world zircon shortage looming?

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compound. A masterbatch consists of pigment plus additives dispersed in a solid polymer carrier, usually in pelletised form. The converter takes the masterbatch and “lets it down” (ie melts it or dilutes it) at concentrations ranging from 0.5% to 25% into clear polymer in order to produced the coloured plastic raw material with the properties required. In the case of a TiO 2 masterbatch, the loading of TiO 2 in the masterbatch is typically between 40% and 80%. So, to obtain a 5% concentration of TiO 2 in the finished product, the let-down ratio (resin:masterbatch) using a 50% TiO 2 masterbatch must be 9:1. If a 60% TiO 2 masterbatch were used, the let- down ratio would have to be 11:1. There are a number of advantages for the converter in using plastics masterbatches. Instead of keeping stocks of ready-compounded material in several different colours, he can simply keep separate bins of masterbatch pellets and thus save on inventory cost and space. Workers at the converter’s factory handle dust- free pellets, which represent less of a health and safety risk than fine- particle pigment powders. It is easier for the converter to obtain optimal dispersion and consistent batch-to- batch colours using masterbatches because the first-stage blending, dispersion and colour development have already been carried out by the masterbatch manufacturer. Masterbatches are normally supplied as polymer-specific products, with the pigments and additives dispersed in the polymer that will ultimately be used for the “let-down” stage. Suppliers also offer universal masterbatches, where the carrier system is compatible with a wide range of polymers. Unless used carefully, universal masterbatches can lead to problems of homogeneity, with adverse effects on the physical and colour properties of the final plastic product. White and black masterbatches, based on TiO 2 and carbon black respectively, are widely used. Calcium carbonate and lithopone, together with TiO 2 , are also incorporated into white masterbatches, particularly in Europe. For yellow and red plastics, iron oxide and mixed metal oxide pigments are often used. However, there has been a rapid decline over the past 10 years in the consumption of some of the other inorganic reds and yellows, based on cadmium sulfide or selenosulfide, lead chromate or molybdate. To some extent, colours based on heavy metal pigments have been replaced by colorants incorporating higher loadings of TiO 2 , iron oxides and organic pigments (eg Hansa yellow). For example, a standard red colorant for polyethylene film used to contain: 82% cadmium pigment, 10% TiO 2 , 5% organic pigment and 3% iron oxide. The replacement colorant contains: 45% organic pigment, 40% TiO 2 and 15% iron oxide. Because of the radical differences in the composition of the “old” and “new” colorant, it can be quite a challenge to attain exact colour matching in the final product. Another colour matching challenge arises from the use of different base polymers. In a car interior, the upholstery and door panels may be made of PVC, the steering wheel of polyurethane, the instrument panels and door trim of polypropylene, the glove-box cover of ABS and the switches of polyamide. But the vehicle designer insists on having a uniform colour for all these items! The colour of plastic products exposed to strong sunlight tends to fade. Moreover, most organic pigments show a much greater tendency to fade than inorganic pigments and this tendency tends to be accentuated in the presence of TiO 2 . Fading of the organic pigment can lead to an unacceptably high level of colour difference, especially with yellows, oranges and reds. Introducing organic ultraviolet-absorbers into the formulation can sometimes improve fade-resistance, but a better solution is to use nickel or chrome titanates as partial substitutes for TiO 2 to provide opacity and background coloration. Weatherfastness is also an important criterion in certain applications: some organic pigments can be adversely affected by conditions of mildly acidic rainfall or high atmospheric moisture levels. Final products, especially plastic films, are becoming thinner and yet the requirement for opacity remains the same as before. Essentially, this necessitates higher loadings of TiO 2 or carbon black in the masterbatch. In the US, loadings of 75-80% TiO 2 are quite common nowadays, whereas European masterbatch formulations are typically still based on 60% loadings. But higher pigment loadings tend to have an adverse impact on viscosity and dispersibility. Clearly, the manufacture of plastics masterbatch is becoming increasingly sophisticated, demanding investment in scientific research and close collaboration with plastics processors and their customers. Ongoing growth of 4-5% per annum in the world’s consumption of plastics provides a good incentive for the leading masterbatch suppliers to meet the technical and market challenges ahead. Reg Adams MARKETS World zircon shortage looming? Global zircon demand is rising much faster than supply, one of the major factors being the continued boom in sales of zircon to the ceramic tile sector in China. Most zircon is generated as a by-product at ilmenite or rutile mines, so that the supply of zircon is geared mainly to the demand for TiO 2 feedstock from pigment manufacturers. World zircon production is estimated at 1.089 M tonnes in full-year 2002 and it is forecast to increase to 1.119 M tonnes in 2003. Australia and South Africa currently account for about 77% of world zircon production, with the major suppliers being Iluka Resources and Richards Bay Minerals (a 50:50 joint venture between Rio Tinto and BHP Billiton). For full-year 2002, world zircon supply increased by 3.8%, but demand rose faster than this, resulting in a deficit of 1200 tonnes. Zircon use in ceramics is expected to rise from 571,000 tonnes in 2002 to 589,000 tonnes in 1993 and to 626,000 tonnes by 2005. Total world 2 JULY 2003 FOCUS ON PIGMENTS World: Plastics Colorants Demand (‘000 tonnes) Total 2300 Titanium dioxide 900 Other white pigments 400 Carbon black 600 Inorganic colours 350 Organic colours 50

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Page 1: World zircon shortage looming?

compound. A masterbatch consists ofpigment plus additives dispersed in asolid polymer carrier, usually inpelletised form. The converter takesthe masterbatch and “lets it down” (iemelts it or dilutes it) at concentrationsranging from 0.5% to 25% into clearpolymer in order to produced thecoloured plastic raw material with theproperties required. In the case of aTiO2 masterbatch, the loading of TiO2in the masterbatch is typicallybetween 40% and 80%. So, to obtaina 5% concentration of TiO2 in thefinished product, the let-down ratio(resin:masterbatch) using a 50% TiO2masterbatch must be 9:1. If a 60%TiO2 masterbatch were used, the let-down ratio would have to be 11:1.

There are a number of advantagesfor the converter in using plasticsmasterbatches. Instead of keepingstocks of ready-compounded materialin several different colours, he cansimply keep separate bins ofmasterbatch pellets and thus save oninventory cost and space. Workers atthe converter’s factory handle dust-free pellets, which represent less of ahealth and safety risk than fine-particle pigment powders. It is easierfor the converter to obtain optimaldispersion and consistent batch-to-batch colours using masterbatchesbecause the first-stage blending,dispersion and colour developmenthave already been carried out by themasterbatch manufacturer.

Masterbatches are normallysupplied as polymer-specific products,with the pigments and additivesdispersed in the polymer that willultimately be used for the “let-down”stage. Suppliers also offer universalmasterbatches, where the carriersystem is compatible with a widerange of polymers. Unless usedcarefully, universal masterbatches canlead to problems of homogeneity, withadverse effects on the physical andcolour properties of the final plasticproduct.

White and black masterbatches,based on TiO2 and carbon blackrespectively, are widely used. Calciumcarbonate and lithopone, togetherwith TiO2, are also incorporated intowhite masterbatches, particularly inEurope. For yellow and red plastics,iron oxide and mixed metal oxidepigments are often used. However,there has been a rapid decline overthe past 10 years in the consumptionof some of the other inorganic redsand yellows, based on cadmiumsulfide or selenosulfide, leadchromate or molybdate. To someextent, colours based on heavy metalpigments have been replaced bycolorants incorporating higherloadings of TiO2, iron oxides andorganic pigments (eg Hansa yellow).For example, a standard red colorantfor polyethylene film used to contain:82% cadmium pigment, 10% TiO2, 5%organic pigment and 3% iron oxide.The replacement colorant contains:45% organic pigment, 40% TiO2 and15% iron oxide. Because of theradical differences in the compositionof the “old” and “new” colorant, it canbe quite a challenge to attain exactcolour matching in the final product.

Another colour matching challengearises from the use of different basepolymers. In a car interior, theupholstery and door panels may bemade of PVC, the steering wheel ofpolyurethane, the instrument panelsand door trim of polypropylene, theglove-box cover of ABS and theswitches of polyamide. But the vehicledesigner insists on having a uniformcolour for all these items!

The colour of plastic productsexposed to strong sunlight tends tofade. Moreover, most organic pigmentsshow a much greater tendency tofade than inorganic pigments and thistendency tends to be accentuated inthe presence of TiO2. Fading of theorganic pigment can lead to anunacceptably high level of colourdifference, especially with yellows,oranges and reds. Introducing organicultraviolet-absorbers into theformulation can sometimes improvefade-resistance, but a better solutionis to use nickel or chrome titanates aspartial substitutes for TiO2 to provideopacity and background coloration.Weatherfastness is also an importantcriterion in certain applications: someorganic pigments can be adverselyaffected by conditions of mildly acidic

rainfall or high atmospheric moisturelevels.

Final products, especially plasticfilms, are becoming thinner and yetthe requirement for opacity remainsthe same as before. Essentially, thisnecessitates higher loadings of TiO2or carbon black in the masterbatch. Inthe US, loadings of 75-80% TiO2 arequite common nowadays, whereasEuropean masterbatch formulationsare typically still based on 60%loadings. But higher pigment loadingstend to have an adverse impact onviscosity and dispersibility.

Clearly, the manufacture of plasticsmasterbatch is becoming increasinglysophisticated, demanding investmentin scientific research and closecollaboration with plastics processorsand their customers. Ongoing growthof 4-5% per annum in the world’sconsumption of plastics provides agood incentive for the leadingmasterbatch suppliers to meet thetechnical and market challengesahead.

Reg Adams

MARKETSWorld zircon shortage looming?

Global zircon demand is rising muchfaster than supply, one of the majorfactors being the continued boom insales of zircon to the ceramic tilesector in China. Most zircon isgenerated as a by-product at ilmeniteor rutile mines, so that the supply ofzircon is geared mainly to the demandfor TiO2 feedstock from pigmentmanufacturers. World zirconproduction is estimated at 1.089 Mtonnes in full-year 2002 and it isforecast to increase to 1.119 M tonnesin 2003. Australia and South Africacurrently account for about 77% ofworld zircon production, with themajor suppliers being Iluka Resourcesand Richards Bay Minerals (a 50:50joint venture between Rio Tinto andBHP Billiton).

For full-year 2002, world zirconsupply increased by 3.8%, butdemand rose faster than this,resulting in a deficit of 1200 tonnes.Zircon use in ceramics is expected torise from 571,000 tonnes in 2002 to589,000 tonnes in 1993 and to626,000 tonnes by 2005. Total world

2 JULY 2003

F O C U S O N P I G M E N T S

World: Plastics Colorants Demand(‘000 tonnes)

Total 2300Titanium dioxide 900Other white pigments 400Carbon black 600Inorganic colours 350Organic colours 50

Page 2: World zircon shortage looming?

consumption of zircon is forecast toreach 1.188 M tonnes/y by 2005.

Industrial Minerals, May 2003, (428), 42-45

Honeywell forecasts strong growth inusage of luminescent pigments

According to Honeywell, USconsumption of luminescent pigmentsfor safety applications increased by50% last year. US consumption overthe next few years is forecast to riseat 20-30% per annum. Meanwhile, inEurope demand is strong forluminescent pigments to provide after-glow in safety guidance systems. Themajor end-uses for luminescentpigments are in: brand security andauthentication (ie anti-counterfeitingmeasures).

Honeywell itself manufactures theLumilux range of pigments at Seelze(Germany) and is keen to widen thepalette of available colours.

Chemical Market Reporter, 24 Mar 2003 (Website:http://www.chemicalmarketreporter.com)

Chinese, German & Indian suppliersdumping optical brighteners in the US?

The position regarding possibledumping of optical brighteners in theUS market is a little confused. In earlyApril 2003, the US International TradeCommission announced that it hadbegun investigating allegations thatoptical brighteners from China,Germany and India were being sold inthe US at less than fair value. Theinvestigation was apparently sparkedoff by a complaint from Ciba SpecialtyChemicals. Then, on 10 April, the USDepartment of Commerce (USDC)announced that it had receivednotification from Ciba that the companywanted to drop its complaint.

On 14 May, the USDC reportedthat it had received an anti-dumpingpetition from Ciba. Supplementaryinformation was provided on 27 Mayand 29 May. Ciba alleges that exportsof optical brighteners from India arebeing unfairly subsidised by the IndianGovernment. The formal petitionnames the products under scrutiny as:4,4’-diamino-2,2’-stilbenedisulfonicacid (DAS) and stilbenic fluorescentwhitening agents (SFWA). DAS isessentially an intermediate, which isquite widely used to produce SFWA,which are synthetic organic productsnormally used as fluorescent

brightening agents in the productionof certain textiles, papers anddetergents.

Federal Register, 8 Apr 2003, 68 (67), 17084-17085 &10 Jun 2003, 68 (111), 34582-34584 & 10 Jun 2003,68 (111), 34579-34584 (Website:http://www.gpoaccess.gov/fr/advanced.html)

India levies duties of up to $358 pertonne on Chinese anatase TiO2

The Designated Authority in theDirectorate General of Anti-dumping &Allied Duties has investigated claimsof dumping of Chinese anatase-typeTiO2 on the Indian market, followingcomplaints by Travancore TitaniumProducts (TTP of Trivandrum),Kolmak Chemicals (of Kolkata) andKilburn Chemicals (of Chennai). Theinvestigation focused on importsduring calendar year 2002. Thecomplaints were upheld and provisionalanti-dumping duties have beenimposed as follows: $303.70 per tonneon imports from Shaugan ChemicalWorks; $313.01 per tonne on importsfrom Guangxi Dahua ChemicalWorks; $342.34 per tonne on importsfrom Guangxi XiXing MeiXiangTitanium Manufacturing Co; and$358.04 per tonne on imports from allother Chinese suppliers.

Business Line, 14 Jun 2003, 10 (164), 4

China’s organic pigments outputapproaches 100,000 tonnes/y

China’s production of organic pigmentsincreased by 11.15% to reach 95,700tonnes in 2002. Meanwhile, thecountry’s production of dyesincreased by 31.33% to reach421,300 tonnes. The production ofdisperse dyes increased by 29% to226,000 tonnes, while the output ofreactive dyes increased by 34.1% to38,000 tonnes.

The leading producer of organicpigments was Shanghai BASF, a51:49 joint venture between BASFColorants and Shanghai Dyestuffs.This company increased its organicpigment output by 2.23% to 11,302tonnes in 2002. Hebei JiehongPigment & Chemical Industrial Co Ltdwas the second largest producer, with8400 tonnes.

The leading producer of dyes wasZhejiang Longsheng Group Co Ltdwith an output of 70,892 tonnes in2002, up 56.4% on the 2001 figure. In

second place was Zhejiang RuntuChemical Industrial Group Corp,which registered a 52% increase inoutput to 59,412 tonnes last year.

Exports of organic pigments roseby 13.4% to 82,000 tonnes, worth$79.49 M. Major destinations were:Taiwan (21,600 tonnes, valued at$52.72 M); the United States (13,320tonnes, valued at $51.78 M); andGermany (7420 tonnes, valued at$40.6 M). Imports of organic pigmentsinto China increased by 11.1% to30,340 tonnes, with Taiwan andJapan being the major suppliers.

China Chemical Reporter, 26 Apr 2003, 14 (12), 21-24

7%/y growth in demand for minerals inNorth American plastics

Minerals used as reinforcements,pigment extenders and fillers findapplication in a variety of end-useapplications in paint, paper, plastics,rubber, inks, etc. In this context, totalNorth American demand exceeded 15M tonnes, valued at $1.9 bn, last year.The paper industry is the dominantend-use sector, accounting for roughly50% of consumption by volume. Untilabout 10 years ago, the plasticsindustry was a comparatively minorconsumer, but it is now the secondlargest, with an intake of 2 M tonnes,valued at $500 M. (These figuresexclude TiO2 consumption).

The plastics sector tends toconsume relatively expensiveminerals, the average price tag being$225 per tonne – about twice theoverall average for all end-usesectors. Plastics compounders workwith a variety of minerals, includingcalcium carbonate, talc, aluminatrihydrate (ATH), silica, mica, kaolin,diatomite and wollastonite. Since1980, the tonnage consumption ofthese minerals in plastics hasincreased by 7%/y. Over the sameperiod, North America’s consumptionof plastics has increased by 4-5%/y.In 1980, about 9% of all plasticsincorporated minerals. By 2002, thefigure had risen to 15%.

Some of the attractive markets formineral-filled plastics include:polypropylene for decks, railings,automotive interior panels and seatbacks; polyvinyl chloride (PVC) forwindow/door frames; nylon for high-heat connectors, automotiveunderhood applications; ATH and other

JULY 2003 3

F O C U S O N P I G M E N T S