76 Pigment Dispersion 76.1. Introduction 76-1 76.2. A Brief Introduction to Pigments, 76-2 Pigment Definition + Pigment Particles 76.3. The Dispersion Process. 76-4 Pigment Wetting» Paticle Deaggregtion and Deagglomerstion + Dispersion Stabilization 764. The Role of Surface Energy. 76-6 Surface Energy and Surtace Ate Surface Energy and Pigment Wetting» Sutfce Energy and Destabilization ofthe Dispersion Surface Energy and the Acid-Base Concept 763. Mechanisms for the Stabilization of Dispersion. .u.768 Charge Stabilization» Steric or Entenpic Sabilaton 76.6. Surface Treatment 76-9 Surfactants Polymeric Dpersans Surface Modifying Agents 76.7 Surface Treatment during Pigment Manufactute....76-10 768. Surface Treatment of Pigments: Application 76-11 Organic Pigments «Inorganic Pigments 769. The Characterization and Assessment of Dispersion. 76-17 ‘Theodore G. Vernardakis 76.10 Conclusion. 76-17 [RCM tas USA, te Relerences. 76-18 76.1 Introduction ‘The dispersion of pigments in fluid media is of great technological importance to the coatings manu- facturers who deal with pigmented systems. The basic aim is to change the physical state of pigments to achieve desired effects in specific application systems. The dispersion process involves the breaking down, and separation of the aggregated and agglomerated particles that are present in all pigments in their normal form aller their manufacture. Dispersion is not considered to be a process of pulverization but rather a process of particle separation, homogeneous distribution of the particles in a medium, and stabilization ofthe resultant system to prevent reaggregation, reagglomeration, flocculation, and settling. ‘The process of dispersion must be done efficiently and in the shortest time possible to draw out of the pigment its maximum color properties at the least cost. ‘The topic of pigment dispersion in fluid media has been covered extensively in the literature.-* ‘Theoretical aspects of pigment dispersion apply equally well to inorganic and organic pigments. In this chapter, the practical examples of surface treatments apply primarily to organic pigments, but similar tueatments can be carried out on inorganic pigments as well. 76-176.2 Coatings Technology Handbook, Third Edition 76.2 A Brief Introduction to Pigments 76.2.1 Pigment Definition Materials are colored by the use of pigments or dyes. Pigments are colored, black, white, or fluorescent particulate organic or inorganic solids; usually they are insoluble in, and essentially physically and. chemically unaffected by, the vehicle or substrate in which they are incorporated. They alter appearance by selective adsorption and/or by scattering of light.” Pigments usually are dispersed in vehicles or substrates for application (e.g, in inks, paints, plastics, or other polymeric material). Pigments retain a erystal or particulate structure throughout the color- ation process ‘Asa result of the physical and chemical characteristics of pigments, pigments and dyes differ in their application: when a dye is applied, it penetrates the substrate in soluble form, after which it may or may. not become insoluble, When a pigment is used to color or opacify a substrate, the finely divided, insoluble solid remains throughout the coloration proces. ‘Organic pigments are highly colored, inert synthetic compounds that are usually brighter, purer, and richer in color than inorganic pigments. Generally, however, they ae less resistant to sunlight (some fade badly on exposure to light), to chemicals (greater tendency to bleed in solvents), and to high processing temperatures (lower heat stability); quite often too, they ate more expensive than inorganic pigments Pigments are classified by the Colour Index according to specific pigment name and constitution number. For example, phthalocyanine blue is known by the C.l. name Pigment Blue 15, and its C1. number is 74160, while titanium dioxide is C.L. Pigment White 6, C.I. 77891. The great number and variety of organic and inorganic pigments make it impossible to treat them all in this chapter. References should. be consulted for information on pigment types, chemical and physical properties, methods of preparation, grades, specifications, and applications. See, for example, References 8-11 76.2.2 Pigment Particles Pigments are normally produced in a wet presscake form, which upon drying and grinding or spray drying assumes the form of a fine dry powder. Presscakes, either at their normal pigment content (20 10 4096) or as “high solids” (50 to 6036), are used by the manufacturers of aqueous pigment dispersions for paint, textile, and ink applications, as well as by those who produce flushed colors for oil ink or coatings applications. Dry pigment powders are used in a host of other systems such as solvent inks, coatings, and plastics, Pigments in the presscake or dry powder form are composed of fine particles, normally in the submicrometer size range. Their color properties are generally influenced by particle sie and particle size distribution; therefore, an assessment on the degree of dispersion must, above al, be considered in terms of these critical measurements.” In general, color properties, such as strength, transparency, gloss, sheology, and lightfastness of all pigmented systems, are affected to a greater or lesser extent by the size and distribution of the pigment particles in the dispersion. For example, phthalocyanine blue is first prepared commercially in a “erude” pigment form having a large particle size, up to 25 jim. As such, it has litle color value and must therefore be reduced to smaller, finer particles to enhance its coloristic properties. After particle size reduction (down to 0.03 to 0.15 jim), an excellent pigment is obtained, Which exhibits a high degree of tinctorial strength, transparency and gloss. Typical electron micrographs of these two materials, showing particle size, are reproduced in Figure 76. Pigment particles normally exist in the form of primary particles, aggregates, agglomerates, and fgcculates, Primary particles are individual crystals and associated crystals as they are formed during the manufacturing process (Figure 76.2). They may vary in size depending on the conditions of precip- itation and growth, which are controlled by the pigment manufacturer. The scanning electron photomi- crograph of Figure 76.2 for micronized sodium chloride (although this is nota pigment) is used only to illustrate the individual and associated crystals that make up the primary particles of a compound. ‘Aggregates are collections of primary particles that are attached to each other at their surfaces or crystal faces and show a tightly packed structure. Agglomerates consist of primary particles and ageregates joinedPigment Dispersion 76-3 FIGURE 76.1. Scanning electron photomicrograph of copper phthalocyanine blue crude (top) and transmission electron photomicrograph of copper phthalocyanine blue pigment (hottom) showing particle size diflerences;Pig- ‘ment Blue 15 at the corners and edges ina looser type of arrangement. Aggregates are formed during the manufacturing process in the course of the ripening petiod of the precipitates. Agglomerates, most often, are formed. during the drying of the presscakes and the subsequent dry milling of the pigment lumps. Figure 76.3, shows typical arrangements of aggregated and agglomerated pigment particles, Flocculates consist of primary particles, aggregates, and agglomerates, generally arranged in a fairly ‘open structure, as shown in Figure 76.4, Flocculates may be broken down easily under shear, but they will form again when such shear forces are removed and the dispersion is allowed to stand undisturbed.