COVER STORY
PAINTS AND COATINGS Consolidation among PAINT MATERIAL MAKERS brings opportunities as well as risks MARC S. REISCH, C&EN NORTHEAST NEWS BUREAU
FEW PEOPLE SIT AROUND watching
paint dry, but enough people buy the stuff to make it a major market for the chemical industry. Polymers, emulsions, pigments, coalescents, and other paint ingredients are a showcase of the industry's invention and ingenuity. Paint material makers are consolidating, however, driven by the paint business' slow growth, complications wrought by growing environmental regulations, and difficulties in passing on increases in raw material and energy costs. In some cases, the consolidators are combining acquired technologies with inhouse skills to spur new growth. In other cases, raw material suppliers are adopting advances in areas other than paint as away to boost both paint material innovation and profits. In 2005, paint formulators worldwide sold $86 billion worth of architectural, MORE ONLINE
product, and special-purpose coatings, according to a study of the market by Euromonitor International. The study, conducted for paint maker Akzo Nobel and published earlier this year, concludes that the global market has been growing at about 3% annually in dollar terms over the past four years. The pace of growth is likely to increase to more than 5% annually over the next 10 years, thanks to rapid growth in the Asia-Pacific region and Eastern Europe. Because of the large number of ingredient makers and paint formulators scattered across the globe, the size of the global paint business is difficult to gauge, so estimates vary. Phillip G. Phillips, managing director of Chemark Consulting, sets the value of the market at just $72 billion. North America and Western Europe are mature, stable markets growing at about the same rate as the economy overall. But the fastest grow-
ing markets are in the rapidly industrializing countries of the Asia-Pacific region, where Phillips says paint sales are growing at about 14% annually. Despite the growing value of paint sales, paint prices have not kept pace with consumer price indexes in North America and Western Europe. Phillips attributes the lag to the overcapacity that plagues both regions' paint industries. The resulting competition limits price increases and even forces some paint makers to fold. Phillips counted 2,000 North American paint makers in 1975, but he counts only about 900 today. In Western Europe, the story is much the same, with 2,700 paint makers declining to 1,000 today. The tough competition also makes it difficult for paint makers to pass along increases in energy and raw material costs. Phillips blames paint makers and material
Enhancing paint with jazzy special effect pigments and with cyclodextrins that can add fragrance to or remove odors from a room is described on C&EN Online, www.cen-online.org. WWW.CEN-0NLINE.ORG
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COVER STORY
The $1.8 billion purchase extended Cytec's geographical reach in Asia and gave U.S. shipment values and paint prices rose in all categories in 2005 the firm new positions in the ARCHITECTURAL COATINGS SPECIAL-PURPOSE COATINGS PRODUCT COATINGS3 fast-growing powder and SHIPMENTS SHIPMENTS SHIPMENTS radiation-curable coatings MILLIONS MILLIONS MILLIONS markets. The UGB busiOF GAL $ BILLIONS $ PER GAL $ BILLIONS $ PER GAL OF GAL OF GAL $ BILLIONS $ PER GAL nesses also included former 2005 795 $8.92 $23.33 $11.22 402 $3.64 156 $5.99 $14.90 2004 804 8.62 22.77 10.72 404 3.53 5.87 155 14.53 Solutia and Hoechst coat2003 762 20.42 8.01 3.37 10.51 399 5.54 165 13.88 ings resins operations that 2002 710 18.31 7.61 10.72 409 3.15 172 5.56 13.59 UCB acquired in 2003. 2001 667 7.04 21.18 407 3.41 10.55 5.57 161 13.69 Jean-Marc Durbuis, Cya Sold to original equipment manufacturers. SOURCE: Bureau of the Census tec's global business director for powder coatings, says the combination of Cytec and UCB operations suppliers for not doing enough to convince well on their own, Phillips says. Such is the puts the firm's focus on higher growth paint buyers that paint is a valuable commodity. case with BASF, which makes pigments technologies such as water-based alkyd and One way out of the price conundrum and urethane systems, for instance, as well acrylic resins, polyurethane dispersions, and would seem to be controlling more of the as formulated paint for automobiles and ultraviolet-light-curable resins. While the value chain by manufacturing both paint coil coatings. It is also the case for DuPont, global paint market lumbers along at roughraw materials and finished paint products. which supplies paint makers with the widely 3% growth per year, the markets Cytec With a few exceptions, though, companies ly used white pigment titanium dioxide and serves grow at 5-10% annually, Durbuis says. haven't pursued that business model. For also formulates car paints. instance, when paint raw material maker In powder coatings, Cytec supplies the Rohm and Haas bought Morton Internapolyester and acrylic resins used to make MORE COMMONLY, though, raw material tional in 1999, it also acquired an automoheat-fusible paint. According to Durbuis, suppliers have a hands-off attitude toward tive paint business. It recently sold that the company is linking this powder knowthe finished paint business. Instead, they business to Nippon Paint for $230 million. how with its expertise in ultraviolet-curlook to buy businesses that extend their able coatings to help formulators develop Akzo Nobel found that it could not reach and profit potential in paint materials. new markets for UV-curable powders and leverage its coatings resins business and In 2005, for example, Cytec Industries UV-curable polyurethane dispersions. sold it in 2004 to New Zealand-based resins bought UCB's surface specialties business. maker Nuplex Industries for $140 million. "Akzo could buy coatings resins from other makers comparable to what it made itself at about the same price," Phillips says. Some paint material suppliers do also make coatings, but they succeed at it by operating the businesses in silos that do
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In 2005, paint formulators worldwide sold $86 billion worth of architectural, product, and special-purpose coatings.
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and oil-field chemicals into the coatings industry. Indeed, thanks to an earlier partnership with Tomah, Air Products has already trans ferred Tomah alcohol alkoxylate technology for cleaning products to the waterborne paints market. Laurie Marshall, marketing manager for coatings and adhesives, says the new Carbowet surfactants are for archi tectural paint formulations and replace alkylphenol ethoxylate wetting agents that are persistent in the environment and suspect ed of being endocrine disrupters. THE NEW ADDITIVES are simple drop-in replacements for the alkylphenol ethoxylates in most cases, Marshall says. "They will also enable us to expand our pres ence in architectural coatings." The combination of Carbide and Dow Chemical "has acceler ated cross-platform learning," says Graves Clayton, North Ameri can coatings market manager. As a result, a Dow-developed opacifier used for paper is being adapted for coatings. Use of the Ucarhide opacifier will reduce the need for more expensive titanium dioxide, he says. Like Celanese, Dow sees opportunities for VAE because of more stringent environ ment regulations. The firm has developed the first in a new line of ethylene-modified polymers that it claims have better perfor mance properties than traditional VAEs. The new Evocar emulsion is resistant to water and blocking, such as when a painted door gets stuck to a painted frame. It is also an inherently low-VOC product that will meet California's demanding new 50-g/L requirements, Clayton says. Although not due to an acquisition, Ciba Specialty Chemicals also transfers product developments from one platform to an other. For instance, the firm often develops light stabilizers and antioxidants to im prove the durability and weather resistance of plastics and then transfers them to the coatings business, says Colin C. Mackay, head of coating effects for Ciba. Another example is silver-ion-based bactericides developed for plastics but now being used in coatings, he says. Ciba also develops photoinitiators used in radiation-curable coatings, and for this market, it is developing a new process, along with partners in a consortium, to instantly cure large three-dimensional objects such as entire car bodies. The con WWW.CEN-0NLINE.ORG
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sortium members have developed a plasma chamber filled with an inert gas such as helium or nitrogen, says technical manager Eugene V. Sitzmann. A short microwave burst in the cham ber creates a UV light that instantly cures coatings in every nook and cranny that the gas has penetrated. "It is like placing a car inside a light bulb," Mackay says. Even the most complex 3-D object can cure with minimum VOC emissions, he claims. Rohm and Haas managers say their
coatings raw material ON-LINE A lab business is more often technician asourceofnewideas E ^ t i n g for other business plat- o n pj|0t | j n e forms. For instance, the HIHH1 firm's Ropaque styrene acrylic hollow spheres were developed to replace more expensive titanium dioxide in paint formulations. But now the firm has developed a market for the hollow spheres in personal care sunscreens under the SunSpheres name, says Luis Fernandez, business unit director for architectural and functional polymers. Some firms are concentrating on slimmed down paint material portfolios. Eastman Chemical sold off its Lawter and McWhorter resins businesses in 2004 and now focuses on its traditional coatings additives, adhesion promoters, low-VOC solvents, and coalescent agents. "We look for ways to leverage internal technology to satisfy customer needs," says David C. Stump, general manager of the global coat ings business. An example is Eastman's development of Optifilm coalescents, introduced two years ago for use in low-VOC formulations that meet the new California requirements. Whether they have reduced their heft, like Eastman, or enlarged their presence in the market, like Cytec, all the key players acknowledge that invention and ingenuity in developing raw materials is still the key to success. •
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COVER STORY
mous thermal spray consulting firm in Surrey, England, says metals and ceramics can be applied to various surfaces using a variety of thermal spray techniques. For instance, wire flame spray and wire arc spray techniques are used to coat large metallic structures such as bridges with anticorrosive coatings. "Basically, anything you can't put into a galvanizing bath" is a candidate for these spray techniques, he says. The equipment used for wire arc spray coating resembles welding equipment, in which two electrodes form an electric arc. In the wire arc process, air or an inert gas such as nitrogen is fed into a spray gun. The gas passes over melting wires and propels molten droplets onto the target. Heat source temperatures can run as high HEATED ENCOUNTER
High-velocity oxygen fuel spray gun applies a durable tungsten carbide cobalt coating onto a pump sleeve.
THERMAL SPRAY GOES COOL New COLD SPRAY TECHNIQUE for high-performance coatings is the latest thing in surface modification MARC S. REISCH, C&EN NORTHEAST NEWS BUREAU
MOST COATINGS have a functional purpose as well as a decorative one. Paint protects a car's body against the elements while adding razzle-dazzle to its appearance. Some coatings, though, are mainly functional, and as a class, thermal spray coatings are the most functional of all. Traditionally, thermal spray coating applies metals, ceramic, plastics, and mixtures of these materials at temperatures ranging from 4,500 to 30,000 °F. Such coatings provide surer footing on oil-rig platforms and increase the durability of auto transmission components. Thermal spray coatings are typically used to impart improved wear, corrosion, and abrasion resistance in applications where curb appeal does not matter as much as performance under rugged conditions where traditional polymer paints alone just won't do. But a nascent technology, cold spray, can be used to apply functional coatings at or near room temperature. Cold spray is less energy and heat intensive than existing processes and provides a novel means of coating or altering a variety of materials. One new entrant, Dow Corning, has launched a business to commercialize and license cold plasma spray technology. Industrial gas firm Praxair, long involved in
the thermal spray services and equipment business, has commercialized a slightly different cold spray technology. Traditional thermal spray coating is a substantial business. Markus Heusser, head of Sulzer Metco Thermal Spray, pegs the global market for thermal spray powders and equipment at just less than $1 billion annually. Sulzer Metco is a Switzerland-based thermal spray services provider as well as a maker of thermal spray equipment. Overall, Heusser says, the market grows at about the same rate as gross domestic product, which means slower growth rates in Western Europe and the U.S., and higher growth rates in the rapidly expanding economies of Asia. The market for thermal spray coatings is even larger if thermal spray applicator sales are included. Alejandro Pena, vice president of thermal spray consumables for Praxair Surface Technologies, places the global market at about $2.5 billion. Gordon England, who heads an epony-
as 15,000 °F.
Wire flame spray coating is a little different. A spark is used to ignite an oxygen and fuel mixture in a spray gun that is holding a metal rod. After the rod turns molten, it is disintegrated by a stream of air and then propelled onto the object to be coated. Temperatures are generally below 4,500 °F. Both wire arc and wire flame spray techniques have been around for a while, England says. A more recent development is the high-velocity oxygen fuel (HVOF) gun, which allows application of "extreme wear" coatings such as tungsten carbide or chromium carbide. The paper industry uses such coatings to increase the useful life of paper machine rollers. The HVOF gun mixes oxygen and a fuel to achieve temperatures of about 5,000 °F. MORE ADVANCED are high-temperature plasma spray guns, says England, who calls such equipment a "universal tool to spray virtually any material." The high temperature and control over coating thickness offered by plasma spray makes it a favorite to apply ceramic coatings, he adds. Potential applications include coating jet engine turbine blades and airplane landing gears.
Using metal powders, the cold spray process produces a very clean, oxide free, electrically conductive coating. WWW.CEN-0NLINE.ORG
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Other plasma spray uses include application of a biocompatible coating, such as hydroxyapatite, over artificial joint implants. Plasma spray equipment uses two electrodes to form a plasma gas consisting of argon and hydrogen or argon and helium. The gas melts metal, ceramic, and carbide powders at temperatures that may exceed 30,000 °F. The technique to spray metal, polymers, and other particles at or slightly above room temperature is still experimental, England says. This cold spray process flings powders at high velocity to produce a coating that flattens and adheres to the
equipment, which uses a jet of cold plasma to cover a substrate with a uniform coating just tens of nanometers thick. According to Program Manager Andy Goodwin, Dow Corning began working on cold spray processes as far back as 1996 when it undertook a research project with the University of Durham, in England. As work with the university progressed, the
company found the technology increasingly promising. To bring it to the industrial market, however, the firm needed to focus on developing the appropriate equipment. In 2001, Goodwin recalls, Dow Corning bought equipment know-how from an Irish firm and then set up shop in Cork, Ireland, to come up with a commercially viable cold
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substrate. Using metal powders, the process produces what England calls a "very clean," oxide-free, electrically conductive coating. Metal, metal composites, paper, and plastics can serve as substrates for such coatings, he adds. But the pressure and volume of gas used in cold spray technologies "is alarmingly large," England says. Where helium is used for cold spray, manufacturers "need to think about building gas recovery systems, otherwise gas costs will be very high," he says. Alternatively, they could use less expensive gases such as nitrogen. According to England, Russian scientists originally developed cold spray technology in the mid-1980s as an alternative to HVOF thermal spray. Although he says industrial users are interested in the process, he considers it largely experimental at this time. Dow Corning is one firm, however, that hopes to take cold spray technology from lab curiosity to the industrial production line. In August, it began to offer industrial clients its PlasmaStream technology and
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spray plasma process. This summer, with several patents in hand, Dow Corning and equipment fabrication partners brought out new cold plasma spray equipment. Equipment in the SE-iooo series comes in widths of 1-8 feet depending on cus tomer needs, says Gary Lord, a Dow Cor ning commercial manager. SE-1000 series equipment is suited for coating textiles and
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COVER STORY
regulatory authorities in the state over the contribution that paint-derived VOCs make to smog compared with VOC s from automobiles. Since 2000, Dunn-Edwards has distributed recycled paints processed by Amazon Environmental, also based in California, under the Recover brand. "Consumers generally think of recycled paint as garbage," says Robert Wendoll, Dunn-Edwards' director of environmental affairs. "And smearing garbage over their walls is not appealing to most people." The new standards, he says, will assure consumers, architects, and specifiers that the certified recycled paints are viable materials. The recycled paints Dunn-Edwards distributes are now undergoing certification through Green Seal, Wendoll adds. Pamela McAuley, vice president of development for Hotz Environmental Services, a family-owned concern in Hamilton, Ontario, has collected and processed industrial and household waste for 17 years. "We realized we had a lot of reusable paint and so we started to recycle the paint in small batches," she said. The firm participated in the dialogue leading up to the Green Seal certification standards. Hotz, which collects overruns as well as incorrectly labeled paint from paint manufacturers, exports about 500,000 gal of recycled latex and solvent-based paint annually to countries such as Malaysia, Mexico, Chile, and China. Manufacturers, who pay a small fee to Hotz, are "sensitive" about the sale of recycled paints domestically, McAuley says. Minimizing use of resources is also behind Rohm and Haas's introduction of a new acrylic resin product line under the Avanse name. According to Luis Fernandez, business unit director for architectural and functional polymers, Avanse works at the interface of the pigment and resin binder, forming a tighter lock between pigment particles than in other resins. The result is a more opaque film that provides one-coat coverage for architectural and industrial applications. Formulators can also reduce costs by using less pigment than they normally would, Fernandez says. Rohm and Haas is also trying to reduce the use of petrochemical raw materials. Using $3.75 million in grant money received in 2004 fr°m the Department of Energy, Rohm and Haas is working with agricultural processor Archer Daniels Midland to develop polymer technology that can remove as much as 30% of petrochemical raw
materials now being used to manufacture paints and coatings. Archer Daniels is contributing low-VOC biomass-derived coalescing agents to the ongoing project. The University of Minnesota is performing analytical chemistry and polymer characterization testing. Other firms are trying to introduce new biomass-derived raw materials into coatings on a larger scale. DuPont plans to bring biomass-based polymers to the automotive refmish market by 2008. Together with its partner, British sugar producer Tate & Lyle, DuPont is constructing a plant in Tennessee to make 1,3-propanediol, a raw material for the polymers, from corn sugar. DuPont first undertook the Tennessee project to supply 1,3-propanediol for the manufacture of its Sorona fibers for clothing and carpets. John McCool, vice president and general manager of DuPont Automotive Refinish Systems, says 1,3propanediol from the Tennessee plant will also be used to develop a new generation of sealers, primers, and clear coats. The new finishes are being derived from renewable resources and will have low-VOC emissions and deliver what McCool calls "superior performance at a competitive price." International Specialty Products (ISP) is looking to nature for inspiration. Ray Fahmy, marketing manager, says the firm recently introduced a new in-can preservative based on glycine, a naturally occurring amino acid. The glycine used in ISP's Nuosept 44, an aqueous solution of sodium hydroxymethylglycinate, however, is synthetically derived. THE CHEMISTRY for Nuosept 44 was originally developed about eight years ago as a baby wipe preservative, Fahmy says. ISP has since introduced glycine-based preservatives in the personal care, household cleaners, and detergents markets. Although the greatest effort seems to be behind the development of more benign waterborne paint systems, work continues on greener solvent-based paint systems. Sometimes these developments can take many years. Seventeen years ago, C&EN reported on industry interest in oil derived from the seed of Vernonia galamensis, a plant native to Africa. Back then, Robert E. Perdue Jr., a taxonomic botanist who had recently retired from the Department of Agriculture's Agricultural Research Service, explained that oil derived from the seed is chemically similar to epoxidized soybean and linseed WWW.CEN-0NLINE.ORG
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oil. Although the two modified seed oils are widely used in paints and coatings, they are highly viscous, semisolid at 50 °F and nonpourable below 32 °F. By contrast, vernonia oil has a low viscosity and is pourable below 32 °F. At the time, Perdue said the oil showed great potential as a reactive diluent in very low VOC alkyd paint systems. He even started his own company, Ver-Tech International,
GREENER in Bethesda, Md., to comPASTURES mercialize the oil. "We Vernonia were on the verge of sucgalamensis cess and then we ran out is the source of money," Perdue says to- of a valuable day. He adds that "we have diluent for alkyd paints. a new plan of action and ^^^™ expect to move ahead." Perdue has some competition now. In August, a London-based firm, Vernique BioTech, announced it had signed a deal to commercialize vernonia oil with the government of Ethiopia. A Vernique partner, Paul McClory, says his privately financed firm hasn't partnered with any paint companies yet. Given the Ethiopian deal, however, "there is no reason why vernonia could not start entering the paint industry next year—obviously on a trial basis—but it should expand exponentially from there," he tells C&EN. The attempt to introduce vernonia oil into commerce is perhaps an extreme example of how long it can take to get a new product on the market. But with the increasing emphasis today on marketing environmentally friendly and renewable ingredients, perhaps the time is finally coming when vernonia oil and other green products will gain greater market acceptance. •
