Wetting and Dispersing Additives

TEGO Dispers

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 Optimal dispersion and stabilization of sible. Only then can color intensity, gloss,
pigment particles is a significant factor in hiding power, lightfastness and weather-
determining the end properties of lac- ing resistance be maximized. Pigment dis-
quers, paints or printing inks. The pig- persion and stabilization, which requires
ments and fillers of the formulation must time and energy, is hardly possible with-
be ground to small-sized particles, wetted out suitable wetting and dispersing addi-
and uniformly distributed as stably as pos- tives.

What occurs during dispersion?

Pigment dispersion can be broken down where

into three steps which occur partly con-
secutively and partly concurrently: wet-
s : free surface energy of the solid
ting, dispersion and stabilization. sl : Interfacial energy solid/liquid
l : Surface tension of the liquid
Wetting  : Contact angle solid/liquid

Wetting the pigment particles is essential With spontaneous wetting or spreading,

for them to be finely distributed in a liq- the contact angle is zero so that the cosine
uid. Air entrapped in the pigment powder term is 1. This occurs when:
must be fully removed and the pigment
particle completely surrounded by the liq- s sl = l
uid medium. The processes involved in
wetting a solid are approximately
described by the Young equation:
For the liquid to wet the solid, the surface
tension of the liquid must be lower than
s = sl + l cos  that of the solid. A liquid with lower sur-
face tension wets pigments better than
or one with higher surface tension. An addi-

s sl tive which promotes wetting must there-

= cos  fore primarily reduce the surface tension
l of the liquid.

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 However, wetting and dispersing addi- lowers the viscosity of the millbase. This Every dispersion process to break up
tives do not only lower the surface ten- allows higher pigment loadings to be aggregates and agglomerates requires
sion of the liquid. As their pigment affinic achieved, which is particularly important energy. The work needed is given by:
groups cause them to be adsorbed onto for the mechanical dispersion process.
the pigment surface, they also alter the Millbase formulations which have been
dW =  dA
boundary surface. The surface tension is optimized in this manner are suitable for
no longer that between pigment and liq- all modern grinding equipment such as where
uid but between additive and liquid. dissolvers, bead mills and three-roll mills. W: interfacial surface energy
: surface tension
Wetting and dispersing additives lower In the dispersion process itself, the pig- A: interface area
the surface tension of the liquid and the ment agglomerates are broken up into
interfacial tension between pigment and primary particles and smaller pigment This equation indicates that, for an
liquid so that wetting is promoted in two aggregates. Usually aggregates cannot increase of the surface dA during disper-
ways. be broken up. The primary particles in sion (by breaking up agglomerates), an
aggregates are so strongly bound surface energy input dW is needed which is pro-
to surface that it is practically impossible portional to the surface tension . The
Dispersion to break them apart. Account is taken of smaller the surface tension, the greater
this in pigment manufacture and the the increase in surface area for a particular
The pigment particles are now wetted by proportion of aggregates specifically amount of energy applied. Equally, for a
the surrounding binder solution and their controlled. Their amount can affect the particular change in surface area in the
surface coated with the surface-active color tone of a pigment. presence of a dispersing additive (that is
additive. The additive reduces the interac- at reduced surface tension) less dispersion
tions between the pigment particles and energy is needed.

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 Stabilization Dissociation of the adsorbed additive with pigment-affinitive groups are used.
molecules into bound anions and freely These groups attach themselves to the
In the dispersion process, the aggregates moving cations forms an electrochemical pigment surface and thus ensure adsorp-
(fig. 1a) are broken up into primary parti- double layer around the pigment parti- tion of the additive. The polymer seg-
cles and smaller agglomerates. Formation cles. Each pigment particle is situated in a ments are responsible for compatibility in
of primary particles results in an increase solution of oppositely charged ions which organic systems. They also stabilize the
of the boundary area with the liquid are relatively firmly bound to the pigment. dispersion by protruding into the solvent.
medium (fig. 1b). The higher the interfa- Both attractive and repulsive forces If the pigment particles come too close,
cial tension, the more strongly will a solid depend on the interparticle separation. the polymer segments interpenetrate and
attempt to reduce the interfacial area. The With a strongly pronounced double layer, their mobility is reduced, thus lowering
particles, therefore, reagglomerate to repulsion predominates and the disper- the entropy. The pigment particles sur-
form so-called flocculates (fig. 1c). The sion is stable. If the electrochemical dou- rounded by the polymers move away
term flocculate indicates an agglomerate ble layer is disrupted, for example by from each other to balance this entropy
occurring in suspension. Dispersing addi- addition of an electrolyte, attractive forces loss.
tives suppress the formation of floccu- dominate and the dispersion breaks up.
lates. Electrostatic interactions can be quantita- With the complex demands made of wet-
tively described by the zeta potential, , ting and dispersing additives, it is useful
To stabilize the fine distribution of parti- which is a measure of the potential at the to combine electrostatic and steric effects.
cles, the additive molecules must be shear layer of a moving particle in a dis- This is often known as electrosteric stabi-
firmly adsorbed onto the pigment surface. persion. As  approaches zero, the ten- lization.
This means that the additive molecules dency of the particles to agglomerate
require groups or segments which can increases Modern wetting and dispersing additives
interact strongly with the pigment surface for waterborne application use elec-
by ionic bonding, dipole interactions or Solventborne paint systems cannot be trosteric stabilization. Only such additives
hydrogen bridges. Depending on whether stabilized electrostatically. Particle floccu- can fulfill the high demands made on sta-
the formulation is water- or solventborne, lation is instead preferably prevented by bilization and durability.
various mechanisms are possible. steric stabilization. Polymeric additives

In waterborne coatings, electrostatic

repulsion is traditionally the most impor-
tant stabilizing factor. Interactions within
the formulation can be described by the a b c
DLVO-theory (named after Derjagin,
Landau, Verwey and Overbeek). In inter-
preting the stability of waterborne disper- air
sions, the interplay between attractive
and repulsive forces is considered.

liquid liquid liquid

Figure 1: Schematic representation, (a) agglomerated, (b) dispersed, (c) flocculated pigments

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 electrostatic stabilization steric stabilization electrosteric stabilization

dispersed dispersed dispersed

particle particle particle

Figure 2: Stabilization
of dispersed particles:
(a) electrostatic
(b) steric
(c) electrosteric

A further possibility of preventing pig- change in the rheological properties: at

ment particles approaching each other rest, the viscosity is very high so that the
and thereby flocculating is controlled pigments can no longer easily precipitate.
flocculation. In this, the structure of the The different mobility of the pigments,
additives allows them to mutually interact. which is also partly responsible for flood-
The individual additive molecules adsorb ing and floating, is prevented by pigments
onto the pigment surface and by interac- binding to flocculates of the same color
tion with each other form a three-dimen- (fig. 3).
sional network. This network causes a
However, the three-dimensional network
can compromise the flow of the coating
and thus reduce gloss. Controlled floccu-
Figure 3: Simplified diagram (not to scale) of controlled flocculation lation is therefore mainly used in solvent-
by crosslinking of the additive molecules borne primers and fillers. This method is
Network formed by secondary valences not used for waterborne coatings; a simi-
lar effect can be achieved there with asso-
ciative thickeners.

organic pigment inorganic pigment

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 desired multifunctionality necessitates
Structure of wetting and dispersing deliberate combinations of different wet-
additives ting agent components.

In principle, every wetting agent has one

Wetting and dispersing additives are wetting agents are of low molecular or more adhesion groups which can
amphiphilic compounds, i.e. they are both weight and dispersing additives are of dock with the pigment and a more-or-less
hydrophilic and lipophilic. Their special high molecular weight. Because of the long segment which can be solvated. This
molecular structure allows them to enable complexity of amphiphilic substances, general principle is shown in the follow-
or facilitate dispersion of pigments and which contain unique functional groups, ing simplified schematic diagram:
fillers in the solvent. In addition, they it is not easy to develop a simple model.
should stabilize the dispersion. The boundaries are not fixed as the

Wetting and dispersing additives can be

classified in different ways. In the litera-
interfacial active compounds
ture, there are assignments according to
chemical structure or separation into ionic
anionic [R - (CnH2n) - COO] -K+
and non-ionic products. Other classifica-
tions are made by field of application,
cationic [R - N - (CH3)3] + CL-
waterborne or non waterborne, or by pig-
ment type, organic or inorganic. A classi-
amphoteric R3 - N+ - CH2 - COO-
fication by molecular size is also possible:

non-ionic R - O - (CH2 - CH2 - O)n - H

Figure 4: Schematic diagram of the structure of surfactant compounds with various types of head groups

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 The number of adhesion groups is among long-term stabilization of dispersions. Oligomeric and polymeric dispersing
those properties important for the effec- Inorganic pigments can also be split into additives are particularly suited for steric
tiveness of a wetting and dispersing addi- chemical classes. With a few exceptions stabilization. It has been found that block-
tive. Adhesion groups are functional these are oxides, oxyhydroxides, sul- and graft-copolymers are better than
groups which have a special affinity for phides, silicates, sulphates or carbonates3. homo- or copolymers with a random
pigment surfaces. If there is only one These pigments are characterized by polar statistical distribution. Pigment affinic
adhesion group per molecule of dispers- molecular structures so that their interac- groups are incorporated in the additive
ing additive, replacement by a solvent tion with acid groups, such as carboxy, depending on the type of pigment and the
molecule leads immediately to complete phosphate or sulphate, are particularly application (fig. 5).
removal of the additive molecule from the strong.
surface. This leads to flocculation of the Modern high performance polymeric
pigment. Additives with several functional Carbon blacks are a special case. The sur- wetting and dispersing additives suitable
groups cannot so easily be removed and face area of these pigments is many times for all types of pigments have multiple
therefore show especially high perfor- greater than that of organic or inorganic occurrences of all types of adhesion
mance. pigments. On the one hand, a much larger groups, e.g. TEGO Dispers 755 W.
amount of dispersing additive is needed
The type of adhesion group depends on to cover the surface effectively. On the
the particular pigment surface: other hand, carbon black has neither a
Organic pigments usually contain aro- classic organic/aromatic nor an inor-
matic groups so that dispersing additives, ganic/crystalline structure. Experience
which contain, for example, phenyl or has shown that nitrogen-containing dis-
napthyl units, are particularly suitable for persing additives are the most successful.

AB block copolymer graft copolymer

very
soluble

very soluble

BAB block copolymer

pigment anic

very soluble pigment anic very soluble

Figure 5: Copolymers for
steric stabilization

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 on the scattering power of the pigment
The function of wetting and dispersing and the refractive index of the pigment
additives with the surrounding medium (usually
the film forming agent). In a coating with
strong hiding power, the pigment parti-
Wetting and dispersing additives lower the pigment. The smaller the pigment cles scatter the light so strongly that it
the viscosity of a coating formulation. particles, the greater their effective sur- hardly reaches the substrate. If residual
However, that is not their only effect. face area and consequently the higher light is reflected from the substrate, it is
This class of additives has a marked effect their absorbing power. A higher absorb- so strongly scattered that it does not reach
on a whole series of different, essential ing power is associated with higher color the eye. For a coating to scatter the light
characteristics of the formulation. intensity. To ensure that the small pig- optimally, an even, fine distribution of the
ment particles remain finely distributed pigment stabilized by dispersing additives
and do not clump together to form larger is essential.
Color intensity flocculates, they must be stabilized. Dis-
persing additives are necessary for this.
The color intensity is a measure of the Flocculation
ability of a pigment to absorb incident
light and impart color to a medium. It has Hiding power Flocculation is the reagglomeration of
practical importance in coloring white already dispersed particles. In the disper-
base paints: the stronger the color of a The hiding power of a coating is its ability sion process, energy is taken in to break
tinting agent, the more economical it is. to cover the color or the color difference up the pigments and form new surfaces.
The color intensity of such a preparation with the substrate.1 How well the sub- This is, however, an unstable state and floc-
depends significantly on the absorbing strate is hidden depends on the coating culation can occur at any time during man-
power and the average particle size of thickness, the color of the substrate and ufacturing, storing and applying a paint.

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 Pigments also tend to flocculate after the affect leveling. Poor leveling decreases This vertical flooding, also known as
paint has been applied to a surface car- the gloss further. Since wetting and dis- floating, causes the film to appear more
bon black with its high surface area is persing additives inhibit flocculation, they colored than desired. Flooding can be
particularly susceptible. If this occurs, increase the gloss of a coating. made visible by rub-up tests.
a substrate cannot be evenly coated in
black. Dispersing additives inhibit floccu- Horizontal flooding occurs by separation
lation of the pigment particles. Flooding and floating of the color pigments in the drying film
and originates from solvent flows: parti-
These phenomena occur with mixed pig- cles with lower density are entrained with
Gloss ments when the density and/or the parti- the solvent flow and islands with different
cle sizes of the pigments are markedly dif- pigmentation result. These so-called
Light falling on a surface can be reflected ferent. Bnard cells are clearly visible.
directly (specular reflection) or diffusely.
High gloss is obtained when the surface With its high density, titanium dioxide This unwelcome separation of pigment
is very smooth and the diffuse component tends to concentrate at the bottom of the particles can be prevented if they are
of the reflection is small. Pigment parti- drying paint film. Organic colored pig- associated with each other in a controlled
cles or flocculates which protrude from ments have significantly lower density manner by suitable dispersing additives
the surface interfere with the specular than titanium dioxide and, therefore, con- which induce controlled flocculation.
reflection. Flocculated pigments also centrate in the upper part of the film.

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 Evaluation of particle size in the grind guage

Evaluation of wetting and dispersing additives

Particle size With a little practice, the grind guage

allows quick and simple measurement of
The primary criterion which decides the the maximum particle size. However, the
quality of a dispersion is the particle size particle size distribution cannot be mea-
distribution. By measuring the particle sured in this way. The grindometer is of
size or the size of the largest particle, the no use for binder-free dispersions which
endpoint of a dispersion process can be dry very quickly or for particle sizes less
very well established. The grindometer is than 5 m.
the simplest method of measuring the
maximum particle size of inorganic pig- Very small particles and particle size dis-
ments. A sample of the millbase is tributions can be studied with more
brushed onto a grindometer. Large parti- sophisticated measuring methods such as
cles are moved by the doctor blade and laser diffraction or ultrasound. However,
produce stripes in the draw down. The because of their high cost, these methods
size of the largest particles can be read are generally unsuitable for routine use in
directly from a scale. the laboratory.

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 Whether or not the desired particle size very time-consuming but delivers mean- Color intensity according to Kubelka-
has been reached can be easily deter- ingful comparative data and is used mainly Munck:
mined using secondary indices. Thus, by pigment manufacturers.
with organic pigments, the color intensity K (1 R)2
is dependent on the particle size. By mea- An absolute value can be obtained by a FS = =
suring the color intensity at various times method based on a theory by Kubelka- S 2R
during dispersion, changes in color inten- Munck, involving the ratio of reflectance
sity can be followed and the end point of and transmission. The sum of the reflec- with
the dispersion determined. tance values over the complete wave FS: Color intensity
range gives a value for the color intensity. K: Absorption coefficient
S: Scattering coefficient
Color intensity In practice, however, this method has a R: Reflection at infinite film thickness
systematic error as it is based on the (no change in the degree of reflec-
To determine the color intensity, a sample assumption of an infinite film thickness tion)
of the millbase is let down in a suitable and a constant degree of reflection. It is
paint formulation. Assessment is made by not suitable for qualitative assessment of
comparison with the same amount of a a pigment batch. Rub-Up
standard millbase optically or using a
spectrophotometer. The amount of mill- The Rub-Up test is used to test the stabili-
base is adjusted until both samples have zation of pigment particles. It allows the
the same optical properties. The relative compatibility of pigment concentrates,
color intensity of the sample as a percent- tendency to flocculation of pigment parti-
age of the standard is calculated from the cles and flooding phenomena to be deter-
various amounts used. This method is mined. A part of the wet, but already

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 drying, film is rubbed with a finger or important indicator of the stability of a If problems still occur
brush. If the pigment particles have pigment concentrate. If it alters during
demixed or are strongly flocculated, the storage, the pigments are usually inade- In spite of innovative and high perfor-
mechanical rubbing re-establishes a quately stabilized. mance wetting and dispersing additives,
homogeneous distribution. In a drying pigment dispersion is not easy. Unex-
film, the viscosity has already increased The dynamic viscosity of a millbase can pected problems often occur especially
strongly and the re-established homoge- be quickly and simply determined using a with waterborne formulations. We will be
neous distribution of the pigment parti- Brookfield viscometer. This method can, happy to give help and advice to enable
cles is thereby stabilized. The extent of however, only be used for quality control. you to utilize the full effectiveness of our
pigment separation or flocculation is Millbases show pseudoplastic flow behav- additives.
obtained from the color difference ior. Changes in their viscosity are depen-
between the rubbed and non-rubbed dent on the applied shear energy. To
film. The color difference is usually obtain an exact picture of the rheological
quoted as the separation of the color behavior of a millbase, a complete flow
chromaticity, E, which is dimensionless. curve must be obtained using a rotational
If E is less than 0.5, no color difference viscometer which can measure the viscos-
is visible, between 0.5 und 1.0 the color ity of the millbase at different shear rates.
difference is only slightly visible, but a E
larger than 1 is not acceptable. Such a flow curve provides information
about the rheological behavior of the
material from manufacture through trans-
Viscosity port to application. Interactions in the dis-
persion can also be quickly detected.
Literature:
The viscosity of a millbase must be suit- 1
DIN 55987: 1981-02
able for the dispersion unit. If the millbase Detailed information about the theoretical 2
W. Herbst, K. Hunger, Industrial Organic
Pigments, VCH Verlagsgesellschaft mbH,
viscosity is too high, the unit can be dam- basis of viscosity and rheological behavior Weinhein, Germany, 1993, p. 4ff
3
aged. If it is too low, insufficient shear can be found in Technical Background: G. Buxbaum, Industrial Inorganic Pigments,
VCH Verlagsgesellschaft mbH, Weinhein,
force will be transferred to break up the Rheological Additives. Germany, 1993, p. 9
pigment agglomerates. Viscosity is also an

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