Surface Additives

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chemical and physical processes.
 Netz- und Dispergieradditive
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mit interaktiven Grafiken, faszinierenden Animationen und Videos zur Dar-

01
stellung chemischer Prozesse.

Surface defects

During and after the application of a coating system, surface defects can often occur that affect the optical properties of
the coating and its protective function.

Typical surface defects are:

Poor substrate wetting

Cratering
Formation of Bénard cells, floating
Poor leveling, orange peel
Air-draft sensitivity

A key parameter for all these sorts of defects is the surface To avoid these surface defects, additives are used to
tension of the materials involved; in particular, differences in influence the surface tension of the coating and/or minimize
surface tension lead to the formation of surface defects. surface tension differences. Such products are primarily
Surface tension differences can originate from the system polysiloxanes (silicones) and polyacrylates (acrylate
itself (evaporation of the solvent, cross-linking reaction of the additives).
binder) or can be caused by external sources overspray or dust
particles (contamination of the substrate).
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Causes and prevention options

If considerable surface tension differences must be equalized, Polyacrylates can only equalize small surface tension diffe-
polysiloxanes can be used. Depending on their chemical rences and either do not reduce or only slightly reduce the
structure, they can considerably reduce the surface tension of surface tension of the liquid coating.
the liquid coating. They can therefore preferentially be used to
improve the substrate wetting and as anti-cratering additi- They are predominantly used to improve leveling. However,
ves. Given sufficient incompatibility with the coating system, with sufficient incompatibility, these products can also exhibit
polysiloxanes can also have a defoaming effect. Moreover, defoaming properties. In addition, there is the group of
silicone additives also improve the surface slip of the cured low-molecular weight surfactants that are likewise surfa-
coating film, and can therefore help improve scratch and ce active, due to their typical amphiphilic structure (polar/
block resistance. non-polar), and can be used to reduce surface tension.

Surface tension vs. surface energy

Improvement of leveling with additives

 03
Chemical structure of polysiloxanes

Silicone additives, often also referred to as “silicones,” can be used without understanding
their basic underlying chemistry. However, it is helpful to outline and understand several of the
underlying principles of silicone chemistry. In this way, one can readily learn how to understand
and characterize silicone additives. Additionally, the relationship between structural features
and resultant properties will become more understandable.

Polydimethylsiloxane

All silicone additives are derived from the basic structure of silicone properties, such as low surface tension, the long-
polydimethylsiloxanes (see figure). chained molecules are very incompatible, and cause a very
definite cratering (hammertone effect). Accordingly, pure
Varying the chain length creates products with very different polydimethylsiloxanes (silicone oils) are rarely ever used in
properties. While short-chained silicones are relatively modern paints.
compatible in coating systems and have the typical
 Polyether modification

R1

R2 EO : R1 = -H
PO : R1 = -CH3

A more elegant method than controlling compatibility by Polyethers consist of ethylene oxide units (EO) and/or propy-
means of chain length is to modify the silicone basic structure lene oxide units (PO). Polyethylene oxide is very hydrophilic
by adding side chains. (polar), whereas polypropylene oxide by comparison, is rather
hydrophobic (non-polar).
The majority of silicone additives used in coatings today are
such “organically modified polysiloxanes.” In the majority Therefore, the polarity of the entire silicone additive can be
of cases, the modification involves polyether chains (see figu- controlled via the ratio EO/PO: A greater proportion of EO
re) which lead to an improvement of compatibility. The degree increases the polarity and the additive is water-soluble and
of compatibility can be controlled by the number of these more compatible in polar coating systems. At the same time,
side chains (i.e. ratio of dimethylsiloxane units to polyether however, the tendency toward foam stabilization increases.
modifications (x;y). At the same time, this also influences the On the other hand, a greater proportion of PO reduces both
surface tension: Generally speaking, the more dimethyl- the water solubility and foaming tendency.
siloxane units, the lower the surface tension. Furthermore,
the structure of the polyether chains themselves can also be
varied; the key factor here is the polarity.
 Silicone macromers

In the synthesis of “silicone macromers” (see figure), the

chain length of the silicone block can be very precisely adjus-
ted as compared to “organically modified polysiloxanes”.
Using the functional group, which might be, for example,
an amino, methacryl, vinyl or hydroxyl group, these special
components can be further transformed to become active
substances with a defined structure. The additives created in
this manner have tailor-made properties.
 Polymethylalkylsiloxanes

R = alkyl -(CH2)n-CH3

Another method of changing the silicone structure is to

replace one of the two methyl groups of the dimethyl struc-
tures with longer alkyl chains, resulting in polymethylalkyl-
siloxanes (see figure). Compared with polydimethylsiloxanes,
such products clearly demonstrate higher surface tensions,
and exhibit less influence on the surface slip. Such silicones
are often used as the active substance in defoamers. Just like
polydimethylsiloxanes, the polymethylalkylsiloxanes can also
be organically modified with polyether chains. In addition
to typical silicone characteristics, such silicone additives also
exhibit slight defoaming properties.
 Other types of modification (e.g. thermostable modified polysiloxane)

Polyether-modified polysiloxanes are thermally stable up to

about 150 °C; the polyether chains will decompose at higher
temperatures. Through the use of non-polyether structural
elements such as polyester and aralkyl groups (see figure),
various thermally stable products can be produced. These
modified polysiloxanes are thermally stable up to 220 °C and
can be used at much higher baking temperatures.
 Reactive silicones

Generally speaking, silicone additives are non-reactive, i.e.

they do not interfere with the cross-linking reaction of the
binder. For special applications, it can however be desirable
for the silicone additive to be incorporated into the binder
matrix. Reactive products have (at the terminal end of the
organic modification) either primary hydroxyl groups (for reac-
tion with isocyanates or other OH-reactive systems) or double
bonds (for reaction with UV-curable systems).
 Silicone surfactants

Silicone surfactants are polyether-modified dimethylsiloxa- Compared with the fluorosurfactants, which are also fre-
nes, but in this case the molecular weights are considerably quently used when low surface tensions are required in
lower than the usual molecular weights of most other silicone coatings, the silicone surfactants have the advantage of not
additives. The siloxane chain consists of just a few Si-O units, increasing the system’s tendency to foam.
and on average contains just around one polyether chain. For
this reason, they have a quite pronounced surfactant struc-
ture (polar/non-polar). In aqueous systems, such products
significantly lower the surface tension without simultaneously
increasing the slip of the coating. If a greater slip is required,
the silicone surfactants can easily be combined with other
silicone additives which are suitable for aqueous systems.
 04
Chemical structure of polyacrylates

The basic components (monomers) of polyacrylates are acrylic acid esters. With the C=C
double bonds, this molecule can be polymerized into long-chained polyacrylates. If, instead of
acrylic acid esters, methacrylic acid esters are used, polymethacrylates are created.
 Polyacrylates

R1 = -H: acrylat
-CH3: methacrylat

Usually, it is not acrylic acid itself that is polymerized, it is the range; the number of monomer units is typically between 40
acrylic acid ester, whereby in the monomers the hydrogen and 800. Using just one type of monomer for the polyme-
atom of the -COOH group is replaced by a different R-group. rization produces homopolymers, whereas co-polymers are
Possible modifications are: alkyl-, polyether- and polyester- created if several different types of monomers are used.
chains. The acid group can also be neutralized with an amine.
Reactive groups (e.g. OH) can also be incorporated into the For liquid coatings, the polyacrylates are available either as
side chains; such modified acrylate additives can be integrated a solvent-free additive (100 %) or in a diluted form (~50 %).
into the coating film matrix during the cross-linking reaction For use in powder coatings, the polyacrylates are absorbed
of the binder. The molecular weight can be varied over a wide onto inert carriers (acrylate content ~60 %).
 05
Methods of measuring surface tension

Static surface tension

The wetting of a surface with a liquid depends on the surface
tension of the liquid. The definition of surface tension is the
work that must be applied in order to enlarge the surface of
a phase.

The Du Noüy ring method is used to determine the surface

tension of a liquid. A platinum-iridium ring is drawn out of
the liquid while, at the same time, the maximum force caused
by the tension of the liquid lamella during the movement of
the ring is measured.

Du Noüy ring method

Dynamic surface tension
In fast application processes, the surface-active substances
must be mobile in order to cover the newly created surfaces
as quickly as possible and thereby keep the surface tension
constant.

The bubble pressure method is used to determine the dy-

namic surface tension. Bubbles with different surface ages
are generated within the liquid, and the maximum internal
pressure of the bubbles is determined.

Bubble pressure method

Contact angle measurement
The hydrophobic or hydrophilic properties of solids can be
determined with the help of the contact angle measurement
of water. To determine the free surface energy of solids, con-
tact angle measurements are carried out with defined liquids,
and these measurements are then used to calculate the free
surface energy using different models (OWRK, Wu, etc.). In
this way, the wetting behavior of liquids on these solids can
be characterized.
Young’s equation

Contact angle measurement

 06
Substrate wetting

Substrate wetting Aqueous coating systems, due to their water content, have
a higher surface tension than solvent-borne coatings, and
therefore exhibit greater wetting problems. Silicone additives
Substrate wetting primarily depends on the surface tension reduce the surface tension of the coating thereby resulting
of the liquid coating material and the critical surface tensi- in a better wetting of the substrate. Silicones with dimethyl
on of the substrate to be coated. It is generally the case that structures are preferable here, as these provide a rather re-
the surface tension of the coating should be lower than or duction of surface tension. Especially for aqueous systems,
equal to the surface energy of the substrate in order to achie- silicone surfactants are also suitable. In addition, in aqueous
ve a good wetting. Poor wetting, i.e. a crawling or beading systems, silicone-free surfactants based on alcohol alkoxylates
of the coating will occur if the surface tension of the coating can also be used as these also significantly lower the dynamic
is higher than the surface energy of the substrate. Substrates surface tension as well.
with a generally lower surface tension (e.g. plastic parts) or
contaminated surfaces (oil residue, release agent) are therefo- Additives based solely on polyacrylates are not suitable
re difficult to wet. for improving substrate wetting.

Different reduction in the surface tension as a result Different wetting properties of a coating on leather
of two different additive (with and without additive)
 07
Floating

Floating, leveling problems, and air Cross-section of Bénard cells:

draft sensitivity separation of pigments
(floating)
Solvents evaporating from a coating film cause vortex
flows in the respective film. These arise because the more
solvent-rich materials from the lower layers of the film must
be continuously transported to the surface. This leads to the
formation of a macroscopically visible cell structure (Bénard
cells). Differences in density, temperature and, especially, sur-
face tension are the driving forces of these movement proces-
ses. Various surface defects can ultimately result from these
Bénard cells: floating, leveling problems, air draft sensitivity.

Floating
In a pigmented coating system, the pigments also participate
in the vortex motion, and if the various pigments differ in
their mobility, the flow processes can cause them to separate
from one another. The pigments are then no longer homoge-
neously distributed within the coating surface (floating). On
horizontal surfaces, the cell structure itself is visible; on vertical
surfaces striation can be seen (silking).

Formation of Bénard cells in the liquid coating

 08
Leveling

Leveling Leveling – surface flow control

The formation of Bénard cells also leads, in many cases, to
paint surfaces that are not uniformly smooth; rather, pronoun-
ced deformation or surface textures can occur. The coating
exhibiting non-optimal flow will show varying degrees of a
defect called “orange peel”.

Air draft sensitivity

Depending on the drying conditions and the characteristics of
the solvent mixture, the drying of the wet film or resin soluti-
on can occasionally become so strongly influenced by surface
defects that the entire top surface of the film is completely
disrupted. This extreme effect is called “air-draft sensitivity”
and is generally caused by air-draft conditions that place ext-
reme stress on the upper layers of the coating. It is an especi-
ally common occurrence in furniture coatings.
The wave-scan simulates visual observation. The wavy bright- The wave-scan analyzes the size of the structures: in order to
ness pattern on the surface is optically scanned in the same take into consideration the resolution of the eye at different
way the human eye sees it. A laser point light source illumi- distances, mathematical filtering is used to divide the optical
nates the sample at an angle of 60 °; a detector on the other profile into long-wave (LW) and short-wave (SW) sections.
side then measures the reflected light. The wave-scan device
is moved over the sample across a defined range and measu-
res the optical brightness profile from point to point.
 09
Preventing cratering

Prevention of cratering case of a poor substrate wetting. By using a silicone additive,

the surface tension is lowered and the coating is therefore
much less susceptible to disturbances or disruptions, irrespec-
The causes of cratering are diverse. Cratering can occur, for tive of whether they originate from the environment (over-
example, from overspray: if fine spray droplets of an over- spray, dust particles, etc.), from the substrate (contamination),
spray of a different coating material fall onto a freshly coa- or even from the coating itself (gel particles). The coating
ted surface that is still liquid and mobile, these droplets can process can be carried out more reliably through the use of
cause cratering if their surface tension is less than that of the silicone additives. In this case, when the greatest possible
surrounding coating film. Surface tension differences of 1-2 reduction in surface tension is needed, the use of silicone
mN/m are already sufficient to cause spreading of the over- additives as anti-cratering agents is preferred.
spray droplets and, in consequence, cratering. If the surface
tension of both materials is the same or if the spray mist has a Polyacrylates have barely any influence on the surface tensi-
greater surface tension, there are no spreading processes and on and are therefore ineffective as anti-cratering additives.
therefore also no cratering. Small dust particles falling onto
the liquid coating can provoke the same effect as overspray
droplets. Craters can also be the result of a contaminated
substrate (e.g. fingerprints or similar). If this contamination
has a lower surface tension, it will cause cratering when the
coating is applied. The occurrence if these effects is a special

Cratering
 10
Surface slip

Surface slip Tape release

Silicone additives improve the surface slip properties of coa- Good tape release properties are often required, especially in
tings. Often, however, it is not the slip itself but rather the ad- (but not limited to) the field of furniture coatings. This means
dition of slip properties along with other features of a coating that adhesive tape and labels can be removed from the coa-
that are of prime interest. Obviously, surfaces with higher slip ting easily and without leaving any residue. Silicone additives
are more scratch resistant, less easily soiled, easier to clean, have an impact on this property. Specific additives are also
and more resistant to blocking. The level of improvement in provided with acrylic functions and can therefore be incorpo-
the surface slip again depends on the chemical structure of rated into the binder matrix in radiation-curable formulations.
the silicones and is directly linked to the proportion of di-
methylsiloxane groups. Products with many dimethylsiloxane
groups result in a high surface slip, while methyl alkyl poly-
siloxanes do not increase slip very much. Silicone surfactants,
due to their small chain length, do not noticeably increase slip
in the majority of coating systems. If more slip is nonetheless
required, they must be combined with other silicone additives.

Measuring surface slip Demonstration of increasing and reducing surface slip

 11
Cleanability

Improving cleanability BYK-SILCLEAN 3700 makes coating surfaces simultaneously

hydrophobic and oleophobic, which results in reduced dirt
pick-up and improved cleanability. Water resistance is enhan-
The use of special silicone additives also makes it possible to ced and whitening (blushing) avoided.
reduce the dirt pick-up of coatings and improve cleanability.
It can also be used to improve anti-graffiti and tape release
Such a special additive for solvent-borne coating systems is properties. Moreover,
BYK-SILCLEAN 3700. It is a hydroxy-functional silicone-modi- BYK-SILCLEAN 3700 also improves substrate wetting, leveling
fied polyacrylate and, due to its surface activity, it migrates to and surface slip. For aqueous systems, the same properties
the coating surface. Due to its primary OH groups, it can be can be achieved by using BYK-SILCLEAN 3720.
incorporated into the polymer matrix in many coating for-
mulations (e.g. 2-component polyurethane, alkyd melamine,
polyester melamine, acrylate epoxy, epoxy phenol) during the
cross-linking reaction. In this way the additive is permanently
fixed at the coating’s surface and the specific surface pro-
perties contributed by the silicone are also more permanent,
including during outdoor exposure.

“Easy to clean” effect using BYK-SILCLEAN 3701

 12
Practical information

Silicones as a general class of products have an unearned In connection with silicones, there are two factors, however,
reputation in the industry for poor recoatability and intercoat which can negatively influence intercoat adhesion:
adhesion. However, through proper choice and application,
this does not have to be the case. Due to their surface activity, (1) Dosage of the silicone additive,
silicone additives migrate onto the coating surface and, as
they usually have no reactive groups, they are not incorpora- (2) Baking temperature of the first coating.
ted in the cross-linking mechanism of the binder, i.e. they re-
main mobile even after baking. This can be demonstrated, for For each binder/silicone combination there is an optimum
example, by the fact that solvent can be used to wipe them quantity of silicone; higher dosages will not provide greater
off the surface again. When recoating a silicone-containing benefits (more wetting, anti-cratering effect, slip, etc.), but
coating layer, the silicones then do not remain in the first layer can cause undesirable side effects, such as impaired intercoat
(i.e. the interface between the two coating films); due to their adhesion.
mobility and surface activity they migrate to the new surface,
i.e. that of the second coating film. No silicone remains bet- In the case of an overdose, some of the silicone molecules
ween the two coating films, and for this reason the intercoat remain in the interface between the two coating films and
adhesion is not negatively influenced, either. adversely affect adhesion. When using silicones, it is therefore
particularly important to use a series of tests to ascertain the
optimum dosage and then not exceed it.

In addition, the baking temperature also has an influence

on intercoat adhesion; when the first (silicone-containing)
coating layer is overbaked, the adhesion of the second layer
can be considerably reduced. This is due to the fact that at
higher temperatures (140 °C-150 °C) the polyether chains of
the additives are degraded by oxidation.

During these degradation processes, reactive groups are

created, so that the silicone additive is now incorporated in
the binder matrix and therefore loses its ability to migrate.

When overcoating, the decomposition products remaining

between the two layers adversely affect adhesion by acting as
a release layer. Since the thermal instability mentioned above
is caused by the presence of polyether chains, it is therefore
possible (by exchanging the polyether chains with more ther-
mally stable groups) to avoid this effect. For example, silicone
additives with polyester or aralkyl modifications remain stable
at temperatures of up to 220 °C – 250 °C.
 Intercoat adhesion can be assessed
with the aid of cross-cut testing.

are not defoamers, yet they contribute defoaming proper-

Defoaming ties in addition to the typical silicone properties. Silicones
which can be used as defoamers must be adjusted to become
even more incompatible. Polyacrylates can also have a defoa-
Foam can be caused by silicones, but silicones can also be
ming effect at a sufficiently high incompatibility
used as defoamers. The critical factor here is the polarity
and compatibility of the silicone additive. A highly compatible
silicone additive with lower surface tension tends to stabilize
foam. If this leads to problems with foam, products with a
higher surface tension should be used instead. These products

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