84 High Temperature Pigments 84.1 Introduction 84.2. The Technology CColor Mechanism + Chemical Structure» Production Methods 84.3. Pigment Types, 844 Rutile Pignents «Spine! Pigments» Zion Stains 844 Pigment Properties 84s 845 Typical Applications 84-6 Surface Codtngs + Ceramic» Building Materials» Glas * Helen Hatcher Plastics Rockwood Pigments Bibliography 84-8 84.1 Introduction High temperature pigments can be defined as chemical substances that impart color to a substrate of binder and retain their color and finish at elevated temperatures. ‘There are many everyday applications where consumers require aesthetically pleasing finishes, in the latest fashion colors that last. There are many diverse, high performance applications that require careful pigment selection to ensure that the coloration is long-lasting; rarely will a consumer be aware of the technological considerations that apply when designing such products ‘Chemically, high temperature pigments are inorganic compounds. Although many chemical classes potentially fall into this category, an important family of pigments is termed complex inorganic color pigments (CICPs), otherwise known as mixed metal oxides (MMOs) or complex inorganic pigments (CPs). These pigments are heat stable to temperatures exceeding 1832°F (1000°C), suitable for the ‘majority of applications. High performance pigments also include cadmium pigments, able to withstand. temperatures of up to 752°F (400°C), and bismuth vanadate pigments, with heat stability of up to 392°F (200°C). These pigments exhibit excellent color properties but will not be covered in this review. ‘There are two distinct clases of CICPs, similar in chemistry but differentiated by end market and by particle size; pigment-grade for plastics, surface coatings, building materials, and glass applications, and. ceramic-grade for ceramic applications. It is interesting to note that some colors are more heat stable than others. For example, black is a strong absorber of infrared (IR) radiation and therefore retains heat. Hence, black pigments and dark. colors require better heat stability than lighter colors or pastel shades. Recent technology advances include pigments that provide color and functionality by building in the ability to reflect IR rays away from the substrate or binder, and hence, lowering the heat buildup and. prolonging the lifetime of the product. These products are promoted by Energy Star for their benefit to the environment in terms of energy-saving initiatives. 84184.2 Coatings Technology Handbook, Third Edition | TT FIGURE 841. Periodic table. 84.2 The Technology 84.2.1 Color Mechanism Complex inorganic color pigments are synthetic, highly crystalline metal oxides, differentiated from simple metal oxides, as they contain two or more metals, The color of the compound is determined by the combination and location ofthe transition metal ions in the oxidic host lattice, otherwise known as chromaphores. The transition metals are responsible for generating electronic d-d transitions, which are energetically weak, and therefore, the colors produced ate not as bright and intense as other pigment types, for example, organi pigments. “Transition metal ions can easily substitute for metal ions in the host latice if they have equal electronic charge. Often, combining several metals with different valence states produces a charge-balanced pai, demonstrating the complexity of the formulations used, Although transition metals are the color-forming, centers, the hue can be shifted with dopants, that is, noncolored ions that can either occupy interstitial sites in the lattice, distorting the latice shape, or can substitute into sites the lattice producing a charge imbalance. These structures may be inherently more unstable and may produce less durable pigments. 84.2.2. Chemical Structure Complex inorganic color pigments are dominated by two crystal structures, rutile and spinel, although there are many others. Rutile pigments are largely titania-based, doped with metals such as nickel, chromium, of antimony at low levels. 84.2.3 Production Methods Complex inorganic color pigments are produced commercially by solid state reaction, by heating imimate mixtures of metal oxides, salts, or hydrates at high temperatures between 1112°F (600°C) to 2:High Temperature Pigments 843 TABLE #41. Crystal Structre Types Crystal Typical ——Typial Coloring Structure Formula Piginent Type Metal” Cor Rutile (NisbTO, Ni Yellow Spine (Cozn)al.0, Co Blue Zircon (vzasio, —-V_— Turquoise Hematite (FeCe).0, —FelCr—Blck/Brown Cassverite (Goznsio, _Co__Blue utile FIGURE 84.2 Crystal structure types, (1400°C). Intimate raw material mixtures are produced by wet milling techniques to ensure that all components are finely divided. The surfaces of grain boundaries are often coated to achieve the best reaction. Mineralizers can be used to aid the rate of reaction to ensure completion with minimum heat work; these ae frequently used when producing zircon pigments ‘The calcination process can be a batch process, loading the pigment manually into refractory saggars and firing in intermittent Kilns, or it can be a continuous process using state-of-the-art rotary firing techniques. “The pigments have developed their full color during firing but are refi particle siz, dependent on the application, Pigments for surface coatings, are usually designed with a fine particle size and a narrow particle size distribution, for maximum tinting strength; conversely, pigments for ceramic applications tend to be coarser, with a wider size distribution, for maximum masstone color strength, cd by milling to the required asti, and glass applications FIGURE 843 Saggar fring844 Coatings Technology Handbook, Third Edition FIGURE S44 Miling ‘TABLE 84.2 Common Rutile Pigments Colour Index Typical Reference No. Formula Color Main Comercial Avalale Grades ‘low (ISHITIO, Yalow BASE KIOIT and Fetro PRS Yalow 216 (Sn-ZnTLO, —Yellow/Orange Rockwood MHLOOL, SH 1002, 441003 Brown 24 (CrSb)TO, Butt BASF K2011 and Ferro PK6O70 Brown 164 (MaSb)TIO, Dark brown BASF K2711 84.3 Pigment Types 84.3.1 Rutile Pigments Rutile pigments consist primarily of titania, 70 to 90 wt. They represent the largest class of pigments, with Brown 24 being the most significant, followed by Yellow 33. As with all CICPs, the coloring metal ions are trapped tightly within the host lattice and therefore are not extracted in use. The extractable ‘metal content of all pigments is carefully controlled, making them suitable for food contact applications The color shade can be altered by substituting antimony with niobium, tungsten, or barium; however this increases the unit cost of the formulation, and therefore, these pigments are not regularly encountered. Yellow 216 is the most recent innovation, introduced to the market in 2003, The range of yellow to orange colors is more intense than with the conventional titanates, with superior tinctorial strength. They contain a new Sn-Zn color center not reported in the industry before, surprisingly intense for two noncolored metal ions and probably caused by bandgap transitions, although this is still being investi- gated. This new chemistry comes at a time when increasing environmental concerns surround certain heavy metals; it offers an attractive alternative. Manganese browns ate gaining popularity, particularly in North America, as the best ion: available for PVC claddings and vinyl sidings ee browns 84.3.2 Spinel Pigments Spinel pigments are largely aluminates or chromates, These formulations are modified by a number of dopant metals, each supplier striving to achieve unique shades. Generally speaking, titanates and alumi nates offer brighter, cleaner shades than chromates. “Many ceramic-grade glaze stains and decorative colors are available fom the main supplies listed here.High Temperature Pigments 845 TABLE 4.3 Common Spine! Pigments (Colour Index Reference Main Commercially Available Grades Green 50 Gueen Faro PKAOIS, Rockwood 34K48, Shepherd 223 Green 26 CaCO, Green Rockwood 34K6, Ferro PKA047, Shepherd 179 Green 50 (CoZn.C2)TL.O, Turquoise Ferro PKS500 Blue28 Goal, Rockwood 341.200, Ferro PKSO91, Shepherd 3 Bue36 —(CaCNALO, Rockwood 341.2001, Ferro PKS095, Shepherd 9 Yellow 119 ZaFe,0, Rockwood Mapico 104 Brown 29 Brown BASF K2075, Black 2 Rockwood 340, Ferto PKSORS, Shepherd 1 ‘TABLE 84.4 Common Zircon Pigments Colour index ‘Typical, Main Commercially Reference No. Formula Calor ‘Available Grades (PZ), Yelow JAE CS2800, IM CTI3O0 (VzZNSIO, Turquoise IM C2800, IM CT1500 (Fe22)8i0, Corl JM 14M929, IMCT100 (GiZpSi0, Red JM c32803, IM C1805 Orange (CAZ)80; Red J 32202, M C1202 84.3.3 Zircon Stains Zircon glaze stains can be divided into two groups: doped and encapsulated (or included) colors Praesodymium, vanadium, and iron dope the zircon lattice by substituting into zirconium sites, and form the basis of the triaxial colors, so called as they represent three corners of a cyan, magenta, yellow color set and therefore offer extremes of ceramic color. They are blended together to form a wide color palette for high temperature applications. Cadmium zircon colors, however, are made by encapsulating discrete cadmium selenide pigment particles by zircon, producing a two-phase product. Encapsulation ofthe coloring compound is optimized by ensuring that the pigment phase is formed before the zircon phase, in a competitive reaction, 84.4 Pigment Properties Complex inorganic color pigments are called high performance pigments because they are extremely durable in use. Further, these pigments show: + Outstanding color retention afte exterior exposure, in the presence of UV light, moisture, and heat + Excellent heat stability + Very good opacity to visual and ultraviolet (UV) light + Good chemical resistance against attack from solvents, acids, and alkalis, + Chemically inert, combining well with other inorganic and organic pigment types + Nonmigratory in polymers and plastics, showing no color bleed. + Highly refractive, with a tendency to abrade softer materials ‘Complex inorganic color pigments can actually enhance the overall lifetime of the coating or colored object. The pigment acts functionally by absorbing oF reflecting UV radiation away from the binder, Most organic binders will degrade photocatalytically in such conditions, particulaely in the presence of titania, which catalyses free-radical formation and accelerates the aging process. ‘These pigments are often used in conjunction with high color strength pigments to impart opacity and durability to a formulation, reducing the cost of the organic component of a formulation,84.6 Coatings Technology Handbook, Third Edition Photo-catalyeed ‘Chain Reaction 0 fo 5 uree © 0 PriepaP 0+ Ha =T0 0 (Oxidation of Adsorbed Hydroxyl Rellection . cre * Onsen Santae * © "0 # Se 0 0 F0% of 0908 0 0% o Tranamission FIGURE 845 Mechanism of photocatalytic degradation, ‘Transmission (%) os. Increased UV ‘Absorption 700 200 300°» 400~«800-«00=« 7000 Wavelength (rm) — Cobalt Aluminate Blue = Organic Blue = Utramarine Blue FIGURE 846 UV absorption of blue PVDF coil coatings. 84.5 Typical Applications Complex inorganic color pigments are the pigments of choice where colored objects are subjected to high temperatures, UV light, or harsh chemical environments either during the manufacturing process 84.5.1 Surface Coatings The highest performance surface coatings applications are usually for exterior applications such as coil coatings (used for building claddings), roofing, general construction parts, exterior paints (for example, masonry), and industrial and architectural paints.High Temperature Pigments 807 Coil coatings usually adopt an acid catalyzed curing process that can be reactive to some pigment types. Coil-coated parts are bound by lengthy manufacturer guarantees of up to 25 years; hence, the highest performance pigments are required, Exterior masoney paints can be based on permeable silicate paint technology to allow the underlying concrete or mortar to “breathe.” These paints are highly alkaline and are not compatible with organic or Ultramarine pigments. With the increasing use of universal color tinters, formulated to be equally com patible with solvent-, water-, and silicate-based paints, CICPs are growing in popularity because of theit ‘wide compatibility Heat-resistant paints are used for barbeques, wood-burning stoves, car exhausts, and engine parts. ‘These are largely silicone based, pigmented with copper chromite spinel black (CI Pigment Black 28). 84.5.2 Ceramics A wide range of colors is available for applying to a range of tableware substrates, to suit all designs applied to elaborate dinner sets, hotelware, giftware, decorative ornaments, and collectables: + Porcelain + Bone and vitreous china + Earthenware + Stoneware ‘The same color palette is also used in the structural business to deliver high temperatue fired color to sanitary-ware and floor and roof tiles. Color is supplied asa glaze stain, where color pigment is supplied in powder form, or as a decorative color, supplied as a powder blend of liquid ink and containing a glass frit for glaze formation. It ean also be applied as a predesigned decal transfer, ready for direct application, 84.5.2.1 Glaze Stains ‘The color palette typically consists of the following + Zircons (Praesodymium Yellow, Iron Coral, Vanadium Blue, Cadmium Red) chrome Tin Pink alt Aluminate or Silicate Blue + Iron, Nickel, Chromium Browns and Blacks ‘Supplied as standard range color powders, they ate blended to the desired custom colors and combined with transparent oF opaque unleaded glazes for firing onto tableware and sanitary-ware 845.22 Decorative Color Decorative colors for tableware, giftware, and collectables are selected by firing technology: + On-glaze color: twice-fited color applied and fired directly onto the substrate before the top glaze is applied and fired + In-glaze and underglaze color: once-fied color applied onto or under the top glaze and fired simultaneously ‘TABLE 845 Traditional Glaze Compositions BO, GO KO NAO MO SiO, TO, ZO, Glaze Eect, o) 5) 6) HH) HOW) ‘Transparent 1252250 980 360 280100 677) a7 — Opaque 15226 ase 3.22250 092 6470009 60848 Coatings Technology Handbook, Third Edition Decorative colors are supplied as powder blends, custom powder blends color-matched to customized colors, or as liquid inks. They ae available in 25 color sets or four-color CMYK sets for four-color printing techniques. 84.5.2.3 Decal Transfer Designs CICPs are supplied as preprepared custom and standard color designs for tableware applications. 84.5.3. Building Materials C1CPS are widely used to color cement and concrete and mortar and grouting for outdoor pavings, swimming pools, and roof tiles. The alkalinity of the cementitious materials used demands inorganic pigments to ensure long-lasting coloration, 84.5.4 Glass Glass enamel producers traditionally opt for CICPs largely in automotive and decorative applications Heated rear windscreens contain black copper chromite, because a pleasing jet black appearance is retained afler firing at elevated temperatures, without interference with the glass frit or the silver con ductive track. Decorative glass applications use a wide range of colored pigments, for example, the Pepsi red and blue trademark decorations for drinking bottles. 84.5.5. Plastics Rigid PVC extruded or molded parts are used for window profiles, gutterings, and joints. These build up heat during the summer months and will readily degrade unless steps are taken to prevent it. Stabilizers are added to PVC to absorb UV light; careful selection of the pigment system used can also add value to the finished goods Silicone rubbers are frequently colored from compounded color concentrate, pigmented with CICPs. Copper chromite spinel black isa common colorant for production of nonconductive electronic housings and spatk plug casings. The pigments used in such applications must be carefully controlled for extract- able metals, because silicone polymers often contain residual monomers that can initiate premature polymerization, Engineering polymers, used in automotive interiors and many domestic appliances, require high processing temperatures and, therefore, require CICPs for coloration, Bibliography Budnikoy, PP, and A. M. Ginstling, Principles of Solid State Chemisty, It ed. London: Maclaren & Sons Lad, 1968 Colour Index International, The Society of Dyers and Colourists, Bradford, England, 1997 Cotton, FA. and G, Wilkinson, Advanced Inorganic Chemisty, th ed, New York: John Wiley & Sons, 1988, Johnson Matthey Ceramic Materials Division, Product Manual, Issue 1, May 1999 Nassau, K, The Physics and Chemistry of Color, Advisory ed. New York: John Wiley & Sons, New York, 1983,