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DISPERSING PROCESS

High quality coatings of high brilliance and color strength are characterized by a perfect pigment dispersion, optimal pigment particle
size, and long-term stabilization of the dispersed particle in the formulation.

The dispersion of a pigment in liquid coatings, paints or inks to produce stable suspension, can be divided into the following three
processes:

Mechanisms in the dispersion process

Pigment wetting: All of the air and moisture is displaced from the surface and between the particles of the pigment aggregates
and agglomerates (clusters) and is replaced by the resin solution. The solid/gaseous interface ( pigment/air) is transformed into
a solid/liquid interface (pigment/resin solution).

Grinding stage: Through mechanical energy (impact and shear forces), the pigment agglomerates are broken up and disrupted
into smaller units and dispersed (uniformly distributed).

Stabilization of pigment suspension: The pigment dispersion is stabilized by dispersing agents in order to prevent the
formation of uncontrolled flocculates. The resultant suspension is stabilized due to the adsorption of binder species or molecules
at the pigment surface.

The choice of the more efficient dispersing agents is strongly related to the chemical nature of the pigment and the resin solution (for
the paint manufacturer, it is essential to distinguish between organic and inorganic types). This topic is discussed further in Formulating
an optimum dispersion.

Pigment wetting

The wetting step consists of replacing the adsorbed materials on the surface of the pigments and inside the agglomerates (water,
oxygen, air, and/or processing media) by the resin solution.

The complete wetting out of the primary sized pigments particle helps to enhance the technical performance of a liquid coating that
depends very much on interaction between the pigment particles and the binder system. Dispersing additives, which adsorb on the
pigment surface, facilitate liquid/solid interfacial interactions and help to replace the air/solid interface by a liquid medium/solid interface.

Replacement of air and water by the resin

The efficiency of the wetting depends primarily on the comparative surface tension properties of the pigment and the vehicle, as well as
the viscosity of the resultant mix. The adsorption mechanism depends on the chemical nature of the pigment and the types of
dispersing agents used. (visit dispersants families)

Thermodynamic consideration:

The spontaneous wetting process (on wetting solid surfaces) is driven by minimization of the free surface energy. Forced wetting
processes (in non-wetting conditions) require the application of external force, and spontaneous de-wetting will take place when the
force is removed.

Thermodynamic condition for wetting requires the work of liquid/solid adhesion (Wa) to be as high as possible and, for unlimited
wetting, at least more than a half of the work of cohesion (Wk) is required: Wa> Wk.

Velocity of penetration of a liquid into a powder can be explained in terms of the Washburn equation (1921):

Washburn equation

where h is the depth (or height) of penetration during the time t, - is the surface tension of the wetting liquid, - its viscosity, - the
wetting angle, r - mean radius of capillaries, C - structural coefficient, associated with parameters of the porous structure, W - energy
(heat) of wetting.

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The wetting step of dispersing processes can be intensified by the use of wetting agents and/or binders with lower viscosity and
surface tension. On the other hand, a resting of pigment/binder premixes prior to their dissolving or grinding helps to accomplish the
wetting stage and always eases and accelerates dispersing processes.

Grinding stage

After the wetting stage, it is necessary to de-aggregate and deagglomerate the pigment particles. This is usually accomplished by
mechanical action provided by high impact mill equipment.

In the grinding stage, the cohesive forces inside the agglomerates have to be overcome. Energy is added to the system and therefore
smaller particles (with a larger interface to the resin solution) are formed. This results in loosened inter-particle contact durability, that
eases the destruction of pigment clusters under the action of shear stresses, applied in dissolvers, mills etc.

Pigment dispersing

As the pigment powder is broken down to individual particles by mechanical shear, higher surface areas become exposed to the
vehicle and larger amounts of additives are required to wet out newly formed surfaces.

Once dispersed, the primary particles have a tendency to re-agglomerate. This process is called flocculation. From a structural
standpoint, the flocculates are very similar to the agglomerates; nevertheless, the interstitial spaces between the pigments are now
filled with resin solution rather than air.

The grinding process can be regarded as a de-flocculation process. In the absence of stabilizing agents, effects such as reduced color
strength, decreased gloss, and altered rheology then may occur.

Stabilization of pigment suspension - Overview

1. overview
2. Colloidal stabilization
3. Electrostatic stabilization
4. Steric stabilization

The aim of stabilization is to keep the pigment particles separated as achieved in the last step, and to control the degree of pigment
particle size through the let-down and filling phase, storage and and later in coating films during film formation.

Flocculated pigment suspensions are characterized by the non-uniform spatial distribution of particles, which are allowed for immediate
interparticle contacts. This results in worse rheology (structural viscosity, blob-flow), low storage stability (in paints) and poor optical
and color properties (in coatings).

It is well known, that even well grinded but not stabilized, fine particle size pigment suspension can easily be destroyed by the letting
down into a non-suitable paint base: flocculation typically breaks down when shear is applied and will form again, when the shear is
removed.
Therefore, immediately after grinding pigment suspensions must be stabilized by the addition of additives, whether they are intended to
be used immediately in let-down or as pigment preparations (colorants).

Dispersing agents avoid flocculation

Stabilization is achieved through absorption of stabilizing molecules on the pigment surface, so that repulsive forces prevent other
particles from approaching close enough for the attractive van der Waals forces to cause agglomeration. To know more about the
factors influencing the stability, take a look at the colloidal stabilization.

There are two principal mechanisms for the stabilization of pigmented dispersions:

Electrostatic stabilization: electrostatic stabilization occurs when equally-charged local sites on the pigment surface come into
contact with one another. Two particles having the same charges give a repelling effect. The resulting Coulomb-repulsion of the
charged particles allows the system to remain stable.

Steric stabilization A pigment is said to be sterically stabilized when the surface of the solid particles are completely covered by

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polymers, making particle-to-particle contact impossible. Strong interactions between polymers and solvents (organic solvent or
water) prevent the polymers from coming too closely into contact with one another (flocculation).

Stabilization of pigment suspension - Colloidal stabilization

Stability of dispersion is a result of interpay of the heat (kinetic) energy of particles, attractive interparticle forces and repulsive forces,
all act persistently between any neighboring particles.

Possessing kinetic (thermal) energy and being subjected to Brownian movement, colloid particles persistently approach one another
and collide . Without restricting factors their approachment may occur so close that even relatively short-range van der Waals forces
will be capable to joint particles irreversible, thereby destroying the dispersion. Alternatively, having a certain source for interparticle
repulsion, capable to prevent particles from immediate contacts,a dispersion can persist indefinitely without significant changes in
particle size and properties.

Attraction/ repulsion between two particles

The existence of sufficient repulsive forces between neighboring colloid-size particles is therefore a matter of life or death for any
dispersion. Those repulsive forces arise when lyophilized near-particle layers interfere : the persistent exchange of the molecules of
water between the near-surface layer and the non-changed water outside the layer creates the repulsive force, similar to osmotic
pressure (Figure 1). The repulsive forces can be of different nature:

Compression of electrical double layers, which surround the particles,

Osmotic pressure in non-ionically stabilized system (Derjagin, Fischer),
Chain elasticity in the dispersions stabilized with polymer surfactants, entropic repulsion (Mackor),
Barrier-type stabilization with polymeric dispersants.

Practically, three systems of coating stabilization can be used in aqueous medium:

1. the use of ionic surfactants or chemical lyophilizers which produce carboxy, ammonium etc. ions, see electrostatic stabilization
2. non-ionic stabilization, owed to the adsorption of non-ionic surfactants or corresponding chemical modification of the polymer
phase (or surface only) with non-ionic lypophilic fragments, see steric stabilization
3. combined ionic non-ionic stabilization, which is widely used in technologies of latexes, emulsions and paints, allowing to achieve
prominently high disperse stability toward the action of various destabilizing factors.

As we are able to calculate of interparticle forces, we can characterize dispersion stability via "potential curves" (Figure), where
potential energies of attractive and repulsive forces and total interaction are expressed as a function of distance between particles
"Potential barrier" is the energy particles shouldn't be able to overcome on expense of their heat energy in order to maintain the
dispersion steady.

Potential energy curves between two particles

Stabilization of pigment suspension - Electrostatic stabilization

The pigment particles in the liquid paint carry electrical charges on their surfaces. Through the use of additives, it is possible to
increase the charges and, furthermore, to make all pigment particles equally charged.

Classic colloidal science explains electrostatic stabilization in terms of an electrical double-layer. A charge is generated on the pigment
surface, and a more diffuse cloud of oppositely charged ions develops around it. As two particles approach each other the charge
effectively provides a barrier to closer particle interactions. Stabilization increases along with the thickness of this layer.

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Electrostatic stabilization

Chemically speaking, the additives used for dispersion in such systems are polyelectrolytes - high molecular weight products which
contain a multitude of electrical charges in the side chains.

In addition to polyphosphates, many polycarboxylic acid derivatives are utilized as polyelectrolytes in the coatings industry. The
polyelectrolytes adsorb onto the pigment surface and consequently transfer their charge to the pigment particle. Through electrostatic
repulsion between equally charged pigments, the flocculation tendency is dramatically reduced so that the deflocculated state is
stabilized.

Electrostatic stabilization is effective in media of reasonably high dielectric constant, principally water; although even in water-based
coatings systems, steric stabilization, or a combination of steric and charge stabilization will often provide better overall performance.

Stabilization of pigment suspension - Steric stabilization

Charge stabilization is not be effective in media of low dielectric constant (the vast majority of organic solvents and plasticisers), and
steric stabilization is required to maintain dispersed particles in a stable non-flocculated state.

Steric stabilization relies on the adsorption of a layer of resin or polymer chains on the surface of the pigment. As pigment particles
approach each other these adsorbed polymeric chains intermingle and in so doing they lose a degree of freedom which they would
otherwise possess. This loss of freedom is expressed, in thermodynamic terms, as a reduction in entropy, which is unfavorable and
provides the necessary barrier to prevent further attraction. Alternatively one can consider that, as the chains intermingle, solvent is
forced out from between particles. This leads to an imbalance in solvent concentration which is resisted by osmotic pressure tending to
force solvent back between the particles, thus maintaining their separation.

Steric stabilization
One fundamental requirement of steric stabilization is that the chains are fully solvated by the medium. This is important because it
means the chains will be free to extend into the medium, and possess the above mentioned freedom. This requirement is usually
expressed by saying that the medium needs to be a better-than-theta solvent (i.e. a relatively good solvent) for the polymer chain. In
systems where the chains are not so well solvated they will prefer to lie next to each other on the surface of the pigment, providing a
very much smaller barrier to inter-particulate attraction.

The greater steric repulsion generated by the addition of polymeric dispersants moves the minimum in the Potential Energy Curve, and
thus reduces the overall viscosity.

This stabilization mechanism occurs in solvent- based systems and in water-reducible systems which contain solvated resins. Through
specific structural elements composed of pigment affinic groups (polar) and resin-compatible chains (nonpolar), these dispersing
agents exhibit definitive surface active properties. In other words, they not only stabilize the pigment dispersion, but they also function
as wetting additives.

Formulating an optimum dispersion

Dispersing agents are not just additives to conventional millbases. The choice of the most suitable dispersing agents is sometimes
difficult and their usage require sometimes specific guidelines.

In this part of the Dispersion Center we will discuss the main items that have to be taken into account when formulating a pigment

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solution. To learn more about how to formulate an optimum dispersion, click on the links below:

Dispersant Choice
Grinding medium
Pigments**/Fillers
Order of addition
Surface Area

Dispersant Choice

With any effective polymeric dispersant, the two-component structure is made up from a polymeric chain and a pigment affinic anchor
group. The nature of the polymeric chain is critical to the performance of the dispersant. If the chains are not sufficiently solvated, then
they will collapse on to the pigment surface, allowing the particles to aggregate or flocculate. This need for compatibility with the
medium extends throughout the final drying stages of any applied coating. If it ceases to be compatible, flocculation may occur leading
to reduced gloss and tinctorial strength.

In order to meet the need for good compatibility, several different polymer chains can be utilised effectively covering the variety of
solvents encountered. The structure of some dispersing additives can be described as one or more spatially close anchor groups with
a number of polymer chains. Other dispersing additives are designed to improve the flocculation resistance of pigments (particularly
non-polar, organic pigments) and have higher molecular weights through the attainment of more complex polymer like structures.

The molecular weight of the dispersant is sufficient to provide polymer chains of optimum length to overcome Van der Waals forces of
attraction between pigment particles. If the chains are too short, then they will not provide a sufficient thick barrier to prevent
flocculation. This will lead to an increase in viscosity and a loss of tinctorial properties.

Dispersant choice involves a number of criteria, and the nature of the pigment, the resin involved and the solvent can all affect the
performance of the polymeric additive.

Grinding Medium

Anchoring of the polymeric dispersant to the pigment surface can be affected by competition between the resin and dispersant for the
surface of the particle. Once the anchor group of the dispersant is attached to the pigment surface it will remain firmly attached.
Molecules of resin, however, are transiently adsorbed on the surface of the pigment, and even though not firmly anchored they can
hinder the dispersant anchoring process.

Minimal-resin solids (or resin-free systems) can be used in the dispersion, as long as good let-down stability is sufficiently available.
Dispersant technology is now more advanced, and in some systems dispersing without resin is possible.

As an example Avecia SOLSPERSE 43000 polymeric dispersant would be recommended for dispersing various pigments in resin-free
dispersions for general industrial and decorative water-based paints. A key benefit of using this kind of product is the wide resin
compatibility it offers in various resin systems, including polyester, acrylic, polyurethane, alkyd and epoxy.

Pigments / Fillers

The choice of dispersant is also related to the surface nature of the pigment. The polarity of the surface of the pigment differs from
organic (non-polar) to inorganic (more polar), and this means that the nature of the dispersant anchor group is critical for optimum
adsorbtion. The choice of anionic anchor group should allow for better performance with inorganic pigments and a cationic anchor
group should be more appropriate for organic pigments.

The surface area of the pigment also affects the level of dispersant used, and in general, if too little is used then the full benefits will not
be realized. If too much is used, it can be shown that the thickness of the protective barrier is actually reduced as a result of
overcrowding on the pigment surface. Therefore the use of an excess level of dispersant actually leads to final coating properties which
are inferior to those obtained with an optimized dosage. Furthermore, film properties such as adhesion or hardness can be adversely
affected by the use of an excess of dispersant because of the free molecules in the drying film.

The Table below show a range of typical starting point formulations for inorganic and carbon black based decorative universal tinters
using polymeric dispersant (Avecia Solsperse).

Pigment C.I. No. Pigment % Talc Solsperse 6100 Solsperse 6200 Solsperse 6300 Antifoam Water
Iron Oxide - Yellow PB7 30.0 - - 16.5 5.5 0.3 35.7
Carbon Black PB7 30.0 - - 16.5 5.5 0.3 35.7
Bismuth Vanidate PY184 50.0 10.0 8.0 - 8.0 - 24.0
Titanium Dioxide PW6 58.0 5.0 4.0 - 4.0 - 29.0

Order of Addition

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The usual way of incorporation of dispersant in a coating formulation would be in three stages:

1. Mix the dispersant in the millbase solvent or in the resin/solvent mixture,

2. Add any other additives,
3. Add the pigment, in stages, and disperse in the normal manner.

In case you want to optimize a Polymeric dispersant millbase, 4 stages are involved. The following example explaining using Avecia
Solsperse products (referred to as a ladder series).

Stage 1 - Calculation of % AOWP of Polymeric hyperdispersant

The theoretical amount of Polymeric dispersants (e.g. Avecia Solsperse) agent required in a millbase is 2mg Polymeric agent per sq.
meter pigment surface area.

Example:
Pigment surface area - 70m2/g
Therefore 140mg Polymeric agent/1g pigment are required = 14g agent/100g pigment i.e. 14% AOWP
Synergists (if required) are used with the Polymeric in ratios between 4:1 and 9:1 [Polymeric:synergist].

Stage 2 - Determines the higher pigment content required

(Can be performed on lab. shaker e.g. Red Devil)

Using the % AOWP of Polymeric agent (calculated above) + synergist (if required) prepare a series of
millbases with increasing pigment contents in a GRINDING MEDIUM containing APPROXIMATELY 10%
SOLID RESIN. Note: the ratio of [hyperdispersant:pigment] must be maintained.

The pigment concentration giving the same viscosity as the control should now be used in Stage 3.

Stage 3 - Determines optimum amount of Solsperse Hyperdispersant

(Can be performed on lab. shaker e.g. Red Devil)

Using the higher pigment content established in Stage 2: Carry out a series of Polymeric agent dosages
around the theoretical % AOWP (+ any synergist required) to optimize the required agent dosage. Determine
the best hyperdispersant dosage by measuring desired property.

Stage 4 - Optimizes final pigment concentration

(Should be done in equipment representative of bulk production)

Using the % agent on weight of pigment established in Stage 3: Prepare final ladder series of pigment
contents - maintaining [agent:pigment] ratio determined in Stage 3 to determine optimum amount which gives
best final product.

Surface Area

As a general rule, 2-2.5mg of polymeric dispersant, per square meter of pigment surface area will be close to the optimum amount
required.

A ladder series of polymeric dosage levels should be evaluated based around this 2-2.5mg/m2 level. Measurement of dispersion
viscosity will show a minimum at the optimum dosage; although it is also possible to measure gloss or color strength of the coating
which will show a maximum at the same optimum dosage.

2
Typically, the surface area of phthalocyanine blue pigment is 50 m /g:

So a typical dosage would be :

Phtalocyanine blue pigment 30.0 (i.e: 10% active dispersant on the weight of pigment)
Polymeric dispersing agents 3.0

Dispersants families - Introduction

The choice of the dispersing agents is a key issue in the coating and ink industry. Formulators have to find the most suitable products
for their formulation taking into account the final application of their coating, the coating system (water based, solvent based, etc.) and
the other additives.

The role of the dispersing agents is to enhance the dispersion process and ensure a fine particle size in order to stabilize pigments in

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the resin solution. As explained earlier, an efficient dispersant has to perform the three main functions : pigment wetting, dispersing,
and stabilizing. Dispersing agents generally differ for aqueous and solvent-based coatings.

In term of chemical structure one can divide dispersing agents into the two following classes:

Polymeric dispersants
Surfactants

The main differences of those two types of dispersants being the molecular weight, the stabilization mechanism and the resulting let
down stability.

Polymeric disperants - Description

1. General description
2. Anchor groups
3. Polymeric chains

Polymeric dispersants stabilize paints, coatings and ink systems via a steric stabilization mechanism previously described. They have a
two-component structure which combines the following two very different requirements:

1. It must be capable of being strongly adsorbed into the particle surface and thereby possess specific anchoring groups
2. The molecule must contain polymeric chains that give steric stabilization in the required solvent or resin solution system.

There are many copolymer/functional polymer configurations that might be expected to give effective polymeric dispersants. Six
possible arrangements are illustrated in Figure 1:

Figure 1: These anchor onto the particle surface either through functional
groups (b and c) or through polymeric- blocks (a and d-f). The steric
stabilization polymer chain is either anchored to the particle surface at one
end (b, d, and f) or at both ends (a, c, and e).

Polymeric dispersants differentiate themselves from the other types of dispersing agents through considerably higher molecular
weights. Because of its structural features, a polymeric dispersant is bound to numerous sites at the same time, forming durable
adsorption layers upon many pigment particles. Optimal steric stabilization is achieved when the polymer chains are well solvated and
properly unfurled, therefore they must be highly compatible with the surrounding resin solution. If this compatibility is obstructed, the
polymer chains collapse causing the steric hindrance and the resulting stabilization to be lost.

In order for additives to be effective, the adsorption into the pigment surface must be durable and permanent. The surface properties
of the pigment particles are therefore crucial to the additive's effectiveness:

With pigments possessing high surface polarities, such as inorganic pigments that are ionically constructed, the adsorption of
any dispersing additive is relatively easy.
However, for pigments with nonpolar surfaces, such as organic pigments whose crystals are composed of nonpolar individual
molecules, a proper adsorption is rather difficult to obtain with conventional additives. The wide range of anchor groups that
polymeric dispersants provide make them very efficient to anchor on pigments with nonpolar surfaces.

In the traditional method of stabilizing pigments in water, the stabilizing charges used are often disturbed by impurities, such as other
ions, or the presence of other pigments with different zeta-potentials. This leads to a destabilizing effect, caused by the reduction of
the repulsive forces. Steric stabilization can avoid this issue, making polymeric dispersants very useful for dispersing all types of
pigments, even the organic ones, that are very difficult to be deflocculated by traditional wetting and dispersing additives.

The level of the polymeric dispersant used is very important, since performance depends on the optimum amount of saturation by the
dispersant of the pigment surface.

Polymeric disperants - Anchor groups

It does not matter whether the previously discussed polymer chains are provided by polymeric dispersants containing either single
chains or up to many hundreds of chains. The essential requirement is that the chains are successfully anchored to the pigment
surface, and that the surface of the particles are covered with a sufficient density of chains to ensure minimum particle-particle
interaction.

As shown in the picture below the anchoring function of a polymeric dispersant may be a single functional group, or an oligomeric or
polymeric chain:

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Schematic molecular structure of dispersants

Studies have shown that steric stabilization chains anchored at only one end are most efficient. Given that steric stabilization is
entropically driven in non aqueous media, this conclusion is not surprising. Anchoring both ends of the polymer chain will clearly inhibit
its freedom of movement, even before it starts to intermingle with the steric stabilization chains of an adjacent particle.

Anchoring Mechanisms

As the nature of the surface of pigments differ, according to their chemical type, many different chemical groups can be found as
anchor groups for polymeric dispersants. This wide range of anchoring possibility enables polymeric dispersants to disperse inorganic
pigments as well as pigments with polar surfaces. The actual anchoring can then take place through a variety of mechanisms:

Anchoring Through Ionic or Acidic/Basic Groups.

When a pigment particle has a relatively reactive surface (eg: inorganic pigments) it is possible to form an ion-pair bond between a
charged site on the particle surface and an oppositely charged atom or functional group on the dispersant. This situation is illustrated in
Figure 1a and is effective because organic solvents normally have a relatively low dielectric constant, so charge separation is not
favored.

Figure 1: Anchoring through Ionic or Acidic/Basic Groups

In fact, many inorganic pigment particle surfaces are quite heterogeneous, with both positive and negative sites. It is therefore quite
common to find that a pigment can be dispersed by using polymeric dispersants with either negatively or positively charged anchor
groups, as illustrated in Figures 1b and 1c .

Examples of functional groups that can be used to anchor polymeric chains to charged or acidic/basic surfaces include amines;
ammonium and quaternary ammonium groups; carboxylic, sulfonic, and phosphoric, acid groups and their salts ; and acid sulfate and
phosphate ester groups.

Anchoring Through Hydrogen-Bonding Groups.

Although most organic pigment particles and some relatively inert inorganic particles such as quartz do not have charged sites on their
surface, they may have hydrogen-bond donor or acceptor groups, such as esters, ketones, and ethers It is therefore possible for a
hydrogen bond between the particle and an anchor group on the polymeric dispersant to form. Even individual hydrogen bonds will be
weak. A strong interaction may be developed between the pigment particle and a polymeric dispersant containing many hydrogen-bond
donors and acceptors in its anchor chain, see figure 2

Figure 2: Anchoring by hydrogen bonding to a

polymeric group.

Polyamines and polyols are used to anchor via hydrogen bonding, either donor or acceptor. Polyethers can be used to anchor via
hydrogen-bond acceptance.

Anchoring Through Polarizing Groups.

An interaction can also take place between polarized or polarizable groups on an organic pigment particle surface, and similarly
polarized or polarizable groups on the anchoring function of the polymeric dispersant. Again, these interactions will often be relatively
weak, but strong interaction may be developed with a polymeric dispersant possessing an anchor chain composed of several of these
groups.

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Figure 3 : Anchoring through polarizing groups

Polyurethanes are commonly used as polarizable anchor groups.

Anchoring Through Solvent-Insoluble Polymer Blocks.

It is possible to anchor a polymeric dispersant onto a pigment particle surface simply via van der Waals interactions and without
recourse to ionic, hydrogen-bonding, or polarizing effects. The polymeric block within the dispersant must simply be insoluble in the
medium, see figure 4.
It is possible, for example, to disperse a pigment in an aliphatic hydrocarbon using a polymeric dispersant based on poly(tert-
butylstyrene) chains, which are solvent-soluble, and polystyrene chains, which are not solvent-soluble.

Figure 4 : Anchoring through solvent insoluble

polymer blocks.

Polyurethane anchor groups are said to operate via this mechanism. In fact, it is very difficult in practice to distinguish between this and
the previous two adsorption mechanisms. Most polymeric anchor chains probably anchor via a mixture of electrostatic forces (hydrogen
bonding and/or polarization) and van der Waals forces. One of the mechanisms may be dominant, but the most effective polymeric
dispersants probably maximize the effect from all three mechanisms.

Derivatives of the Dispersed Particle.

Some organic pigments (phthalocyanine blues and dioxazine violet are good examples) are not very responsive to any of the anchoring
mechanisms just described . In such systems it can be very difficult to obtain anything other than dispersions of relatively low pigment
concentration, and these dispersions are prone to flocculation on letdown. Then the only way to solve the issue is by modifying the
chemical structure of the particle itself in order to make it act as the anchor group. This system works most effectively on higher
molecular weight pigments with large planar structures, because the anchor group can pack very closely onto the pigment particle
surface and maximize the van der Waals attractive forces between particle and anchor groups.

The copper phthalocyanine molecule has been modified by the addition of polymeric chains to give a particularly effective dispersing
agent for copper phthalocyanine pigments. Alternatively, derivatives with substituted ionic groups can be used to activate the surface of
a pigment and make it receptive to the charged anchor group of a polymeric dispersant. This mechanism is illustrated in the figure 5
below.

Figure 5 : synergists

Polymeric disperants - Polymeric chains

The nature of the polymeric chain is critical to the performance of polymeric dispersants. If the chains are not sufficiently solvated, then
they will collapse on to the pigment surface allowing the particles to aggregate or flocculate. The need for compatibility with the
medium extends throughout the final drying stages of any applied coating. If it ceases to be compatible, flocculation may occur leading
to a decrease of surface properties such as losses in gloss and tinctorial strength, etc.

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The molecular weight of the polymeric dispersants must be sufficient to provide polymer chains of optimum length to overcome Van der
Waals forces of attraction between pigment particles:

If the chains are too short, then they will not provide a sufficiently thick barrier to prevent flocculation. It means that too low a
molecular weight will cause dispersion instability and will lead to an increase in viscosity and a loss of tinctorial properties.
When the chains are too long, they have a tendency to "fold back" on to themselves. Too high a molecular weight will also
give reduced performance.

Ideally the chains should be free to move in the dispersing medium. As previously said: chains with anchor groups at one end only, have
shown to be the most effective in providing steric stabilization.

Finally, for good surface coating properties and performances, the polymer must be fully compatible with the coating resin after the
solvent has evaporated off and the resin has been cross-linked.

Chemistry of the Steric Stabilization Chain

In order to meet the need for good compatibility, several different polymer chain types are utilized in the polymeric dispersant range,
effectively covering the variety of solvents encountered.

Examples, spanning the range of solvent from nonpolar aliphatic hydrocarbons to alcohol/water includes:

Polyisobutylene
Polyesters
Poly methyl methacrylate
Polyethylene oxides

The amount of polymeric dispersant used is also an important parameter to consider. Many surface coating systems will tolerate a
polymeric dispersant at low levels of addition, but problems will be caused at higher loading. Some systems are particularly tolerant to
the presence of polymeric dispersants. Long-oil alkyd resins for air-drying paints and resins used in publication gravure inks and offset
lithography inks are all good in this respect. Similarly, paper or wooden substrates tend not to give major adhesion problems. Higher
quality stoving or two-pack paint systems and many packaging ink systems pose much more severe requirements.

It is therefore vital that after an initial screening of polymeric dispersants for rheological and color/gloss changes, their effect on the
performance of the surface coating be checked by the appropriate tests.

Surfactants

Surfactants are conventional low molecular weight dispersing agents. Surfactant molecules are able to modify the properties and, in
particular, they lower the interfacial tension between the pigment and the resin solution.

This surface activity arises because the surfactants' structure consists of two groups of contrasting solubility or polarity. In aqueous
systems, the polar group is known as a hydrophilic group and the non-polar group as hydrophobic or lipophilic. In non-aqueous
systems, the polar group is known as the oleophobic group and the non-polar group as oleophilic. Surfactants are classified according
to their chemical structure and, more specifically, their polar group: anionic, cationic, electroneutral and non-ionic (see figure 1).

As with the polymeric dispersing agents, their effectiveness is determined by:

The absorption of the polar group onto the pigment surface. The anchoring groups can be amino, carboxylic, sulfonic,
phosphoric acids or their salts.
The behavior of the nonpolar chain in the medium surrounding the particle. This part of the molecule (aliphatic or aliphatic-
aromatic segments) must be highly compatible with the binder system.

The stabilization mechanism of surfactant-like dispersing agents is electrostatic: the polar groups forming an electrical double layer
around the pigments particles. Due to the Brownian movement the pigment particles frequently encounter each other in the liquid
medium thus having a strong tendency to re-flocculate on the let down stage.

Because of their chemical structure (eg: low molecular weight) and the electrostatic method of stabilization, surfactants may cause the
following defects:

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_ Water sensitivity: Surfactants generally have a tendency to provide water sensitivity to the final coating, thus making
them inappropriate for use in outdoor applications.
_ Foam formation: Many surfactants generate foams which lead to surface defects (e.g.. fish eyes, craters) on the final
coating. If foaming occurs at the milling stage it can also cause a loss of production capacity.
_ Interference with intercoat adhesion.

Over the past years specific surfactants have been developed to minimize these defects, and some provide other advantages to the
final paints such as defoaming/dearation or difficult substrate wetting.

The most widely used surfactants for pigment dispersion in coating formulations are:

Fatty acid derivatives

Phosphate esters
Sodium polyacrylates / polyacrylic acid
Acetylene diols
Soya lecithin

For more information, click on the links above.

Fatty Acid Derivatives

Nonionic fatty acid derivatives such as the alkyl phenol ethoxylates (APEs) and fatty alcohol
ethoxylates (FAEs) are one of the main types of surfactant used in coating applications as
wetting and dispersing agents for pigment particles, particularly in decorative emulsion
paints and water based inks.

Typical structures of fatty alcohol ethoxylates (FAE) and alkyl phenol athoxylates

These type of surfactants help stabilizes the aqueous dispersions of organic pigment
particles by the steric stabilization mechanism. Most of the time, they are used in
combination with an anionic surfactant which provides stabilization of the dispersion by the
electrostatic stabilization mechanism, but concerns over the APEs nonionic surfactants has
led to the recent apparition of new product blends advertised as APE free.

Coating formulated with these types of nonionic dispersing agents are sometimes subjected
to foaming, water sensitivity, intercoat adhesion and blistering

Phosphate Esters

Due to the anionic structure of the phosphate group, phosphate esters dispersing agents
provide steric stabilization to the pigment solution. It offers the following benefits:

Efficient dispersing agents in waterborne coatings

Good wetting properties on difficult surfaces
Anti-rusting properties
Effective with polymeric rheology modifiers

The chemical structure of various phosphate esters are shown in the figure below.

Structures of various phosphate esters

Phosphate esters surfactants are used in waterborne coatings for their wetting and
dispersing properties and the economical alternative to other dispersing system that it
provides. Phosphate esters are sometimes used in combination with non-ionic surfactants to
enhance dispersion stability, especially reduce reflocculation issues.

Polyacrylic acid/ Sodium polyacrylate

Polyacrylic acid (PAC) and salts of polyacrylates are anionic surfactants used as
dispersants in water based coating and ink formulations. They generally consist of low
molecular weight polymers that are able to keep the pigment particles suspended in the
resin solution by imparting a negative charge to the particles (electrostatic stabilization).

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Polyacrylic Acid structure and conversion to sodium polyacrylate

Acetylene Diols

To reduce the side effects of standard surfactant types of dispersing agent such as
foaming, oligomeric acetylenic ethoxylate glycols have been developed with multi-functional
properties and especially defoaming property which benefit water based coatings:

defoaming/low foam
excellent wetting
reduced millbase viscosity/allows higher pigment loading
improved color strength development
enhanced flow and levelling
reduced water sensitivity

The multi-functional properties of the gemini surfactant are related to its unique chemical
structure (Carbon-Carbon triple bond, two symmetrical oxygen atoms, ethoxylate branched
chains) containing two hydrophobic groups and two hydrophilic groups attached by a short
chain coupler.

Typical structure of ethoxylated acetylene diols

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