FEATURE

Four Steps to Effective

Pigment Dispersions
Starting from Scratch.

Jadel Baptista, Technical Director, LANSCO COLORS, Warwick, RI

Introduction better fastness properties when used in the mentioned applica-

Pigments are designed and produced to be insoluble particles tion, than in most industrial paint applications. The difference
used to impart color in a variety of materials. They can be in performance is due to the solvents used in these systems.
classified as organic, inorganic, effect, and functional. The di- Solvent-based architectural paints, are based on acrylic and/or
verse range of pigment chemistries, the end use requirements, medium/long oil alkyd resins, and the preferred solvent used in
and the broad range of colors available create a challenge for this application is mineral spirits. In waterborne applications,
chemists in selecting the optimal pigment or additive for a acrylic emulsions or water-soluble acrylics are used. Pigment
given application. Proper pigment and additive selection is Yellow 74 is slightly soluble in mineral spirits but is not sol-
critical in determining the performance of the finished coating uble in water (Figure 1), therefore it will maintain its crystal
as well as the production efficiency. Understanding the various structure. However, in industrial coatings applications, where
pigment types, properties and chemical families will help the the most commonly used solvents are aromatics, esters and
formulator in determining the most effective pigment chem- ketones, Yellow 74 will have higher solubility which will have
istry and manufacturing processing, thus avoiding potential a negative influence on its fastness properties such as heat sta-
problems with the final coating and application. This paper fo- bility, weathering, overspray migration, and opacity. Choosing
cuses on pigment families and their application in waterborne, the correct pigment for the desired application should be the
solventborne and universal dispersions. The theory behind first step during the coatings formulation process in order to
processing, selection of wetting and dispersing agents, and the formulate a stable system. Formulators are advised to consult
differences between co-grinding and single pigment dispersion their pigment suppliers in order to obtain the appropriate pig-
are discussed. ment solubility information.
In addition to solubility, resistance to acids and alkalis, heat
Pigments vs. Dyes – Is Solubility stability and weatherfastness/lightfastness, should be considered
Important? in order to formulate a stable system that meets end use require-
Pigments are inorganic or organic colorants that are virtually ments. Figure 2 shows some important points to be considered
insoluble in the application medium while dyes are colorants during the initial formulating stage. The formulator should al-
that are soluble in the application medium. Understanding ways keep in mind that the same pigment chemistry may not
this difference is the most important concept to help with perform equally in all coatings systems.
the correct colorant choice. Dyes are organic molecules with
brighter undertone, higher transparency, and they generally Organics vs. Inorganics – Are they
demonstrate inferior fastness to UV exposure versus pigments. different?
Organic pigments vary regarding their chemical structure and Organic pigments are synthetic materials based on carbon usu-
surface treatment; some can behave like a dye, losing their ally derived from petrochemicals. They generally are not stable
crystal structure when exposed to solubilizing conditions. at elevated temperatures and have partial solubility in strong
This structural change will negatively impact the pigments solvents, but do not dissolve in water. Inorganic pigments are
fastness properties. A good example of this is Pigment Yellow metal salts and oxides, some natural and some synthetic, that
74, widely used in architectural paints. This pigment will have generally are stable at elevated temperatures and do not dissolve

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 Four Steps to Effective Pigment Dispersions FEATURE

components, and pigment interactions. Paying proper atten-

tion to these variables will provide the highest probability of
developing a stable formula.

Dispersibility
Pigments must be properly wetted, de-agglomerated/dis-
persed and uniformly distributed and stabilized (Figure 3) in
order to achieve maximum color intensity, gloss, and hiding
power. Stabilization of a pigment dispersion requires time
and energy. Dispersed pigments have a strong tendency to
return to their initial agglomerated state. Due to this strong
tendency, proper selection of wetting and dispersing agents
Figure 1. Solubility of PY 74 in different solvents. is critical in obtaining a stable formula. Surfactants or wet-
ting additives are normally defined as amphiphilic chemis-
tries with low molecular weight while dispersing additives
are oligomers able to stabilize the pigments and avoid re-
agglomeration. The different types of wetting and dispersing
agents are described in Table 1.

Figure 2. Pigment selection criteria.

in solvents. Due to their stable chemical structures, most inor-

ganic pigments have better weatherability, dispersibility and
opacity than organic pigments, however they will typically have
lower chromaticity and tinctorial strength.
Table 1. Wetting and dispersing agents – chemical types.
Pigment Impurities
Pigments with the same color index identification produced by
different manufacturers or different manufacturing processes
could potentially have different performance in spite of being
coloristically similar. This is due to impurities which can be
the result of unreacted raw materials, by-products, inorganic
salts, and contaminants in the water. These impurities may
cause adverse effects on weatherfastness, dispersion stability, Figure 3. Steps for a stable pigment dispersion.
and solvent fastness.
In order to provide assurance that pigments do not have ex- Wetting
cessive impurities, the pigment manufacturer should test for pH, To properly wet a pigment, the air/solid interface needs to be
conductivity, oil absorption, and viscosity in specific testing sys- replaced by a liquid/solid one. Therefore, the less air entrapped
tems. They may even consider doing additional viscosity stabil- in the system, the more effective the wetting will be. It’s all
ity and dispersibility testing for certain pigments as needed. In about surface tension! For a liquid to wet a solid, its surface
addition to approving a pigment for color, coatings formulators tension must be lower than the free surface energy of the solid.
should always verify the stability of the final coating in deter- Therefore, liquids with low surface tension are more effective at
mining the proper pigment or pigments for a given system or wetting and this is why wetting additives are so valuable to the
application. formulator. They will reduce the surface tension and will adhere
to the surface and coat the pigment to create an additive/liquid
Factors Affecting Color Development interface. Generally solvent-based systems more readily wet a
Pigment color development is dependent on five variables: pigment due to the lower surface tension of solvents when com-
dispersibility, energy input, process dwell time, system pared to the higher surface tension of water (Table 2).

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FEATURE Four Steps to Effective Pigment Dispersions

Electrostatic Stabilization
Table 2: Surface tension of common solvents used in coatings Used in water-based systems and mostly with inorganic pig-
Solvent Surface tension, mN/m ments, additive molecules adhere to the pigment surface,
through ionic bonding, hydrogen bonds, and/or dipole interac-
Mineral Spirits 25.20
tion and cause the particles to repel each other through elec-
Xylene 30.10 trostatic forces. Pigments with high conductivity may not be
MEK 24.60 stabilized through electrostatic stabilization. Zeta potential (the
Ethyl Acetate 23.90 potential difference existing between the surface of a solid par-
ticle immersed in a conducting liquid, e.g., water, and the bulk
Water 72.80
of the liquid), serves as a reference as to how stable the formula
will be. Pigment dispersions with a potential between +30 mV
Deagglomeration and -30 mV have a high probability of being unstable. The pH,
In this phase of the dispersion process, pigment agglomer- once the pigment has been incorporated into the formula, can
ates are separated into smaller aggregates and primary par- be a good indicator of stability; dispersions with pH values be-
ticles. The lower the surface tension of the vehicle in which tween 4 and 7.5 are more prone to have dispersibility/stability
the pigment is being incorporated, the lower the energy that issues, indicated by the Zeta potential value as it will most likely
will be needed to disperse the pigment. Deagglomeration is be between +30 and -30 mV. The addition of a pH modifier can
achieved through the use of mechanical energy developed by be necessary in some cases.
the use of high-speed dispersers and various types of grinding Formulas where the dispersion must be acidic due to the final
equipment. A Cowles blade fitted on the shaft of a high-speed application having a pH lower than 4 is recommended, and for
mixer can be an efficient means of dispersing a pigment. High alkaline dispersions a pH higher than 7.5 is good. The closer
Shear blades are a highly recommended type of Cowles blade to zero the Zeta Potential is, the more prone re-agglomeration
(Figure 4) which is well suited for pigment dispersion. Other will be with WB dispersions. Electrostatic stabilization is accom-
types of blades include a High Vane blade or a Combination plished by dispersion agents with cationic or anionic molecular
blade which also can be used depending on the viscosity of groups, e.g., quaternary ammonia salts and alkylpolyamines
the dispersion and the need to move/blend the raw materials (cationic) or polycarboxylic acids and sulfonated organic sub-
during processing. stances (anionic).
In order to ensure a good
laminar flow and increase the
efficiency of dispersion it is
recommended that the blade
diameter is approximately
1/3 of the tank diameter, and
also that the blade is approx-
imately 0.5 to 1.0 diameters
off the bottom of the tank.
The recommended tip speed Figure 4. High shear Cowles blade.
for a system with viscosity be- Steric Stabilization
tween 70-100 Krebs units is between 4,000 – 6,000 fpm. The Used in both water- and solvent-based systems, the addi-
following equation can be used to determine the tip speed: tive anchoring groups will adhere to the pigment surface. The
Shaft RPM x 0.262 x blade diameter (inches). Pigments with compatibility of the system is dependent on the functional seg-
a harder texture can be more finely dispersed by using a me- ments of the polymer that compose the hydrophobic portion.
dia mill, which produces significantly more shear, such as Regarding steric stabilization, the additive will physically reduce
horizontal, vertical and basket mills. In order to disperse the the mobility of the pigment particles and therefore avoid/mini-
pigment to a nano level, the use of 0.3-0.5 nm grinding media mize flocculation or re-agglomeration. This type of stabilization
is recommended. is accomplished mainly with nonionic dispersing agents.

Stabilization
Due to the increased surface area of the solid particles dur-
ing the deagglomeration/grinding stage, the pigments that are
deagglomerated need to be stabilized in order to avoid issues
such as flocculation, color shift, sedimentation and stability
loss. The stabilization process takes place by incorporating
dispersion additives which achieve stabilization through the
following mechanisms.

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 Four Steps to Effective Pigment Dispersions FEATURE

Amount of Surfactant Selection • Inorganic pigments (oxides, sulfides, silicates, etc.) -

Too much or too little of a surfactant can be detrimental to Dispersants containing acidic groups, i.e, phosphate, car-
the stability of a pigment dispersion. The determination of the boxy, or sulfate are recommended.
optimal level is based on the rule of 2-2.5 mg of polymeric dis- • Carbon blacks (diazonium surface treatment) - Dispersants
persant needed per square meter of pigment surface (Figure 5). containing nitrogen.
This rule must be applied initially, after which the formulator
is advised to do a ladder study to determine the optimal level Pigment Dispersibility – Co-Grinding vs.
based on viscosity changes, the occurrence of flooding and float- Single Pigment Dispersion
ing, oven stability and freeze-thaw stability evaluations when Pigment chemistries vary in texture and the amount of energy
necessary. required to achieve full color development will differ from one
to another. A good way to determine the pigment’s optimal dis-
persion time is by doing a dispersibility study in which the for-
mulator will determine the time and energy needed to develop
the pigment to its full strength by evaluating its coloristic prop-
erties. Figure 6 shows the dispersibility of selected PB 15:2, PG7,
PY74 and PY 65 pigments. These pigments were evaluated for
strength and color in 30 minute intervals, where the dispersion
made with 15 minutes of grind time was used as the standard.
Pigments were ground beyond their optimal level which can be
confirmed when a loss of color strength is observed. This type of
Figure 5. Selecting the amount of surfactant. evaluation is important in determining the optimal processing
time for a pigment in a selected formulation. As can be seen in
Dispersing Agent Selection Figure 6, some pigments develop their strength and color faster
The recommended type of dispersant adhesion group depends than others. This is a key factor to consider when co-grinding
on the pigment surface. The following suggestions may help for- pigments as it may not be possible to achieve optimum color
mulators select the most effective dispersant chemistry for the development and consistency by this means. It is for this reason
pigment being evaluated. that single pigment dispersions are recommended as the best
• Organic pigments (aromatic surface treatment) - Dispersants means of obtaining the full color development value of a given
containing phenyl or naphthyl groups are recommended. pigment.

Figure 6. Dispersibility study.

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FEATURE Four Steps to Effective Pigment Dispersions

Table 3. Physical properties for various CI pigments.

Additionally, not all pigments have the same behavior in a spe-

cific coatings formula due to variations in their physical (i.e., sur-
face area, oil absorption, particle size) and chemical properties (i.e.,
chemical structure, surface treatment) as show in Table 3. It should
be noted that there is no direct correlation between the physical
properties of various color indexes and this provides additional rea-
soning as to why co-dispersion of pigments is not recommended.

Conclusion
Pigments are a key component in a coating formulation and proper
selection and dispersion is critical in determining the performance
of the coating. In a recent study regarding the requests for technical
assistance received over the past 2 years, it was noted that near-
ly 80% of the formulation issues were resolved by modifying or
changing the pigments being used in the formula. It is a mistake to
assume that all pigments will perform the same from one formula
to another. This assumption could also prove to be costly with re-
spect to the coating development and manufacturing process. The
keys to achieving a stable coating with the optimum performance
and value are: proper pigment selection, proper additive selection,
and the appropriate means to achieve complete dispersion. It is for
this reason that we strongly suggest that formulators consult with
their raw material and equipment suppliers to better understand
their options and potential issues when formulating a coating. CW

References
1. BASF, little helpers love great achievement - Practical Guide
to Dispersing Agents, 2016
2. Hunger, Klaus, Thomas Heber, Martin U. Schmidt, Friedrich
Reisinger, and Stefan Wannemacher. Industrial Organic Pigments
Production, Properties, Applications.Weinheim, Bergstr; Wiley-
VHC, 2013. Print.
3. Surface Coatings. London: Chapman & Hall, 1993. Print.
4. “Surface Tension Values of some Common Test Liquids for
Surface Energy Analysis”. N.p.,n.d. Web 29 June 2017

Acknowledgements
The author would like to acknowledge Frank Lavieri, Mark
Freshwater, Ralph Svenningsen, and Belinda DeSousa from
LANSCO COLORS for their contributions.

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