2/4/13 How to Eliminate Foam in Coating Formulations - Article

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SpecialChem | Johan Bieleman - Jan 31, 2011 2 ratings
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Foam
De-foaming
Test methods
Selection criteria Among the
following coating
additive categories
Foam control is one of the main issues to be addressed by the formulator of all waterborne and for organic solvent borne what is the one you
coatings.
look for technical
Foam can develop, and is a major concern, during all stages of a liquid paint:
datasheets the most
1.
2.
during production, notably during pigment grinding
during filling
often?
3. during transportation
4. during application Antistatic agents
Flame retardants
Often foaming problems are encountered during production as result of poor system design (mixer, tank, pump inlet, -outlet,
leaky seals) and often during the pigment grinding process, where high speed dispersing equipment is used and foam
Light stabilizer / UV
stabilizing surfactants are added as wetting and dispersing agent. absorbers
Anti-gelling agents
Foam formation leads to inefficiency, long grinding time, and limits the batch size; it also leads to storage instability and
Plasticizers
other problems.
Photoinitiators
Presence of foam during filling of the cans effects effective volume per can and unit costs and may give problems such as can
overflow. Article - APIC Report 2010-Second
Part-Latest New s Out Of Asia Pacific
Foam is also generated during various application processes, such as spraying, rolling or dipping. Some of the application
Article - Calculating VOCs
problems encountered and linked to excessive foam formation are
Article - Infrared Analysis of
Coated Vinyl Materials
surface imperfections such as cratering
loss-of-adhesion
gloss reduction
loss of opacity.

All 4 cases are frequently dealt with for waterborne paints; for organic solvent borne paints foam formation is mainly Article
encountered during the application process. Take a pow der…

In order to fight foam formation defoamers are required. Formulating Water Based Inks for
Flexible Packaging Films
Foam How to Eliminate Foam in Coating
Formulations
Foam is defined as a dispersion of a gas (usually air) in a liquid or solid phase. Foam is unstable in a pure liquids. Foam is Conductive Coating Method to
stabilized by surface active components -surfactants- in the formulation, like emulsifiers, wetting agents and thickeners. The Inhibit Marine Biofouling
surfactants reduce the surface tension of the liquid. When air is introduced into a surfactant containing solution, bubbles will Ultraviolet light and Electron beam
be formed and rise to the surface (figure 1). Curable Coating Technology

No surfactants, no lamella. Air escapes(left)

With surfactants, lamella surrounding air bubble(right)

However, on reaching the surface, the bubble will not break as it is surrounded by a lamella of surfactant molecules, which
impart elasticity to the bubble walls (figure 2).
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impart elasticity to the bubble walls (figure 2).

Foam bubble surrounded by surfactant

stabilised lamella

Meta-stable foam is formed when the elasticity resists deformation. Strictly considered indefinitely stable foam in liquids does
not exist. The meaning of film elasticity was first proposed by Gibbs and refers to surfactant flow occurring in deformed and
stretched foam lamellae. Due to the deformation, the concentration of surfactant per unit area decreases and consequently
surface tension rises and tends to counteract further expansion.

The Marangoni effect refers to forces counteracting the drainage of liquid and surfactant by gravity of the bubble wall.
Following the drainage, surfactant molecules move downwards, resulting in a surface tension gradient between the top and
down side in the bubble wall, which induces an upwards counter flow of surfactant and liquid molecules. Stabilized foam will
only be de-stabilized by external forces, such as gravitation, thermal effects, mechanical disruption or defoaming surface
active agents (defoamers).

In relation to the size of the bubble a distinction is made between macrofoam and microfoam. Related to the size is the
location of the foam bubble.

Macrofoam is typically present at the coating surface and stabilized through a lamellae of surfactant double layers.

Microfoam is entrapped air present in the entire coating material. Microfoam is very much stabilized by high liquid viscosity of
the coating material and surfactants surrounding the micro-bubble, fixing these in the coating material. Due to the small size
of the bubble, forces (Stoke's Law) pushing the bubble upwards, are much lower as compared to macrofoam bubbles, keeping
the microfoam bubble in place.

Microfoaming is frequently noticed in airless spaying applications and effects properties such as gloss and film protection.

Besides the incorporation of air, gasses can be formed as a result of chemical reactions in the paint, for instance 2 pack PUR
systems, in which carbon dioxide is formed from the reaction of iso-cyanate with water. The risk of foam stabilization can be
limited to some extend during the formulation and application process by selecting proper, low foaming components and
working conditions, but not totally excluded. However, defoamers are needed, certainly in almost every water based system.

De-foaming

Strictly defined, defoamers are a class of additives destroying existing foam. Anti-foaming agents hinder the formation of
foaming. Main products as used in the paint industry have both defoaming as well as foam prevention features; therefore both
classes will be indicated here as "defoamers".

Additives combating micro-foaming are known as de-airators.

In order to be efficient the defoamer must compete with the foam stabilizing surfactant and therefore must have a low surface
tension and a low solubility in the foaming liquid phase.

Furthermore, no unwanted side effects such as cratering or haziness may be generated by the defoamer. The efficiency of the
defoamer is related on the ability to enter the foam lamellae and penetrate into the surfactant layer, surrounding the foam
bubble and subsequently spread over the surface area.

This can be expressed as follows:

Entering coefficient E: E = f - d+ int. (1)

Spreading coefficient S: S = f- d- int. (2)

In which: f = surface tension of liquid medium to be defoamed

d = surface tension of defoamer
int. = interfacial tension between defoamer and the liquid to be defoamed.

Both (E) and (S) need to be positive for efficient defoaming activity, indicating the requirement of a low surface and interfacial
tension for the defoamer.

Next to the entering and spreading ability, the viscosity and compatibility of the defoamer with the foaming medium are of
importance. Low defoamer viscosity contributes to an efficient distribution. Incompatibility ensures the defoamer concentration
build-up at the interface liquid/air. This condition is met if the specific gravity of the defoamer is lower than the foaming
medium.

The composition of defoamers is extremely divers. However, a characteristic component of defoamers is a surface active
agent, typically a hydrophobic compound (such as fatty acid amide or a low HLB nonionic) or polysiloxane. The surfactant
component determines the surface activity as well as ensuring proper distribution of the defoamer in the liquid medium. Pure
polysiloxanes with extremely low surface tension are preferred for organic solvent containing paints; for aqueous systems
compositions of surfactants, including minor polysiloxanes additions are commonly selected.

Defoamers for aqueous systems are often dissolved in mineral oil, which supports additional hydrophobicity and contain
dispersions of hydrophobic small sized particles, like waxes, fumed silicas.

The function of the hydrophobic particles is explained as to act as a de-wetting particle. Depending on the composition, the
particle may act as adsorptive substrate for the surfactants. Once penetrated into the lamellae around the foam bubble, foam
stabilizing surfactant molecules are being adsorbed onto the solid hydrophobe (figure 3) inert ingredient infringing in between
the surfactant chains, surrounding the foam bubble (figure 4).

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Defoamer's hydrophobe adsorbing

surfactant: weakening lamella

Both mechanisms result in local weakening the lamellae causing foam bubbles to burst.

Defoamer penetrating surfactant film:

weakening cohesive force in the
lamella

Test methods

Several test methods are known for determining the efficiency of defoamers.

Essential is to select the method that is most practice related.

All starts with analyzing the moments of highest foam formation risk. Usually part of this is the pigment dispersion process
as well as the application process. Roller application, dipping, and spray applications are conditions of intensive contacts
between the paint and air.

Depending on main risks of foam formation in practice, the best corresponding laboratory test method is chosen. Or in case
of tinting systems, the mixing step using a paint shaker.

A method related to dispersion or mixing conditions is the agitation test.

The paint shaker is often used to simulate foaming in paints during tinting. A common method is to evaluate the various
candidates at 2 or 3 concentrations and shake the paints for 3 minutes. After this, the specific gravity of the paint is
determined: the higher the specific gravity, the lower the presence of foaming.

Next to this also an application test is assessed by determining the paint film after application. Presence of foam, microfoam
is best judged using a microscope or magnifier; furthermore gloss or haze, as well as color.

Essential is to repeat the test after storage of the paint. As stated before, defoamers are typically formulated in a condition of
showing a limited compatibility. Consequently some risk of separation or adsorption may be assumed. Typically the paint is
oven aged for 4 weeks at 50°C.

Testing in liquid non-aqueous systems is often difficult, as the amount of foam is typically much less compared to aqueous
syems. However, main criteria for defoaming in non-aqueous systems is usually determined during application; airless
spaying, dipping, rolling and defoaming in high-build systems are practical examples of critical conditions for foaming.

Selection criteria

Selecting the proper type of defoamer from the huge number of available products requires some basic selection criteria. The
applicability of defoamers strongly depends upon the specific paint system and process utilized. One of the selection criteria
to be made is between silicone based or silicone free defoamers.

Silicone or polysiloxane based defoamers excel in low surface tension and good solubility, making these products first
candidates for use in solvent borne systems, where the low surface tension of the solvent, has to be passed in order to create
good defoamer spreading features. Furthermore polysiloxanes are preferred in clear systems for reasons of not effecting
transparency. However, polysiloxanes are more sensitive for effecting adhesion and recoatibility and are typically more
expensive compared to polysiloxane free defoamers.

Therefore polysiloxane free defoamers are preferred for main applications in decorative systems, including waterborne
pigmented systems such as emulsion paints.

In order to combat macro-foaming optimal defoaming properties are obtained by ensuring limited compatibility of the defoamer
with the foaming system. Selecting best defoamer is very much a process to find the right balance between defoaming
efficacy and coating appearance features (figure 5).

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Defoamer selection balance

Poor compatibility results in high risk for creati ng film surface defects, whereas excellent compatibility generally means
poorer defoaming properties. Micro-foaming, present throughout the liquid medium, is best avoided using defoamers, here
named de-airators, which are well soluble in the liquid phase.

Literature:

1. Additives for Coatings, J H Bieleman Ed., 2000, Wiley-VCH\

2. S Mahiall, JOCCA 1992, 10, p. 405

3. H Semmier, W Heilen, ECJ 2000, 06, p.710

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SpecialChem4Coatings Members Reactions

Simple & Useful - Apr 07, 2011

posted by Nourhan Dem irdjian, R&D - Applied/ Form ulation/ Product developm ent at Waterproofing Technologies
Very comprehensive yet brief article on a very complex subject.
alert moderator | add y our reaction

Blew my bubbles of ignorance away! - Feb 09, 2011

posted by Ashok Kum ar, Marketing / Sales at Kuw ait Chem ical Mfg Co - United Oil Projects
An excellent article.

The mechanics of formation and factors for selection very lucidly conveyed.

What additional factors need to be considered in case of highly filled products like putties & texture coatings?
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