Inorganic Pigments

SIC 2816

Companies in this industry

Industry report:

This industry classification is comprised of establishments engaged in manufacturing inorganic color pigments, white pigments, and black pigments, including animal black and bone black. Carbon black is classified in SIC 2895: Carbon Black. Organic color pigments are classified in SIC 2865: Cyclic Organic Crudes and Intermediates, and Organic Dyes and Pigments.

Industry Snapshot

Inorganic pigments serve the purpose of imparting color to various compounds. They also add properties such as rust inhibition, rigidity, and abrasion resistance. Pigments are insoluble substances that can be incorporated into a material to selectively absorb or scatter light. Depending on the specific pigment used, different visual effects are produced. Inorganic pigments may be obtained from a variety of naturally occurring or synthetically produced mineral sources. The counterparts, organic pigments, are carbon compounds derived from petroleum sources.

Organization and Structure

In comparison with organic pigments, inorganic pigments are generally better able to withstand the affects of sunlight and chemical exposure. They provide superior opacity, which means they can render a substance or object opaque by prohibiting light from passing through it. Inorganic colors, however, tend to be less bright, pure, and rich than their organic counterparts. Because inorganic pigments possess less tinting strength, more pigment is needed to produce the desired effect. This generally makes them more durable. Almost all inorganic pigments are completely insoluble. Consequently they do not bleed or leach out of coatings, inks, or plastics. In addition, inorganic pigments are usually less expensive than similar organic colors.

Pigments differ from dyes as a result of their distinctive chemical natures. Dyes are soluble, and to impart color they are dissolved in a carrier and applied by a process that involves chemical changes. Pigments however, remain unchanged physically and chemically. They function without altering their crystalline, particulate, or metabolic structures.

Inorganic pigments are classified as single-metal oxides, mixed-metal oxides, and earth colors. Single-metal oxides include pigments made from titanium, zinc, cobalt, and chromium. Mixed-metal oxides include pigments such as cobalt aluminate blue, which is used in ceramic glazes, and nickel antimony titanate, manganese antimony titanate, and chromium antimony titanate, which are used for outdoor coatings and plastic siding. Earth colors, including siennas, ochers, and umbers, are generally made from iron oxides and lead chromates. A method of high-temperature firing called calcination is used to produce pigments with improved heat resistance.

Pigment manufacturers supply inorganic colors in a variety of forms such as powders, pastes, granules, slurries, and suspensions. Pigment users include manufacturers of paints and stains, printing inks, plastics, synthetic textiles, paper, cosmetics, contact lenses, soaps and detergents, wax, modeling clay, chalks, crayons, artists' colors, concrete and masonry products, and ceramics.

The largest selling individual pigment within the inorganic pigments classification is titanium dioxide (TiO2), a white pigment with opacifying characteristics. Titanium dioxide is by far the most widely used white pigment in the world. It is a solid that melts at over 1800 degrees Celsius. It has a higher refractive index than any other substance except diamonds. It is polymorphous and exists in three crystal structures: rutile, anatase, and brookite. To utilize titanium dioxide's special properties, it must be developed to an ideal particle size. Most often, the particle size is one half the wavelength of visible light, or about 0.3 microns.

Background and Development

The use and exploitation of color dates back to the prehistoric era. Pigments were made by grinding naturally colored materials into minute particles and then mixing them into a binder material. Some of the substances used to produce paintings on cave walls were still used during the twentieth century. For example, the reds used to produce the drawings in the Lascaux caves of southern France were made from red iron oxide.

Use of Lead.
During the early twentieth century, the pigments industry relied heavily on lead-based ingredients. One ingredient, lead carbonate (white lead) was known to be toxic as early as the late nineteenth century, and although some countries began imposing restrictions on its use in the 1920s, the United States was not among them. The toxicity of lead carbonate, especially to children who ate paint chips, received increasing publicity. By the mid-1960s paint manufacturers were required to phase out its use.

According to industry researchers, lead carbonate caused lead poisoning because of its solubility. The solubility enabled it to interfere with the human body's biochemical system. Investigators claimed that other lead pigments suffered from non-specific adverse publicity resulting in regulations that failed to differentiate between soluble and insoluble lead compounds. A reduction in the use of lead chromate pigments during the 1970s resulted in increased costs of more than $1 billion because available replacements were inferior. In the late 2000s, this problem still existed and lead carbonate was still in use to some degree; advancements in the industry continued to make substitutes that were economically feasible and comparable in color strength.

To address issues such as environmental matters, tariffs, toxicity, and worker health, the Dry Color Manufacturers Association (DCMA) was formed. Originally organized in 1925 and headquartered in New York City, the trade association moved to New Jersey and then to Washington, D.C. In 1993, the organization changed its name to the Color Pigments Manufacturers Association Inc. (CPMA), and as of 1997, it was located in Alexandria, Virginia.

Titanium Dioxide.
Growth in production and demand for titanium dioxide continued to increase in the early and mid-2000s, as did the demand for specialty color pigments. As a result, prices increased and some companies moved to increase capacity. Paint and coatings manufacturers used almost half of the titanium dioxide produced in the United States. Other users included the plastics, rubber, printing inks, floor coverings, ceramics, textiles, cosmetics, and paper industries.

Manufacturers used two basic processes to make titanium dioxide. The sulfate process, which produced slightly less than half of the world's supply of titanium dioxide, was the older method. It used sulfuric acid to dissolve the titanium dioxide. Further refinement was required to produce different grades of the finished product.

The newer method, called the chloride process, centered around the use of chlorine and accounted for 51 percent of the world's titanium dioxide capacity. By this method, chlorine was reacted with titanium-containing minerals to produce titanium tetrachloride. The titanium tetrachloride was reacted with oxygen to form titanium dioxide and recyclable chlorine. Advantages of the chloride process included its ability to create higher grades of titanium dioxide without additional handling, its use of less labor and equipment, and its ability to produce in a continuous, as opposed to a batch, process.

The chloride process also produced a smaller volume of waste by-products. Up to 12 tons of waste material were generated when the sulfate process was used in making one ton of titanium dioxide from ilmenite. The chloride process generated four to five tons of waste in producing the same amount of titanium dioxide. A large part of the wastes generated by the chloride process, however, consisted of iron chloride. Disposal of iron chloride created controversy because of its acidic properties and hazardous nature. To reduce the amount of iron chloride waste, manufacturers were forced to rely on higher priced rutile or other purified forms of titanium-containing raw materials. High grade rutile generated only about 70 pounds of iron chloride to yield one ton of titanium dioxide.

New and existing grades of titanium dioxide became more similar to each other as paint formulas were standardized around the world. Slight regional differences, such as particle size or degree of opacity, were being phased out by the industry. Leaders in this trend were DuPont's R-706 multi purpose pigment for coating applications and SCM's RCL535.

Titanium dioxide was also being used to create synthetic pearlescent pigments. Pearlescent pigments, a twentieth-century innovation, were developed in an attempt to create the visual sense of depth associated with natural pearls. Initial pearlescent pigments were made from crystals obtained from fish scales. Rosary bead manufacturers were among the first users of these products.

Researchers identified two chemical compounds with similar light reflective properties. One of these, carbonate white lead, was withdrawn because of its toxicity. The other, bismuth oxychloride, found wide use in applications such as cast polyester buttons, automotive paints, fingernail enamels, cosmetics, wall papers, and plastics.

Synthetic pearlescent pigments, however, failed to exactly duplicate those of fish scales. The search for other synthetic pearlescent pigment compounds led to the use of such minerals as mica. Mica, when coated with titanium dioxide, was judged to reflect light in a manner suitable for use in pearlescent pigments.

Iron Oxides.
The second largest family of pigments was iron oxides. Although iron oxides produced pigments in a wide range of colors, reds accounted for almost half the consumption. In the early 1990s, synthetic iron oxides had two-thirds of the market. Industry forecasters expected increased interest in synthetic iron oxide pigments because they offered improved color strength over naturally occurring ores. The primary users of iron oxide pigments were paint and coatings manufacturers.

Lead Chromates.
Lead chromates represented the third largest family of pigments. Traffic paint manufacturers used about 43 percent of the pigments produced in the early 1990s. Despite their popularity, lead chromates were being subjected to increasing congressional scrutiny because of concerns about lead toxicity and environmental integrity.

Silica encapsulation involved encasing pigment particles or crystals within a shell of silica (a glass-like substance). Researchers claimed that encapsulated lead chromate pigments were protected from chemical, photochemical, and thermal degradation. The encapsulation process also reduced their toxicity by making them less soluble in the body. Researchers also claimed that silica encapsulation improved the brightness and intensity of the pigments, making them better suited for use in high-temperature applications such as plastic manufacturing.

Environmental Impacts.
Questions about environmental degradation and the toxicity of heavy metals challenged the inorganic pigment industry throughout the early and mid-2000s. Heavy metals such as lead, cadmium, chromium, and mercury were associated with ailments including cancer and liver disease. The U.S. Congress and the Environmental Protection Agency (EPA) considered legislative and regulatory initiatives to control, limit, and in some cases ban, the use of several of the industry's essential raw materials. Some manufacturers responded by backing away from heavy-metal pigments. Others defended their formulations and offered evidence that if raw materials were banned, certain colors would become unavailable.

In addition to struggling with direct toxicity problems, pigment manufacturers faced allegations that their disposal of heavy metals used in pigments were threatening the nation's water supplies. Products undergoing incineration or degradation in landfill sites created a potential hazard as heavy metals were released into the environment. As a result of this growing environmental concern, the Conference of North East Governors (representing nine northern states) and the legislatures in several other states, began working to ban heavy metals in packaging materials.

An often-cited example of the difficulties faced by industries forced to switch away from heavy metal inorganic pigments was the problem of the Pennzoil oil bottle. The Pennzoil oil bottle depended on yellow lead chromate for its recognizable bright yellow plastic. During the early 1990s, yellow lead chromate cost between $1.00 and $1.50 per pound, but as legislation was expected to continue to limit the use of lead chromate, the company was forced to look for substitutes for the ingredient. One commonly used substitute cost between $6.00 and $7.00 per pound and other organic yellows cost up to $30.00 per pound. Facing a similar situation, Caterpillar (a manufacturer of heavy equipment) switched from its traditional color to a less bright yellow.

Current Conditions

Revenue for U.S. inorganic dye and pigment manufacturers reached $6.1 billion in 2008, up from $4.6 billion in 2006, according to a report by Supplier Relations US LLC. Despite these figures, growth in the industry was expected to decline, as chromate and other heavy metals were gradually phased out across the industry. Chromate pigments were being increasingly replaced by organic and complex inorganic pigments, which offer superior chemical resistance, and the outlook for those was much brighter. According to a 2009 report by The Freedonia Group, worldwide demand for dyes and organic pigments were expected to increase 3.5 percent annually through 2013.

In 2007, the industry's 96 establishments employed 7,606 people, according to the U.S. Census Bureau. About 64 percent of employees were production workers. Figures from Dun and Bradstreet showed that Ohio, Pennsylvania, and Texas accounted for the most establishments in the industry in the late 2000s.

Industry Leaders

In the mid-2000s, DuPont Coatings & Color Technologies of Wilmington, Delaware, was the number-one maker of titanium dioxide in the world. The company was also the world's largest provider of automotive coatings. Annual sales in the mid-2000s approached $6.2 billion. Another leader in the industry was Huntsman Corp. of Salt Lake City, Utah, which employed 12,600 people and had sales of $10.2 billion in 2008. Kronos Worldwide Inc. is a third leader in inorganic pigments. Headquartered in Dallas, Texas, it is a leading maker of titanium dioxide, of which it produces 40 different grades. Kronos's sales in 2008 were more than $1.3 billion.

Another major company is Ferro Corp. of Cleveland, Ohio. Ferro began operating in 1919 as a frit manufacturer. Frit is a special glass material used to produce porcelain enamel and ceramic glaze. Color pigments for the ceramics and coatings industries were added to the company's product line in 1939. The company began supplying pigments to the plastics industry in 1947. By 2008, Ferro had 5,638 employees and sales of $2.2 billion.

America and the World

The United States exported more inorganic dyes and pigments than it imported, according to Supplier Relations US LLC. In 2008, the value of exports was $2.0 billion, up from about $1.6 billion in 2006. In 2006 Canada received the largest share of those exports, accounting for 17.4 percent, followed by Belgium (14.9 percent), Mexico (13.1 percent), China (5.7 percent), and Brazil (5.3 percent). U.S. imports in 2008 remained essentially flat at $1.1 billion. The top source countries for U.S. imports of inorganic dyes and pigments were Canada, China, Germany, Japan, and Mexico.

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News and information about Inorganic Pigments

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