Pigments in the battle against forgery

Pigments in the battle against forgery

FOCUS ON P I G M E N T S A MONTHLY REPORT FROM REG ADAMS SEPTEMBER 2005 PIGMENTS IN THE BATTLE AGAINST FORGERY In this issue MARKETS 3-5 Degussa ...

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FOCUS ON P I G M E N T S A MONTHLY REPORT FROM REG ADAMS SEPTEMBER 2005

PIGMENTS IN THE BATTLE AGAINST FORGERY

In this issue

MARKETS

3-5

Degussa & Ferro raise their prices in North America No relaxation on anti-dumping measures in EU or US against Chinese ZnO & indigo World consumes 1.66 M tonnes/y of coloured pigments & 6.4 M tonnes/y of barytes Chinese suppliers account for 25% of world iron oxides

PLANTS

5-6

Nubiola to renovate Bulgarian iron oxide pigments plant DIC will build 10,000 tonnes/y organic pigments plant & 18,000 tonnes/y resins unit in China Tokai to add carbon black capacity in China & Thailand Ampacet adds masterbatch capacity in Mexico, Poland & United States Fuji expands astaxanthin plants in US & Sweden

COMPANIES

6-8

CVC creates Xsys out of assets from BASF & Akzo Nobel Huber buys Alu-Chem’s ATH assets PAI Partners buys Hansen’s food colorants business for $1.4 bn

EVENTS

PIGMENTS

AN INTERNATIONAL NEWSLETTER MONITORING TECHNICAL AND COMMERCIAL DEVELOPMENTS IN THE PIGMENTS SECTOR ISSN 0969–6210

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Forgery – the art and crime of making or adapting objects, money or documents with the intention to deceive – has become much more prevalent and difficult to detect in recent years, partly because of the widespread availability of equipment such as colour photocopiers and colour-matching instruments. Traditionally, forgery was associated with fake works of art, such as the prints churned out by 16th Century imitators of Albert Dürer, all signed “AD” to enhance their value. The forgery of coinage has an even longer pedigree, while the production of substantial quantities of counterfeit paper money has been employed not only as a means of personal enrichment but also as a means of warfare, as deployed by the British Government in its attempts to undermine the value of the “Continental dollar” during the American Revolutionary War (1775-1783). To make it relatively easy for ordinary members of the public to spot forged banknotes, the authorities in most areas commission designs involving fine detail with raised intaglio printing on special grades of paper. In more recent times, banknote designs have included holograms and embedded strips or microdots. Software programs such as Adobe Photoshop have been deliberately modified by the manufacturers to obstruct the manipulation of scanned images of banknotes. But forgery nowadays extends beyond works of art and currency reaching into many different product sectors. At the high-security end of

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the spectrum, there are counterfeit postage-stamps, passports, visas and identity-cards. In the so called “transition-security” segment, there are forged credit-cards, cheques, admission tickets and gift vouchers. And in the “consumer-security” segment, there are so called “pirate goods”, including CDs, DVDs, software, pharmaceuticals, perfumes, designer-label clothing and spare parts for machines, vehicles and aircraft. The existence of these forged items can endanger the health and wealth of individual citizens, companies (as genuine producers and retailers) and entire national economies. Not surprisingly, therefore, there are severe penalties for committing forgery and a considerable amount of effort and resources go into detecting and deterring forgeries. The penalties can have unusual ramifications. For example, in January 2002 the US Government imposed Counterfeits as a percentage of Legitimate World Trade, by Product Sector Aircraft parts Clothing Films Music Perfume Pharmaceuticals Software Toys Watches Vehicle parts

10% 22% 12% 33% 5% 6% 43% 12% 5% 7%

Estimates for 2002 Source: OECD

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F O C US trade sanctions on the Ukraine for the alleged persistent failure to crack down on the pirate production of CDs and other optical media products. This meant that Ukrainian TiO2 pigment suppliers were suddenly barred from access to the US market, a market that had been worth nearly $20 M to them in 2001. At various times, other countries where pirate production is alleged to be rife – North Korea, China, Taiwan – have been similarly threatened with far-reaching trade sanctions. Pigment chemists have played an important role in the detection of forgeries. In the 1990s, the Dutch Government was so concerned about the seemingly inexorable rise in the number of genuine Rembrandt paintings catalogued by art galleries and private collections around the world that it set up a committee of experts to determine which paintings were in fact forgeries or copies, as distinct from genuine originals. With access to scientific methods including scanning electron microscopy, radiography, laser-induced breakdown spectroscopy or X-ray fluorescent spectroscopy, the Committee found that some of the works attributed to and apparently signed by Rembrandt incorporated pigments such as Schweinfurt green, ultramarine and Prussian blue. Rembrandt flourished between 1606 and 1669, but Schweinfurt green (an emerald shade) and ultramarine were not produced until 1814, while Prussian (ferrocyanide) blue was not known prior to the 18th Century. The total number of genuine Rembrandt paintings determined by the Dutch Government Committee was 280 – less than half the previously accepted figure. This caused a substantial drop in the valuation of a number of important art gallery holdings (Ref 1). Sophisticated forgers are careful to use only the pigments that would have been appropriate to the era of the master-painter. Hans van Meegeren, who produced and then “discovered” paintings attributed to Vermeer, was one such specialist during the 1930s and 1940s. He insisted on using paintbrushes made from badger bristles in order to eliminate the risk that a stray bristle of modern provenance might be left on the canvas. He was also attentive to the issue of craquelures. Over several

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centuries, the pigments in old paintings tend to become very hard and shrink slightly, leading to the formation of a network of fine cracks and crazings across the entire surface – these are known as craquelures. With a truly old painting, the craquelures blacken with dust and dirt. So to mimic this process, forgers sometimes use modern additives with their oil paints to increase the drying speed; sometimes they try to achieve the effect by slow baking or by scratching the surface with a needle and then wiping with black ink. Although these tricks may deceive the eye of the art critic, modern laboratory analysis should assist in establishing the age and authenticity of a work of art. During the 1940s, Van Meggeren was famous for trading one of his Vermeer paintings for about 200 works of art that had fallen into the hands of Field-Marshal Herman Goering. While some Dutch citizens despised Van Meggeren either for his criminal forgery activities or because he had actively collaborated in trading with the Nazi occupying forces, he was a folk-hero (in the eyes of other Dutch citizens) for having duped Goering and a number of fine-art snobs. In 1957, a dealer in rare books based in Newhaven (Connecticut) bought an allegedly old map, purportedly drafted by Viking or Norse cartographers (800-1100 AD), which clearly shows the coastline of North America designated as Vinland. In 1965, cartographic experts at Yale University declared the map to be genuine and recommended its outright purchase by the Beinecke Library at Yale for about $1 M with money donated by the billionaire, Mr Paul Mellon. The Vinland Map clearly challenged the received wisdom that the American continent had lain undiscovered by the civilised world until the voyages of Christopher Columbus during the 1490s. Indeed, the Vinland Map called into question the significance of 12 October, celebrated in the US and other American countries as Columbus Day, a public holiday. In 1974, Dr Walter McCrone and his team of analytical chemists ran a series of tests on the Vinland Map, using polarised light microscopy, which detected the presence of commercially manufactured anatase grade TiO2. Subsequent tests showed that the

TiO2 particles had a rounded (as distinct from an angular) morphology and that they had a very narrow particle size distribution. These findings strongly suggested that the TiO2 had been manufactured commercially via conventional sulfateroute technology, entailing the formation of hydrated titanyl sulfate, followed by calcination, milling and screening (Ref 2). While it is certainly true that sulfate-route technology for making anatase TiO2 pigment was pioneered in Norway, that was not until 1916 – at least 800 years after the Viking cartographers were supposed to have created the Vinland Map! As well as playing an important role in the detection of forgery, pigment chemists are also playing an important role in deterring forgery or at least making it harder for the criminal to produce counterfeit products and counterfeit packaging. This subject was discussed at length by Dr Klaus Christian Ullmann (Technical Marketing Manager with Merck KgaA, Darmstadt) in a recent article in ‘Ink Maker’ (Ref 3). Dr Ullmann pointed out: “A basic level of security can be achieved by printing with spot colours that cannot be reproduced by photocopiers or digital printers. Also, a metameric pair of inks can be used for the same design. The pair will match under certain lighting conditions (such as natural daylight), but they will not match under the wavelengths typically used by colour copiers or scanners.” Pearlescent pigments are extremely useful in the security printing inks sector. They consist of mica (a natural sheet silicate) ground into small flakes (typically 5-200 microns) which are subsequently coated with TiO2 or with iron oxide. The unique optical properties of these pigments are a combination of light absorption, light reflection and interference. A TiO2 pigment coating of 40-60 nanometres results in transparent silver-white pigments. A thicker layer yields interference pigments. For the consumer security sector, decorative and security features can be combined. Dr Ullmann notes: “In printing, the colour of the background plays an important role and may be integrated as part of the overall security concept. When a red interference pigment is printed on a black background, all the

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F O C US transmitted light is absorbed, resulting in a lustrous brilliant red colour. On a white background, the transmitted light which is complementary to the red interference colour is diffusely scattered and competes with the colour caused by interference at phase boundaries. So the print looks red at a specular angle and it looks light green when viewed from any other angle of observation. Different effects can be produced by different combinations, eg blue interference pigment on a red background. Pearlescent pigments might also be used in combination with highly transparent organic colorants which will greatly affect the resulting optical effects. By applying additional metal oxide layers on the surfaces of the pigment particles, it is possible to enhance the optical effect and to increase the variety of possible colour flip-flops. It is important to use high and low refractive materials alternately. The next step in improving the optical effect of pearlescent pigments is the replacement of natural mica flakes with transparent synthetic carriers, like silica or alumina. Now it is possible to see a variety of colours on the printed substrate when the viewing angle is changed. Again, by varying the thickness of the metal oxide coating, different colour travels are achieved. Certain pearlescent pigments for the high-security market are strictly limited in their availability to the market. The customer company can be sure that the optical effects on its product are unique or at least it knows exactly who else is using the same specific custom-made pigment. The addition of covert security features to the security ink makes it possible to further increase the level of security of the product. The overt optical features allow the customer to immediately identify the (branded) product as legitimate, while the covert features can be used by trained personnel for more sophisticated identification, either in the field or in the laboratory. One option is to add microtaggants to the ink that consist of small spherical particles which differ in size and colour. Each colour and size corresponds to a numerical value and so it is possible to create a unique code system, producing batches of particles for an individual customer all carrying the same code.”

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Dr Ullmann went on to describe the application of pearlescent and colourvariable pigments for different types of printing process – gravure, flexographic, intaglio and screen printing – with regard to pretreatment of the pigment, concentration, binder systems, viscosity adjustment, etc. But the battle against forgeries is similar to the pharmaceutical researcher’s battle against infectious viruses: it is an ongoing battle. In his concluding remarks, Dr Ullmann wrote: “Whatever security technique is applied, usually within one or two years the counterfeiters will catch up. Therefore, it is important to develop and use new features in order to stay always one step ahead.” Reg Adams 1) Adams, Henry: “Rembrandt or not Rembrandt”, Smithsonian Magazine, Dec 1995, 4-8 2) McCrone, Walter C: Journal of Analytical Chemistry, 1988, (60), 1009-1018. 3) Ullmann, Klaus Christian: Ink Maker, Apr 2005, 83 (3), 16-22

MARKETS North American carbon black prices increased by energy surcharges Effective 15 September 2005, Degussa Engineered Carbons LP will be increasing the “energy surcharge” applicable to prices for its shipments of carbon black to customers in North America. Most of its carbon black grades will be increased by $0.030.04 per pound. Rubber and Plastics News, 5 Sep 2005, 35 (3), 4

Ferro raises North American prices for complex inorganic pigments Effective 15 July 2005 or as soon as permitted by contracts, Ferro Corp increased its list prices by 5-15% for all its complex inorganic pigments sold to North American customers in the paint and plastic markets. Press Release from: Ferro Corp, Cleveland, USA, Tel: +1 216 875 6205, Website: http://www.ferro.com (15 Jul 2005)

Chinese traders use Kazakh depots to circumvent EU anti-dumping duties Nearly four years ago, the European Union imposed anti-dumping duties

on zinc oxide imported from China. These measures were originally enacted as Regulation 1827/2001 and they were then extended as Regulation 408/2002. The antidumping duties range from 6.9% to 28%, depending on the zinc oxide product grade. In recent months, EU domestic suppliers have alleged that various Chinese traders have been circumventing the anti-dumping measures by trans-shipping their products via Kazakhstan. The EU suppliers point to a sudden upsurge in imports of zinc oxide consigned from Kazakhstan and in most cases declared as being material of Kazakh origin. On 27 June 2005, EuroMétaux lodged a formal complaint with the European Commission, calling for an investigation. EuroMétaux stated that its complaint had the backing of a number of producers, collectively representing more than 45% of total EU production of standard and premium quality zinc oxide (containing at least 93% ZnO and classified under TARIC code 2817.0000.13). On 4 August 2005, Regulation 1289/2005 was formally adopted, authorising the European Commission to investigate the matter. Official Journal of the European Communities L Legislation, 5 Aug 2005, 48 (L204), 7-10 (Website: http://europa.eu.int/eur-lex)

US unlikely to relax anti-dumping duties on Chinese synthetic indigo On 2 May 2005, the US International Trade Commission (ITC) initiated a review of the anti-dumping duties imposed on imports of synthetic indigo from various Chinese suppliers. As a result of previous investigations, anti-dumping duties were imposed on: Liyang Skyblue Chemical, China Jiangsu International Economic Technical Cooperation Corp, Wonderful Chemical Industrial Ltd and Jiangsu Taifeng Chemical. (See also ‘Focus on Pigments’, Jun 2003, 3). The review was described as an “expedited sunset review” and its prime objective was to determine whether revoking the anti-dumping duties on Chinese synthetic indigo would be likely to lead to a recurrence of material injury to US domestic suppliers. At least one “domestic interested party” (presumably a US

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