Zirconium and Hafnium

By Charles Skidmore MinChem Ltd UK Zirconium and hafnium are often thought to be rare elements, but they occur widely in the Earths crust, being more plentiful than copper, with a concentration of 0.028%. They are found in the minerals zircon sand (zirconium silicate ZrO2.SiO2) and baddeleyite (ZrO2), with zircon being the main source. These minerals are generally found together with titanium and iron orebodies and are separated out during the commercial mining of these deposits. All zirconium and hafnium compounds, including the metal, oxide and salts, are derived from zircon sand or baddeleyite. Hafnium is always present in 1.5 3.0 weight % and has an almost identical chemistry to zirconium. This makes it difficult to separate the two and this is only done when absolutely necessary, such as for zirconium nuclear applications and the preparation of hafnium compounds. Zircon sand Events in 2004 continued the trend in 2003, with the undersupply that began in 2002, deepening further and leading to a global shortage approaching 100,000 t. This has resulted in continuing increases in zircon prices and major uncertainties in the long-term position. Supply shortages forced up prices almost on a quarterly basis throughout 2004. The dramatic price increases have caused major headaches downstream, including changes in product formulation, a cutback in zirconium chemical output in China and some substitution by cheaper alternatives. All zircon markets continued to grow in 2004 but it is the continuing rapid expansion of the ceramics markets in China that has led to the shortfall in supply. Zircon sand occurs throughout the world and is the most abundant zirconium mineral. It is normally recovered from heavy mineral sands (found predominantly in beach deposits) where the associated titanium minerals, generally rutile and ilmenite, are recovered separately. Zircon sand is also obtained during rare earth processing. Australia, South Africa and the US continue to be the main sources with a world reserve thought to be in excess of 100 Mt. Zircon is normally produced from heavy mineral sands by dredging and/or dry mixing operations the specific method being dependent on the orebody location, zircon concentration and associated impurities. To achieve the higher qualities demanded by the various markets, zircon is processed further using mechanical abrasion, chemical attack and thermal processing (calcination). This results in zircon with a wide range of physical and chemical properties, which

normally determine its end use. However, owing to the shortages, some substitution between markets has been occurring. A considerable volume of zircon sand is used as mined, in a coarse particle size, for use in abrasives, foundries, refractories (steel, glass, cement, metal), TV tubes, and for zirconium metal, oxide and chemical production. In these markets, the lower reactivity of zircon sand, due to its lower surface area, is compensated for by processing the sand at high temperatures (fusion, sintering, chemical attack). In applications where zircon is not attacked so aggressively, and temperatures are lower, the surface area needs to be increased. This is achieved by milling to finer particle sizes, as found in zircon flours (generally (<200 or <300 mesh), or in smaller sizes (5-6 micron and below)) as opacifier grades. These products are used predominantly in ceramic frits, which are special glasses made to provide an impervious, long lasting and easily maintained coating on various ceramic products. The zircon particles reflect light and so impart a white opaque colour to the final glaze. Generally, zircons with low impurities, finer particle sizes and narrower particle distribution lead to the best opacifiers. Every day we all come into contact with the end product, be it in tiles (wall and floor), tableware (plates, bowls) or sanitaryware (toilets, bidets, washbasins). Since the desired effect is the formation of an intense white colour, other species present such as colouring transition metal ions (Fe and Ti) need to be minimised. Consequently the higher-quality grades (generally referred to as ceramic or premium grades) have a maximum 0.10% TiO2 and 0.05% Fe2O3. Lower-quality grades with higher Ti and Fe levels are used in refractory and foundry applications, although with recent shortages some lower grade has been used to augment flour and opacifier production. In 2004, zircon output remained at around 1.1 Mt, similar to 2003. Shipments from Australia were under 400,000 t (2003: 450,000 t), South African movements were similar to 2003 level at 370,000 t (the 2002 level of 420,000 t was not recovered) and US sales remained at 140,000 t, similar to 2003. Output from Ukraine, India, Vietnam, Brazil, Malaysia, China and Russia also saw little change, with a combined contribution of around 130,000 t (2002 level). The ongoing problem of zircon being inextricably linked to titanium minerals and markets continued. Historically, titanium ores and downstream TiO2 pigments have been in oversupply. This has led to little price improvement and, with increasing environmental, social and other operating costs, has led to low profitability. The heavy mineral sands mining industry has always centred more on titanium ore recovery than zircon, the latter being considered a by-product. Hence, with low demand for titanium ores, there has been little incentive to increase output, and this has resulted in little zircon growth. This situation is changing with rationalisation in the TiO2 pigment supply market, including a

decrease in TiO2 production capacity (three of the top four suppliers have decreased capacity in the last year). As a result of this reduced output, and also because of tighter titanium feedstocks such as rutile, TiO2 selling prices have been lifted. This higher demand for titanium ores has been benefiting zircon and several existing mines have lifted output in the latter half of 2004 and into 2005. The largest world producer is Iluka Resources Ltd, with operations in Australia/US and production/sales of approximately 375,000 t (similar to 2003). Considerable work in 2004 centred on cost reduction and operational efficiency improvements, the return of US profitability and the development of its Lulaton project in Georgia, US and CRLs Enterprise deposit in Australia. Developments in the Murray Basin in southeast Australia are key to Ilukas long-term position. Its Douglas and KWR sites in Victoria should lift output by 64,000 t (Douglas in the fouth quarter of 2005, and KWR in the third quarter of 2007). Other projects include Jacinth (52% zircon) and Ambrosia (66% zircon) both in South Australia where reconnaissance is being undertaken. Iluka continued to increase prices throughout 2004 and asked for a further increase of approximately US$100/t for the first quarter of 2005. An extra 12.5% has been requested for the third quarter of 2005. Similar moves have been made by other producers continuing to quote on a quarterly basis. Also in Australia, TiWest saw a similar output to 2003 at around 80,000 t. In South Africa, Richards Bay Minerals (RBM), owned by Rio Tinto and BHP Billiton plc, is the worlds second-largest producer. In 2004, production difficulties continued, a serious fire leading to a fall in output, to well under 240,000 t (2003 level). Anglo American subsidiary, Namakwa, remains in third place with operations in the Western Cape. A serious fire in the mineral separation plant in October 2003 halted production for three months and led to a fall in output of about 80,000 t in 2003, though some recovery occurred in 2004, bringing output close to 2002s level at 100,000 t. Also in South Africa, Ticor SA (Kumba Resources 60%, Ticor 40%) located close to Richards Bay in Kwa Zulu-Natal Province, maintained output at 50,000 t, similar to2003. In the US, Du Ponts Florida plant maintained its 2003 output at around 70,000 t in 2004. All zircon markets continued to grow in 2004, with total demand approaching 1.2 Mt. Ceramics (mainly tile and sanitaryware) consumed 52% of total output of zircon at around 600,000 t. In recent years, the ceramics market has shown steady annual growth of over 5%, with China taking over 125,000 t and producing around 36% of the worlds tiles. This has been fuelled by strong building activity, growth in private home ownership and preparation for the 2008 Olympics. Much of the zircon shortage in Asia is centred on the ceramic tile

demand in China. To meet demand for zircon flour and opacifiers, Shenyang Astron Mining Industry Ltd (Astron), based in Shenyang but Australian registered, is increasing its zircon milling capacity by 12,000 t/y, with a new plant in Shanghai due on stream in 2005. The Italian flour/opacifier-maker, Industrie Bitossi SpA, part of Colorobbia Group, will also install a plant in Guangdong, rising to 30,000 t/y. Ceramic tile output is also increasing in other southeast Asia countries such as Thailand, Malaysia and Indonesia, and also in Eastern Europe, Turkey and Iran. European ceramics markets remained static at around 270,000 t, with little or no growth, particularly in Italy. Refractory requirements for zircon saw a dip, falling to 162,000 t in 2004 (2003: 180,000 t). European-based producers continued the trend to move production to China. All refractory users, and particularly steel makers, have pressed for increased performance and consequently there has been a continuing fall in refractory consumption per tonne of product made. For example in China, the steel industry has seen a fall from 55kg per tonne of steel output to around 20kg/t in 2002. This increased performance has not been mirrored by increases in refractory prices, leading to pressures to cut costs and a move to cheaper manufacturing bases. Foundry uses for zircon in investment casting (a method of precision-casting of metals using moulds made from zircon) also remained similar to 2003 levels at around 166,000 t. This was due to a slower aerospace industry market (turbine blades). Sports goods, such as golf club production, remained buoyant. The use of zircon to block X-ray emissions in cathode ray tubes (CRT) found in computers and TV monitors also continued to rise slowly (94,000 t compared with 90,000 t in 2003). The development of alternative electronic-display methods, for example, liquid crystal displays/thin film transistors, may, in the longer term, temper the growth of zircon usage in this industry. In addition to the movement in the ceramics industry, the use of zircon in zirconium chemicals and synthetic zirconia in China jumped significantly (65,000 t in 2004 compared with 45,000 t in 2003). In world terms, this lifted zircon usage for zirconium metal, oxide and chemical manufacture to over 115,000 t (2003: 110,000 t). This market, like the ceramic opacifiers, needs good-quality zircon containing low impurity levels. Premium grade is in very short supply and this has added extra pressure, particularly in China, with some zirconium chemical producers unable to find material and so chopping output. Taking all the world markets together, Europe continued to absorb the largest zircon share (2004: 405,000 t, similar to 2003), with China next at 248,000 t (225,000 t). North America came next at 175,000 t (similar to 2003) and was similar to other Asia-Pacific offtake. Japan saw an increase throughout the year and is now around 63,000 t (55,000 t).

As can be seen from Figure 1, prices moved up with zircon opacifiers in China in the US$1,200-US$1,600/t range ex plant, depending on sizing. Figure 1: Zircon sand / flour / opacifier prices Shipping Terms Pricing June 2004 Sand FOB Australia US$/t bulk 420-550 FOB South Africa US$/t bulk 410-550 FOB US US$/t bulk 400-530 Flour (95% below 45 micron) US$/t bagged 800-940 FOB Europe US$/t bagged 800-950 FOB Asia Micronised (d50 5 micron) FOB Europe US$/t bagged 900-1,050 FOB Asia US$/t bagged 900-1,100
FOB = Free on Board The prices given are the most up to date at the time of writing

May 2005 550-700 550-700 570-700 950-1,150 950-1,250 1,100-1,500 1,200-1,600

The outlook is for continuing tightness in supply well into 2005and higher pricing, although the rate of increase may slow. Demand is expected to peak at 1.2Mt in 2005-06 and, with new output starting to emerge in 2005, the year should see a gradual easing to normality, provided that no other emergencies arise. The Boxing Day tsunami also contributed to the shortness of zircon by halting the planned resumption of operations by Lanka Mineral Sands Ltd (LMS). This could release up to 70,000 t of zircon, which would cut the zircon shortfall considerably. As all main producers are maximising output, new developments in Australias Murray Basin and the Corridor sands project (CSP) in Mozambique, together with prospects in Sri Lanka (LMS), India, Canada (Alberta) and the FSU, should restore supply/demand balance in the next few years. Baddeleyite Throughout 2004 and into 2005, the long-established customers for South African baddeleyite (zirconium ore) continued to reformulate their products using synthetically-derived feedstock made from zircon sand, namely fused monoclinic and stabilised zirconias. This trend began in the early 1990s with the closure of Foskors mine and then became irreversible with the curtailment of operations at PMC, together removing around 18,000-19,000 t/y of output. Markets in refractory, ceramic, abrasive and other applications were forced to move to alternative supplies. Since the 1970s, baddeleyite output was centred on two operators based at Phalaborwa in the Northern Province of South Africa. Palabora Mining Co (PMC), a subsidiary of Rio Tinto plc, recovered zirconium ore containing 99% ZrO2+HfO2 as a by-product of its open-pit copper mine. The complex orebody produced a diverse product mix including high-grade copper, magnetite, precious metal slimes and naturally-occurring ZrO2, namely baddeleyite. As a result of the

geological changes found as the mine went deeper, and modifications to the mine geometry, output of baddeleyite came to an end in 2001, with PMC switching to an underground block-caving mining method. Production of zirconium sulphate (also known as acid zirconium sulphate AZST or orthosulphate) which was made from baddeleyite, rather than the normal and now, universally used zircon sand, also came to an end as zirconium ore feedstock disappeared. This ended PMCs position as market leader in zirconium ore and sulphate after some 30 years. Maximum annual output was achieved by PMC in the late 1980s when some 13,000 t of oxide and 3,000 t of sulphate were sold. Around this time, PMC investigated the possibility of building a zirconium chemical plant in the US but this was shelved when a domestic supplier expanded operations. Instead, a novel design zirconium basic sulphate (ZBS) plant was completed in the early 1990s based at Phalaborwa (see under zirconium chemical section). This plant was based on using zircon taken from PMCs sister company Richards Bay Minerals (RBM). After significant operational problems, including a serious fire, PMC sold the plant to black empowerment group, Maxima Investment Consolidation (Pty) Ltd in November 2004. After a period of closure, this plant is again being offered for sale by Maxima. PMCs main competitor in baddeleyite was the South African state-owned Phosphate Development Corp Ltd (Foskor). Foskor now has South Africas Industrial Development Corp (IDC) as sole shareholder. Its output declined to zero in the early 1990s after reaching a maximum yearly output of 6,000-7,000 t. Unlike PMC, Foskor retained and developed its markets for zirconium ore by purchasing a synthetic zirconia plant from Fukashina Steel of Japan. After initial teething problems, this plant has grown and now manufactures monoclinic and fused stabilised zirconias, and has an annual capacity in excess of 6,500 t. The products are sold to refractory, abrasive and ceramic pigment markets. The worlds only remaining commercial source of baddeleyite is in Russia, in the southwestern part of the Kola Peninsula, close to the Finnish border and alongside the Russian districts of Apatity, Kandalakha and Polyarnye Zory. Kovdor town is the administrative centre of the area. This remotely situated mine, operated by A O Kovdorsky Gok (Kovdor) and 95%-owned by Eurochem Mineral Chemical Co (Eurochem) based in Moscow, recovers iron ore, apatite concentrate and baddeleyite from a complex orebody. With a turnover in excess of 140 million in 2004, Kovdor saw a growth of 8-9% over the previous years results. Output comprised 5.3 Mt of iron ore concentrate, 1.83 Mt of apatite concentrate (largely sold to other Eurochem enterprises as feedstock for the manufacture of phosphorus) and some 8,300 t of baddeleyite concentrate. This latter figure was some 50% higher that the previous years sales, a considerable portion coming from stockpiles and previously worked material.

Currently, Kovdor produces around 6,500 t/y of baddeleyite and expects to increase this to 8,000 t/y over the next few years. Kovdors main sales continue to be directed towards the abrasive and refractory markets, particularly in the East, and some 90% of production exported. In recent years Kovdor has also been developing pigment grades of baddeleyite to replace PMCs Zirconium Ore Grade 5, which was used to make lower-cost blue/yellow ceramic colours. Although synthetic zirconias are used in this market, the colour, shade and strength found in PMCs Zirconium Ore Grade 5 has been difficult to replicate without using baddeleyite. As well as increasing baddeleyite output, Eurochem also plans a number of large-scale investments centred on ore-beneficiation, new mining equipment, larger mining trucks and a major modernisation of the mill and concentrator. The main aim is to lift mined volumes and reduce costs. It is expected that baddeleyite and other product output will continue for a further 20-30 years. The mine operates around the year despite the harsh winters, using feedstock from the open pit and part-processed tailings. As further developments occur in ore recovery, separation and purification, new products and applications may be developed. The Norwegian fusion plant Nako Narvik AS, built to take baddeleyite feedstock from Kovdor, remains closed, despite attempts by the bank owners to find a partner or buyer. It was thought that, with increasing zirconia prices and developing shortages, the plant might re-open, either based on baddeleyite or zircon-sand feed. However, as both of these feedstocks are in tight supply, this seems unlikely. Technical matters relating to the uranium and thorium content of baddeleyite and synthetic zirconia (fused monoclinic and stabilised grades) continue to be debated at specific radioactivity conferences and related mineral user-group meetings. There is a continuing trend by the legislators to tighten up on acceptable levels of U + Th contained in baddeleyite (and zircon sand) from a production, shipment, bulk storage and end-use consideration. Specifically this is controlled with regard to worker, environment/waste and transport regulations. Work has been focused on the education of likely problem sites, with emphasis on risk assessment. Varying levels of legislation around the world have been subject to comparison and attempts are being made to harmonise the variations. In general, synthetic zirconias are less radioactive than baddeleyite but this is dependent on the zircon sand feedstock used. Figure 2 outlines the market position for baddeleyite and synthetic zirconia, including both fused monoclinic and stabilised zirconia.

Figure 2: Markets for baddeleyite / synthetic zirconia in 2004 Baddeleyite (t) 6,800 500 1,000 0 0 0 0 Synthetic zirconia (t) 14,000 14,000 2,500 3,000 850 650 5,500 Total (t) 20,800 14,500 3,500 3,000 850 650 5,500 Growth Increase Increase Level Level Level Level Increasing

Refractories Ceramic pigments Abrasives Electronics Oxygen sensors Glass/gemstone s Advanced ceramics/catalys t Total

8,300

40,500

48,800

Around 70% of refractories produced worldwide are used in the steel industry (with cement, chemicals, ceramics, glass, others each 4-6%). Despite a continuing rise in world steel output, the use of baddeleyite/synthetic zirconia increased only marginally in 2004. This was due to the continuing reduction in the rate of refractory consumption per tonne of steel output. Refractory production continued to grow in China in line with the huge increase in steel making. Western producers reinforced their position in the market by establishing wholly-owned or joint-venture companies and transferred some manufacturing to these plants. Similar moves are happening in the glass, ceramic and other refractory fields. Ceramic and plastic colour pigment output increased further in 2004, with Asia, specifically China, showing gains. This demand is being fuelled by Chinas insatiable growth in ceramic tile output. Alumina-zirconia (AZ) abrasives were manufactured first by Norton in the US. AZ alloy can contain up to 40% zirconia and is made by fusing alumina, zircon and baddeleyite/fused monoclinic zirconia in an electric arc furnace. These products offer an exceptional cutting action and increased lifetime. These facts, together with changes in the metal forming market (more precise, near net casting), have led to almost zero growth. Electro-ceramic markets utilising zirconias insulator or conductor properties, continued to grow slowly in filter, buzzer, spark generator and other lead zirconate titanate (PZT) applications. In glass applications there have been new developments in frit and other surface coatings. This has been offset by market saturation in the cubic zirconia field, and some replacement by alumina, leading to little or no growth in this sector.

The varied uses of zirconia in the advanced ceramic, fuel cell and catalyst (industrial and autocatalyst) areas continue to grow. Zirconia of much higher purity (and price) can be made in partially (PSZ) or fully stabilised (FSZ) forms by careful chemical processing under controlled conditions. These grades offer novel mechanical and electrical properties. The advanced ceramics field saw continuing interest in fuel cells and industrial/ automotive catalysts. Other applications using zirconias superior mechanical properties continued to grow slowly although volumes remain relatively small. (See later in zirconium metal, oxide and chemicals section.) Prices for baddeleyite and synthetic zirconia (see Figure 3) moved up in 2004, reflecting increased prices for zircon sand, shipping rates, other raw materials, fuel and Chinese export tax rebates. Additional zirconia output, particularly in China (see later), led to more fierce competition, which tempered the increases, and some grades were more affected than others. Figure 3: Prices for fused monoclinic ZrO2 / stabilised ZrO2 and baddeleyite US $ / t CIF Main Ports EC, US, Japan June 2004 May 2005 Monoclinic zirconia * Refractory / Abrasive 2,200 2,800 2,500 3,200 Grade * Ceramic Pigment Grade 2,700 3,700 3,000 3,800 Structural / Electronic Grade 3,300 4,800 3,300 4,800 High Purity Advanced 15,000 25,000 15,000 25,000 Ceramic Grade Stabilised Zirconias Refractory Grade 3,400 4,200 3,300 4,800 High Purity Advanced 25,000 75,000 25,000 75,000 Ceramic Grade
* Baddeleyite price levels in the lower half The prices given are the most up to date at the time of writing

Zirconium metal, oxide and chemicals As the zircon feedstock shortages deepened throughout 2004 and into 2005, some Chinese producers of various zirconium chemicals were forced to cut production and this led to price increases over and above the increment caused by the zircon-sand price hikes. Overall demand for metal, oxide and chemicals continued to grow and key markets are given in figure 4. Figure 4: Major zirconium and hafnium chemical production and application
Product Abbreviation Formula World Production Capacity in tonnes Application

Zr silicate

ZrO2.SiO2

1,100,000

Zr oxychloride

ZOC

ZrOCl2.8H2O

80,000

Zr sulphate

ZOS

Zr(SO4)2.4H2O Zr5O8(SO4)2 H 2O ZrOCO3 x H2O x

10,000

Zr basic sulphate

ZBS

25,000

Zr basic carbonate

ZBC or BZC

25,000

Ammonium carbonate Zr acetate

Zr

AZC ZAC

(NH4)3ZrOH(CO3)
32H2O

15,000 2,000

H2ZrO2(C2H3O2)2 K2ZrF6 ZrO2

Potassium hexafluorozirconate Zr oxide

KFZ

1,000 45,000

Zr metal

Zr

10,000

Hf metal

Hf

N/A

Hf dichloride Hf dibromide Hf oxide Hf carbide Hf nitride

HfCl2 HfBr2 HfO2 HfC HfN

N/A N/A N/A N/A N/A

Opacifier in ceramic tiles, sanitary ware and table ware Steel/glass refractories Foundry/investment casting TV/Computer glass Production of Zr chemicals/oxides Manufacture of Zr/Hf metal/ chemicals Manufacture of other Zr chemicals Titania coating Antiperspirant Oil field acidising agent Manufacture of other Zr chemicals Titania coating Leather tanning reagent Manufacture of other Zr chemicals Titania coating Leather tanning reagent Manufacture of other Zr chemicals Paint driers (siccatives) Antiperspirant Catalyst Paper coating (insolubiliser) Fungicidal treatment of textiles Manufacture of other Zr chemicals Water repellent in textiles/paper Catalyst production Grain refiner - Mg/Al alloys Flame proofing of textiles Refractories Ceramic colours Abrasives Electronics Oxygen sensors Glass/gemstones Catalyst Advanced ceramics See Fig 2&5 Chemical processing plant Nuclear fuel rod/core components Explosives Alloys Pyrotechnics Military Orthopaedics Aerospace alloys, nuclear refractories, control rods, cutting tips, sputtering agent, plasma coating, military Catalyst Special refractories Optical coatings, electronics Nuclear control rods Cutting tools, coatings

N/A = information Not Available

Zirconium metal is an important refractory material and is used in alloyed and unalloyed forms. Its outstanding metallurgical properties, such as resistance to high temperatures and chemical attack, lead to its use in challenging engineering applications such as chemical reactors with hot, corrosive environments. More recently, zirconium has been used in professional flute manufacture due to its ability to lift the musical quality. In 2001, Smith and Nephew introduced its biocompatible zirconium alloy knee replacement to the world of orthopaedics, with thousands now in use. The same alloy containing zirconium in an oxidised form was applied to the bearing surface in artificial hip joints in 2003. This new technology addresses two primary concerns surgeons have about hip implants: wear and fracture. Both can lead to premature implant failure and additional surgery. Future potential includes shoulder and hip fracture implants. Hafniums ability to capture neutrons means that hafnium has to be removed where the zirconium metal is used in nuclear applications eg, nuclear fuel rod claddings, reactor cores and related engineering. With the slowdown in new nuclear reactor installations worldwide, zirconium metal producers have concentrated on developing new markets. Zirconium oxide occurs naturally as the mineral baddeleyite but the majority of the worlds supply is made synthetically by removing silica from zircon sand (zirconium silicate) using a variety of techniques based on thermal dissociation (where the resulting product is referred to as fused monoclinic zirconia) or chemical splitting (resulting in zirconium being converted to chemical-grade zirconia). Thermal dissociation techniques include electric arc fusion to dissociate ZrO2 from SiO2 and plasma dissociation followed by leaching. Chemical splitting can involve attack with carbon at 2,000C or carbon/chlorine to make carbide tetrachloride, and then hydrolysis/calcinations. An alternative chemical splitting process involves reaction with alkali or alkali earth oxide (sodium hydroxide/carbonate or lime) followed by hydrolysis/calcination/acid leaching. Chemical-grade (monoclinic) zirconia are usually made by onward processing and calcination of zirconium oxychloride (ZOC), basic carbonate (ZBC) or other species. Monoclinic zirconia undergo an 8% volume change when they are heated to 1,170C, at which temperature the tetragonal form occurs. Continued heating results in a further change to the cubic phase at 2,370C. This catastrophic volume change in the monoclinic/tetragonal transformation is avoided by the addition of a cubic oxide (eg, MgO, CaO or Y2O3) to baddeleyite and fused monoclinic zirconia during processing at high temperatures. This results in fused, fully stabilised zirconia (FSZ) in the cubic phase, which is stable from room temperature to its molten state. This material has a uniform thermal expansion curve, hence rapid volume changes are eliminated, which means the ceramic article being produced, eg, a refractory nozzle, does not crack or shatter on cooling.

Similar cubic additions are used in chemical-grade zirconia, particularly yttria, though these tend to be added during chemical processing to result in an intimate contact of cubic oxide/zirconia. Where the stabilised oxide is present in concentrations less than those required for complete stabilisation in the cubic phase, then the resulting zirconia will be a combination of cubic and tetragonal and/or monoclinic phases so-called partially stabilised zirconia (PSZ). The development of PSZ in the 1970s led to the start of the zirconia advanced ceramics markets. It was realised that these new materials offered superior mechanical properties to metals (stronger, better heat and wear resistance) and had a novel electrical make up (conductor as well as insulator). This led to a wide range of applications, which are shown in Figure 5. Figure 5: Applications for zirconia in advanced ceramics A. Utilising ZrO2s superb mechanical properties USE Structural ceramics Bioceramics Low wear ceramics Forming dies Metal filtration Cutting applications Coatings Gemstones Glass Jewellery/Watches APPLICATION Various components, pumps, bearings, seals, valves, optical fibre connectors. Hip and knee replacement joints, dental ceramics. Grinding medias, engine components, textile thread guides, printer heads. Extrusion of copper / wire. Removal of impurities during casting. Blades, scissors, cutting tools. Plasma spray. Zirconia single crystal in various colours. Lenses, glass fibre, laboratory equipment. Scratch resistant bracelets/faces.

B. Utilising ZrO2s interesting electrical properties USE Fuel Cells Oxygen sensors APPLICATION ZrO2 is used in solid oxide fuel cells as the electrolyte. Oxygen concentrations affect yttria stabilised ZrO2 conductivity and this property can be used to control emissions in auto engines, furnaces and gas boilers. water This is the reverse of the fuel cell. Magneto-hydrodynamic generators for current generation where zirconium electrodes are used

H2 from electrolysis MHD electrodes

Filters, transducers, Use in mobile phone filters, acceleration and underwater resonators, other PZT detection sensors. Production of buzzers for clocks, timers, uses automobiles etc. Ultrasonic motors (utilising sound rather than electrical power). Catalysts For industrial and automobile exhaust applications using ceria-doped ZrO2. The range of applications for zirconium chemicals, as seen in Figure 4, continues to diversify with major uses in catalysts, chemical manufacturing, healthcare, metals, as a paint drier (siccative), and in paper, textile and titania coatings. Key items made are zirconium acetate (ZAC), zirconium basic carbonate (ZBC), ammonium zirconium carbonate (AZC), zirconium oxychloride (ZOC), zirconium acid sulphate (ZOS/ZST) and zirconium basic sulphate (ZBS). Over recent years, China has added significant new capacity and remains the powerhouse of zirconium chemical production, with a total annual capacity of over 100,000 t. Smaller volumes emanate from India, South Africa, the UK and the US. ZOC continues to be the basic building-block chemical used to make other species, and Chinese capacity now exceeds 60,000 t. Several producers have been unable to purchase enough zircon-sand feed to maintain output, and production volumes have fallen in the latter half of 2004 and into 2005. In China, zircon sand has been selling at prices up to US$1,000/t and this has led to big increases in ZOC prices, almost double those of 1-2 years ago. Since ZOC is used to make ZBS, ZBC and chemical grade zirconia, the price increases have been pushed down the line, leading to large cost increases for the various customers. ZOC continues to replace ZOS/ZST in pigment (TiO2) coating due to its lower cost and higher solubility, with the choice being dependent on the manufacturing process and type of scrubber used in the acid treatment system. Antiperspirant markets also moved ahead as personal hygiene sales grew in markets outside the EC and the US. The use of ZOS/ZST in leather tanning saw little or no growth possibly because of substitution by synthetics and low fashion interest. ZBS continued to be used primarily as an intermediate for ZBC, AZC and other products, with China again a major source. As noted, PMC sold its ZBS plant in South Africa during 2004 to Maxima Investment. After consideration, this group decided not to run the plant and has offered it for sale. Major consumers of ZBC all pushed ahead. The use of ZBC in paint driers is closely linked to catalytic action, the zirconium compound speeding up the physical change from the liquid to the solid state (O2 is absorbed leading to oxidative cross-linking). The catalyst industry uses ZBC as a precursor to other zirconium compounds/special oxides.

AZC is mainly used in paper coating to improve print adhesion and in textiles to fix antifungal species such as Cu, Cr or Hg to the cellulose fibre. As mentioned, China continued to increase capacity in zirconium product output. Shenyang Astron Mining Industry Ltd (Yingkou Astron Chemical Co Ltd) saw further growth in fused and stabilised zirconium oxides (additional furnaces installed in 2003 lifted annual capacity to 13,000 t) and chemicals (new ZOC production being added during the second quarter of 2005). Although based in Shenyang, Astron is an Australian public-listed company. Being a major importer and user/seller of zircon sand into the Chinese market, Astron has also been working to secure long-term supplies. In a joint venture with Carnegie Corp Ltd of Australia, zircon concentrate from the old British Titan Products mineral sand deposit in Gambia has been shipped to China for processing. Despite water shortages in Gambia, which has hindered the operation of mining equipment, this project continues to develop. Astron has also acquired 100% of Zirtanium Ltd, which owns large zircon deposits in the Murray Basin in western Victoria. The 117 Mt Horsham deposit, discovered in the 1980s by CRA/Rio Tinto, but relinquished by CRA owing to separation problems with the very fine grain size, should yield 30,000 t/y of zircon, together with other titanium minerals, once large-scale mining begins. Astron is also planning to enter the titania business by processing feedstock from Zirtanium and other interests, and has been courting Londons AIM (Alternative Investment Market) to raise funds. Asia Zirconium Ltd (Jiangsu Xinxing Chemicals Group), one of the first Chinese makers of zirconium chemicals in the 1970s, was successfully floated on the Hong Kong Stock Exchange last year. With total annual capacity of 35,000 t ZOC and 6,000 t ZBC, it is one of the largest manufacturers. Recent developments include nanometric zirconium oxide and further plant expansions. There are now a total of approximately 40 zirconium chemical plants in China although lack of adequate zircon-sand feedstock has pushed some close to going out of business. Canadian-based rare-earth producer AMR continued to develop its Chinese and Thailand plants in 2004, producing zirconium oxide and chemicals for the catalyst, fuel cell and electronic markets. Sydney based rare-earth company Lynas Corp, increased its shareholding in AMR to approximately 20%. In Japan, four companies were involved in fused zirconia/chemical production: Daiichi Kigenso Kagaku (DKK), Fukushima, Tosoh Corp and Sumitomo Osaka Cement (SOC). DKK, has its headquarters in Osaka and a relatively new plant in Gotsu on the northern coast of Honshu, well away from the earthquake zone. It continued to developed its catalyst, fuel cell and advanced ceramic grades of PSZ. In May 2005, DKK announced the building of a new plant devoted to zirconia manufacture for SOFC (solid oxide fuel cells). This 16,500m2 plant will be situated in Fukui Technoport in Fukui Prefecture on the Sea of Japans coast, north of Nagoya, and also remote from the threat of earthquakes. Final annual

manufacturing capacity of 2500 t will be achieved within three years and involves an investment of US$40 million. Products will include yttrium, scandium and stabilised zirconias. The decision to expand further comes after DKKs successful float on the Tokyo Stock Exchange in December 2004. In the US, Southern Ionics Inc (SII) further reinforced its position in the chemical, catalyst and renal dialysis markets. In the latter market, SII is close to FDA approval in the US for a new home dialysis kit to be made by Renal Solutions Inc. This will reduce the need for regular hospital visits and also compete with other systems used at home such as CAPD (Continuous Ambulatory Peritoneal Dialysis). Eka (part of Akzo Group and Formerly Hopton Technical), strengthened its paper coating markets and ATI Wah Chang based in Albany, Oregon, pressed ahead in aerospace, chemical, automotive, nuclear and medical applications for its range of speciality materials such as zirconium and hafnium metal/alloys. Working with Smith and Nephew, a significant improvement in knee and hip replacements has been made. MEI continued to refocus on advanced technology markets. In the UK, MEL (sister company to MEI US) moved further away from commodity zirconium chemicals concentrating on higher added value products such as fuel cell and catalyst markets. UCM Group (formerly Universal Abrasives and incorporating Unitec Ceramics UK and Universal America, US) has manufactured electro-fused zirconia for over 30 years. It has consolidated production in the US, having closed its UK site. Advanced ceramic grades of zirconia continue to be made in Stafford, UK, with sales/marketing being split between the UK and US, depending on the market. In India, Bhalla Chemical continued to increase output, with the announcement of a new plant in Rajastan. In Tamil Nadu, the 500 t/y zirconia and 250 t/y zirconium sponge plant being developed by Nuclear Fuel Complex (NFC) of Hyderabad moves closer to completion at Tuticoru. Ukraine-based Vilnihorsk State Mining and Metallurgical Plant (VSMMP) began offering yttria-stabilised zirconia to augment the zirconium oxide, zircon and related mineral range. In Australia, Australian Fused Materials (AFM) once again sold all of its 4,500 t output of fused zirconia in 2004, and continues to press for an additional furnace to lift volumes. This expansion has been prevented thus far by shareholder differences. The largest zirconia producer is the French industrial giant, Saint Gobain, with plants in Australia, the US, China and France. Total production capacity for zirconium chemical and zirconia production is thought to be approximately 40,000 t/y, of which around one third is fused monoclinic and chemical-grade zirconia.

In South Africa, Geratech Beneficiation Ltd continued to develop its factory in Krugersdorp, which is only 20% utilised, by the addition of more zirconium sulphate output. Geratech would like to process locally most of the South African produced zircon sand now shipped to China for zirconium chemical production. This goal for the country to convert its mineral output into high added value products rather than selling the basic mineral has been raised several times before in Australia and China. As ocean shipment becomes more costly due to fuel increases, and more difficult due to security constraints, there is strong pressure for this to happen. However, environmental costs play a key role in zirconium chemical production and China still has the lowest cost per tonne in this regard, although things are changing. All producers of zirconium metal, oxides and chemicals have been affected by the continuing shortage of zircon sand and resulting price increases. Over 100,000 t/y of zircon is consumed in making these products, some 10% of world output. Security of supply is now paramount and large consumers such as Astron have bought into the zircon-mining industry to ensure adequate feedstock and also to develop business in the related titanium minerals field. With higher raw material, fuel and freight costs, particularly in China, zircon metal, oxide and chemicals are now considerably more expensive than in 2003. Hafnium metal and chemicals Hafnium is normally present at 1.5-3.0% by weight in zircon sand and baddeleyite, and is removed when zirconium is used for nuclear applications. All hafnium compounds derive from this difficult extraction process based on the Kroll process. Hafnium is found in various alloyed and unalloyed forms such as plate, strip, sheet, rod, wire and tube similar to zirconium metal. It is also converted into the oxide and other reactive chemical species (see Figure 4). Hafniums strong ability to absorb neutrons led to its use in controlling nuclear reactors. Rods containing hafnium are raised or lowered to regulate the nuclear reaction. Hafnium metal finds extensive use in aerospace alloys, in medical and other special products. Hafnium metal and compounds are produced in the US (Westinghouse Electric Co, ATI Wah Chang), in Europe (Cezus, France) and in Russia, China and Ukraine. Additional nuclear-related material is no doubt produced clandestinely. World output of hafnium compounds is similar to 2003 but the higher zircon feedstock cost has led to increased pricing.