PAINT AND COATINGS ADDITIVESFORMULATING WITH MIKE

Introduction to Additives, Part 4: Dispersants

By Mike Praw, Senior Applications Scientist – Paints, Coatings and Inks, Indorama Ventures: Integrated Oxides and
Derivatives, The Woodlands, TX

Photo: Davizro, iStock / Getty Images Plus, via Getty Images

December 14, 2021
This is the fourth article in our series on additives, and will cover dispersants and surfactants used to stabilize pigments in
coatings. Dispersion is the process where a non-soluble solid is suspended in a liquid and stabilized against settling,
separation, agglomeration or aggregation. The concentration of solids in the liquid must be uniform during mixing. Once
mixing is removed, the mixture must be stable. For paints and coatings, pigments are being dispersed into a resin/solvent
matrix, and stability against settling, flooding, floating or flocculation is required.
Generally, pigments are divided into three main types: primary, extender and specialty. Primary pigments tend to be
expensive and give coatings color and hiding. Extender pigments are added to control gloss, lower cost or influence other
physical properties. Specialty pigments are added for a specific purpose and include anti-corrosive, effect pigments and
nanoparticles. Since primary pigments tend to greatly affect the cost of a coating, using them optimally is necessary.
So why do we disperse pigments? Properties of the coating such as viscosity, tint strength, opacity, dispersant demand and
photo stability all depend on the particle size of the pigment (Figure 1). From Table 1 and Figure 1 you notice some

properties compete.

FIGURE 1 » Coatings properties based on pigment particle size.

TABLE 1 » Particle size preferences based on coatings property.

The ultimate particle size for a pigment is determined by the manufacturer and optimized during processing for the right
balance of properties. Pigment dispersing occurs by breaking up agglomerations and aggregates; the primary particle size of
the pigment should remain unchanged. You are dispersing the pigment by returning it, as close as possible, to its primary
size. You are not grinding the pigment or reducing the primary particle size.
Ideally, a good dispersion will break up clumps (aggregates and agglomerates, Figure 2) and will ensure a uniform pigment
concentration in the coating. It maximizes hiding power and tint strength while eliminating grit. Figures 3 and 4 highlight the
hiding difference between a good and poor dispersion.
FIGURE 2 » Aggregates and agglomerates. FIGURE 3 » Hiding differences between a good and poor dispersion.

FIGURE 4 » Hiding differences between a good and poor dispersion.

Dispersion Stability
There are several issues related to dispersion stability, which are detailed below.
Settling and Syneresis
Settling takes place when the pigment has a higher density than the liquid media (most cases). The pigments can rise and
agglomerate at the surface when the pigment has a lower density than the media. This is rare and generally happens when
using hollow spheres or some resin-based pigments. Both settling and rising rates are governed by Stokes’ Law, which states
the rate of settling (or rising) is proportional to the particle size and density difference (between the particle and liquid), and
inversely proportional to the viscosity. In coatings terms, large, dense pigment particles and a low viscosity will result in
rapid settling.
Syneresis is like settling but it is a stratification of liquids in a coating, normally based on gravity. In extreme cases in a
water-based paint, enough water will separate out that latex resins will undergo coalescence.
Both settling and syneresis are caused by different compatibilities and densities of liquids in a coating. Changing or
increasing the surfactant in a coating to aid in compatibility, and adjusting the rheology package, especially in the low-shear
region, will aid in the stability of a uniform coating. Too many formulators will only adjust the rheology package and not
completely solve the issue. Optimizing the surfactant package in a coating is critical for good stability. An optimized
surfactant package will:
 Stabilize the pigments from re-agglomerating or re-aggregating, as the larger agglomerates or aggregates will settle
out faster.
 Cause any settling to be soft and easily re-incorporated.
 Act as a humectant, keeping water within the resin matrix to prevent syneresis.
Figure 5 highlights settling and syneresis.
FIGURE 5 » Settling and syneresis.

Surfactant Stripping
Coatings contain multiple surfactants, and often more than one of each type (pigment dispersants, flow and leveling agents,
substrate wetters, emulsion polymerization surfactants, etc.). A white base paint may have a TiO2 dispersant and a colorant
acceptance surfactant. Different colorants may each have a different dispersant. This is all well and good if they work
together properly. However, often the surfactant from one coating’s raw material will have a greater affinity to another,
especially if the latter raw material is surfactant starved. Since formulators do not know which or how much surfactant comes
in each raw material, this can lead to a serious issue called surfactant stripping.
For example, we add a colorant to a coating that contains a partially stabilized/surfactant-starved resin emulsion. The
surfactant used in the colorant works well and stabilizes the colorant by itself, but when added to the coating, it has a higher
affinity to the resin and moves off the pigment, now leaving the pigment improperly stabilized. This is how surfactant
stripping operates, i.e. in this case the resin stripped the surfactant off the pigment, but any raw material can strip surfactant
of another raw material. Adding a universal stabilizer surfactant will help prevent this. Figure 6 shows this process.

FIGURE 6 » Surfactant stripping.

Flooding and Floating

When a coating is drying and solvent is evaporating, convection currents develop due to concentration gradients of the
solvent (water is a solvent, and the use of the word solvent includes water). On a non-porous substrate, solvent concentration
will be lowest at the air/coating interface. On a porous substrate, it is more difficult to determine, as solvent is absorbed into
the substrate and evaporates at the same time. Since pigments have different densities, particle sizes and affinities to the
solvent and resin, their mobility in the coating can be vastly different. These differences can lead to flooding and floating
issues.
Floating occurs when there are vertical differences in color, when viewed in the cross section of the coating, and is typified
by Bènard Cells. This can lead to silking if the coating does not flow out well and there are irregular coating thicknesses
during brush application. Flooding occurs when the different pigments move to the surface at different rates during drying of
the coating, as is the case with floating. The difference is the surface tension at the air-liquid interface is low so you obtain a
uniform surface color, as opposed to the irregular color of floating, which is different from the coating’s color. Both types of
defects lead to differences in color/shade when different levels of shear are applied, such as brush, roller and/or spray
(Figures 7-8).
FIGURE 7 » Floating. FIGURE 8 » Flooding.

Flocculation
Another issue related to dispersion stability is flocculation. Pigments, if not stabilized after the dispersion process, can re-
agglomerate or re-aggregate, and this will lead to a loss of hiding, gloss change and many other coating issues. If the
destabilized aggregates or agglomerates only contain pigments and surfactants, this is called flocculation. If another raw
material acted as a seed for the agglomerate growth, this is called seeding. An example of seeding is pigment being adsorbed
on the surface of a resin particle and growing. Figure 9 highlights flocculation and seeding.

FIGURE 9 » Flocculation and seeding in a coating.

Selecting the Right Dispersant

So how are issues like flocculation, settling, flooding and floating solved? We add an agent to help in the dispersion process.
These additives are known as dispersing agents or dispersants. The dispersants help in all three stages of the dispersion
process:
 They help the liquid wet out the pigment and help remove air trapped on the surface or within agglomerates.
 They then help in the dispersion process by allowing the agglomerates and aggregates to break up easier.
 They help stabilize the dispersion and coating to prevent flocculation, settling, flooding or floating.
 It is obvious that the dispersant choice is critical for an efficient dispersion and a stable, quality paint.
The objectives when selecting a dispersant fall into three catagories:
1. The dispersant can increase the performance of the coating; it will increase color strength and gloss, while also improving
compatability and stability.
2. Dispersants are also process aids that help in pigment wetting, decrease dispersion times and help control mill-base
viscosity.
3. The last part they play is to affect the coating formulation. Dispersants allow higher pigment loading, improve color
stability and can help with rheology control.
So what criteria do you use when selecting dispersants? The most important is the type of pigment being dispersed and what
properties you are looking for. Ionic dispersants work best with inorganic primary pigments (titanium dioxide, iron oxides,
etc.) and extender pigments. Non-ionic or polymeric dispersants are generally classified by their molecular weight. Low-
molecular-weight dispersants are economical solutions for inorganic primary and extender pigments. Medium-molecular-
weight dispersants or blends of dispersants give the broadest compatibility with pigments and resins, leading to a more
universal system. High-molecular-weight dispersants are used when you require the lowest viscosities, highest color strength
and highest gloss. High-molecular-weight dispersants are generally best for expensive organic pigments, as they maximize
color development.The higher the molecular weight of the dispersant, the more you will need, as you get fewer molecules per
unit weight. You have to balance out the increased cost of higher-molecular-weight dispersants versus the cost of the
increased performance of the pigments.
Ionic and non-ionic dispersants use different stabilization mechanisms. Ionic dispersants rely on charge stabilization from the
repulsive forces of the electric double layer, known as electrostatic repulsion.
Non-ionic dispersants use the physical repulsive forces of the polymer chains as well as osmotic pressure. The polymer
chains attract water through osmosis, which swells the polymer chains and physically prevents particles from getting too
close together. This combined effect is called steric repulsion. Steric repulsion is the more robust of the two methods. Some
dispersants will combine both stabilization methods for additional performance – this is known as electrosteric stabilization.
Figures 10 and 11 demonstrates the different stabilization mechanisms.

FIGURE 10 » Dispersant stabilization mechanisms: charge versus steric stabilization.

FIGURE 11 » Dispersant stabilization mechanisms: steric versus electrosteric stabilization.

Higher-molecular-weight dispersants stabilize pigments by steric (or osmotic) stabilization. To achieve this, two criteria must
be met:
1. The dispersant must strongly adsorb to the pigment; and
2. The dispersant must sufficiently extend out into the solvent or resin phase.
When pigment particles approach each other, a concentration gradient forms as the polymer chains become more
concentrated between the pigments. This increases the osmotic pressure, so solvent moves into the region to lower the
concentration gradient. This leads to the pigment particles being forced back apart and they are prevented from flocculating.
So, which is better? It really depends on the coating and what you are trying to achieve, but overall, a combination of charge
and steric stabilization, and low to medium molecular weight will give you the best performance in a coating, especially in
base/colorant systems.

Determining the Best Dispersant Level

Like any other additive, more is not better. In fact, performance will decrease once past the ideal level. To determine the best
dispersant and approximate the ideal dispersant level, a design of experiment will be the most efficient tool. However, once
the dispersant is identified, a ladder study is best to determine the optimum level needed. The standard method is to measure
mill base viscosity with increasing dispersant level, and plot it. Figure 12 shows the determination of dosage level of a
dispersant.

FIGURE 12 » Determination of the dosage level of a dispersant.

The key is not to formulate on a pinhead. In Figure 12, we see that the red curve has the lowest viscosity and is the preferred
dispersant, but its curve has a narrower plateau than the green or purple curves. At dispersant concentration 1, the red
dispersant is the obvious choice. It uses less dispersant and has the lowest viscosity. But what if the concentration change
between 1 and 3 is so small your production process cannot consistantly weigh out the dispersant accurately within the range
of the curve? Then the purple curve would be better. While the purple curve is the flattest of the three curves, in almost all
areas the green curve has a lower viscosity and is preferred over the purple curve if the red dispersant cannot be used.
So why lower viscosity? As you increase the level of dispersant in the mill base, viscosity drops to the optimum level, then as
you increase the dispersant level, dispersant/dispersant interactions will increase viscosity and make dispersion more
difficult.
Pigments vary in their hydrophilic/hydrophobic nature and because of this, so do dispersants. The Hydrophilic/Lipophilic
Balance (HLB) of a surfactant goes up to 20, with 20 being completely water soluble. The lower the number the more
hydrophobic (lipophilic) it is. Most pigment dispersants have hydrophobic and hydrophilic portions. In aqueous systems the
hydrophobic region attaches to the pigment and the hydrophilic region extends into the water phase. The opposite is true for
solvent and 100%-solids based systems. Because of this, choosing the correct structure and HLB of the dispersant is critical
to a stable dispersion. For example, a dispersant for titanium dioxide and calcium carbonate in an aqueous system was
dispersed with both a hydrophobic and hydrophilic dispersant (high and low HLB). As expected, a more hydrophilic
dispersant worked the best (lower levels and quicker dispersion).
Often water sensitivity is a concern in coatings for either scrub or corrosion resistance. While this may lead you to consider a
hydrophobic surfactant, you will need more of it and it may not give optimum opacity, gloss and tint strength. Often a
hydrophobic surfactant will remain in the resin matrix, resulting in long-term water sensitivity, while a hydrophilic surfactant
may leach out quickly giving better long-term water resistance.
One other type of dispersion mechanism is controlled flocculation. In this method, the dispersant attaches to both the pigment
and itself to form a three-dimensional structure that stabilizes the dispersion. The advantage can be increased stability, but
you need significantly more dispersant that can create other issues in a coating. Figure 13 shows this ad hoc network.

FIGURE 13 » Controlled flocculation dispersants.

Polymeric dispersants are made with different chemistries, with urethane, acrylic and polyester being predominant. However,
the increased use of renewable/green chemistries has changed how we look at dispersants.
Conclusion
There are many options to determine which dispersant to use and how to optimize the system. Overall, you want a dispersant
that yields a robust system that is easy to formulate, and optimizes the desired properties with the minimum cost. You need
the proper dispersant because even quality dispersions can become a flocculated mess if the system is not stable. A good
dispersion is the most important factor in making a high-quality coating. It takes planning and preparation, but it is easily
obtainable.
While optimizing the use of additives is time consuming, it is worthwhile since you will have a more robust coating often at a
lower price. The thing to remember is more is not better when it comes to additives.
For information, email Michael.Praw@us.indorama.net.