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Iluka-Zircon and Other

Mineral sands contain titanium dioxide and zircon, which have properties making them useful for many applications. Titanium dioxide is used primarily as a feedstock for white pigment (over 90% of consumption) and to produce titanium metal. It has high strength and is lightweight, corrosion resistant, and protects against UV damage. Zircon has attributes making it useful in ceramics. These minerals have no close substitutes for many of their important uses.

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0% found this document useful (0 votes)
275 views13 pages

Iluka-Zircon and Other

Mineral sands contain titanium dioxide and zircon, which have properties making them useful for many applications. Titanium dioxide is used primarily as a feedstock for white pigment (over 90% of consumption) and to produce titanium metal. It has high strength and is lightweight, corrosion resistant, and protects against UV damage. Zircon has attributes making it useful in ceramics. These minerals have no close substitutes for many of their important uses.

Uploaded by

Arief Mahdi
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Mineral Sands Products: Attributes and Applications

Mineral sands refers to heavy minerals (“HM”) with a specific gravity greater than 2.85,
and consists of two core product streams: first, titanium dioxide (“TiO2”) in the form of
rutile, ilmenite and leucoxene and, second, zircon. Ilmenite is used in its natural form
and also to manufacture titanium slag and synthetic rutile products.

Titanium dioxide and zircon products have physical and chemical properties which make
their application important to a wide range of end use applications. While some partial
substitutes exist, none have the inherent attributes of, for example, titanium dioxide’s
utilisation in pigment production or zircon’s attributes in the manufacture of a range of
ceramic applications.

TITANIUM DIOXIDE

The titanium dioxide products of ilmenite, rutile, leucoxene, as well as upgraded


products of synthetic rutile and titanium slag, are used principally as feedstocks for the
production of white pigment. This application accounts for over 90 per cent of global
titanium dioxide feedstock consumption. The remainder is used for the production of
titanium sponge, used in the manufacture of titanium metal, as well as in welding as an
electrode flux.

2008 TiO2 Demand by Industry Sector

All TiO2 Demand = 6,200 kt TiO2

Other
Metal
4%
5%
2008 Pigment Demand = 4,700 kt TiO2

Paints &
57% Coatings

24% Plastics

9% Paper

6% Other

3% Ink
91%
1% Fibre
TiO2 Pigment

Source: TZMI

Iluka Resources – Mineral Sands Products: Attributes and Applications 1


The value in use of naturally occurring titanium and upgraded ilmenite products is in
large measure influenced by their respective titanium dioxide content, shown in the table
below.

TiO2 Content of Titanium Dioxide Products


Form of Titanium % TiO2 Content
Rutile 92 - 96
Leucoxene 65 - >90
Titanium Slag / Synthetic Rutile 88 - 94
Ilmenite 48 - 55

Titanium Dioxide Pigment

Titanium dioxide has a high refractive index (refer to the table below), which means that
it is able to scatter and bend light strongly. When enough titanium dioxide pigment is
used in a medium almost all visible light will be reflected, giving the appearance of it
being opaque, white and bright. Opacifiers are most effective when their refractive index
differs from the medium in which it is suspended. In this regard, titanium dioxide has a
significant advantage over other commercially available pigments.

This quality is utilised extensively in the manufacture of paints and coatings, plastics,
paper and in a range of other applications, including inks, fibres, rubber, food, cosmetics
and pharmaceuticals. Plastics is the fastest growing sector, with its major application in
the packaging industry.

Refractive Index of Some White Pigments


Pigment Refractive Index
Rutile TiO2 2.70
Anatase TiO2 2.55
Zinc Sulphide 2.37
Antimony Oxide 2.30
Lithopone 30% 1.84
Zinc Oxide 2.02
White Lead 2.00
China Clay 1.57

Source: Huntsman Tioxide, Manufacturing and General Properties of Titanium Dioxide Pigments

Titanium dioxide has the ability to asborb ultraviolet (“UV”) light, efficiently transforming
destructive UV light energy into heat. When added to materials such as paints and
plastics, it prevents UV degradation including fading, peeling and cracking. Titanium
dioxide is also used as a component in the manufacture of sunscreens, cosmetics and
skin care products designed to protect human skin from UV damage.

Rutile and synthetic rutile, utilised in the pigment industry, have a relatively high titanium
dioxide content (greater than 88 per cent), and contain low levels of contaminants that
can affect the chlorination process which is used in pigment production.

Iluka Resources – Mineral Sands Products: Attributes and Applications 2


Titanium dioxide pigment is non-toxic and biologically inert, making it safe for use in a
range of consumer applications such as in foods, cosmetics and pharmaceuticals.

There is no economic or environmentally safe alternative to titanium dioxide in pigment.


Titanium dioxide replaced lead in consumer end use applications, such as paint, due to
public health issues related to lead toxicity.

Titanium Metal

High grade titanium dioxide products are the principal feed source for the manufacture of
titanium metal. Titanium is an important strategic material, used in commercial
aerospace (the fastest growing segment) and in military and industrial applications, as
well as in a range of commercial, infrastructure and consumer applications.

Significant governmental and commercial R&D work is being undertaken to attempt to


determine a commercially applicable means of cost-effectively transforming titanium
dioxide directly into titanium metal, as opposed to the current batch production process.
If this were to occur, titanium metal would be expected to substitute for high quality steel
(stainless steel) in many applications, given its superior attributes. Data suggests that if
the cost of titanium is reduced by 50 per cent, the annual consumption of titanium could
increase by 220 per cent (Norgate and Wellwood, 2006).

Titanium metal is characterised by its high strength-to-weight ratio and corrosion


resistance. It has the highest strength-to-weight ratio of any metal. In its unalloyed form,
titanium metal is as strong as steel but 45 per cent lighter, and while 60 per cent heavier
than aluminium has twice the strength.

A significant advantage of reducing weight in commercial and military aerospace


applications is fuel efficiency. Titanium alloys are used in aircraft engines (up to 20 - 30
per cent of the engine) and in airframes. Approximately 42 per cent of a fighter jet
(engine and airframe) is typically made from titanium materials (TZ Minerals
International, 2005). The Boeing A380 Airbus uses approximately 67 tonnes in the
aircraft body and approximately 10 tonnes in its engines.

The high corrosion resistant property of titanium metal makes it suitable for industrial
applications, used in highly corrosive environments, such as chemical processing plants
and desalination plants. When titanium is exposed to oxygen in the air and/or water, it
immediately forms a stable, strongly adherent protective oxide film that is resistant to
many highly corrosive environments, particularly oxidizing and chloride-containing
process streams. As long as oxygen is present, the oxide film will self-repair if it
undergoes any mechanical damage. Titanium metal is also used in heat exchangers, in
propeller shafts, rigging and other parts of vessels exposed to salt water.

In consumer markets, sporting equipment makes use of the benefits of the high strength-
to-weight ratio property of titanium metal in the manufacture of a range of sporting
goods, such as golf clubs and tennis racquets. Medical and dental industry applications
of titanium metal utilise its non-reactive properties (inertness), enabling its use in
implants, such as hip replacements, heart pace makers and joint and bone
reconstructive surgery.

Iluka Resources – Mineral Sands Products: Attributes and Applications 3


2008 Titanium Metal Use Demand = 321kt TiO2

44% Industrial

35% Aerospace

11% Defence

10% Consumer and emerging

Source: TZMI

Welding Electrode Fluxing Agent

Rutile and other higher grade titanium dioxide products are important constituents of
welding flux, responsible primarily for slag forming properties. The requirements of the
slag are to shape the molten weld pool, hold the pool in place during positional welding
and protect it from atmospheric contamination, while being readily removable and
preferably self-detaching. As such, titanium dioxide is used extensively in ship building
and other fabrication applications which employ welding.

Developing Applications: Titanium Dioxide Nanomaterials

Significant research into nanotechnology in the last decade has shown promising new
applications for titanium dioxide. As an example, titanium dioxide nanoparticles are used
in dye-sensitised solar cells (“DSSC”), a relatively new photovoltaic technology which
mimics the way plants convert sunlight into energy, although in this case the sunlight is
transformed into an electrical current. The potential applications are widespread and
range from lightweight low-power markets to large-scale applications.

Other areas of research for the application of titanium dioxide nanoparticles include as
an arsenic removal agent in water treatment facilities, cancer treatments (ability to target
and destroy cancer cells), and cement that absorbs pollution.

Iluka Resources – Mineral Sands Products: Attributes and Applications 4


ZIRCON

The largest end-use of zircon is as an opacifier in the manufacture of ceramics based


products, including tiles, sanitary-ware and table-ware. A rapidly growing sector for the
use of zircon is the production of zirconia, zirconium-based chemicals and zirconium
metal. These compounds exhibit many different properties making them suitable for
diverse industrial and chemical applications. The other main end use markets for zircon
include refractories, foundry, and CRT glass (television glass).

Zircon Consumption by End Use Market in 2008

2008 Zircon Demand = 1,262 kt


Other
TV Glass1.4%
3.0%

Foundry
13.2%

Refractory
12.6% Ceramics
53.4%

Fused Zirconia
9.0%

Chemicals
7.4%

Source: TZMI, Roskill, Iluka

Ceramics

Ceramic applications include the manufacture of floor and wall tiles, sanitary-ware and
table-ware. In the ceramics industry zircon is used as an opacifier in glazes and opaque
frits (a type of ceramic glass added to glazes for water, abrasian and chemical
resistance), and as a whitener in porcelain tiles.

Glazes are typically a silica based glass coating that provides the underlying ceramic
body with a waterproof, abrasion and chemical resistant covering. Zircon opacifier is
added to the glaze to mask the underlying colour of the ceramic clay body.

Zircon is an effective opacifier due to its high refractive index. Finely milled zircon
crystals are able to scatter all wavelengths of visible light therefore making ceramics
appear white. An effective opacifier has a refractive index that differs greatly from the
medium in which it is suspended. The difference in refractive index of zircon particles
(1.96) and glass matrix (~1.5) in a glaze results in the reflection and refraction of light.

Zircon has the additional benefit of its high hardness (7.5 on Mohs scale) making it
resistant to scratching and mechanical damage.

Iluka Resources – Mineral Sands Products: Attributes and Applications 5


Most zircon used in ceramics is consumed by tile producers in the form of a finely milled
zircon sand, approximately 1.5 microns in size.

Ceramics End Use (2008 demand = 674kt zircon)

89% Tiles

Tableware
11% Sanitaryware
Other

Source: TZMI, Roskill, Iluka

Foundry and Investment Casting

Of the three broad categories of foundry casting techniques: die casting, sand casting
and investment casting, the latter two use zircon.

Zircon in the Foundry Industry (2008 demand = 167kt zircon)

67% Sand Casting

29% Investment Casting

4% Cosworth Casting (Aluminium)

Source: TZMI, Roskill, Iluka

Sand Casting

Zircon sand is ideal for casting a range of molten metals into moulds due its low thermal
expansion coefficient, high thermal conductivity (causing it to chill the cast giving a better
surface finish) and its non-wetability by molten metal which also improves surface finish
and increases the recoverable sand.

Zircon is the most expensive of the moulding sands commonly used and, as such, silica
sand (the least expensive), is predominantly used for foundry moulds. Zircon continues
to be used where high dimensional accuracy is required.

To improve the finish on the casting, a mould wash can be applied to the sand mould.
The main constituent of mould wash is zircon flour and it is the fine particle size and high
chill factor (high thermal conductivity) of zircon that improves the surface finish.

Iluka Resources – Mineral Sands Products: Attributes and Applications 6


Investment Casting

Investment casting is used to make specialty and high precision metal components in
aerospace such as jet turbine blades, automobiles and medical instruments.

Investment casting is a technique where the mould is formed around a blank of the part,
by applying layers of high quality refractory. Zircon flour and sand form the initial layers
of the refractory shells to provide high dimensional accuracy and excellent surface finish,
thereby minimizing machining and cleaning of the cast part.

Refractories

Steel production and glass production are the main refractory sectors that consume
zircon and zirconia based refractories. Zircon is used in refractory products for its
stability at high temperatures and non-wetability against molten metals.

In the steel industry, zircon refractory products include bricks used to line steel making
furnaces, injector nozzles and casting channels for refined steel continuous casting.

In glass production, there is no cost effective substitute for zircon.

Zircon in the Refractory Industry (2008 demand = 159kt zircon)

Alumina-Zirconia-Silica
55% (AZS accounts for 80%
of glass industry refractory)
Other Refractory
25% (Glass, Steel, Cement Industries)
Zircon Refractory Products
10%
(Mainly steel industry end use)

Source: TZMI, Roskill, Iluka

Zirconia - Fused Zirconia, Zirconium Chemicals

Zirconia is present in the natural form as the mineral baddeleyite. With increased
demand for zirconia and decreasing production of baddeleyite, synthetic zirconia is
produced from zircon via two different routes – fused zirconia and chemically derived
zirconia from zirconium oxychloride (“ZOC”).

Physical Properties of Zirconia


Property Value
Specific gravity 5.6 – 6.1
Hardness (Mohs scale) 8.85
Melting point 2,500 – 2,600°C
Refractive index 2.15 – 2.18
Thermal expansion co-efficient 7.5 – 13 x 10-6 °C
Source: TZMI

Iluka Resources – Mineral Sands Products: Attributes and Applications 7


Fused zirconia products are of lower chemical quality than those produced by chemical
processing methods. Fused zirconia is used in higher volume/lower value segments of
the market such as refractories, abrasives and ceramic pigments.

Chemical production of zirconia is a relatively high cost process and therefore used in
higher value/lower volume applications, such as catalysts used in automotive exhaust
systems to control emissions, electronic circuit boards, and piezoelectric sensing
devices. In advanced ceramics, chemically produced zirconia is used exclusively in the
production of cutting edges, high wearing pump parts and bioceramic parts.

A growing use of chemically produced zirconia is in the telecommunications industry for


ferrules for fibre optic cables. The advantages are that fine zirconia powders achieve
smoother surface finishes, which is important in achieving high performance
connectivity, with the thermal expansion coefficient of zirconia close to that of optical
fibre. Zirconia also has the qualities of elasticity and impact resistance.

Zircon in Fused Zirconia (2008 demand = 113kt zircon)

Zirconia
31% Refractories
(Steel Industry)
25% Ceramic Pigments

7% Abrasives

1% Electronics

Source: TZMI, Roskill, Iluka

ZOC – Zirconium Chemicals

Zirconium oxychloride (“ZOC”) is further processed to form numerous zirconium


chemicals, in particular, for the production of zirconia and zirconium metal. China
dominates global production of ZOC with approximately 95 per cent of global production
capacity. In China, the biggest market for domestic ZOC is for zirconia used in ceramic
pigments. Zirconium chemicals are utilised in a range of manufacturing and end use
applications, which include paper coatings, paint driers, antiperspirants, printing inks and
paints and catalysts.

Iluka Resources – Mineral Sands Products: Attributes and Applications 8


Zircon in Chemicals (2008 demand = 93kt zircon)

Gemstones+
42% Technical
Ceramics
21% Nuclear (Metal)

13% TiO2 coatings

9% Cosmetics

9% Paper coatings

4% Paint Dryers

2% Other

Source: TZMI, Roskill, Iluka consensus

Zirconium Metal

One of the major applications for zirconium metal is as a structural material in the
chemical processing industry. Zirconium metal exhibits excellent resistance to corrosion
in most organic and inorganic acids, salt solutions, strong alkalis and some molten salts.
Areas in the chemical industry where zirconium is used include heat exchangers,
reboilers, evaporators, tanks, reactor vessels, pumps, valves and piping.

Since zirconium owes its unique corrosion resistance to an adherent, inert oxide film, it is
used in condensers.

The other major use of zirconium is for structural material used in nuclear reactor cores.
Zirconium metal is used to hold the uranium fuel pellets (fuel bundles) because of its low
thermal neutron absorption cross-section, which refers to the ability of a material to
absorb thermal neutrons. The lower the thermal neutron absorption, the greater the
efficiency of a nuclear reactor. In this regard, zirconium metal is an excellent material.

CRT Glass

Cathode ray tubes (“CRTs”) generate x-rays which must be attenuated to reduce the risk
of radiation related health effects, principally cancer. Zircon in CRT glass acts an
effective x-ray absorber and has the added benefits of increasing the strength and
hardness of the glass.

Whilst the use of zircon in this end application has decreased with the steady
replacement of CRT televisions and computer monitors with LCD and plasma screens,
zircon is used in plasma screens to enable the manufacture of faceplate glass which is
much thinner and of greater dimension.

Iluka Resources – Mineral Sands Products: Attributes and Applications 9


Zircon Sand Attributes

Different zircon sands display varying physical and chemical properties which will
influence their end use market applications. For example, key zircon attributes for
ceramic manufacture include:

ƒ whiteness index, or ceramic grade;


ƒ iron oxide content below specified levels;
ƒ titanium dioxide content below specified levels;
ƒ aluminium oxide content below specified levels;
ƒ thorium and uranium content typically below 500ppm in the US and other markets;
and
ƒ ease of milling, influenced by grain hardness.

Other zircon end use applications have varying product constituent requirements.

Similar to titanium dioxide, the purchase decision is strongly influenced by product


technical considerations.

While substitutes for zircon exist, for example, in applications such as ceramic
manufacture, those substitutes typically possess one but not all of the attributes of
zircon. For example, fine clays, felspars and kaolin possess the attribute of whiteness
but not hardness.

Iluka Resources – Mineral Sands Products: Attributes and Applications 10


Appendix 1 Titanium Feedstock Production Processes

Sand Deposits
Mining Hard Rock (Dredge or Dry Mining)

Wet Concentration

Processing
Dry Concentration

Key Products Ilmenite Leucoxene Rutile Zircon


Ex Mine

Key Upgraded Titanium Slag Synthetic Rutile


Titanium Products

Titanium
High Purity Pig Iron Tetrachloride TiCl4

Major Pigment
Production Sulphate TiO2 Process Chloride TiO2 Process
Processes

Titanium Sponge

Final Products White Pigment Titanium Metal

End Uses Foundries Paints Plastics Paper Other: -Aerospace Welding -Opacifiers/Glazes
-Inks -Chemical Plants Electrode -Zirconia/Zirconium
-Cermaics -Golf Clubs Flux chemicals
-Fibres -Refractories/Foundry

Source: TZMI

Iluka Resources – Mineral Sands Products: Attributes and Applications 11


Appendix 2 Generic Structure of the Zircon Industry

Zircon Sand

Fusion with Thermal High


Caustic fusion
carbon Milling dissociation temperature
chlorination

Sodium zirconate
Impure zirconia and silica
Micronised
Zircon
Acid
Zircon
Reaction with Reaction with dissolution
Fused Flour
NaOH acid
Zirconia Zirconium
Frits tetrachloride

Soluble Zirconium
zirconium salt oxychloride
Foundry sand, mould
washes, investment
casting shells
Firing Insoluble Reaction with Reaction with
zirconia filtrate NaOH NH2OH or NaOH
Reduction with
Ceramic tiles, magnesium
sanitary ware (Kroll process)
Zirconium hydroxide
precipitate
Glassmaking
Sintering,
Sintering,
firing or
firing or fusion
fusion
Zirconia in
Zirconium
glass screens, Calcination
chemicals
display panels

Chemically produced zirconia

Ceramic Abrasives Engineering Refractories Catalysts Electronic Solid Gemstones, Antiperspirants, Zirconium
pigments ceramics components electrolyte glass, lasers, paint driers, paper metal
devices cosmetics coatings etc

Source: IAEA

Iluka Resources – Mineral Sands Products: Attributes and Applications 12


References

Information is drawn predominantly from internal Iluka sources. External references relate to the following:

Huntsman Tioxide,1999, Manufacturing and General Properties of Titanium Dioxide


Pigments (unpublished), Tioxide Group, London, p 12.

International Atomic Energy Agency, 2007, Radiation protection and NORM residue
management in the zircon and zirconia industries, IAEA, Vienna, p 6.

Norgate, T and Wellwood, G, 2006, The potential applications for titanium metal powder
and their life cycle impacts, JOM 58(9), p 58.

Roskill Information Services Ltd, 2007, The Economics of Zirconium (12th Ed.), Roskill
Information Services Ltd, London.

TZ Minerals International Pty Ltd, 2005. The Global Zircon Industry: New era – new
dynamics, TZ Minerals International Pty Ltd, Perth, pp 103-105, 107-109, 112-116.

TZ Minerals International Pty Ltd, 2009. Mineral Sands Annual Review 2009, TZ
Minerals Pty Ltd, Perth, p 1, 65, 128.

Other Information

Further Mineral Sands Industry information is available on Iluka’s website


www.iluka.com (refer Mineral Sands Briefing Information – under Investor Relations and
Media)

- Mineral Sands: An Overview of the Industry


- Information on Iluka’s Titanium Dioxide and Zircon Customers
- Historical Pricing for Iluka's Mineral Sands Products
- Historical Sales by Region for Iluka's Mineral Sands Products

Inquiries should be directed to:

Dr Robert Porter
General Manager, Investor Relations and Corporate Affairs
Phone: + 61 8 9360 4751
Mobile: +61 (0) 407 391 829
Email: robert.porter@iluka.com

Iluka Resources – Mineral Sands Products: Attributes and Applications 13

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