming anionic emul-
sifiers [88], [89], oligomeric carboxylates [90],
and low foaming nonionic coemulsifiers [91]
have all been proposed as agents for the preven-
Vol. 15
Figure 10. Foaming behavior of anionic primary emulsifiers
at 25  C
a) Nonylphenol 4 EO sulfate; b) Lauryl alcohol 4 EO
sulfate; c) Lauryl alcohol 50 EO sulfate; d) Lauryl alcohol
30 EO sulfate; e) Nonylphenol 10 EO sulfate; f) Lauryl
alcohol 10 EO sulfate; g) Nonylphenol 25 EO sulfate
EO ethylene oxide.
tion of foaming during emulsion polymerization.
The correct choice of the primary emulsifier for
the polymerization is also important because
substances in this category vary widely in their
foaming tendencies (Fig. 10).
Differences are also observed, in various sus-
pension (S) polymerizations, with regard to
foaming. For example, S-PVC charges contain-
ing poly(vinyl alcohol) as a protective colloid
foam more readily than those in which cellulose
ethers are used to stabilize the suspension. Foam
is commonly combated at this stage by spraying
the stirring vortex with antifoaming agents, but
mechanical means are also employed, including
spraying with water [92] or bursting the bubbles
with a propeller [93].
In the synthesis of both poly(vinyl chloride)
and synthetic rubber, the polymerization reaction
is usually terminated before complete conversion
which necessitates the recovery of unreacted
monomer. In the case of synthetic rubber, the
latex is freed from monomeric butadiene in large
decompression vessels. Less volatile monomers
such as styrene are removed by passing the latex
through a column against a flow of rising steam.
A significant improvement was introduced in
1965 by BASF, which resulted in simpler, quick-
er, more efficient monomer recovery. In the
BASF process, steam is passed at high velocity
through the boiling polymer dispersion to pro-
duce a steam dispersion foam mixture that
Vol. 15
carries residual monomer with it. This mixture is
then subjected to rapid decrease in pressure,
during which the foam is destroyed. Steam is
separated from the broken dispersion foam, and
the latter is returned to the boiling polymer
dispersion [94].
In the case of S-PVC, demonomerization [95]
involves either the use of a multicompartment
vessel equipped for countercurrent vapor remov-
al [96] or countercurrent vapor removal through a
continuously operating column [97]. For E-PVC,
the method of choice is spraying in conjunction
with a pressure gradient [98].
Foaming during monomer removal [99] is
caused by surface-active protective colloids or
emulsifiers. Foam control by purely mechanical
means may suffice, but in most cases antifoaming
agents are employed. Among the criteria used in
choosing them are
1. effectiveness with respect to the nonionic
protective colloids in the case of suspension
polymerization;
2. effectiveness with respect to the anionic
emulsifiers in the case of emulsion
polymerization;
3. stability to acidic or alkaline conditions, de-
pending on the method of PVC manufacture
employed; and
4. long-term stability and activity consistent
with multistep, continuous stripping ope-
rations.
Silicone antifoaming agents are generally
avoided, particularly for poly(vinyl chloride)
destined to be made into film or where foam
might be expected to play a role in further
processing.
The choice of possible antifoaming agents for
use in the manufacture of poly(vinyl chloride) or
for the preparation of polymer dispersions is
often severely restricted by the fact that proposed
ingredients may have to be approved by a na-
tional health agency such as the FDA (United
States) or the Bundesgesundheitsamt (Federal
Republic of Germany).
5.5. Paint and Coating Industry
In the paint industry, foam formation can inter-
fere with various processing steps. In addition,
Foams and Foam Control 587
inadequate foam control (or use of the wrong
foam-controlling agent) can negatively influence
the decorative value or surface-protective func-
tion of the finished product. Foam problems may
be encountered during pigment dispersion, intro-
duction and mixing of the pigment dispersion and
binder, transfer of the finished paint into cans, or
final applicationwhether by brush, sprayer, or
dipping [100].
Paint formulations are prepared in some types
of stirring apparatus by blending a mixture of
pigments and fillers with water to form a paste.
The water is supplemented with dispersing
agents [101], wetting agents, or a suitable com-
bination of the two.
Dispersion is most commonly effected today
with the aid of a dissolver. The shear forces
required, coupled with the effects of dispersing
and wetting agents, result in formation of a
prodigious amount of foam, which is further
stabilized by the presence of thickening agents
such as poly(vinyl alcohol) or hydroxyethyl
cellulose. The nature of the pigments themselves
is also a factor. Finely divided pigment particles
(e.g., carbon black or phthalocyanine blue) tend
to promote foam formation. Foam control is
complicated further by the presence of iron oxide
pigments, which have a tendency to adsorb and
thus neutralize the effect of antifoaming agents.
In the paint industry, the antifoaming agent
should be tailored to the specific application at
hand [102], [103]. Screening tests should be
performed to verify that a particular antifoaming
agent is effective and application tests should be
conducted in its presence [104].
A pigment dispersion containing the defoa-
mer is applied with a sponge roller to a piece of
molded fiberboard, whose smooth side has been
sealed with the appropriate polymer dispersion.
After the paint has dried, the appearance of the
coating is compared with samples comprising a
graduated test scale (Fig. 11). A given antifoam-
ing agent must be evaluated further for micro-
foaming, a particularly frequent problem with
modern aqueous coatings. This is done by exam-
ining paint applied to a glass plate and exposed to
incident light from two neon tubes [103].
Air introduced into a nonaqueous paint pro-
duces a spherical rather than a polyhedral foam
(see Chap. 2). If insufficient time is available for
air to escape during the drying process, cavities
or pinholes may form during baking: e.g., rapid
588 Foams and Foam Control Vol. 15

Figure 11. Comparison scale for evaluating the effects of foaming during application of an emulsion paint
A) Comparison scale; B) Grade 1; C) Grade 10

evaporation of solvent near the surface may
result in the surface becoming closed, and bub-
bles entrapped in the lower layers may burst at a
later stage in baking when the coating has be-
come so viscous it cannot flow into developing
vacancies. The most effective remedy is incor-
poration of high-boiling solvents or solvent
mixtures.
The decisive factor, with respect to foam
behavior and foam control for water-borne coat-
ings (e.g., acid-functional acrylic polymers
cross-linked with melamine) is the bulk viscosity
of the mixture, which is often dictated by the
proposed application conditions [105]. The in-
creasing use of such coatings in the automotive
industry has resulted in concern about foaming
during the removal of paint residues. These
residues (oversprays) are withdrawn from the
spray booth through a circulating water system.
Special coagulating agents are added to cause
pigment agglomeration, after which the pigment
is precipitated with the aid of a flocculant
(Fig. 12). Surface-active substances tend to
cause foam formation in the constantly recircu-
lated water; this, in turn, may clog the circulat-
ing system and reduce the effectiveness of the

Figure 12. The ESKA (Entsorgung von Spritzkabinen Anlagen) system for removal of residual paint in the automotive
industry (D
urr Anlagenbau, FRG)
a) Coagulation tank (pit); b) Flocculation tank; c) Settling tank; d) Sludge buffer; e) Decanter; f) Sludge cart
Vol. 15
precipitating steps. In severe cases, the coating
process itself can be affected [106]. Special
silicone-free antifoaming agents have been de-
veloped exclusively for this application.
5.6. Construction Industry
Since 1945, polymer dispersions have played a
rapidly increasing role in the construction indus-
try. The plasticizing influence of such dispersions
permits a reduction in the amount of water re-
quired to make cement and similar materials
workable. More important, however, the addition
of polymer dispersions to mortar leads to greater
tensile strength in bending, and plaster contain-
ing both polymers and mineral binders has better
adhesion and less tendency to crack.
Increased amounts of emulsifiers and dispers-
ing agents are required to stabilize polymer dis-
persions. These increase the risk that foam pro-
duced during mixing of the latex and the cement
or mortar will result in undesirable entrapment of
air bubbles, thereby reducing the ultimate stabil-
ity of the solidified mass. Antifoaming agents
utilized in this context must be stable to alkali and
must not have an adverse effect on key properties
relevant to the construction trade (e.g., nonflam-
mability requirements) [107].
In some cases, powder defoamers are added
directly to the cement or mortar mix [108], [109];
silicone antifoaming agents are also used [110].
Appropriate low-foaming dispersions utilizing
antifoaming agents with good long-term stability
could be offered by latex manufacturers them-
selves, thereby obviating the need for subsequent
introduction of foam-control substances [111].
5.7. Adhesives Industry
Most industrial adhesives are applied mechani-
cally. The entrapment of tiny air bubbles during
application may change the material flow char-
acteristics and result in an uneven or damaged
adhesive layer along with a corresponding reduc-
tion in the tensile strength of the adhesive bond.
The foaming tendency and the extent of foam
formation depend upon the nature of the binding
agents and other components added to the for-
mulation. Natural binders such as starch, soy
protein, cellulose ether, and natural rubber
Foams and Foam Control 589
either are inherently surface-active materials or
contain impurities that are surface active, such
as saponin (in starch) or lipoproteins (in natural
rubber latex). Synthetic binders contain surface-
active stabilizers. Soaps based on fatty acids or
rosin acids are present in synthetic rubber latex;
poly(vinyl acetate) dispersions contain hydro-
xyethyl cellulose or poly(vinyl alcohol); syn-
thetic anionic or nonionic emulsifiers are found
in acrylate and methacrylate polymers. Foam
stability is enhanced by thickeners such as
methyl cellulose or polyacrylate, which in-
crease the viscosity of the mixture and thus
inhibit the degradation of foam once it has been
produced.
Antifoaming agents for adhesive applications
must be chosen for their suitability with respect
to the particular surface-active agents in ques-
tion. Adhesives that may come in contact with
food or the human body must meet relevant legal
requirements (Chap. 7).
Under certain conditions, foam can be turned
to technical and economic advantage. For exam-
ple, controlled foam formation in the Nordson
Foam Melt process [112] results in hot melts with
prolonged open time as well as improved flow
and filling characteristics and more rapid setting.
The amount of adhesive required is also reduced.
5.8. Textile Industry
Most chemical processes associated with the
textile industry occur at the fiber surface and in
aqueous medium. Surfactants improve the wet-
tability of fiber surfaces, help displace adsorbed
air, aid in the emulsification and dispersion of
textile auxiliaries, and facilitate removal of soil
from fabric surfaces.
The increased rate of machine operation and
material transport in modern textile mills implies
an enormous expenditure of mechanical energy.
Foam formation must be anticipated in any
operation in which air is permitted to enter the
treatment baths. The detrimental effects of foam
may be qualitative, as in the case of spoiled
goods (fabrics showing irregularities in surface
treatment, undesirable depositions, spotting), or
quantitative in the sense of requiring more com-
plicated machinery or reduction in output.
Three general approaches have been taken to
solving the textile industrys foam problems:
590 Foams and Foam Control
1. Mechanical technological solutions
2. Introduction of foam inhibitors
3. Use of low-foaming surfactants in the formu-
lation of textile auxiliaries
In most cases, a combination of measures is
required.
Pretreatment and dyeing are the most impor-
tant and critical textile processing steps with
respect to foam control, but other stages in the
process (e.g., fiber manufacture or fabric sizing,
imprinting, and finishing) also present foam
problems.
5.8.1. Pretreatment
The processing of cotton and spun rayon involves
alkali treatment and mercerization; fabric is sub-
jected to various concentrations of sodium hy-
droxide in the presence of wetting agents that are
usually anionic in nature. Especially with the
dry-in-wet process, but also with wet-in-wet
technology, some introduction of air is inevitable.
The preferred method of foam control relies on
phosphate esters of alcohols containing four to
eight carbon atoms (e.g., tributyl phosphate).
These esters are stable in solutions containing
high concentrations of alkali and electrolytes.
Other pretreatment steps conducted in a
strongly alkaline medium rich in powerful an-
ionic and nonionic surfactants include boiling off
(alkali extraction of cotton) and bleaching, par-
ticularly when hydrogen peroxide is used as the
bleach. Both processes are amenable to either
continuous or batchwise implementation.
Batch treatment is increasingly carried out in
jet or overflow systems. If the processing equip-
ment is not completely filled with liquor, a more
or less intensive but, in any event, disruptive
foaming can be anticipated as a result of the high
flow rates and rapid material transport. Foam at
this stage interferes with homogeneous treat-
ment of the fabric, which has a tendency to float.
In addition, mixtures of surfactants and anti-
foaming agents tend to separate as a result of the
high shear forces present in the circulating
pumps. Foam residues (including silicone
defoamers) may also remain on the fabric and
cause spotting. Therefore, low-foaming wetting
agents should be selected from the outset, and
silicone-containing foam control agents must be
Vol. 15
avoided. The usual alternatives are formulations
based on tributyl phosphate.
Continuous processing in an open-width unit
also presents severe foam problems, because
surfactant may be present in concentrations up
to ten times that required for a batch process.
Rotor jet agitation of the treatment bath and spray
jet equipment aggravate the situation.
Mixed ether formulations [84] represent one
modern solution to such foam problems, espe-
cially in bleach baths. Their foam-inhibiting
power is particularly noteworthy at bleach-bath
temperatures above the cloud point of the
additives.
The use of low-foaming wetting agents can
largely obviate the need for supplementary foam
control agents in a peroxide bleaching bath.
Moreover, these surfactants are biodegradable.
Hydroxyalkane ether sulfonates prepared by SO3
sulfonation of mixed ethers of unsaturated fatty
alcohols are especially suitable [113].
5.8.2. Dyeing
Dyeworks are the largest consumers of foam-
control agents in the textile industry. Because
water is the only feasible solvent for dyeing and
all water-insoluble dyes must be introduced as
dispersions, dyeing involves many surface-ac-
tive auxiliaries such as wetting agents, dye dis-
persants, and leveling agents.
The foam problems associated with dyeing
are comparable to those encountered during pre-
treatment (Section 5.8.1), in part because much
of the processing machinery (both batch and
continuous) is similar. The same applies to dye
posttreatments, which include steps designed to
improve fastness, as well as various finishing
operations using fabric softeners (usually cation-
ic) or other processing aids (e.g., finishes for
improving sewability).
Dyers often utilize special silicone antifoam-
ing agents, but preparations devoid of silicones
are also used.
5.8.3. Foam Application of Textile
Auxiliaries
Even though foam is generally regarded as a
disruptive influence in textile manufacture, it can
Vol. 15
also serve a useful function, as in the case of foam
application technology [114], [115], particularly
because this opens the way to energy-efficient
drying. Foams also play a structural role in
certain finished products such as carpet backing,
and foam is useful in situations calling for appli-
cation of a substance to only one side of a fabric.
Foam technology has become an established
part of such operations as rotary screen printing,
fabric coating, bonding of nonwoven fabrics,
backing (upholstery fabrics), and certain types
of dyeing.
5.9. Leather Industry
Almost every stage of leather processing from
rawhide to consumer product involves contact
or treatment of the leather with surface-active
compounds. During processing of the hides in the
beam house, and subsequent tanning, dyeing, and
fat-liquoring, inconvenient foam is countered
largely with the aid of silicone foam-control
agents. In many cases, the necessary treatment
aids contain appropriate foam-regulating
additives.
The problems faced during leather finishing
are considerably more complex. Many finishing
agents contain surfactants or are applied in the
form of emulsions (e.g., casein solutions, silicone
emulsion for use as a feel agent, wax emulsions,
nitrocellulose emulsions). Pigmented disper-
sions contain wetting or dispersing agents, and
aqueous acrylic resins are polymer emulsions
that incorporate anionic or cationic emulsifiers.
Foam formation during finishing and coating can
lead to serious process disruption. The choice of a
suitable antifoaming agent is often difficult be-
cause it must be both highly effective and, at the
same time, compatible with other aspects of
the process; it must in no way lower the quality
of the final finish [116].
5.10. Pulp and Paper Industry
The paper industry is one of the major consumers
of foam-control agents. Foam is a problem at
every stage from pulp and paper fabrication
through coating and printing, as well as in the
reprocessing of wastepaper and the treatment of
wastewater.
Foams and Foam Control 591
5.10.1. Pulping
The alkaline conditions required by the sulfate
pulping process result not only in the solubiliza-
tion of lignin but also in the production of soap.
The soap originates from resin acids found in the
resin ducts of coniferous trees and from fats and
resins located in the parenchymal cells of decid-
uous trees. The soap is responsible for the gener-
ation of considerable amounts of foam. Depend-
ing on their degree of dispersion, colloidal and
finely dispersed cellulose particles and fibrils can
stabilize this foam. The resulting fiber suspension
is washed in multistage brown-stock washers at a
temperature of more than 82  C and a pH of ca.
12, to remove most of the residual cooking liquor.
The antifoaming agents must therefore be effec-
tive at high temperature and alkali-stable [117].
In addition to the sulfate process, sulfite pulp-
ing is still of some importance, particularly in
Europe. In this process, lignin is solubilized and
extracted from the wood in the form of lignin-
sulfonate. Sulfonation is performed using a hot
aqueous solution of sulfites or hydrosulfites,
sometimes in the presence of excess sulfur diox-
ide. Sulfite pulping liquor is acidic, and foam
generation is due to the presence of ligninsulfo-
nates and other surface-active materials contain-
ing sulfonate groups. The resulting demands on
any potential antifoaming agent are, therefore,
different from those in sulfate pulping [118].
Foam controllers for pulping must be effec-
tive against large-scale foam production. In ad-
dition, they must be capable of dissipating gas
entrapped in small bubbles stabilized by minute
cellulose fibers. This gas consists of air as well as
carbon dioxide arising from fermentation of raw
materials or chemical reactions associated with
hard water. Insufficient attention to this problem
results in a pulping mixture that is difficult to
filter, and the washed pulp is likely to contain
undesirable tall oil residues.
5.10.2. Pulping Liquor Disposal
Both economic and environmental considera-
tions require that spent liquor from the pulping
operation be subjected to further, extensive treat-
ment. Evaporative measures are complicated by
foam due to the presence of dissolved soaps
derived from fatty acids and abietates. Such
592 Foams and Foam Control
foams can be controlled with the aid of mixtures
of organic solvents and nonionic surfactant
[119]. Suitable wastewater defoamers can also
be obtained by reacting fatty acid esters, fatty
alcohols, or paraffinic hydrocarbons with liquid
or gaseous sulfur dioxide [120].
5.10.3. Air Content of Pulp Suspensions
A common problem in paper manufacture is
entrapment of air as a result of the turbulence
associated with rapidly moving machinery. Dis-
persed air can lead to tiny bubbles in the paper or
to foam on the surface, thus reducing the rate of
subsequent moisture removal and lowering prod-
uct quality. The seriousness of the problem can
be reduced by incorporating degassing devices
but high-speed processes require supplementary
chemical measures to further suppress foaming
and minimize air content.
Most of the standard wetting agents are un-
suitable for degassing purposes. The most effec-
tive air release agents are slightly water-soluble,
nonionic surfactants such as water-in-oil emul-
sifiers. Ethoxylation products based on fatty
alcohols, fatty acids, or ricinoleic acid play a
particularly important role [121].
5.10.4. Conversion to Paper
Foam formation in the paper-making machine
results from mechanically introduced air that
interacts with surface-active compounds present
in added sizing agents. Foam of this type inter-
feres with the formation of a closed fiber struc-
ture. It also inhibits drying and causes irregulari-
ties in the paper surface. Choice of an appropriate
foam-control agent is difficult because of adverse
potential effects on the sizing process, contami-
nation of the rollers, or further disruption of the
integrity of the paper surface [122].
5.10.5. Paper Coating
The binders utilized in paper coating are water
soluble starch, cellulose ethers, and casein or
aqueous polymer dispersions based on copoly-
mers of styrene butadiene and acrylic esters.
The synthetic binders are particularly likely to
Vol. 15
Figure 13. Deinking process
Flotation causes dislodged ink pigments to be collected by air
bubbles and removed along with the foam
cause foam problems and surface disturbances.
Air cannot be excluded to a sufficient degree
from the coating materials themselves; hence, the
addition of chemical foam-control agents is com-
mon practice [123]. These differ from the anti-
foam preparations employed in paper making
and must conform to the synthetic emulsions
used in coating materials.
5.10.6. Waste Paper Deinking
Air is deliberately introduced during the flotation
deinking of paper waste. This induces the forma-
tion of air bubbles at the surface of the printing
ink pigments and reduces the effective density of
the pigment particles. The particles rise to the
surface thus separating the ink from the fibers
(Fig. 13). The solid particles in the foam are
separated from the aqueous phase by centrifuga-
tion or passage through a belt filter press [124].
5.11. Phosphoric Acid Manufacture
The phosphoric acid used in fertilizers is pro-
duced primarily by the wet process in which
phosphate-containing minerals are reacted with
aqueous sulfuric acid. The accompanying release
of carbon dioxide and silicon tetrafluoride leads
to vigorous foaming, especially at the onset of the
reaction. Foam may also be encountered during
subsequent vacuum evaporation of the crude
phosphoric acid. These foams are stabilized by
insufficiently wetted, finely divided crystallites
of the water-insoluble mineral gypsum. Powerful
Vol. 15
wetting agents provide a reliable solution to the
problem. Anionic surfactants such as oleic acid,
dioctyl sulfosuccinate, sulfonated tall oil, or
mineral oil are especially useful [132]; they are
often introduced in combination with fatty alco-
hols and nonionic surfactants (e.g., fatty alcohol
and fatty acid ethoxylates). A mixture of a high
molecular mass, water-insoluble, polyacryl-
amide flocculating agent and sulfonated tall oil
fatty acids is particularly effective [133].
5.12. Wastewater Treatment
Wastewater entering a treatment plant is first
freed of voluminous material by filtration
through a coarse sieve. It is then passed through
a series of channels designed to reduce its veloc-
ity so that sand and gravel settle and are left
behind. The water then enters a large sedimenta-
tion container, from which the sludge is trans-
ferred into ponds or digesters.
The water emerging from a sedimentation unit
still contains dissolved solids and colloidal par-
ticles derived from organic matter, and it may be
subjected to further treatment by activated
sludge. This requires that the liquid be brought
into intimate contact with air, either by mechani-
cal action or by using finely divided airstreams.
Aeration is a rather violent process and may lead
to serious foam problems.
Although foam is particularly undesirable at
the stage of activated sludge treatment, it can also
be encountered elsewhere in the process. In
addition, foam buildup may occur in large bodies
of water or streams. Such foam not only inter-
feres with the control, observation, and manage-
ment of water, but also reduces the effectiveness
of water purification measures.
As the surface activity of the impurities pres-
ent increases, so do the tendency toward foam
formation and the stability of the resulting foam.
Materials of low surface activity lead to forma-
tion of unstable foams, which dissipate without
the need for special intervention.
Analysis of the water emerging from the
treatment plant does not permit accurate deter-
mination of the cause of a particular foam epi-
sode. For this reason, foam-control agents are
usually selected on the basis of laboratory ex-
periments and field trials. Nonetheless, certain
criteria can be applied in their selection. One of
Foams and Foam Control 593
the criteria is the pH of the wastewater: an
antifoaming agent that is effective only in alka-
line medium is clearly of little interest if neutral
water is to be treated. Second, an antifoaming
agent that is to be introduced at the biological
stage of wastewater treatment must not have a
detrimental effect on the microorganisms re-
sponsible for purification. In addition, some
antifoaming agents may have a positive or a
negative effect on the flocculating process. Any
foam control measures taken must be compati-
ble with the particular flocculation procedure
employed.
6. Testing Methods
Because of the variety of industrial processes in
which foam formation occurs and the various
effects of defoamers, three fundamental types of
foam-related tests are used:
1. Tests to assess the foam-producing potential
of a particular substance
2. Tests of the effectiveness of a given antifoam-
ing agent
3. Tests to establish the effect of a particular
antifoaming agent on the final product
Numerous standard test procedures have been
developed. Usually, the foams are generated by
one of the following techniques:
1. The test solution is confined within a cylin-
drical container and agitated with a perforated
plate (DIN 53 902, p. 1).
2. A defined volume of the test solution is poured
from a specific height onto the surface of the
same liquid (free-fall circulating method or
Ross Miles test; DIN 53 902, p. 2).
3. Air is introduced directly into a test liquid,
through a capillary (DIN 51 381), a standard-
ized paper disk (DIN 515 666), or an appro-
priate sintered-glass device (ASTM D 892
72).
In these procedures, either the time required to
obtain a particular quantity of foam or the volume
of foam produced under test conditions is mea-
sured. Additional information can be derived
from measurement of the time required to dissi-
pate the foam.
594 Foams and Foam Control
Additional methods for establishing the foam-
ing capacity of surfactants, particularly those
relevant to the detergent industry, are given in
[12].
As many of the factors influencing foam
formation as possible must be considered. Test
conditions should be analogous to those ex-
pected in the field, especially with respect to
temperature and the means of air introduction.
Standard test conditions often have to be modi-
fied to ensure their relevance to a specific
situation.
7. Legal Aspects
Numerous restrictions apply to the use of anti-
foaming agents in the manufacture of foods and
other commercial products. Some take the form
of prohibitive laws and ordinances, while others
involve lists of permitted agents (positive lists).
A multitude of regulations exist worldwide; the
discussion that follows is confined largely to the
Federal Republic of Germany and the United
States.
Paragraph 11 of the German Food and Con-
sumer Products Law of 15 August 1974 explicitly
prohibits the use of additives in food products
[134]. However, certain exceptions are permitted
if the additives are removed completely prior to
distribution or if they are removed as completely
as possible and, at the same time, confer no
undesirable taste or odor and pose no health risk.
Examples of the unavoidable introduction of
antifoaming agents are provided by the yeast,
sugar, and potato chip industries.
The use of plastics in the context of food
products is covered by recommendations of the
Plastics Commission (Kunststoff-Kommission)
of the Federal Health Office (Bundesgesundheit-
samt, BGA), which must in turn comply with the
Food and Consumer Products Law [134]. For
example, recommendation XIV of the Bundes-
gesundheitsamt (Synthetic Polymer Dispersions)
contains under the heading Processing Aids a
section entitled Antifoaming Agents.
The U.S. Code of Federal Regulations gives a
list of permitted substances, along with their
chemical constitutions and allowable levels in
food products (Title 21, Food and Drugs,
x 173.340, Defoaming agents). Other relevant
material includes defoaming agents used in coat-
Vol. 15
ings (x 176.200) and defoaming agents used in
the manufacture of paper and paperboard
(x 176.210).
Defoamers are also mentioned in x 240.1051
(Materials authorized for the treatment of wine).
Those defoamers listed in x 176.200 are implic-
itly allowed under x 177.1200 (Cellophane) and
x 177.1400 (Water-insoluble hydroxyethyl cel-
lulose film), and the list in x 176.210 also applies
to x 175.105 (Adhesives).
Under the auspices of the Joint Expert Com-
mittee on Food Additives of the FAO WHO,
efforts are being made to establish international
guidelines. The use of foam-control additives in
food products is thus subject to constant critical
review with respect to both the nature and the
amount of substances used.
8. Economic Aspects
Foam problems arising in industrial processes are
a matter of immediate concern, because they can
rapidly lead to serious economic consequences.
For example, an automatic paper-making ma-
chine or bottle-washing unit may have to be shut
down, and inadequate degreasing during metal
treatment or surface irregularities resulting from
foam or from use of the wrong antifoaming agent
might lead to defective products. On the other
hand, a certain amount of foaming may be per-
mitted in a production line operating at less than
full capacity to avoid the extra cost of foam-
control measures.
These factors introduce a large measure of
uncertainty into predictions of the market for
antifoaming agents. The demand for foam-con-
trol agents in the United States has been estimat-
ed at 136 000 t/a, and world demand is thought to
be almost twice this value.
Because of the multitude of industries ser-
viced, the marketing of antifoaming agents ne-
cessitates a high level of specialization. More-
over, provision of an adequate level of customer
service is also necessary. Suppliers of antifoam-
ing agents differ markedly in their orientation
and in their range of product lines. Thus, some
suppliers specialize in specific types of material
(e.g., silicone antifoaming agents), while others
address the concerns of particular industries (e.g.,
suppliers to the textile industry). Table 2 lists
commercial antifoaming products.
Vol. 15 Foams and Foam Control 595

Table 2. Summary of commercial antifoam products

Trade name Firm Application

Afranil BASF, FRG paper industry

Agitan Munzing Chemie GmbH, FRG wide assortment for various industrial
applications
Alkaterge Angus Chemical Co., USA fermentation
Antimussol Sandoz, Switzerland textile and paper industries, cutting oils
Antispumin Chemische Fabrik Stockhausen, FRG paper, textile, and sugar industries
Bayer-Entschaumer Bayer, FRG silicone defoamers
Baysilone-Entschaumer Bayer, FRG silicone defoamers
Bevaloid defoamers Bevaloid Ltd., UK wide assortment for various industrial
applications
Byk Byk Mallinckrodt, FRG paint and coating industry
Contraspum Zschimmer & Schwarz, FRG wide assortment for various industrial
applications
Degressal BASF, FRG detergent and cleansing industry
Dehydran Henkel KGaA, FRG wide assortment for various industrial
applications
Dow Corning Antifoam Dow Corning, USA silicone defoamers
Etingal BASF, FRG paper and textile industries
Foamkill Lehmann & Voss, FRG wide assortment for various industrial
applications
Foammaster Henkel KGaA, FRG wide assortment for various industrial
applications
Fumexol Ciba Geigy, Switzerland textile industry
General Electric Silicone AF General Electric, USA silicone defoamers
Mazu Mazer Chemicals, USA wide assortment for various industrial
applications
Nopco Henkel KGaA, FRG wide assortment for various industrial
applications
Plurafac BASF, FRG low-foaming nonionic surfactants
Polymekon T. Goldschmidt, FRG paint and pigment industries, silicone
defoamers
Ralulac Raschig GmbH, FRG emulsion paints, leather and textile
industries
Repriman Henkel KGaA, FRG paper industry
Respumin Bayer, FRG silicone defoamers
Sentry Simethicone Union Carbide, USA pharmaceutical, cosmetic, and food
processing industries
SAG-Silicone-Antifoams Union Carbide, USA silicone defoamers
Surfinol Air Products, USA low-foaming wetting agents
Tego-Entschaumer T. Goldschmidt, FRG paint and pigment industry, silicone
defoamers
Tegosipon T. Goldschmidt, FRG paint and pigment industry, silicone
defoamers
Texadril Henkel KGaA, FRG low-foaming wetting agents
Troykyd Troy Chemical Corp., USA wide assortment for various industrial
applications
Viscasil General Electric, USA silicone defoamers
Wacker-Silikon-Antischaummittel Wacker, FRG silicone defoamers

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598 Foams and Foam Control Vol. 15

133 United States Steel Corp., US 4 581 156, 1984 (D. M.
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Further Reading
M. H. Gerardi: Microscopic Examination of the Activated
Sludge Process, Wiley, Hoboken, NJ 2008.
H. Z. Kister: Distillation Troubleshooting, Wiley, Hoboken,
NJ 2006.
S.-T. Lee, C. B. Park, N. S. Ramesh (eds.): Polymeric Foams -
Science and Technology, CRC Press, Boca Raton, FL
2007.
S.-T. Lee, D. Scholz (eds.): Polymeric Foams - Technology
and Developments in Regulation, Process, and Products,
CRC Press, Boca Raton, FL 2008.
A. Saint-Jalmes, D. J. Durian, D. A. Weitz: Foams, Kirk
Othmer Encyclopedia of Chemical Technology, 5th
edition, John Wiley & Sons, Hoboken, NJ, online DOI:
10.1002/0471238961.0615011304211809.a01.pub2.
D. R. Woods: Successful Trouble Shooting for Process En-
gineers, Wiley-VCH, Weinheim 2005.