This article written by AFCONA technical team.
All copyrights reserved and belong to AFCONA Additives @ 2005
1. Introduction
It is difficult to go through a whole day without coming in contact with foaming materials.
The soap and tooth paste that we used in the morning before going to bed, the polyurethane foam seat
cushion of the sofa or car seat, or the foamed polystyrene take away boxes that fill our food in the
restaurants.
In the above cases, foams are desired to achieve the finishing or result that we needed.
However for paint manufacturers and applicators, in order to ensure a smooth and even final paint film,
foam will be one of the main task to overcome especially for those paints that are applied by brush and
roller.
Thus additives like defoamer are needed to prevent the formation of bubbles when liquid
paints are subjected to external mechanical disturbance during application and production.
1.1 Foam
In general term, foam can be defined as dispersing of gas (normally air) in liquid. It can
be generated during production of a coating like in grinding phase, mixing and filling or during application.
It also can be produced when liquid paint wetted porous surface like wood substrate. As a paint
formulator, foams that are generated during application and porous surface wetting process are the
problem that he or she wanted to solve.
Not all foams are the same. Some are transit type like the bubbles in Champaign and
some are stubborn type like the foam in shaving cream depending on the viscosity of the medium and the
surfactants involved.
2. Foaming or Defoaming
Foams are generated if a disturbance force is applied to a liquid. The question is what is
the lifetime of the generated foam. There are many physical and chemical factors involved in determining
the stability of the foams or bubbles.
2.1 Theoretically Approach
The stabilization of a bubble is depending on the elasticity of their thin liquid membrane.
Thus higher elasticity will result in a more stable bubble and vise versa. In order for us to understand
more on the importance of this factor, let us look at Gibbs elasticity parameter that is shown below.
dγ E = Elasticity Parameter Diagram 1: Gibbs Equation
E = 2A -------- A = Bubble Surface Area On Elasticity.
dA γ = Liquid Surface Tension
According to Gibbs Equation, in order for a bubble to obtain some elasticity, the surface
tension of the liquid has to change accordingly with the surface area of the bubble so that the values of
dγ/dA will always more than zero. Any single foam that fails to change it surface tension during the
contraction and expansion of the bubble will lead to bursting of the bubble due to high rigidity.
Pure liquid has almost the same surface tension all around the surface and it will almost
stay as it is in any situation as long as no external material been added or changed it physical status from
liquid phase to gas or solid phase. Thus, Gibbs Elasticity equation illustrated to us that pure liquid is not
able to stabilize any foam.
Unfortunately in most of our coating formulations, there is no single formulation that
involved only pure single liquid with same molecular structure and same molecular weight. Thus we still
need to deal with this problem constantly.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
3. Destabilize Foam Factor
3.1 Gravity Force
When foam is form, due to gravity forces, the liquid on the bubble will withdraw from
bubble towards the bulk liquid. When the thickness reached it critical thickness which is nearly 100A°, a
simple movement of molecule on that thin layer will result in bursting of that bubble. This process take
place very fast within a few second. Further illustration show in diagram 2.
STEP 1: Liquid STEP 2: The thickness of
withdrawing from bubble bubble top layer will reduce
layer toward the bulk resulting from step 1
liquid due to gravity force Diagram 2:
Process of destabilized
force by gravity resulting
in bubble bursting.
STEP 3: If there is no any
opposite force or static effect to
stop the withdrawing process, the
process will continue until
reaching critical thickness that
any small movement of the liquid
molecule is enough to break the
thin liquid membrane.
The above illustration supports the Gibbs equation as given on the previous page. Thus,
no liquids are able to stabilize any foam in their original/pure form.
4. Foam Stabilizing Factors
4.1 Marangoni Effect
As we understand from previous explanation on how foams can be destroyed. Thus, in
order for a bubble to be stabilized, a second material need to be added to ensure a more elastic bubble
film. Most of the time a surfactant that can reduce the surface tension as well as very compatible with the
system can serve the purpose.
Marangoni effect will explain the effect of surfactant in stabilizing the bubble by using
surface tension difference that had been generated during the withdrawal of liquid from the bubble to the
bulk liquid.
When a bubble is generated by an external sheer force, the usual withdrawal process by
gravity forces will take place immediately. This withdrawal process will result in more surfactants being
drain away together with the liquid from the top part of the bubble making it thinner. Therefore it created
a situation were by the top part of the bubble would have higher surface tension than other parts.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
Surface tension is a state of energy where it flow from low surface tension to high surface
tension. The liquid on the bubble will flow from low surface tension area, the lower area of the bubble,
towards the high surface tension area, the top area of the bubble, and this will create another opposite
force that caused a re-flow process of the liquid back to the top part of the bubble. When these two forces
achieve an equilibrium before the critical thickness of the foam, we will have a stabilized foam or bubble.
The whole process is illustrated more in diagram 3.
STEP 1: Liquid STEP 2: The effect of the
withdrawing from bubble withdrawal process, the top part
toward the bulk liquid due have less thickness than other parts
to gravity force making less surfactant can be
occupied on top.
Diagram 3: Process of
developing stabilized force
by Marangoni Effect
STEP 4: The withdrawal and re- STEP 3: Surface tension gradient
flow forces will come to an appear as top part have high
equilibrium status and if it is surface tension that the other parts.
achieved before the critical When opposite force is created, the
thickness, than we will have a liquid will flow from low surface
stable bubble. tension area will flow to high
surface tension area. The liquid
will begin to re-flow back to the
top.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
4.2 Static Effect
Surfactants always carries a polar or electrical charged head with a hydrocarbon tail. In
the liquid layer of the bubble, the surfactants will oriented themselves as in diagram 4. So, when the liquid
withdrawal process started, it will bring the polar/charged head of the surfactants close to each other.
Therefore the same charge of those polar/charged heads will start to repel each other.
The direction of this repulsion forces are heading to the centre of the bubble for those surfactants in the
inner layer and creating an opposite force on the opposite direction of the bubble centre. An equilibrium
state will be achieved thus resulting in a static phase that stop further drainage of liquid to the bulk liquid.
If the equilibrium state of the layer of bubble is thicker than the critical thickness, stable foam is created.
Diagram 4: Process of
developing stabilized force
by Static Effect
5. Criteria’s To Be A Defoamer
All AFCONA defoamers are based on 2 main criteria in order to ensure that they will
perform as what have been designed. Both requirements are necessary to work together side by side to
ensure excellent performance.
The two basic requirements are as below.
1) A defoamer must have limited compatibility with the system and must able to do so
after long term storage.
- A limited compatibility will ensure the defoamer will be de-wetted by bubble layer
liquid in order to destabilize the Marangoni and Static Effect. The de-wetting process that
takes place will push away the liquid on the layer of bubble and this will accelerate the
drainage process that leads to bubble breaking. A more detailed explanation will be
shown in Diagram 5.
2) A defoamer must be able to reduce the surface tension of the system.
- In order for a defoamer to enter particular foam, they must be able to penetrate and
spread evenly on the foam of the liquid layer resulting in a lower surface tension and it
can be explained by the equation below.
A positive value of Penetration Parameter, E, will ensure that a defoamer will go into the
liquid layer of the bubble.
E = γl - γd - γdl >0 where, γd = defoamer surface tension
γl = liquid surface tension
γdl =defoamer and liquid surface tension
A positive value of spreading parameter, S, that will ensure that a defoamer will be evenly
spread through the whole bubble.
S = γl - γd - γdl >0
The whole process can be illustrated below in diagram 5.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
Defoamer
Droplet
Due to the limited When the
Defoamer is Defoamer is
compatibility of the drainage process
penetrating to the spreading on the
defoamer to the reached beyond
bubble membrane by bubble membrane
liquid system, de- the critical
a positive by a positive
wetting process takes thickness of the
penetration spreading parameter.
place. Thus the liquid layer of bubble,
parameter
will be pushed away defoaming
from the defoamer effect will
Diagram 5: and this will commence.
Process of AFCONA Defoamers accelerate the
destabilizing bubbles to achieve drainage of the liquid
defoaming effect. on the bubble to the
bulk liquid.
6. Compromising In Using Defoamers
Diagram 6:Compatibility factor that influence
the effectiveness and side effect of a defoamer.
If the defoamer have good
compatibility with system:
No Defoaming Effect
No Cratering
If the defoamer have very bad
compatibility with system:
Possible For Good Defoaming Effect
Consistent Cratering Problem
Thus a compromising factor is
needed in order to achieve a
balance between compatibility
and incompatibility in the system.
this is known as limit
incompatibility:
Good Defoaming Effect
No Cretering Problem
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
As explained previously, one of the main criterion to be a defoamer is that it has to have
some limit compatibility. Thus the compatibility or incompatibility of a defoamer with the system plays a
main role in determining the effectiveness of a defoamer. However, we know that an incompatible
material will also cause cratering problem. Thus, as shown in diagram 6, a certain extend of compromise
is needed when using a defoamer.
Materials that have good compatibility with the system will in fact stabilize the foam and
will not have any deforming effect at all, but no tendency to cause cratering. However this will not serve
our purpose to solve the foam problem.
Materials which are very incompatible with the system will have the possibility as a good
defoamer but the drawback is that it will also give cratering site effect. That is why sometimes they need
high shear force to improve the incorporation in order to ensure all defoamers added are well disperse
through out the system to avoid craters.
Therefore, in general term, normally a defoamer that is more compatible with the system
will have less defoaming effect than the one that less compatible.
7. Defoamers
Defoamers in today’s market are mainly based on 2 chemical materials, i.e., High
Molecular Weight Polysiloxane and Silicone Free High Molecular Weight Polymers. The chemical nature
for Polysiloxane can give better surface tension reduction than the non-silicone, thus it will give better
incorporation due to better penetration and spreading factor as explained above. Due to it low surface
tension, it also gives better deareation performance.
However, intercoat adhesion caused by silicone based material is also a cause of
concern among paint chemists. Based on our experience, in most cases, this is not true for Polysiloxane
bases defoamers. In order for us to have a better understanding, let us look at the molecular weight in
relation to the viscosity that is used for this purpose.
FLOW CONTROL SLIP/LEVELING DEFOAMING HAMMER FINISHES
5-50 mPaS ~ 100 mPaS 5000-50000mPaS >50000 mPaS
Diagram 7:Defferent molecular weight silicone used in different application.
Due to its very high molecular weight compared to the slip and leveling additive, it act as
a heavy polymer that can’t really migrate to the surface of the finishing coat in order to affect the inter
coat adhesion. Silicone based defoamers will not give any slip property and this further prove that it will
not surface to the top of the coating.
Non-silicone polymer normally can’t beat the surface tension reduction ability as
compared to silicone polymers but they have advantages on having a better limit compatibility than the
Polysiloxane. Thus it will have better defoaming and anti-foam effect but harder to incorporate. Therefore
higher sheer force need to be applied in order to ensure no crater is obtained. However this factor still
depends on the concentration of the solution.
Some terminology that involve defoamers are define below:
Defoaming - Defoaming performance of a defoamer is determine by how fast a defoamer can destroy
foam in a liquid system. Faster defoaming ability is desired by most paint formulators.
Deareation - Deareation is the process of moving the foam from the inner layer of the paint to the
surface of the liquid. Foam only can be destroyed on the surface of the liquid and a faster
deareation property is desired by most formulator.
Anti-Foam - Anti-foam is referring to a defoamer that have the ability to prevent foam formation or
suppress the bubble formation after the system has been agitated. Less foam formation
after the agitation is a good anti-foam defoamer and this is also the most desired
performance that most paint formulator wanted.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
8. Defoamer Testing Method
Defoamers need to be carefully selected to suit certain resin system. Usually, the most
direct method to choose a defoamer is by incorporating it into the system and applied it to see the desired
effect. If the result obtained served its purpose as a defoamer, then we will proceed with other property
tests. The other tests are cratering, gloss influent in final coating, on line test and so on in order to ensure
that it can be use in the formulation.
Here, we recommend a method that we can make a good comparison between a few
defoamers simultaneously. The purpose of this method is to ensure that we are getting the best defoamer
as well as de-aeration effect for a particular system. This test is also quite easy to carry out.
Requirements : Red Devil / TOUCH TC-0188 Shaker
High Speed Mixer
Glass Jars (100ml)
Polyester Foil
Applicators
a) For Normal Solvent based system
Procedure
Fill the glass jars to a certain level (Not more than half) with the coating system +
defoamers. Make sure that the level is almost the same. Mark the top level with a marker. Put the glass
jars into the shaker. It also can be carry out by using a High Speed Mixer but make sure that the time and
the speed are the same for each separate samples. However TOUCH TC-0188 shaker is more preferable
as we need to compare those samples in accurate dispersing time and as well as same sheer force in
order for us to judge more precisely the defoaming and de-aeration properties.
Result
Observation
i)Defoaming effect comparison
Immediately after shaking or mixing, mark the increase foam level. Leave the glass jars
aside and record the foam level over 1 minute, depending on how fast the foam disappear. The sample
with the lowest foam level will indicate the best defoamer among the samples that you have been tested.
However, for resins with low viscosity, the foam level is unclear after it is taken out from the shaker
making it difficult to determine the level of foam. Thus, we need to look at the tested samples on how
much foam is trapped on the surface and during this observation time, the one with the least foam will be
the best defoamer for the system.
ii) Deareation effect comparison
Deareation is the process of moving the foam from the inside of the liquid to the surface
of the liquid. So, in order for us to judge the de-aeration property, we observe at the entrapment of micro-
foam that still maintained inside and the surface of the liquid. The least entrapment over a period of time
will have the best de-aeration. However, please take note that a good de-aerator doesn’t mean that it will
be a good defoamer.
iii) Anti-form effect comparison
Anti-foam is referred to a material that have the ability to prevent foam formation or
suppress the bubble formation after the system has been agitated. Based on the test conducted above,
we will also be able to see the anti-foam performance of a defoamer. Immediately after the shaking or
mixing, observe the quantity of foam generated on the surface. The more foam generated means less
anti-foam performance. Thus a good anti-foam material will be able to prevent foam formation as much as
possible after agitation.
iv) Site effect comparison
As mentioned earlier, defoamer will gives some side effects due to it incompatibility with
the paint system in order to be an effective defoamer. Due to it lower surface tension, most of the time it
will change the leveling performance of the system as well as creating cratering problem. To check the
side effect, apply the selected defoamer systems and apply it on Polyester sheet with an appropriate
thickness of an applicator. Observe the leveling performance as well as crater formation.
Final Stage
A selected defoamers will need to go through the real application for final confirmation of
the its performance.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
b) For water based emulsion paint system
For water based emulsion, the same way to pre-select a defoamer as descript in normal
solvent based system above also can be used. The same procedure as mentioned in normal solvent
based can be applied and the same observation can be seen to the determine the defoaming, deareation
and anti-foam performances.
Please see diagram 8 for illustration of the observation.
Defoamer A Defoamer B Defoamer A Defoamer B
Immediate result after shaking Result after 3mins
Defoamer A Defoamer B Defoamer A Defoamer B
Result after 6mins
Result after 9mins
Diagram 8: Selection of defoamer on water based emulsion where defoamer A is much
better than defoamer B on anti-foam and defoaming effect
However in water based system, due to the system have high surface tension and this
will result in easy foaming and foam is always a problem to be solved. The defoamers selected have to
be effective in the pre-mix stage as well as in the final let down stage. Further more in the formulation of
emulsion, it involve thickener where the rheology of the paint is rather higher. Thus in such conditions,
after the above pre-selection, full set real testing is needed, start from pre-mix, after mix and later real
application by roller or brush on a big panel.
Water based defoamer for emulsion are normally recommended to divide the additional
of defoamer in to 2 steps. 40-50% of the total amount require defoamer is needed in the pre-mix stage
and the rest should be added in the let down stage. Most defoamers for emulsion paint, are not stable
under high sheer force, it become more compatible to the system and can not performance the
defoaming property any more. Thus it need to be added again in the let down stage in order to boost
back the defoaming performance in the system.
This article written by AFCONA technical team. All copyrights reserved and belong to AFCONA Additives @ 2005
