How to disperse and stabilize pigments

http://www.inkline.gr/inkjet/newtech/tech/dispersion/

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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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. In the grinding stage. the primary particles have a tendency to re-agglomerate. Therefore. that eases the destruction of pigment clusters under the action of shear stresses. This results in loosened inter-particle contact durability. From a structural standpoint. Flocculated pigment suspensions are characterized by the non-uniform spatial distribution of particles. when the shear is removed. The resulting Coulomb-repulsion of the charged particles allows the system to remain stable. overview Colloidal stabilization Electrostatic stabilization Steric stabilization The aim of stabilization is to keep the pigment particles separated as achieved in the last step. which are allowed for immediate interparticle contacts. The grinding process can be regarded as a de-flocculation process. 3. applied in dissolvers.inkline. higher surface areas become exposed to the vehicle and larger amounts of additives are required to wet out newly formed surfaces. This is usually accomplished by mechanical action provided by high impact mill equipment. mills etc. effects such as reduced color strength. take a look at the colloidal stabilization. Steric stabilization A pigment is said to be sterically stabilized when the surface of the solid particles are completely covered by 2 of 12 07/03/2011 3:34 PM . the interstitial spaces between the pigments are now filled with resin solution rather than air. that even well grinded but not stabilized. whether they are intended to be used immediately in let-down or as pigment preparations (colorants). low storage stability (in paints) and poor optical and color properties (in coatings). 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. 2. and altered rheology then may occur. In the absence of stabilizing agents. To know more about the factors influencing the stability. Stabilization of pigment suspension .gr/inkjet/newtech/tech/dispersion/ The wetting step of dispersing processes can be intensified by the use of wetting agents and/or binders with lower viscosity and surface tension. the cohesive forces inside the agglomerates have to be overcome. Pigment dispersing As the pigment powder is broken down to individual particles by mechanical shear. This process is called flocculation. immediately after grinding pigment suspensions must be stabilized by the addition of additives. the flocculates are very similar to the agglomerates. 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. Two particles having the same charges give a repelling effect. it is necessary to de-aggregate and deagglomerate the pigment particles. and to control the degree of pigment particle size through the let-down and filling phase. decreased gloss. 4. On the other hand. Energy is added to the system and therefore smaller particles (with a larger interface to the resin solution) are formed.Overview 1. Once dispersed.How to disperse and stabilize pigments http://www. blob-flow). It is well known. storage and and later in coating films during film formation. nevertheless. This results in worse rheology (structural viscosity. 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.

A charge is generated on the pigment surface. owed to the adsorption of non-ionic surfactants or corresponding chemical modification of the polymer phase (or surface only) with non-ionic lypophilic fragments. As we are able to calculate of interparticle forces. furthermore. making particle-to-particle contact impossible. Classic colloidal science explains electrostatic stabilization in terms of an electrical double-layer. Stabilization increases along with the thickness of this layer.Electrostatic stabilization The pigment particles in the liquid paint carry electrical charges on their surfaces. similar to osmotic pressure (Figure 1). Alternatively. emulsions and paints. 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. all act persistently between any neighboring particles. colloid particles persistently approach one another and collide . allowing to achieve prominently high disperse stability toward the action of various destabilizing factors. capable to prevent particles from immediate contacts. 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. The repulsive forces can be of different nature: Compression of electrical double layers. Chain elasticity in the dispersions stabilized with polymer surfactants. Fischer). attractive interparticle forces and repulsive forces. combined ionic non-ionic stabilization. non-ionic stabilization. Potential energy curves between two particles Stabilization of pigment suspension . Barrier-type stabilization with polymeric dispersants. three systems of coating stabilization can be used in aqueous medium: 1. entropic repulsion (Mackor).gr/inkjet/newtech/tech/dispersion/ polymers.inkline. see electrostatic stabilization 2. it is possible to increase the charges and. Stabilization of pigment suspension . As two particles approach each other the charge effectively provides a barrier to closer particle interactions. and a more diffuse cloud of oppositely charged ions develops around it. which is widely used in technologies of latexes. Through the use of additives. thereby destroying the dispersion.a dispersion can persist indefinitely without significant changes in particle size and properties. the use of ionic surfactants or chemical lyophilizers which produce carboxy. 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. which surround the particles. we can characterize dispersion stability via "potential curves" (Figure). ammonium etc. having a certain source for interparticle repulsion.Colloidal stabilization Stability of dispersion is a result of interpay of the heat (kinetic) energy of particles. ions. Strong interactions between polymers and solvents (organic solvent or water) prevent the polymers from coming too closely into contact with one another (flocculation).How to disperse and stabilize pigments http://www. Practically. Possessing kinetic (thermal) energy and being subjected to Brownian movement. 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. to make all pigment particles equally charged. see steric stabilization 3. Osmotic pressure in non-ionically stabilized system (Derjagin. 3 of 12 07/03/2011 3:34 PM .

This stabilization mechanism occurs in solvent. Stabilization of pigment suspension .inkline. Alternatively one can consider that. as a reduction in entropy. In other words. steric stabilization.e. providing a very much smaller barrier to inter-particulate attraction. the flocculation tendency is dramatically reduced so that the deflocculated state is stabilized. although even in water-based coatings systems. principally water. In addition to polyphosphates. but they also function as wetting additives. This requirement is usually expressed by saying that the medium needs to be a better-than-theta solvent (i. a relatively good solvent) for the polymer chain. and possess the above mentioned freedom. The polyelectrolytes adsorb onto the pigment surface and consequently transfer their charge to the pigment particle. Steric stabilization One fundamental requirement of steric stabilization is that the chains are fully solvated by the medium. In this part of the Dispersion Center we will discuss the main items that have to be taken into account when formulating a pigment 4 of 12 07/03/2011 3:34 PM . Steric stabilization relies on the adsorption of a layer of resin or polymer chains on the surface of the pigment.based systems and in water-reducible systems which contain solvated resins. Formulating an optimum dispersion Dispersing agents are not just additives to conventional millbases. Electrostatic stabilization is effective in media of reasonably high dielectric constant. they not only stabilize the pigment dispersion.How to disperse and stabilize pigments http://www. Through electrostatic repulsion between equally charged pigments.Steric stabilization Charge stabilization is not be effective in media of low dielectric constant (the vast majority of organic solvents and plasticisers). The choice of the most suitable dispersing agents is sometimes difficult and their usage require sometimes specific guidelines. 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. The greater steric repulsion generated by the addition of polymeric dispersants moves the minimum in the Potential Energy Curve. This leads to an imbalance in solvent concentration which is resisted by osmotic pressure tending to force solvent back between the particles. the additives used for dispersion in such systems are polyelectrolytes . in thermodynamic terms. or a combination of steric and charge stabilization will often provide better overall performance. which is unfavorable and provides the necessary barrier to prevent further attraction. This loss of freedom is expressed. as the chains intermingle.gr/inkjet/newtech/tech/dispersion/ Electrostatic stabilization Chemically speaking. and steric stabilization is required to maintain dispersed particles in a stable non-flocculated state. solvent is forced out from between particles. thus maintaining their separation. Through specific structural elements composed of pigment affinic groups (polar) and resin-compatible chains (nonpolar).high molecular weight products which contain a multitude of electrical charges in the side chains. these dispersing agents exhibit definitive surface active properties. and thus reduces the overall viscosity. This is important because it means the chains will be free to extend into the medium. 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. many polycarboxylic acid derivatives are utilized as polyelectrolytes in the coatings industry.

No.0 10. and in general. organic pigments) and have higher molecular weights through the attainment of more complex polymer like structures. This need for compatibility with the medium extends throughout the final drying stages of any applied coating.0 30. Once the anchor group of the dispersant is attached to the pigment surface it will remain firmly attached. the two-component structure is made up from a polymeric chain and a pigment affinic anchor group. If the chains are not sufficiently solvated. Molecules of resin. Pigment Iron Oxide . and even though not firmly anchored they can hinder the dispersant anchoring process. The polarity of the surface of the pigment differs from organic (non-polar) to inorganic (more polar). polyurethane. flocculation may occur leading to reduced gloss and tinctorial strength. Other dispersing additives are designed to improve the flocculation resistance of pigments (particularly non-polar. Pigment % Talc Solsperse 6100 Solsperse 6200 Solsperse 6300 Antifoam Water PB7 PB7 PY184 PW6 30.5 16. and this means that the nature of the dispersant anchor group is critical for optimum adsorbtion. Furthermore.7 35. Minimal-resin solids (or resin-free systems) can be used in the dispersion. The surface area of the pigment also affects the level of dispersant used. To learn more about how to formulate an optimum dispersion. Dispersant technology is now more advanced.5 5. and the nature of the pigment. allowing the particles to aggregate or flocculate.inkline. however.0 4. The nature of the polymeric chain is critical to the performance of the dispersant. 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.3 0. 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. it can be shown that the thickness of the protective barrier is actually reduced as a result of overcrowding on the pigment surface.7 24. 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.0 8. then they will not provide a sufficient thick barrier to prevent flocculation.0 29.How to disperse and stabilize pigments http://www. click on the links below: Dispersant Choice Grinding medium Pigments**/Fillers Order of addition Surface Area Dispersant Choice With any effective polymeric dispersant. the resin involved and the solvent can all affect the performance of the polymeric additive. if too little is used then the full benefits will not be realized. The structure of some dispersing additives can be described as one or more spatially close anchor groups with a number of polymer chains. Pigments / Fillers The choice of dispersant is also related to the surface nature of the pigment. several different polymer chains can be utilised effectively covering the variety of solvents encountered.0 16. alkyd and epoxy. as long as good let-down stability is sufficiently available. 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.0 58.0 4. If the chains are too short. If too much is used.0 Order of Addition 5 of 12 07/03/2011 3:34 PM . 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). and in some systems dispersing without resin is possible.0 5. If it ceases to be compatible. 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.5 8.5 5.gr/inkjet/newtech/tech/dispersion/ solution. including polyester.Yellow Carbon Black Bismuth Vanidate Titanium Dioxide C. Dispersant choice involves a number of criteria. In order to meet the need for good compatibility. This will lead to an increase in viscosity and a loss of tinctorial properties.I. are transiently adsorbed on the surface of the pigment.3 35. then they will collapse on to the pigment surface. A key benefit of using this kind of product is the wide resin compatibility it offers in various resin systems.0 50. acrylic.0 0.

Calculation of % AOWP of Polymeric hyperdispersant The theoretical amount of Polymeric dispersants (e. Surface Area As a general rule. Stage 4 .70m2/g Therefore 140mg Polymeric agent/1g pigment are required = 14g agent/100g pigment i. The role of the dispersing agents is to enhance the dispersion process and ensure a fine particle size in order to stabilize pigments in 6 of 12 07/03/2011 3:34 PM . Add the pigment.Determines optimum amount of Solsperse Hyperdispersant (Can be performed on lab.How to disperse and stabilize pigments http://www. 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. 4 stages are involved.5mg of polymeric dispersant.Determines the higher pigment content required (Can be performed on lab. A ladder series of polymeric dosage levels should be evaluated based around this 2-2. the coating system (water based.maintaining [agent:pigment] ratio determined in Stage 3 to determine optimum amount which gives best final product. Add any other additives. Determine the best hyperdispersant dosage by measuring desired property.gr/inkjet/newtech/tech/dispersion/ The usual way of incorporation of dispersant in a coating formulation would be in three stages: 1. Stage 2 .5mg/m2 level. Avecia Solsperse) agent required in a millbase is 2mg Polymeric agent per sq. In case you want to optimize a Polymeric dispersant millbase. shaker e.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 . 14% AOWP Synergists (if required) are used with the Polymeric in ratios between 4:1 and 9:1 [Polymeric:synergist]. 3.0 2 Dispersants families . in stages. Measurement of dispersion viscosity will show a minimum at the optimum dosage. meter pigment surface area.e.0 (i. Typically. 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. Example: Pigment surface area . per square meter of pigment surface area will be close to the optimum amount required. 2-2. the surface area of phthalocyanine blue pigment is 50 m /g: So a typical dosage would be : Phtalocyanine blue pigment Polymeric dispersing agents 30.inkline. The pigment concentration giving the same viscosity as the control should now be used in Stage 3.Introduction The choice of the dispersing agents is a key issue in the coating and ink industry. Mix the dispersant in the millbase solvent or in the resin/solvent mixture. etc.g. although it is also possible to measure gloss or color strength of the coating which will show a maximum at the same optimum dosage.e: 10% active dispersant on the weight of pigment) 3. and disperse in the normal manner. Stage 3 . 2. shaker e. Stage 1 . solvent based.g.g.) and the other additives. Formulators have to find the most suitable products for their formulation taking into account the final application of their coating. Note: the ratio of [hyperdispersant:pigment] must be maintained. The following example explaining using Avecia Solsperse products (referred to as a ladder series).

the stabilizing charges used are often disturbed by impurities. forming durable adsorption layers upon many pigment particles.inkline. c. Because of its structural features. making polymeric dispersants very useful for dispersing all types of pigments. General description 2. a polymeric dispersant is bound to numerous sites at the same time. Polymeric chains Polymeric dispersants stabilize paints. and f) or at both ends (a. The molecule must contain polymeric chains that give steric stabilization in the required solvent or resin solution system. They have a two-component structure which combines the following two very different requirements: 1. even the organic ones. As shown in the picture below the anchoring function of a polymeric dispersant may be a single functional group. Polymeric disperants . such as inorganic pigments that are ionically constructed. such as organic pigments whose crystals are composed of nonpolar individual molecules. The steric stabilization polymer chain is either anchored to the particle surface at one end (b. Anchor groups 3. a proper adsorption is rather difficult to obtain with conventional additives. If this compatibility is obstructed. In order for additives to be effective. caused by the reduction of the repulsive forces. However. Steric stabilization can avoid this issue.Description 1. The essential requirement is that the chains are successfully anchored to the pigment surface.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. Polymeric disperants . therefore they must be highly compatible with the surrounding resin solution. Polymeric dispersants differentiate themselves from the other types of dispersing agents through considerably higher molecular weights. In the traditional method of stabilizing pigments in water. and stabilizing. and e). that are very difficult to be deflocculated by traditional wetting and dispersing additives. As explained earlier. the polymer chains collapse causing the steric hindrance and the resulting stabilization to be lost. dispersing. 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. or an oligomeric or polymeric chain: 7 of 12 07/03/2011 3:34 PM . This leads to a destabilizing effect.blocks (a and d-f). The surface properties of the pigment particles are therefore crucial to the additive's effectiveness: With pigments possessing high surface polarities. The wide range of anchor groups that polymeric dispersants provide make them very efficient to anchor on pigments with nonpolar surfaces.How to disperse and stabilize pigments http://www. Optimal steric stabilization is achieved when the polymer chains are well solvated and properly unfurled.gr/inkjet/newtech/tech/dispersion/ the resin solution. There are many copolymer/functional polymer configurations that might be expected to give effective polymeric dispersants. the adsorption into the pigment surface must be durable and permanent. for pigments with nonpolar surfaces. d. It must be capable of being strongly adsorbed into the particle surface and thereby possess specific anchoring groups 2. the adsorption of any dispersing additive is relatively easy. the stabilization mechanism and the resulting let down stability. an efficient dispersant has to perform the three main functions : pigment wetting. and that the surface of the particles are covered with a sufficient density of chains to ensure minimum particle-particle interaction. 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. such as other ions. coatings and ink systems via a steric stabilization mechanism previously described. Dispersing agents generally differ for aqueous and solvent-based coatings. since performance depends on the optimum amount of saturation by the dispersant of the pigment surface. or the presence of other pigments with different zeta-potentials. The level of the polymeric dispersant used is very important.

Given that steric stabilization is entropically driven in non aqueous media. Again. according to their chemical type. Although most organic pigment particles and some relatively inert inorganic particles such as quartz do not have charged sites on their surface. many inorganic pigment particle surfaces are quite heterogeneous. this conclusion is not surprising. Anchoring both ends of the polymer chain will clearly inhibit its freedom of movement. see figure 2 Figure 2: Anchoring by hydrogen bonding to a polymeric group. so charge separation is not favored. 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. many different chemical groups can be found as anchor groups for polymeric dispersants. but strong interaction may be developed with a polymeric dispersant possessing an anchor chain composed of several of these groups. and acid sulfate and phosphate ester groups. sulfonic. Anchoring Through Hydrogen-Bonding Groups. Polyethers can be used to anchor via hydrogen-bond acceptance. Figure 1: Anchoring through Ionic or Acidic/Basic Groups In fact. ammonium and quaternary ammonium groups. these interactions will often be relatively 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. 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.gr/inkjet/newtech/tech/dispersion/ Schematic molecular structure of dispersants Studies have shown that steric stabilization chains anchored at only one end are most efficient. This situation is illustrated in Figure 1a and is effective because organic solvents normally have a relatively low dielectric constant. even before it starts to intermingle with the steric stabilization chains of an adjacent particle. they may have hydrogen-bond donor or acceptor groups. Even individual hydrogen bonds will be weak. An interaction can also take place between polarized or polarizable groups on an organic pigment particle surface. as illustrated in Figures 1b and 1c . 8 of 12 07/03/2011 3:34 PM . such as esters.How to disperse and stabilize pigments http://www. Anchoring Mechanisms As the nature of the surface of pigments differ. and ethers It is therefore possible for a hydrogen bond between the particle and an anchor group on the polymeric dispersant to form. and phosphoric. carboxylic. with both positive and negative sites. acid groups and their salts . and similarly polarized or polarizable groups on the anchoring function of the polymeric dispersant. Polyamines and polyols are used to anchor via hydrogen bonding. ketones. This wide range of anchoring possibility enables polymeric dispersants to disperse inorganic pigments as well as pigments with polar surfaces. either donor or acceptor.inkline. Anchoring Through Polarizing Groups. The actual anchoring can then take place through a variety of mechanisms: Anchoring Through Ionic or Acidic/Basic Groups. Examples of functional groups that can be used to anchor polymeric chains to charged or acidic/basic surfaces include amines.

Figure 5 : synergists Polymeric disperants . The polymeric block within the dispersant must simply be insoluble in the medium. If the chains are not sufficiently solvated. It is possible. but the most effective polymeric dispersants probably maximize the effect from all three mechanisms. and these dispersions are prone to flocculation on letdown. 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. Most polymeric anchor chains probably anchor via a mixture of electrostatic forces (hydrogen bonding and/or polarization) and van der Waals forces. hydrogen-bonding. Figure 4 : Anchoring through solvent insoluble polymer blocks. Polyurethane anchor groups are said to operate via this mechanism. see figure 4. Derivatives of the Dispersed Particle. Anchoring Through Solvent-Insoluble Polymer Blocks. In such systems it can be very difficult to obtain anything other than dispersions of relatively low pigment concentration. for example. etc. It is possible to anchor a polymeric dispersant onto a pigment particle surface simply via van der Waals interactions and without recourse to ionic.inkline. Some organic pigments (phthalocyanine blues and dioxazine violet are good examples) are not very responsive to any of the anchoring mechanisms just described . then they will collapse on to the pigment surface allowing the particles to aggregate or flocculate. flocculation may occur leading to a decrease of surface properties such as losses in gloss and tinctorial strength. Alternatively. This system works most effectively on higher molecular weight pigments with large planar structures. One of the mechanisms may be dominant. which are not solvent-soluble. In fact. and polystyrene chains. The need for compatibility with the medium extends throughout the final drying stages of any applied coating. to disperse a pigment in an aliphatic hydrocarbon using a polymeric dispersant based on poly(tertbutylstyrene) chains. 9 of 12 07/03/2011 3:34 PM . If it ceases to be compatible. it is very difficult in practice to distinguish between this and the previous two adsorption mechanisms. This mechanism is illustrated in the figure 5 below. 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.Polymeric chains The nature of the polymeric chain is critical to the performance of polymeric dispersants.How to disperse and stabilize pigments http://www. The copper phthalocyanine molecule has been modified by the addition of polymeric chains to give a particularly effective dispersing agent for copper phthalocyanine pigments. or polarizing effects. 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.gr/inkjet/newtech/tech/dispersion/ Figure 3 : Anchoring through polarizing groups Polyurethanes are commonly used as polarizable anchor groups. which are solvent-soluble.

in particular. for good surface coating properties and performances. In non-aqueous systems.How to disperse and stabilize pigments http://www. 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. surfactants may cause the following defects: 10 of 12 07/03/2011 3:34 PM . It is therefore vital that after an initial screening of polymeric dispersants for rheological and color/gloss changes. they have a tendency to "fold back" on to themselves. the polar group is known as the oleophobic group and the non-polar group as oleophilic.inkline. As with the polymeric dispersing agents. Many surface coating systems will tolerate a polymeric dispersant at low levels of addition. Similarly. Surfactant molecules are able to modify the properties and. have shown to be the most effective in providing steric stabilization. Ideally the chains should be free to move in the dispersing medium. 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. Some systems are particularly tolerant to the presence of polymeric dispersants. The anchoring groups can be amino. Chemistry of the Steric Stabilization Chain In order to meet the need for good compatibility. the polymer must be fully compatible with the coating resin after the solvent has evaporated off and the resin has been cross-linked. This part of the molecule (aliphatic or aliphaticaromatic segments) must be highly compatible with the binder system.gr/inkjet/newtech/tech/dispersion/ 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. Examples. carboxylic. In aqueous systems. more specifically. their effectiveness is determined by: The absorption of the polar group onto the pigment surface. The behavior of the nonpolar chain in the medium surrounding the particle. cationic. When the chains are too long. electroneutral and non-ionic (see figure 1). 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. Surfactants are classified according to their chemical structure and. Too high a molecular weight will also give reduced performance. As previously said: chains with anchor groups at one end only. This surface activity arises because the surfactants' structure consists of two groups of contrasting solubility or polarity. then they will not provide a sufficiently thick barrier to prevent flocculation. their polar group: anionic. Because of their chemical structure (eg: low molecular weight) and the electrostatic method of stabilization. paper or wooden substrates tend not to give major adhesion problems. 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. their effect on the performance of the surface coating be checked by the appropriate tests. Higher quality stoving or two-pack paint systems and many packaging ink systems pose much more severe requirements. phosphoric acids or their salts. but problems will be caused at higher loading. they lower the interfacial tension between the pigment and the resin solution. several different polymer chain types are utilized in the polymeric dispersant range. Finally. sulfonic. Surfactants Surfactants are conventional low molecular weight dispersing agents. The stabilization mechanism of surfactant-like dispersing agents is electrostatic: the polar groups forming an electrical double layer around the pigments particles. the polar group is known as a hydrophilic group and the non-polar group as hydrophobic or lipophilic. effectively covering the variety of solvents encountered.

phosphate esters dispersing agents provide steric stabilization to the pigment solution. fish eyes. click on the links above. and some provide other advantages to the final paints such as defoaming/dearation or difficult substrate wetting. intercoat adhesion and blistering Phosphate Esters Due to the anionic structure of the phosphate group. 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). _ Interference with intercoat adhesion. 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. but concerns over the APEs nonionic surfactants has led to the recent apparition of new product blends advertised as APE free.gr/inkjet/newtech/tech/dispersion/ _ Water sensitivity: Surfactants generally have a tendency to provide water sensitivity to the final coating. thus making them inappropriate for use in outdoor applications. 11 of 12 07/03/2011 3:34 PM . Over the past years specific surfactants have been developed to minimize these defects. 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. Polyacrylic acid/ Sodium polyacrylate Polyacrylic acid (PAC) and salts of polyacrylates are anionic surfactants used as dispersants in water based coating and ink formulations. particularly in decorative emulsion paints and water based inks. they are used in combination with an anionic surfactant which provides stabilization of the dispersion by the electrostatic stabilization mechanism. especially reduce reflocculation issues. craters) on the final coating. If foaming occurs at the milling stage it can also cause a loss of production capacity. _ Foam formation: Many surfactants generate foams which lead to surface defects (e..How to disperse and stabilize pigments http://www. Phosphate esters are sometimes used in combination with non-ionic surfactants to enhance dispersion stability. water sensitivity. Most of the time.g.inkline. 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. Coating formulated with these types of nonionic dispersing agents are sometimes subjected to foaming. 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. 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.

gr/inkjet/newtech/tech/dispersion/ 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. ethoxylate branched chains) containing two hydrophobic groups and two hydrophilic groups attached by a short chain coupler. 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. Typical structure of ethoxylated acetylene diols 12 of 12 07/03/2011 3:34 PM .inkline. two symmetrical oxygen atoms.How to disperse and stabilize pigments http://www.

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