ZIA Technical Handbook On Zirconium and Zirconium Compounds 2019 PDF

Technical handbook on
zirconium and zirconium

compounds 2019
Copyright
c 2019 ZIA
P UBLISHED BY Z IRCON I NDUSTRY A SSOCIATION
ZIRCON - ASSOCIATION . ORG
Document prepared by D.R. Leal-Ayala, J.L. Martínez-Hurtado and J.A. Allwood (first
edition), and D. Densley Tingley and A.C. Serrenho (second edition) and C. F. Dunant
(fourth edition)
The Zircon Industry Association (ZIA) would like to thank the following companies
and persons for providing valuable information: Angelika Priese, Peter Moles, Andrew
Considine, Jorge Masbate, Chris Barrington, Simon Cook, Iluka, Rio Tinto, Roskill,
Imerys and MEL Chemicals.
First edition, June 2013
Second edition, August 2015
Third edition, August 2017
Fourth edition, August 2019
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1 Zirconium, zircon and zirconia definition 9
1.2 Mineralogy and deposits 10
1.3 Mining and processing 12

1.3.1 Zircon sands mining and concentrate production . . . . . . . . . . . . . . . . 12
1.3.2 Zirconia and zirconium metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.4 World production, reserves and market 18

1.4.1 Current production and reserves by country . . . . . . . . . . . . . . . . . . . . . 18
1.4.2 Market behaviour and dynamic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5 Industry structure and consumption patterns 19
2 Material Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1 Zirconium 26
2.1.1 Physical and Mechanical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.1.2 Nuclear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2 Zirconium Compounds 29

2.2.1 Silicates - Zircon Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.2 Oxides - Zirconia Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.3 Borides, Carbides, Silicides and Nitrides - Physical Properties . . . . . . . . 30
2.2.4 Halides - Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3 State-of-the-art applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1 Foundry sands and coatings 35
3.2 Refractories 37
3.3 Ceramics 38
3.3.1 Traditional ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.3.2 Advanced ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.3 Electro-ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.4 Glass 43
3.5 Major industrial zirconia and zirconium chemical applications 44

3.5.1 Gemstones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.5.2 Nuclear industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.5.3 TiO2 coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.5.4 Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.5.5 Paper and printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.5.6 Paints and inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.5.7 Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.6 Minor chemical applications 49

3.6.1 Ammunition and explosives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.6.2 Gas purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4 Emerging R&D – highlights . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

4.1 3D printing consumables and photo-polymerisable ceramics 51
4.2 Solar cells 52
4.3 Shape memory alloys 54
5 Emerging R&D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.1 Advanced coatings and functional materials 58
5.1.1 Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5.1.2 Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5.1.3 Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.1.4 Fabrics and textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.1.5 Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.1.6 Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.1.7 Gems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.1.8 Ceramic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.1.9 Smart coatings with enhanced properties . . . . . . . . . . . . . . . . . . . . . . . 61
5.1.10 Coating technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.2 Advanced ceramics 62

5.2.1 Ceramics with tunable properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.2.2 Ultra-High temperature, high-wear and extreme applications . . . . . . 63
5.2.3 Dental implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.2.4 Composite and alloy fabrication technologies . . . . . . . . . . . . . . . . . . . 64
5.3 Casting and moulding 64

5.3.1 Enhanced modulus refractories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.3.2 Injection moulding ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.3.3 3D printing consumables and photo-polymerisable ceramics . . . . . . 65
5.4 Grinding media and grinding technologies 65
5.5 Biomedical applications 65

5.5.1 Implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.5.2 Dental parts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.5.3 Biocompatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.5.4 Bioconjugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.5.5 Drug delivery and pharmaceutical formulations . . . . . . . . . . . . . . . . . . 68
5.5.6 Bioimaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.6 Catalysis 69
5.6.1 Inorganic catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.6.2 Gas catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.6.3 Organic catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.7 Fuel cells and batteries 73

5.7.1 Proton Exchange Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.7.2 Hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.7.3 Ion transport and conductivity in zirconia . . . . . . . . . . . . . . . . . . . . . . . . 73
5.7.4 Solid Oxide Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
5.7.5 Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
5.8 Adsorption and immobilisation 74

5.8.1 Water, food and biological applications . . . . . . . . . . . . . . . . . . . . . . . . 74
5.8.2 Remediation applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.8.3 Radioactive applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.8.4 Gas storage and adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.8.5 Sorption for catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.8.6 Sorption of zirconium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.9 Sensing 76
5.9.1 High temperature and pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.9.2 Gas sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.9.3 Relative humidity sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.9.4 Biosensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.9.5 Food and drink applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.10 Nanomaterials, nanorods, nanostructures and nanofabrication 78

5.10.1 Nanotubes and ordered arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.10.2 Foils and thin films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.10.3 Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.10.4 Nanofibres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.10.5 Self assemblies, organic templates, and hybrid materials . . . . . . . . . . 79
5.10.6 Nanofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.10.7 Nanoparticles, nanopowders, nanocrystals and composites . . . . . . . 80
5.11 Optical materials 81

5.11.1 Waveguides, fibres and optical substrates . . . . . . . . . . . . . . . . . . . . . . . 81
5.11.2 Nanostructured colour and dyeing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.11.3 Luminescence and emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.12 Electronics and solid state devices 82

5.12.1 Memory devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.12.2 Electrical gates and transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.12.3 Superionic conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.13 Research trends 82
5.13.1 Number of citations per research topic . . . . . . . . . . . . . . . . . . . . . . . . . 83
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
1 — Introduction
1.1 Zirconium, zircon and zirconia definition
Zirconium is a amazing grayish-white metal with unique properties that make it highly
important for a wide range of industrial, commercial and scientific applications. It is the
20th most abundant element in the Earth’s crust and commonly occurs in the mineral
zircon (ZrSiO4 ), in silicate form, and less frequently in the mineral baddeleyite (also
known as natural zirconia, ZrO2 ), in oxide form [1] . Zirconium was first discovered
in Germany in 1789 by Martin H. Klaproth, who discovered the element by analysing
zircon mineral samples. Jöns Jakob Berzelius isolated the metal for the first time in 1824,
but it was not until 1925 that Anton Eduard van Arkel and Jan Hedrik de Boer developed
the iodide or crystal bar process to produce high-purity zirconium, commercialising the
metal soon after in 1930 [2].
Around 97% of zirconium compounds and zirconium metal produced worldwide are
obtained from zircon recovered from heavy-minerals sands deposits (known as secondary
placer type deposits), while the rest is obtained from primary igneous deposits such as
baddeleyite mining (at present, the only commercially significant baddeleyite mining
operation is located in northwestern Russia, near Murmansk) [3]. Zircon has a theoretical
content of 67% zirconia and 32% silica, and it can typically contain a small percentage
of hafnium in the range of 0.2 to 4% [2]. Directly after mining and production of a
heavy mineral concentrate, zircon is separated, beneficiated and commercialised as
zircon sand (zircon). In some cases, an intermediate zircon concentrate is exported to
processing plants in China. Zircon sand is either used directly in certain applications (e.g.
foundry sands) or processed to produce zirconium chemical compounds (e.g. Zirconia)
or zirconium metal. Zirconia’s use has grown enormously in many fields despite its low
availability in natural form (baddeleyite). This can be attributed mainly to the availability
of synthetically produced zirconia, which, as explained by Iluka [4], can be produced
from zircon sand through two different processes: fused zirconia or chemically derived
zirconia from zirconium oxychloride.
10 Introduction
In addition to zircon, heavy mineral sands also contain inclusions of other valuable
minerals such as titanium minerals (ilmenite and rutile), alumina-silicates, magnetite,
iron, and tin, as well as occasional inclusions of radioactive elements such as uranium
and thorium in small amounts. The relative contents of these minerals varies from
deposit to deposit; in some cases zircon is considered as a by-product and in other cases
a co-product of titanium minerals production and there are also cases where zircon is
the principal product and titanium minerals the co-products [1, 3].
1.2 Mineralogy and deposits

Zirconium can be found in up to twenty minerals around the Earth’s crust, most of which
have no commercial importance due to their low zirconia (ZrO2 ) content and uneconomic
quantities [2]. Table 1.1 lists the seven most important zirconium minerals and their
properties. Of these, zircon and Baddeleyite are the most commercially significant
minerals.
Table 1.1: Zirconium bearing minerals (Elaborated with data from: [2])
Mineral Chemical formula Specific Hardness ZrO2

gravity (Mohs’ scale) content
(%)
Zircon ZrSiO4 4.2-4.86 7.5 63-67
Baddeleyite ZrO2 5.5-6 6.5 98-100
Eudialyte (NaC aF e)6 Zr(OH,Cl) 2.9-3 5-5.5 1.2
(SiO3 )6
Caldasite Mixture of fibrous bad- - - 60-75
deleyite, zircon, altered
zircon, and other miner-
als
Vlasovite Na2 ZrSi4 O11 2.97 6 29
Gittinsite CaZrSi2 O7 3.6 3.5-4 40.3
Zirkelite (CaFe)(ZrTiTh)2 O5 4.7 5.5 -
As explained by Elsner [5], zircon develops through early liquid magmatic crystallisation
in albite-bearing acidic rocks such as granites, diorites, syenites and their pegmatites.
All zircon found in other types of reserves and deposits can be traced back to zircon
developed in this way. The map shown in Figure 1.1 elaborated by Towner [2] with
data from Bundesanstalt fur Geowissenschaften und Rohstoffe (BGR) [5], shows the
geographical location and size of the major zirconium deposits found around the world.
As can be seen from this map, zirconium deposits are concentrated in only thirteen
countries, mostly in South Africa, Australia, China and the United States. Two types of
zirconium deposits can be observed:
• Primary igneous deposits classified according to their magmatic or volcanic origin.
• Secondary placer deposits (i.e. heavy-mineral sands).
The large majority of deposits shown in Figure 1.1 are secondary placer deposits (i.e.
heavy-mineral sands). This deposits originated when the zircon that was initially devel-
oped through early liquid magmatic crystallisation in acidic rocks was slowly eroded
23
7 9 ■■
■ 24
■
6
● 8 ■
22
●
1 3
2 ●
● ● 4
5 ●
●
29 30
27 ●●
● ●
● 31
32
25
● ●28
●
26
■
10
1.2 Mineralogy and deposits
●
11
●
13 20 ▴ 45
12 46
■● 33 ● 44
● 43
■ ●21 34 ●
19● 35 ●
● ●42
● 36
●
● 41
14 ● ● 18 ●
37 ●
●
●● 17 40
16 38
15
Top 11producers (2017) 39 ● 47
●
= 100 000 tonnes
6 7
GEOLOGIC DEPOSIT TYPE: Placer (●), Magmatic (■), Volcanic ( ▴ ) 1992 TOTAL RESOURCES [Tons]: 10 -10 , <106 , unreported
UNITED STATES CANADA BRAZIL SOUTH AFRICA MOZAMBIQUE INDIA CHINA AUSTRALIA
1. Soledad Canyon 6. Suncor 10. Pitinga 14. West Cape 20. Pebane 25. Chavara 29. Beihai 33. Eneabba 41. Bridge Hill
2. Kerr McGee Syncrude 11. Mataraca 15. Cape Morgen 26. Manavalakurichi 30. Xun Jiang 34. Jurien Bay Viney Creek
MADAGASCAR
Oak Grove 7. Thor Lake 12. Poços de Caldas Ciskei Coast 27. Chatrapur 31. Guangdong 35. Cooljarioo Tomago
21. Taolanaro
Natchez Trace 8. Strange Lake 13. Vitoria 16. Transkei Coast 32. Wuzhuang 36. Gingin Stockton
SRI LANKCA
3. Lakehurst 17. Umgababa UKRAINE Sai-Lao 37. Waroona N. 42. Moreton Is.
GREENLAND 28. Pulmoddai
4. Brunswick 18. North Natal 22. Dnepropetrovsk 38. Waroona N. Stradbroke
9. Ilimaussaq NEW ZEALAND
Cumberland Island 19. Bothaville Minninup 43. Fraser Is.
RUSSIA 47. Westport
5. Tail Ridge Capel 44. Agnes Water
23. Lovozaro Barrytown
Green Cove Springs 39. Yoganup 45. Bayfeld
24. Kovdor
40. WIM-150 46. Brockman
Figure 1.1: Location, resources, and geological type of zirconium mineral deposits (elaborated with 1992 data from [2]); and 2017 production
11
data per country (data extracted from [6]

scrapers, bulldozer traps, truck and excavator and front end loader) are used to excavate and
transport the sand to a feed preparation section. Variations to these methods involve different
means of transporting the dry-mined sand: either by pumping or the use of conveyors. Hydraulic
mining with high pressure water is also employed as a variation on both themes, being used in
12dredging (to encourage face rilling) and in dry mining to slurry sand, clay and HM. Introduction
Figure
Figure 3: Dredging
1.2: Dredging operations
operations at CRLworking
showing North Stradbroke Islandand
pond, dredge showing working
floating pond,
concentra-
suction cutter
tor. (Image extracted dredge
from [8] c
) and floating concentrator for the Enterprise operation
(left) and with a floating thickener at the Yarraman operation (right). Both
concentrators are rated at between 3000 and 4000 tph of sand feed (source
Iluka).
by weather and water (weathering) over long geological periods. After weathering,
zircon was transported by rivers to the sea shoreline, where it was concentrated through
the combined action of maritime currents, wind and waves [2]. The relatively high
specific gravity of zircon led to a uniform deposition of the material across the same
coastline areas by the constant concentrating effect of wave actions [7]. In addition,
zircon’s resistance to leaching and abrasion makes it resistant to erosion or dissolution
by water. This natural concentration process occurs not only for zircon but also for other
valuable minerals typically found in heavy-mineral sands such as rutile and ilmenite,
leading to combined heavy-mineral grades of 10 - 20% in most placer deposits. However,
exploitation of deposits with grades as low as 1% might be possible depending on the
technical difficulty of extraction. Most placer deposits are younger than 2 million years
of age (quaternary) [2].
Only a minority of zirconium (3%) is produced from non-placer primary igneous
deposits [3], which can be locate in alkaline granite or granitic rocks, carbonatite
alkali intrusions or altered volcanic tuffs, mostly of Precambrian age [2], with the
only commercially significant magmatic deposit being the Kovdor baddeleyite mining
operation in northwestern Russia.
1.3 Mining and processing

1.3.1 Zircon sands mining and concentrate production
Around 97% of zircon in the world is obtained from heavy-mineral sands mining [3].
This process consists of three main stages: mining, wet concentration and dry separation.
Mining can be performed either by a wet mining process (employing floating dredges,
typical for unconsolidated deposits), or by dry mining methods (employing scrapers,
dozers and excavators, typical for cemented deposits) [8]. Dredging involves the pro-
cessing of large amounts of solids to extract zircon and other valuable minerals from a
water pond. As explained by Jones [8], dredging consists of a floating dredge cutting
the ore under the surface of a pond and pumping the ore slurry to a wet concentrator
floating in the same pond, as depicted in Figure 1.2.
Dry mining techniques are generally employed for hard and cemented deposits with
General Mining Sequence
1.3 Mining and processing 13

Small bund or
drain to aid in
Top soil and directing
sub soil reclaimed tails
removed water
Tailings water
collection point
Overburden
stripping Ore to out of pit
Unconsolidated
mining unit
tails beach
Distance to be Distance to be
approximately greater than
100m 100m
c
Figure 1.3: Schematic view of a typical dry mining site. (Image extracted from [10] ).
high grade ore bodies. Figure 1.3 shows a schematic view of a typical dry mining site,
while Figure 1.4 shows two possible process flows for this operation (although these
may vary depending on the characteristics of each particular mining site). The first step
is to clear the mine area from trees and other plants or rocks, followed by stripping
and stockpiling the topsoil and subsoil separately from the underlying overburden
material [9]. Overburden is stockpiled for replacement purposes at the end of the mine’s
useful life. A typical dry mining operation consists mainly of depositing the ore into a
hopper with the help of dozers, scrapers or excavators, as depicted in Figure 1.4, and
transferring it to the primary separation process [9]. In here, waste material is screened
out of the mix by the action of vibration and rotation separation devices, where large
particles (over 150 mm) are screened out of the mix and mineral sand, silt and clay
mixtures are washed away from rocks [9]. The resulting mineral sand, silt and clay
slurry is then transferred to the wet concentrator.
The wet concentration process, which is employed to produce a high-grade heavy-
mineral concentrate (85-95% HMC) [8], involves the use of a gravity circuit to separate
the valuable heavy mineral sand from the non-valuable and lighter gangue that makes up
most of the input slurry [9]. In this process, described in Figure 1.5, the input slurry is
first passed through a series of hydrocylones which remove very fine particles (usually
of less than 63 µm, mostly clay), which are sent to a fines thickener where they mix with
the quartz sand tails and are subsequently pumped to the mining void. An alternative
route is to send the thickener underflow to a solar evaporation pond where dried clay
can be recovered [8].
The underflow from the hydrocyclones is sent to a constant density (CD) tank which
subsequently pumps it into the wet concentration process distributors above the primary
spirals. Afterwards, the material is passed through the gravity separation circuit con-
sisting of several spiral banks (between four and six stages: primary or rougher spiral
stage, middlings stage, cleaner spiral stage, re-cleaner and scavenger stages) [8]. In this
process, the heavy mineral is effectively separated from the lighter gangue minerals,
mostly quartz sand. An optional magnetic separation step can be added at this point to
separate magnetic ilmenite through the use of wet high intensity magnets.
The final heavy-mineral concentrate is stockpiled and drained before being transferred to
14 Introduction
Various Dry Mining Process Flows

(Iluka operations are primarily dry mining)
Simple Mining Unit:

• Mobile
Secondary Screen • Suitable for dunal
clay and rock
Oversize
• Low M&H cost the
Pri. Screen off grade (dependi
ratio and assembla
Concentrator • Low utilisation as r
Feed by tramming distan
of FEL/Dozer -> n
~100m
65 Autogenous Scrubber
7E
Stationary Mining U
• Design for high en
beneficiation (high
with higher work in
• Autogenous mill /
Oversize allows for higher H
Ore Bin and.
Feeder • Higher opex, often
Tertiary. Screen conjunction with R
and hence double
• Scraper mining wi
plant feed
Secondary. Screen
Concentrator • Truck and Shovel
Feed FEL plant feed
Figure 1.4: Examples of simple (above) and stationary (below) dry mining process flows
c
(Image extracted from [10] ).
Typical Concentrator Process Flows
From Mining
Unit Pre-Concentrator (mob)
Fines Thickener
CD Tank
Gravity
Circuit
Quartz Tails Solar Evap Dam

RHF Stockpile
& reclaim
Magnetic Separation Tails Dam in mine void
Ilmenite Tails Concentrators

Gravity Circuit Feed • Multiple configurations
• Config dependent upon HM
upgrade ratio and mineralogy
• Numerous tails handling and
disposal options
UCC • High utilisation and high VHM
Concentrate
recovery required for maintaining
capital efficiency and minimising
mining costs
c
Figure 1.5: Wet concentration process flow (Image extracted from [10] ).
15
16 Introduction
a secondary concentration process or mineral separation plant. Residual sand is pumped

into the mining pit, while process water from cyclone stackers and the solar evaporation
dam is recycled to a clean water dam where it can be used again in the wet concentration
process [8, 9].
The heavy mineral concentrate obtained from the wet concentration process might
be subjected to attritioning in order to increase separation efficiency by cleaning the
mineral surface prior to electrostatic separation. Additionally, the mineral concentrate
might be subjected to a secondary concentration process in which fine quartz and other
non-valuable minerals are removed to achieve heavy mineral grades of up to 98% [8, 9].
Following these steps, the concentrate is sent to a final mineral separation and zircon
finishing process, where zircon is separated from ilmenite, rutile and leucoxene (HyTi),
as well as from other non-valuable minerals, as shown in Figure 1.6. This process uses
an array of screening, magnetic, electrostatic and gravity separation circuits to achieve
zircon’s separation.
Ilmenite is separated through magnetic separation, while non-magnetic minerals are
sent to a primary electrostatic separation circuit where non-conductor materials are
separated from conductor minerals. The former are sent to a gravity separation circuit
where zircon is separated due to its high specific gravity and subsequently sent to an
additional electrostatic separation circuit to remove residual conductors [8]. Zircon’s
last separation stage involves the use of an air table to remove fine quartz and residual
kyanite. An optional configuration may involve zircon leaching to remove potential
iron oxide coatings to improve the overall quality of the product. Conductor materials
follow an additional electrostatic separation circuit where secondary ilmenite, rutile and
leucoxene are obtained [8].
1.3.2 Zirconia and zirconium metal
There are many different methods employed to obtain zirconia from zircon sands by
chemical decomposition. These methods, although distinct from each other, share three
common features [11]: they all involve the decomposition of zircon by chemical, thermal
or mechanical means; all products obtained from zircon decomposition are subsequently
treated by solubility differentiation; and they all involve the isolation of zirconium
compounds from residual impurities. A detailed exploration of all these methods is out
of the scope of this report. However, a reference list of the most important methods is
provided as follows [11]:
1. Thermal dissociation
2. Decomposition by fusion
(a) Fusion with sodium hydroxide
(b) Fusion with sodium carbonate
(c) Fusion with calcium oxide and magnesium oxide
(d) Fusion with potassium fluorosilicate
(e) Fusion with calcium carbonate (or lime)
3. Chlorination
4. Carbiding process
5. Other zirconia recovery methods
Typical Mineral Separation and Zircon Finishing Process
(options for zircon leach either upstream or downstream of final electrostatic and magnetic finishing)
Feed Bins
Alt. Train
Electrostatic
Separation
Ilmenite Mag Sep and Electrostatics Circuit Conductors
Oversize
waste
Electrostatic
Separation
Circuit
Zircon
N/Cond
SiO2/AlSiO5 Wet Gravity

Tails Circuit
Ilmenite
Zircon Conc.
Electrostatic Zircon Leach (opt config)

Separation
Circuit
Rinsing &
Neutralisation
Secondary Rutile HyTi
Paste Mixer Ilmenite
Pre-heater
Standard Premium Reactor
ZrSiO4, TiO2,
P2O5 Tails Zircon Zircon
c
Figure 1.6: Final mineral separation and zircon finishing process (Image extracted from [10] ).
17
18 Introduction
(a) Fusion with calcium sulphate

(b) Mechanical zirconia processing
(c) Hydrothermal decomposition
(d) Anion-exchange process
Additionally, zirconia can be extracted from baddeleyite employing the following meth-
ods [11]:
6. Recovery of zirconia from baddeleyite
(a) Sulphate method
(b) Oxychloride crystallisation
(c) Precipitation with sulphur dioxide or sodium thiosulphate
(d) Precipitation as phosphate
(e) Purification as hydrated sulphate
(f) Double fluorides procedure
(g) Thermal decomposition of alkali chlorozirconates
(h) Sublimation of zirconium tetrafluoride
(i) Mechanical processing
(j) Sodium metaphosphate method
Furthermore, zirconium and hafnium can be separated with the following methods [11]:
7. Fluoride salt crystallisation
8. Methyl isobutyl ketone extraction
9. Tributyl phosphate extraction
10. Extractive distillation
Reduction to metal can be achieved by the following procedures [11]:
11. Kroll process
12. Sodium reduction zirconium tetrachloride
13. Potassium hexafluorozirconate reduction with calcium metal
14. Calcium or magnesium reduction
15. Electrolysis
1.4 World production, reserves and market

1.4.1 Current production and reserves by country
Table 1.2 shows a breakdown of zirconium mine production (in thousand metric tonnes
of zirconium concentrate) and reserves by country, based on data from the US Geological
Survey [12–14]. Global production of zirconium concentrates in 2014 is estimated to be
accounted for 1.54 million metric tonnes, lower than 2011 production of 1.62 million
metric tonnes, but higher than 2010 and 2012 production.
In addition to the production and reserve figures shown in Table 1.2, the identified
zirconium world resources in 2014 (i.e material that is potentially valuable and has
reasonable prospects for eventual economic extraction) have been estimated to be around
78 million metric tonnes [1,12], distributed mainly among Australia (65%), South Africa
(18%) and India (4%) [1].
Table 1.2: World Zr production 2010-2016 and current world Zr reserves (Elaborated with
data from [6, 13, 14]). 2016 data are estimates only.
Zr mine production Zr reserves

(x106 kg) (x106 kg of ZrO2 )
2010 2011 2012 2013 2014 2015 2016
Australia 540 762 610 850 900 601 450 51,000
South Africa 381 383 400 170 170 330 360 14,000
China 140 150 150 150 140 140 140 500
Indonesia 50 130 60 110 120 110 110 NA
Mozambique 37 44 47 47 56 64 68 1,100
India 38 39 40 41 40 40 40 3,400
United States NA NA NA NA NA 80 NA 500
Other 84 110 109 140 110 150 157 7,200
Total 1,270 1,620 1,420 1,510 1,540 1,520 1,330 78,000
1.4.2 Market behaviour and dynamic

Zircon sand production has historically experienced different periods of shortage and
over-supply accompanied by price volatility. This is a normal phenomenon when
considering that zircon is typically extracted as a by-product or co-product of mineral
sands mining. This means that its production tends to be influenced not only by its direct
demand, but also by the demand for other minerals contained in heavy mineral sands
such as rutile and ilmenite [1, 2]. Examples of this occurred in 1981 when an economic
recession and cutbacks in rutile and ilmenite production caused a shortage of zircon, or
when strong demand for those minerals in the late 1950’s generated an oversupply of
zircon [2]. The economics of mineral mining projects are typically evaluated through
a unit cash cost measure, which considers the grade of the valuable mineral, scale of
the project, mining method and associated costs [15]. Mineral sands mines exploit
more than one mineral (e.g. ilmenite, rutile, zircon) and therefore the assemblage of
the deposit (i.e. the weight of each of these minerals) needs to be considered when
evaluating the revenue per tonne characteristics [15]. This is performed through the
use of a revenue/cash cost ratio curve to evaluate the economic feasibility of particular
deposits [15].
1.5 Industry structure and consumption patterns

The steep zircon production increase observed after the year 2000, as shown in 1.7,
coincided with a considerable growth of Chinese demand for zircon sand. Figure 1.8
illustrates the global zircon production pattern by country for the years 2004-2013.
During this period, Australia continued to be the main producing country.
Figure 1.9 illustrates the evolution on the share of end-use sectors of global zircon
consumption. Over the last few year, the consumption of zircon in chemicals and
foundries has been gaining market share to ceramics. Figure 1.10 shows a simplified
20 Introduction
1.8
1.6
Zr concentrate production (million metric tonnes)
1.4
1.2
0.8
0.6
0.4
0.2
0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 2014 2016
Figure 1.7: Zirconium mineral production 1990-2016 (Elaborated with data from [16] for
1981-2016, [17] for 2012, and [14] for 2013).
version of the global zircon industry and its biggest end-use markets in 2013. This
diagram shows the mass flows of zircon, from mining to end-use sector, as well as some
key intermediate processing steps. The width of the lines represents the amount of mass
following each particular flow. Zirconia is derived from zircon either by a chemical route
that involves leaching and decomposition, or via a fusion process. Similarly, zirconium
metal is obtained either from zircon or zirconia. A more detailed image of the zircon
industry is given in Figure 1.11.
100%
90%
80%
70%
60%
50%
40% Others
30%
Indonesia
20% USA
South Africa
10%
Australia
0%
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Figure 1.8: Global zircon production pattern by country from 2004 to 2013 (Elaborated
with data from [6, 14]).
100%
90%
80%
70%
60%
50%
40%
Others
30% Refractories
Chemicals
20%
Foundry
Ceramics
10%
0%
2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015
Figure 1.9: Global zircon consumption pattern by sector from 2004 to 2013 (Elaborated
with data from [6, 14]).
22
Figure 1.10: Simplified structure of the global zircon industry by sector of consumption in 2013 (Elaborated with data from [14, 18]). Values are
presented in thousands of metric tonnes of zircon equivalent.
Introduction
ZIRCON SAND BADDELEYITE
(ZrO2, SiO2) (ZrO2)
CHEMICAL
MILLING TO MICRONISING CHEMICAL PROCESSING &
ZIRCON FLOUR TO OPACIFIER PROCESSING Hf REMOVAL
CHEMICAL OR
THERMAL
DECOMPOSITION
KROLL
ALUMINA
MELTING REDUCTION
ZIRCONIA
TO FRIT PROCESS
SILICA (AZS)
ZIRCONIA
(ZrO2)
STABILISATION
FULLY OR
1.5 Industry structure and consumption patterns
PARTIALLY
STABILISED
ZIRCONIA
FOUNDRY REFRACTORIES ABRASIVES CERAMIC GRES ZIRCONIA ZIRCONIUM CERAMIC ZIRCONIUM

SAND GLASS GLAZES PORCELLANATO CERAMICS CHEMICALS PIGMENTS METAL
TILES
TZ Minerals International Pty Ltd © 2013 “Zircon Annual Review 2013”
Figure 1.11: Detailed structure of the zircon industry (Courtesy of TZMI).

23
2 — Material Properties
Zirconium is a metallic element located in Group IVB of the periodic table, with an
atomic weight of 91.22 and atomic number 40. As shown in Figure 1.10, it is mostly
used in its silicate form as zircon, and less frequently in its pure form as zirconium
metal and in oxide form as zirconia. Despite this, there is a great diversity of zirconium
compounds that have found their way into academic literature and, to a lesser extent,
into industrial applications. This section presents the physical, mechanical and nuclear
properties of the element zirconium, in addition to the physical properties of some
commonly used zirconium compounds, including zirconia and zircon.
Providing a complete list of zirconium compounds and their properties is a challenging
task that is out of the scope of this report. Therefore, the list of properties and compounds
shown here is not exhaustive. However, the information presented in this section is
intended as a quick property reference for some of the most important commercial forms
of the material: zirconium, zircon and zirconia.
26 Material Properties
2.1 Zirconium
2.1.1 Physical and Mechanical
The physical and mechanical properties of zirconium are given in Table 2.1.
Table 2.1: Zirconium Physical and Mechanical Properties (Elaborated with data from
[19], [20], [21], [22] and [23]).
Property Value
Thermal properties
Atomic number 40
Atomic weight 91.22
Standard state Solid at 298K (25◦ C)
CAS Registry ID 7440-67-7
Group in Periodic Table IVB
Colour Silvery white
Classification Metallic
Oxidation numbers +4, +3, +2, 0, -2
Density 6.45
20◦C(g/cm3 )
Molar volume 14.02 cm3
Melting point 1852 ± 10◦ C
Boiling point 4409◦ C
Allotropic transition 862 ± 5◦ C

HCP to BCC
Thermal expansion 6.39x10−6 / ◦ C k c-axis
Linear coefficient 5.64x10−6 / ◦ C ⊥ c-axis

5.64x10−6 / ◦ C random
[all at 20◦ C]
Continued on next page

2.1 Zirconium 27
Table 2.1 – continued from previous page

Property Value
Thermal conductivity 22.7 W m−1 K−1
Specific heat 0.2759 J/g-◦ C [at 25◦ C]
Molar heat capacity Zr(α)Cp = 6.83 + 1.12x10−3 T

−0.87x105 T −2 (298 − 1135K)
Zr(β )Cp = 7.27(1135 − 1400K)
Heat content Zr(α)HT − H298 (298 − 1135K) =

6.83T + (0.56x10−3 T 2 ) + (0.87x105 T −1 ) − 2378
Zr(β )HT − H298 (1135 − 1400K) = 7.27T − 1163
Entropy 38.89 ± 0.16 J/mole-deg [at 298 K]
Heat of fusion 23 kJ/mole
Heat of vaporisation ∆H0 = 595,153 ± 1465 J/mole
−31, 066
Vapour pressure log P (atm) = + 7.3351
T
−2.415x10−4 T (1949 − 2054K)
Thermal neutron 0.180 ± 0.004 barns/atom

absorption cross section
Electrical properties
Electrical resistivity High-purity crystal bar -44.1

Regular crystal bar -45
Mg reduced, melted -54
[microhm-cm at 20◦ C]
Temperature coefficient 43.5x10−4 /◦ C (0 - 200◦ C)

of resistivity 29.3x10−4 /◦ C (0 - 800◦ C)
Pressure coefficient Pressure (R at pressure /

of resistivity (kg/cm2 ) R at 0 pressure)
0 / 1
40,000 / 0.9914
80,000 / 0.9836
Continued on next page

Table 2.1 – continued from previous page

Property Value
Superconductivity Tc = 0.546 − 0.680K
Electrochemical equivalent 0.2363 mg/coulomb for valence of four
Thermoelectric power Zr versus constantan (0 - 600◦ C)

dE
= 0.05725 - 109.4t x 10 −8 mv/◦ C
dt
Zr versus alumel (0 - 600◦ C)
dE
= 0.02881 - 336t x 10−7 mv/◦ C
dt
Optical and thermionic properties
Emissivity coefficients 0.46(α)-0.50(β ) (5410 Å)

0.43(α)-0.48(β ) (6520 Å)
0.49(α)-0.51(liq) (6500 Å)
Photoelectric threshold 3200 Å
Work function 4.1 volts to 3.7 volts
Magnetic properties
Susceptibility 200 K 1.28 x 10−6 cgs

400 K 1.32 x 10−6 cgs
600 K 1.41 x 10−6 cgs
Mechanical properties
Young’s modulus 68 GPa
Rigidity modulus 33 GPa
Poisson’s ration 0.32 - 0.35
Hardness As low as 60-70 Brinell and Vickers

or 20-30 RB for highest purity Zr
Tensile strength As low as 0.17 GPa

for high purity annealed
2.1.2 Nuclear
The stable isotopes of zirconium are listed in Table 2.2 together with data on natural
abundance, atomic mass and thermal neutron capture cross-section. A very low neutron
absorption capacity can be observed, making zirconium a suitable material for nuclear
reactors, as suggested by [24].
Table 2.2: Stable Isotopes of zirconium (Elaborated with data from [24])
Isotope % Natural Atomic Neutron capture

abundance mass cross-section (barns)
90/40 Zr 51.46 89.9043 0.1

91 Zr 11.23 90.9053 1.0
92 Zr 17.11 91.9046 0.2
94 Zr 17.40 93.9061 0.1
96 Zr 2.80 95.9082 0.1
2.2 Zirconium Compounds

2.2.1 Silicates - Zircon Physical Properties
As explained by [24], zirconium silicates exist in a wide number of minerals, the most
important being zircon (ZrSiO4 - Figure 2.1), which is a very hard, highly refractive,
birefringent and refractory material. Zircon remains stable below 1673◦ C [25], but
it can be dissociated to form ZrO2 + SiO2 if forced beyond that temperature. The
dissociated compounds can recombine again under slow cooling. Zircon is mostly
unreactive to acids at low temperatures, however, it can be attacked by sulphuric acid at
high temperatures and pressures [24]. Some important physical properties of zirconium
silicates are given in Table 2.3.
Zircon is commonly commercialised in sand and milled sand form. The specifications
for such products can vary depending on the intended applications. A thorough review
of zircon concentrates specifications can be found in the work of [5] and [26], who have
compiled the guaranteed specifications for a wide range of commercial zircon sands.
Figure 2.1: Chemical structure of zircon

2.2.2 Oxides - Zirconia Physical Properties

The most commercially important oxide formed by zirconium is zirconia (ZrO2 ). This
compound can either be produced from zircon or obtained naturally from the mineral
baddeleyite (which is mostly composed of zirconia contaminated with zircon, silica and
other iron, aluminium and titanium oxides). In addition to natural zirconia, other types
of zirconia have been developed by stabilising the material at one of its various phases
through the addition of various oxides. Each phase may possess distinct properties
and hence the interest to use the material at different phases for different applications.
As explained by [27], common oxides used to stabilise zirconia include yttria (Y2 O3 ),
ceria (CeO2 ), magnesia (MgO) and lime (CaO). In this way, different types of zirconia
may be formed, including Tetragonal Zirconia Polycrystals (TZP), Partially Stabilised
Zirconia (PSZ), Fully Stabilised Zirconia (FSZ), Transformation Toughened Ceramics
(TTC), Zirconia Toughened Alumina (ZTA), and Transformation Toughened Zirconia
(TTZ). Some important physical properties of zirconia in its basic natural form are given
in Table 2.4.
Although it would be difficult to review the properties of all zirconia compounds available
in the market, [27] has compiled a list of properties for various zirconia products, as
shown in Table 2.5.
2.2.3 Borides, Carbides, Silicides and Nitrides - Physical Properties

The physical properties of some representative zirconium borides, carbides, silicides,
and nitrides are given in Table 2.6.
2.2.4 Halides - Physical Properties

The physical properties of some zirconium halides are given in Table 2.7.
Table 2.3: Physical Properties of Zr Silicates (Elaborated with data from [28] and [24])
Property ZrSiO4 Complex silicates
Melting point (◦ C) 2100-2300 Na2 ZrSi2 O7 , 1470

(Zr sand) Rb2 ZrSi2 O7 , ≥1350
Transition NaHZrSiO5 , 300

temperature (◦ C) Na2 ZrSi2 O7 , 1120
Na2 Zr2 Si2 O9 , 850
Heat capacity 4.1868 ∗ [31.48 + (3.92x10−3 )T

(J deg−1 mole−1 ) −(8.08x105 )T −2 ] [at 25-1500◦ C]
Specific gravity 4.7 (α 2 ) Rb2 ZrSi2 O7 , 3.84

3.9 - 4 (γ 2 )
Resistivity (ohm·cm) 9.9x1013 [at 200◦ C]

2.2x1010 [at 450◦ C]
Dielectric constant 12 [at 17-22◦ C]

8.51 [at 450◦ C]
Zr-O bond length (Å) 2.15, 2.29
Hardness (Mohs) 7.0 - 7.5

(Zr sand)
Coefficient of linear 7.2x10−6

expansion (cm/cm·◦ C) (Zr sand
at 93.3-1093.3◦ C)
Table 2.4: Physical Properties of ZrO2 (Elaborated with data from [24])
Property Value
Melting point (◦ C) 2397
Boiling point (◦ C) 4275
Density:
Monoclinic 5.85
Tetragonal 6.16
Unit cell parameters (Å):

Monoclinic a=5.169 b=5.232 c=5.341 β = 80◦ 450
Tetragonal a=5.085 c=5.166
Cubic a=5.1
Heat of formation -1098.2

(kJ mole−1 )
Heat capacity 4.1868 ∗ [11.62 + 10.46x10−3 T − 1.777x105 T −2 ]

(J deg−1 mole−1 )
Refractive index:
Monoclinic 2.15
Tetragonal >2.15
Magnetic susceptibility (g−1 ) −0.112x10−6
Coefficient of thermal
expansion (deg−1 ):
Monoclinic (at 20◦ C) 7x10−6
Tetragonal (at 20◦ C) 12.8x10−6
Transition temperature 1205

(monoclinic-tetragonal, ◦ C)
Heat of transition 5.95

(kJ mole−1 )
Table 2.5: Physical and Mechanical Properties of Various Types of doped zirconias
(Elaborated with data from [27])
Property Y−TZP Ce-TZP ZTA Mg-PSZ TZ-3Y20A
Density (g·cm−3 ) 6.05 6.15 4.15 5.75
Hardness (HV30 ) 1350 900 1600 1020 1470
Bending 1000 350 500 800 2400

strength (MPa)
Compressive 2000 - - 2000 -

strength (MPa)
Young’s 205 215 380 205 260

modulus (GPa)
Poisson’s ratio 0.3 - - 0.23 -
Fracture toughness 9.5 15-20 4-5 8-15 6

(MPa·m−0.5 )
Thermal expansion 10 8 8 10 9.4

coefficient at 20◦ C
(x10−6 ·◦ C−1 )
Thermal conductivity 2 2 23 1.8 3

(W·m−1 ·K−1 )
Table 2.6: Physical Properties of Zr Borides, Carbides, Silicides and Nitrides (Elaborated
with data from [24])
Property ZrB2 ZrC ZrSi ZrN
Melting point (◦ C) 3050 3500 - -
Heat capacity, 25◦ C 48.27 36.67 - 40.44

Heat of formation -301.86 -196.77 -123.09 -336.74

(kJ mole−1 )
Density 6.1 6.7 5.56 7.18
Coefficient of thermal 5.5 7.5 - -

expansion x106 (deg−1 )
34
Table 2.7: Physical Properties of Zr Halides (Elaborated with data from [24])
Property ZrF4 ZrCl4 ZrBr4 ZrI4 ZrCl3 ZrBr3 ZrI3
Melting point (◦ C) 932 438 450 500
Vapour pressure,
log p(mm) = A-(B/T)
A 12.5 Solid, A = 11.7 12.268 10.59 11.632 8.367
Liquid, A = 9.3
B 11,400 Solid, B = 5700 5945 5730 6246 4671
Liquid, B = 3500
Heat of sublimation α = 205.36 100.48

(kJ mole−1 ) β = 230.27
Heat of formation, -1913.36 -981.81 -760.32 -485.25 -720.12 -632.21 -431.24

25◦ C (kJ mole−1 )
Entropy of formation 339.80 200.96

Free energy of formation -893.46 -722.22 -488.18

25◦ C (kJ mole−1 )
Density 4.5 2.803
Magnetic moment, 0.4 0.4

19.85◦ C (BM)
Mean bond length, 2.1 2.33 2.44 2.55

M-X (Å)
Material Properties
3 — State-of-the-art applications
Zircon consumption by end-use market for the year 2011 is shown in Figure 3.1. Al-
though consumption patterns may change from year to year, this information is useful to
understand the current main uses of zircon mineral and the overall downstream structure
of the zircon industry. Ceramics are by far the largest end-use sector (55%), followed
by foundry applications, chemical applications, refractory uses, glass, and other minor
applications. This section discusses these applications in more detail.
3.1 Foundry sands and coatings

Zircon is widely used in the foundry industry, mostly in the form of sand and flour
(milled sand) for casting and refractory applications. A breakdown of zircon’s foundry
uses is shown in Figure 3.1 [4].
The properties that make zircon a suitable material for these applications include [4, 5,
11, 26, 30, 31]:
• Low acidity: its pH varies between neutral to slightly acid.
• Clean and round grains that allow the material to be easily bonded together.
• Consistent fineness and ability to form fine grains (sizing - when used as zircon
flour).
• High ability to bind with all organic and inorganic sand binders.
• Low thermal expansion coefficient and high spatial stability at increased tempera-
tures.
• High melting point (2,100 - 2,300◦ C).
• High thermal conductivity.
• Chemical stability at high temperatures.
• Low wettability by molten metal.
• Good recyclability.
The aforementioned properties have allowed the wide application of zircon as a moulding
36
Ceramics
55%
15%
4% Others
7%
29%
Foundry
14%
Refractories Chemicals
67% 10% 14% 85%
2% Tiles
Tableware, Sanitaryware, others
Sand casting 4%
Investment casting 11%
Cosworth casting (aluminium) 9%
9%
42%
28%
61% 13%
21% Gemstones, Technical ceramics

Nuclear (metal)
TiO2 coatings
Cosmetics
Alumina-Zirconia-Silica
Paper coatings
Glass, steel and cement industry refractories
Paint driers
Other refractory products (steel industry end use)
Other
State-of-the-art applications
Figure 3.1: Global zircon consumption by end-use market 2011 (Elaborated with data from [26, 29]).
3.2 Refractories 37
base material for Sand Casting and Investment Casting, in addition to its use as mould
coating in Die Casting and in refractory paints and washes to reduce the wettability
of other foundry sands. The advantages of using zircon sand and zircon flour in these
foundry processes can be summarised as follows:
• zircon’s low wettability, consistent grain fineness and ability to form fine grains
allows the creation of high precision castings with good surface finish, prevents
the mineral from sticking to the cast metal and avoids metal penetration into the
mould.
• Its high thermal conductivity allows higher cooling rates than other mould materi-
als, which also results in a better surface finish.
• The higher dimensional accuracy and better surface finish accomplished through
the use of zircon minimises post-casting operations such as machining and clean-
ing of the cast part.
• zircon’s low wettability by molten metal increases the recoverable sand and hence
the recyclability of the material.
• Its chemical stability ensures uniform results when using recycled sand.
3.2 Refractories
The properties that make zircon a valuable material for the Foundry industry also make
it an attractive choice for the refractory industry, which is one of its core applications.
Zircon consumption in the Refractory industry is mainly divided into three product
categories, as shown in Figure 3.1 [4].
As explained by Selby [30], refractories are materials that are designed to maintain
strength, dimensional stability and chemical resistance at high temperature. These
are typically made from alumina, magnesia, clays, binders and zircon or zirconia. In
addition to the properties enlisted in §3.1, there are a few extra characteristics that make
zircon and zirconia suitable materials for Refractory applications: [2, 31, 32]:
• Low solubility in molten silica and molten metal.
• Chemical inertness.
• Resistance to corrosion and erosion.
• Low defect potential.
These properties allow zircon and zirconia to be used in a wide range of refractory
functions, including refractory mortar, firebricks or refractory linings for glass and metal
furnaces [5], as well as fibres, nozzles, slide gates, valves and grouts. Zircon bricks for
glass furnaces contain typically 30-40 % zircon, while nozzles, slide gates, filters, and
ceramic linings normally employ zirconia up to 94%wt [30]. Some of the key benefits
achieved by zircon and zirconia in refractory applications can be summarised as follows:
• The addition of zircon and zirconia to refractory materials increases thermal shock
resistance [32].
• The low thermal conductivity of zircon translates into very low heat losses.
• When fused or combined with alumina and silica (AZS), zirconia provides high-
corrosion resistance to molten glass due to the low solubility of zirconium in
molten silica [11, 31].
38 State-of-the-art applications
• Its corrosion resistance together with its low defect potential and good manufac-
turing ability makes zircon based refractories particularly suitable for the most
exposed hot areas of a furnace [31].
3.3 Ceramics
The most important market for zircon is the Ceramics industry. Within this sector,
zircon is mostly employed as a raw material in the production of ceramic bodies, glazes,
enamels, frits and pigments applied to traditional ceramics, which includes wall and floor
ceramic tiles, porcelain tiles, sanitaryware, washbasins, tableware, special porcelains
and industrial tiles, among others [5, 33]. Around 85% of the total zircon used by the
ceramics industry corresponds to tile production, as shown in 3.1 [4]. The remaining
fraction is distributed between other traditional ceramics like tableware and sanitaryware.
Zircon is also used as a raw material in the production of fused and chemically derived
zirconia, which is commonly employed in advanced ceramic applications such as such
as electroceramics, structural ceramics, pump components and biocompatible devices,
as well as advanced technical ceramics such as oxygen sensors and solid oxide fuel cells.
3.3.1 Traditional ceramics

Zircon as a whitener and opacifier
Zircon has varied applications as a whiteness and opacity enhancer in traditional ce-
ramics. It can be used directly on ceramic compositions to improve the whiteness and
opacity of the entire ceramic body, used in engobes to produce a white and opaque layer
that hides the colour of the body, as a raw material in ceramic glazes to increase their
opacity, or in frit compositions used to produce glossy, opaque, white glazes [33]. In the
case of porcelain tile bodies, whiteness increases with zircon content [33]. When used
in glazes, zircon enhances resistance to abrasion and chemical attack. In frit production,
zircon is first added as a raw material into the batch composition and then added during
the melting process in a glassy phase [33]. Zircon devitrifies when the frit-based glaze is
fired, opacifying the glaze [33].
During ceramic tile manufacturing, zircon is mostly used in the form of flour – to
introduce zirconium to frit compositions – or as micronized zircon to produce glazes,
engobes and ceramic body compositions [33]. Zircon sand is occasionally employed to
improve abrasion resistance of glazed surfaces, particularly for floor tiles [33]. When
used as micronized zircon to opacify glazes, engobes and bodies, smaller zircon particle
sizes lead to increased opacity [33] and higher price.
The properties that make zircon a suitable opacifier material include [4]:
• High refractive index (1.96).
• High number of independent light scatterers with small and round crystals.
Fine zircon grains are capable of scattering visible light, making the ceramics appear
white and opaque [34]. In order for zircon to be an effective opacifier, its refractive index
(1.96) must be higher than that of the glass matrix where it is contained (1.5), which
results in reflection and refraction of light [4].
3.3 Ceramics 39
An additional property that makes zircon attractive for ceramic manufacturing is its
high hardness (7.5 on Mohs scale), which helps to resist scratching and mechanical
damage [4]. Zircon sands used for ceramic manufacturing also need to comply with
specific attributes, including [4]:
• A particular whiteness index depending on the ceramic type.
• Iron oxide, titanium dioxide, and aluminium oxide contents below specified levels.
• Thorium and uranium content typically below 500ppm.
• A grain hardness that facilitates milling to micron size.
Ceramic pigments
Whilst zircon can act as an opacifier, zirconia has an important role in the production
of ceramic pigments used in ceramic tiles, tableware and sanitary ware, among other
products. As explained by Selby [30], zirconia, quartz, sodium fluoride and other
mineralisers (fluxing agents) are fired together at around 900◦ C with small amounts of
other compounds containing Fe, V, Pr, Cd, S, and Se to produce the pigments. Some
of these elements enter the zircon lattice to partly substitute Zr or Si (and act as colour
centres), while others form discrete pigment particles that are enveloped by a transparent
colourless zircon layer, with iron producing pink, vanadium 4+ producing blue and
vanadium 3+ producing orange. These pigments are suitable for this application because
they possess the high temperature resistance required for glazes and enamels and because
they increase the pigment’s resistance to attack by molten glasses [11, 30, 35]. Producing
a black pigment from cellulose in a single step process has been recently described [36].
3.3.2 Advanced ceramics

Advanced Ceramics is a well-known significant commercial application area for zir-
conia. Traditional ceramics such as clays, bricks and tiles are usually hard, porous
and brittle. The term ’advanced ceramics’ refers to ceramic materials that have been
specially designed to improve those characteristics and overcome the issues arising from
traditional ceramic’s poor mechanical properties. Zirconia is an example of material
that can produce an advanced ceramic: in its pure form, zirconia has limited mechanical
applications. However, in its stabilised form (produced by adding calcium, magnesium
or yttrium oxides, resulting in partially stabilised zirconia [PSZ] or tetragonal poly-
crystalline zirconia [TPZ]) or when mixed with other compounds such as alumina (e.g.
zirconia toughened alumina), zirconia becomes an ideal ceramic for a wide range of
mechanically demanding applications. As explained by Elsner [5], the fine tetragonal
crystal phase in PSZ and TZP displays a distinctive characteristic among advanced
ceramics; when exposed to high mechanical stresses, the crystallites transform from
tetragonal to monoclinic. This process results in a considerable volume expansion of
the crystallites, which generates micro fractures in their surrounding matrices. The
volume expansion and micro fractures generated from the crystal conversion process
work as an opposition force against the propagation of fractures generated in the material
during exposure to high tensile stresses, resulting in the stoppage or deceleration of these
fractures. This phenomenon gives PSZ and TZP ceramics a high strength when used at
temperatures under 600◦ C. Additionally, the high fracture toughness is associated with
ferroelastic domain switching in other zirconia ceramics containing the tetragonal phase,
as suggested by Chevalier and Gremillard [37]. In summary, these materials hold the
following important characteristics [5, 38, 39]:
• High temperature stability and melting point.
• High density.
• High bending fracture and tensile strength.
• High fracture toughness.
• High hardness, wear resistance and corrosion resistance.
• Low thermal conductivity.
• Thermal expansion similar to cast iron.
• Young’s modulus similar to steel.
• High chemical stability and purity.
• Oxygen ion conductivity.
• Ionic conductivity above 600◦ C.
These characteristics have allowed the use of zirconia in a wide number of specialty
applications requiring high levels of strength, hardness and toughness, as well as wear
and corrosion resistance. In addition, the ionic conductivity of the material above
600◦ C has led to its use in oxygen sensors and fuel cells. As explained by Chevalier
and Gremillard [37], these characteristics are associated with the stabilisation of the
zirconia tetragonal and cubic phases through alloying with aliovalent ions. The large
concentration of vacancies introduced during this alloying process is responsible for
zirconia’s high ionic conductivity and low thermal conductivity. Market uses for zirconia
and zirconia compounds’ uses are discussed in the following subsections [38, 39].
High stress applications

Due to its good strength, high toughness, fracture, wear and corrosion resistance, zirconia
is commonly employed in the manufacturing of high-stress components such as [40]:
• Precision ball valves (balls and seats)
• Pump seals, valves and impellors
• Bushings
• Thread guides
• Bearings
• Thermal insulators
• Tube and rod mill rolls
• Stamping, extrusion and drawing dies
Abrasives
Stabilised zirconia is widely used in the manufacture of abrasive materials due to its
ultra-hard, tough and dense characteristics. Common zirconia abrasive materials include
Yttrium stabilised zirconia (YSZ) and zirconia toughened alumina (ZTA) [26, 41].
Typical zirconia abrasive products contain around 25-40% zirconia [30], and include:
• Grinding wheels
• Sharpening stones
• Abrasive papers
• Other high density grinding media
3.3 Ceramics 41
Cutting tools
Yttrium stabilised zirconia (YSZ), zirconia toughened alumina (ZTA), and alumina
toughened zirconia (ATZ) are also used to produce cutting blades and cutting tool
inserts [38, 41]. The key characteristics that make zirconia attractive for this application
include [40]:
• Fine grained microstructure allowing for honing very fine and tough cutting edges.
• Low friction and low energy surfaces minimise adhesion to cut materials.
• High hardness and toughness lead to long cutting edge life.
• High hardness allows cutting hard, abrasive and tough materials.
• High hardness and corrosion resistance allows the use of harsh cleaning chemicals
or abrasives without damaging the tool.
Zirconia susceptors
Yttrium stabilised zirconia (YSZ) has found an application as a radio frequency heating
susceptor element. These devices are zirconia ceramic tubes commonly used in induction
heating equipment, manufactured through a plasma spraying process. When exposed
to a radio frequency, the atoms in the zirconia (YSZ) susceptor devices start vibrating,
generating heat as a result. Its high melting point (>2300◦ C) and thermal shock resistance
makes Yttrium stabilised zirconia an ideal material for this application [42].
Ionic conduction
There are three main applications that take advantage of zirconia’s ionic conduction:
- Oxygen sensors
The stabilisation process of zirconia, which occurs by placing it in a solid solution with
4 to 12 mol% MgO, CaO or Y2 O3 , results in the establishment of oxygen ion vacancies
in its crystal lattice, enhancing the mobility of oxygen ions at high temperatures [43].
This condition is exploited during the use of zirconia in oxygen sensors, where stabilised
zirconia is employed as a ceramic solid electrolyte tube with platinum electrodes de-
posited on the inner and outer surfaces, working as a very low voltage battery. The
outer and inner layers of the tube are isolated from each other and exposed to different
gases (e.g. in car engines, the outer layer is exposed to the exhaust gas stream before
the catalytic converter, while the inner layer is exposed to the reference atmosphere).
The difference in oxygen ions between the inner and outer layers generates a drop in the
electrochemical potential, thus producing a very small voltage at the electrodes. The
operation temperature needs to be kept above 350◦ C for the ionic conduction to take
place appropriately [43, 44].
- Ceramic oxygen generators

As explained by Guan [45], a ceramic oxygen generator (COG) is an electrochemical
device that employs an oxygen-ion-conducting electrolyte to electrochemically generate
oxygen from gases such as air, carbon dioxide or water vapour. Yttrium-stabilised
zirconia is the most commonly used electrolyte material due to its great oxygen ion mo-
bility. A typical ceramic oxygen generator arrangement consists of a zirconia electrolyte
crammed between two porous electrodes: input gases are passed through the cathode
where they are electrochemically reduced to form oxygen ions by combining with elec-
trons from an external circuit. Oxygen ions combine to produce oxygen molecules at
the anode, releasing electrons to the external circuit, while an external power supply
provides electron flow in the circuit from the anode to the cathode [45].
- Solid oxide fuel cell membranes

Solid oxide fuel cells employ a similar operation mechanism to ceramic oxygen sensors
and generators, consisting of two porous electrodes separated by a dense, oxygen
conducting electrolyte. As explained by Singhal [46], the high oxygen ion conductivity
of yttrium stabilised zirconia (YSZ) over wide ranges of temperature and oxygen
pressures has led to its use as an electrolyte in solid oxide fuel cells (SOFCs). These
cells employ yttrium stabilised zirconia as an electrolyte through which the oxide ions
O2- migrate from the air electrode (cathode) side to the fuel electrode (anode) side,
where they react with the fuel (H2 , CO, etc) to generate an electrical voltage in a clean
and highly efficient way. Yttrium stabilised zirconia is the most effective electrolyte
tested.
Medical implants and biocompatible devices
In addition to the already mentioned properties, advanced zirconia ceramics have an

excellent biocompatibility, which is defined by the ASTM [47] as the inherent ability of
a material to remain biologically inert with the host in its intended application. Alumina
was traditionally used to manufacture medical prosthesis devices such as hip joints or
femoral ball heads until it was observed that the material suffered from critical fracture
problems in these applications. Zirconia has displaced alumina in this field due to its
higher strength and hardness, wear resistance, stability, resistance to scratching and
bicompatibility with the human body [48–51]. In addition, zirconia-based prosthesis
compete with metal-polyethyene or metal-metal prosthesis because they can significantly
reduce the amount of wear debris generated during their use [48].
3.3.3 Electro-ceramics
Zirconia has dielectric and piezoelectric properties that allow its use in the fabrication
of special electro-ceramics for use in a wide range of applications in the automotive,
aerospace and telecommunication sectors, among many others. The most common
zirconia-based electro-ceramic is lead zirconate titanate (PZT), which has good machin-
ability and can be easily formed into tubes, rings, discs, plates and other complex shapes,
in sizes from microns to centimetres. Important PZT characteristics include [52]:
• As a dielectric, PZT is capable of storing an electrical charge with low electrical
loss, thermal stability and resistance to interference from electromagnetic fields.
• As a piezoelectric, it has the attribute of producing an electrical charge when
mechanically compressed or vibrating when an electrical charge is applied [11].
• As a pyroelectric material, it holds the ability to develop a voltage difference
across its faces when experiencing a temperature change [53].
• As a ferroelectric material, it can have spontaneous electric polarisation that can
3.4 Glass 43
be reversed by the action of an external electric field [53].

As a result of these properties, PZT has been employed in a wide range of products and
industries, including [11, 52, 54, 55]:
• Microwave dielectrics.
• Radio frequency power capacitors.
• AC/DC high voltage capacitors.
• General high voltage capacitors.
• Gas furnaces and fire igniters.
• Microphones.
• Phonograph crystals.
• Ultrasonic transducers for agitation in cleaning tanks.
• Underwater sonars, beacons, and current meters.
• Gyroscopes, accelerometers, and level sensing devices for airplanes.
• Medical high intensity focused ultrasound, medical imaging, phacoemulsification
tools for cataract surgery, dental descaling tools, tissue ablation, medication
delivery, hearing enhancement, and bubble detection.
• Ultrasonic toothbrushes, jewellery cleaners, contact lens cleaners, computer hard
drives, touch screen displays, integrated, and ultra-thin speakers.
• Flow and level sensors for industrial applications, ultrasonic welding, intrusion
alarms, solder dispensing, and machine vibration monitoring.
• Optical switching of telecom lines, buzzers and alarms.
• Mobile phone cameras.
• Automotive power seat controls, distance and contact sensors.
• Nano positioning stages for scientific use.
• Scanning probe microscopy.
• Drill tool monitoring in oil exploration.
An additional application of zirconia can be found in the manufacturing of ferrules for
fibre optic cables. The smooth surface finish achievable with fine zirconia powder leads
to high performance connectivity. Zirconia also possesses a thermal expansion coefficient
similar to optical fibre, in addition to its good elasticity and impact resistance [4].
3.4 Glass
Zircon has found a minor application in the glass sector, where it is commonly used as
an X-ray absorber in cathode ray glass tubes for televisions and formerly in computer
monitors [4, 26, 30]. Zircon flour not only can absorb the X-rays emitted by the electron
gun in the tube, it can also increase the refractive index and toughness of the glass [26,30].
Demand for this application has diminished since the arrival of LCD and plasma screens.
However, zircon is also used in plasma screens to enable the manufacture of faceplate
glass [4]. Zircon content in cathode ray tubes is in the range of 3-5%, while that in LCD
and plasma screens ranges between 1-2% [30].
Zircon and zirconia have also been employed for the production of special glasses for
optical and ophthalmic applications, where the addition of these materials provides
high refractive indices and increases durability and resistance [5]. Examples include
borosilicate glass fibre formulations with 4% zirconia, AR fibre glass with 16-21%
zirconia, and other lead-free crystal glasses with ranges of 0.5-17% zirconia [26].
3.5 Major industrial zirconia and zirconium chemical applica-

tions
Zirconium metal can be extracted from zircon and further processed to form numerous
zirconium chemical compounds employed in a wide range of intermediate manufacturing
processes and end use applications. As explained by Elsner [5], zirconium metal is a
highly reactive element that can form stable bonds with oxygen, sulphur, nitrogen and
carbon, therefore serving as a base material for the production of zirconium chemicals .
Zirconium oxychloride (ZOC) represents the most important zirconium compound due
to its use as a base material for the production of zirconia. Other important zirconium
chemical compounds include (list created by Elsner [26]):
• Zirconium oxychloride (ZOC)
- Formula: ZrOCl2 x 8 H2 O
- Applications: white TiO2 pigment application, antiperspirants and catalysts. It is
also the most popular precursor for manufacturing other zirconium compounds.
• Zirconium sulphate (ZOS)

- Formula: Zr(SO4 )2
- Applications: popular TiO2 pigment particle surface treatment reagent (enhances
weather resistance), substitute for chromium chemicals as a tanning agent in
leather production, accelerator in adhesives, gelatin hardener in photography,
paper pigment, catalysis promoter.
• Zirconium basic carbonate (ZBC)

- Formula: ZrOCO3 xnH2 O
- Applications: aid in paint drying, as a thixotropic aid, as a deodorant, in photo
catalysis and in paper manufacture.
• Ammonium zirconium carbonate (AZC)

- Formula: (NH4 )3 ZrOH(CO3 )3 x2H2 O
- Applications: catalysis, paint drying, water-proof surface coatings for paper and
packaging, printing inks, adhesion promoter for plastics and metals, bonding agent
and accelerator in adhesives, moulding material binder and for waterproof textiles.
• Acetates (ZAC), propionates, and acetylacetonates

- Applications: electro-ceramics, catalytic hardener for epoxy resins and silicones,
paint drying, water repellent for paper and non-wovens, printing ink adhesion
promoter for plastics and metals, thixotropic agent in cements, welding fluids and
clay stabilisers, chromium substitute in aluminium processing, moulding material
binder, gelatin hardener in photography.
• Potassium zirconium hexafluoride (KFZ)

- Formula: K2 ZrF6
- Applications: in Fe alloys, refractory, ceramics and glass and electrical materials
for the nuclear industry; flame proofing of wool.
• Zirconium phosphate
- Formula: Zr(HPO4 )2
- Applications: catalysts in the synthesis of methyl-iso-butyl-ketones and in poly-
merization, hydrogenization, oxidation, hydration and dehydration reactions, in
addition to its use as a catalyst in ion exchange for kidney dialysis and water
treatment.
• Zirconium hydroxide
- Formula: Zr(OH)4 xnH2 O
- Applications: production of catalysts and ceramics, ion exchange applications,
in paints and colorants, in absorbents, in deodorants and as an additive in plastics
and glass.
• Zirconium oxynitrate
- Formula: ZrO(NO3 )2
- Applications: base material for zirconium catalysts, chemicals and ceramics,
used as a white pigment and filler, a moulding material binder, and a bonding
agent and accelerator in adhesives.
• Zirconium hydride
- Formula: ZrH2
- Applications: oxidation promoter in pyrotechnics, gas binder in the manufacture
of vacuum tubes, hardener and bronzer for carbides and ceramics, reservoir for
high-purity hydrogen, hydrogen source in metal foaming, and in zirconium pow-
der alloys.
• Zirconium fluoride
- Formula: ZrF4
- Applications: ceramic paints, optical fibres and special glasses, gemstone pro-
cessing and metal treatment.
The list above has mentioned numerous applications of zirconium chemical compounds.
However, most of these applications represent only a marginal percentage of Zr chemical
uses. The most important applications of zirconium chemicals are summarised in
Figure 3.1, where it can be seen that gemstone production accounted for almost half of
zirconium chemicals market share in 2010, followed by their use in the nuclear industry
(21%), TiO2 coatings (13%), deodorants (9%), paper coatings (9%), and paint driers
(4%). The following subsections discuss the main categories of Figure 3.1 in further
detail, while Section 3.6 focuses on the remaining 2% (labelled as “other” in Figure 3.1),
which concentrates a considerable number of smaller applications.
3.5.1 Gemstones
Zirconia can exist in three phases: cubic, tetragonal and monoclinic. Naturally occurring
pure zirconia (Baddeleyite) is a monoclinic mineral in which the cubic phase is only
stable at high temperatures. In order to stabilise the cubic phase at low temperatures,
zirconia is commonly mixed with oxides such as CaO, MgO and Y2 O3 . For example,
typical market grade cubic zirconia contains 87.5% zirconia and 12.5% yttrium oxide
(Y2 O3 ) [56]. This improves the thermo-mechanical properties of cubic zirconia and
stabilizes it at low temperatures, giving it a very high strength, toughness, and thermal-
shock resistance [57]. This material has become a popular gemstone due to its optically
clear single crystals and high refractive index, in addition to its ability to maintain its
colour and brilliance unaltered [58]. Important properties include:
• High density (1.7 times higher than diamond).
• Hardness: 6.5-8.5 Mohr scale.
• Elastic modulus: 210-233 GPa.
Cubic zirconia is classified as a soft to semi-hard gemstone [58] and it is available
in colourless form or with different colours depending on the dopants applied during
production. Red, orange and yellow gems can be obtained with cerium as a dopant,
while yellow, amber and brown can be obtained with copper, iron, nickel, praseodymium
and titanium oxides. Pink, violet, blue and green can also be produced [59].
3.5.2 Nuclear industry
Zirconium alloys are widely used as structural components in the nuclear industry
such as pressure tubes, fuel channels, guide tubes, grid spacers, for fuel cladding,
for fuel containers, or even as the core structural materials of water-cooled nuclear
reactors [60, 61]. Common alloys include [61]:
• Zircaloy-1 (Zr with 2.5% tin).
• Zircaloy-2 (98.25% Zr with additional Sn, Fe, Ni, Cr and Hf).
• Zircaloy-4 (98.23% Zr, plus Sn, Fe, Cr and Hf).
• Zr-Nb alloys.
• Zr-Sn alloys.
These alloys present good mechanical and thermal properties, excellent corrosion and
irradiation creep resistance, and a low neutron-absorption, which is critical to increase
the efficiency of a nuclear reactor given that the lower the neutron absorption, the greater
the efficiency [4, 60, 61]. These properties are constantly being improved due to the
natural drive for higher efficiencies in the nuclear industry, which leads to either a better
control of the alloys microstructures or the development of new alloys, as explained
by Dupin et al [60]. These materials have to be able to withstand common operational
conditions that include high temperatures and reactive conditions such as irradiation,
oxidation and hydrogen pick-up [61].
Zirconium metal employed in zirconium alloys is obtained from zircon by a carbo-
chlorination process at 2000◦ C, following the removal of hafnium and its subsequent
reduction with metallic magnesium [30].
3.5.3 TiO2 coatings
Titanium dioxide, also known as titania, is widely used as a pigment in the global paints
industry due to its optical properties, non-toxicity and chemical inertness [62]. However,
titanium dioxide has a high photo-catalytic activity under ultraviolet irradiation which
leads to the decomposition of paint films. Zirconium coatings are used on TiO2 particles
to improve their photo-stability and shield the photo-catalytic effect [62].
Titanium dioxide has also been successfully employed as a photocatalyst that can oxidise
and decompose harmful organic contaminants such as bacteria, viruses, volatile organic
compounds (VOCs) and algae spores, among others [63], based on its strong oxidising
properties. This material has been commercialised as a spray that can be applied as a
coating on a wide range of materials, particularly on walls and other interior surfaces
in buildings and houses. Photocatalysts such as titania need to absorb light to be able
to oxidise organic compounds. One limitation of TiO2 is the fact that, due to its large
band gap of 3.2 eV, it can only be activated by UV light [64]. Considering that UV light
covers only 5% of the solar light spectrum [64], it would be desirable if photocatalysis
could also be triggered by the more abundant visible light . Zirconium has been used as
a dopant to increase the photocatalytic activity of TiO2 by increasing the efficiency of
the process and allowing the absorption of visible light [65]. As explained by Kim et
al [64], the addition of zirconium leads to enhanced phase stability, smaller particles,
and increased surface area, which results in increased photocatalytic activity. In this way,
zirconium doped TiO2 coatings have become more effective at triggering the oxidation
reactions necessary to improve air quality in closed building spaces.
3.5.4 Cosmetics
According to the European Commission Scientific Committee on cosmetics and non-food

products and the US Food and Drug Administration [66, 67], zirconium and zirconium
compounds should not be used in cosmetic products with the exception of zirconium
lakes, salts and pigments of colouring agents and the following Aluminium Zirconium
complexes:
• Aluminum zirconium octachlorohydrate up to 20 percent.
• Aluminum zirconium octachlorohydrex gly up to 20 percent.
• Aluminum zirconium pentachlorohydrate up to 20 percent.
• Aluminum zirconium pentachlorohydrex gly up to 20 percent.
• Aluminum zirconium tetrachlorohydrate up to 20 percent.
• Aluminum zirconium tetrachlorohydrex gly up to 20 percent.
• Aluminum zirconium trichlorohydrate up to 20 percent.
• Aluminum zirconium trichlorohydrex gly up to 20 percent.
Aluminium Zirconium complexes are commonly used in antiperspirants, where they
helps to dissolve sweat and stop its flow to the surface of the skin. They are mostly
contained in sticks, gels and other solid products. Toxicity testing has not shown any
significant concerns.
3.5.5 Paper and printing
Zirconium chemicals are widely used in the paper industry as coatings that add strength
and water resistance to paper. Common zirconium compounds used in paper manufac-
turing include [11]:
• Ammonium zirconium carbonate
• Potassium zirconium carbonate
• Zirconium acetate
• Zirconium stearate
Ammonium zirconium carbonate (AZC) is the most frequently used compound for paper
applications. When applied on paper, zirconium ions in this compound link the starch
and synthetic size (coating) to the fibres (crosslinking), as well as the CaCO3 within the
paper [68]. This results in the immobilisation of the surface coating near the surface
and a more tightly bound surface . Zirconium ions have a strong affinity to oxygen and
other reactive groups, which allows them to initiate crosslinking reactions while the
solution cures. Ammonium zirconium carbonate is a valued coating crosslinker due to
its high cure speed, lack of formaldehyde, and the ability to cure carboxylated coating
binders such as latex and protein [68]. The ability of zirconium compounds to replace
formaldehyde, which the paper industry wishes to remove, is well exploited in the paper
industry.
3.5.6 Paints and inks
Zirconium chemicals are employed as additives in paints and inks to promote adhesion to
the substrate and to increase their resistance to heat, scrubbing, water and solvents [69].
Zirconium compounds have also been used as driers in solvent-based paint [70], as well
as thixotropes in water-based paints. Commonly used compounds include:
• Zirconium carboxylates.
• zirconiun propionate.
• Ammonium zirconium carbonate.
• Zirconium acetate.
As a paint drier, zirconium has been employed as a substitute for lead, which has been
banned across most of the world due to its toxicity [71]. In inkjet coatings, zirconium
compounds are used to improve the water-fastness of the coating and print quality. These
compounds reduce ink spread and excessive migration into the coated layer [72]. In
addition, these types of zirconium chemicals promote a better adhesion of the ink to
plastic and metal substrates [11]. As an adhesion promoter in inks, zirconium propionate
has substituted titanium acetylacetonate to improve adhesion to difficult substrates [69].
In this application, zircon is capable of forming covalent bonds with oxygenated species
on the surface of the substrate as well as with the ink resin, working as a solid link
between ink and substrate [69]. Zirconium also acts as a nitrocellulose cross-linking
agent in nitrocellulose based inks. This cross linking increases the molecular weight of
the ink, which results in a higher heat dissipation ability and resistance to scrubbing [69].
Recently, an ink shas been developed for electronic component [73].
3.6 Minor chemical applications 49
3.5.7 Catalysis
During the process of catalysis, a catalyst augments the rate of a chemical reaction
without being consumed in the reaction. In addition to accelerating a reaction, a catalyst
can also make the reaction behave in a more selective manner. Zirconium compounds
are used as catalysts in a large number of chemical processes. The main application
areas of these chemical reactions include [74]:
• Catalyst in pollution control reactions for mobile sources such as cars and trucks
(emissions reduction of CO/HC/NOx and other toxic pollutants) and stationary
sources such as chemical manufacturing, petroleum refineries, oil and gas produc-
tion, etc.
• Catalyst in general refining and chemical reactions such as hydrogenation, oxida-
tion, amination, isomerisation, and Friedel-Craft reaction, among others.
Generally based on zirconia, a large number of zirconium compounds can be employed
as the precursor to catalysts, some of the most common types are [26]:
• Zirconium oxychloride [ZrOCl2 x8H2 O]
• Zirconium sulphate [Zr(SO4 )2 ]
• Ammonium zirconium carbonate [(NH4 )3 ZrOH(CO3 )3 x2H2 O]
• Acetates, propionates, and acetylacetonates
• Zirconium phosphate [Zr(HPO4 )2 ]
• Zirconium hydroxide [Zr(OH)4 xnH2 O]
• Zirconium oxynitrate [ZrO(NO3 )2 ]
• Sulphated and tungstated zirconia
• Aqueous zirconium salts and organic soluble complexes
3.6 Minor chemical applications

3.6.1 Ammunition and explosives
Zirconium powder is highly flammable and can be easily ignited. This property has led
to its use in the following applications [5]:
• Ignition charges.
• Ignition mechanism for automotive airbag inflators.
• Pyrotechnics and squibs.
• Military applications such as incendiary charges.
3.6.2 Gas purification

Getters are materials that can be placed inside a vacuum system to remove small traces
of gas from the system through chemical combination or adsorption . Zirconium is
a highly effective absorbent because its surface bonds with almost any gas species,
including O2 , H2 O, N2 , CO2 and methane [75]. Zirconium getters are typically operated
at temperatures around 350-450◦ C. At this temperature range the adsorption efficiency is
increased because impurities diffuse into the bulk, leaving a bigger surface area available
for adsorption [76]. Typical applications include vacuum systems for semiconductor
manufacturing and other ultra-high purity environments.

4 — Emerging R&D – highlights
In this chapter, three emerging technologies which are making their way to market are
described. They are presented in order of growing potential for the growth in use of Zr.
They are all currently available on the market, albeit not necessarily at scale. They were
chosen based on the explosive growth of citations concerning them, the aforementioned
market availability and their relation to media trends.
4.1 3D printing consumables and photo-polymerisable ceram-

ics
5000
Number of references for 'Zirconium 3d printing'
4000
3000
2000
1000
0
1980 1990 2010 2000 2020
Year
Figure 4.1: Growth in the number of citation on Zr applications in 3D printing technology

topic over time. This graph has been generated by querying Google scholar for papers
published each year corresponding to the search string ‘zirconium 3d printing’.
52 Emerging R&D – highlights
3D printing offers the promise of net-shape manufacturing with very little material loss
during fabrication, as well as creating otherwise impossible geometries. Zirconium
oxide suspensions are highly suitable for what is becoming one of the most promising
3D printing technology, dubbed inkjet. A ceramic suspension – typically zirconium and
other oxide powders in water – is deposited as droplets, the water evaporated, and the
powder sintered to solidify the part [77].
Emerging developments
Additive manufacturing methods have recently been shown to produce ceramics with
mechanical properties comparable to those produced using other methods such as
machining [78]. The applications make use of the freedom offered to shape the products.
Dental prostheses can be printed to match exactly the required shapes. Zirconium-based
ceramics are already widely used for that purpose due to their excellent biocompatibility.
3D printing is a relatively slow manufacturing process. It is therefore more suitable for
low-volume manufacturing. 3D printing is thus very well suited to the production of
moulds for investment casting. In particular, CaO-CaZrO3 ceramic moulds produced
using inkjet 3D printing have been demonstrated [79]. More established is the use of
powder-bed technologies such as laser sintering or selective ion beam melting. All these
technologies depend on the manufacture of suitable ceramic powders.
3D printing can generate geometrically complex shapes useful in solid oxide fuel cells
which benefit from high effective surfaces in their electrodes [80]. Both yttria-stabilised
Zirconium oxide electrolytes and cathode interlayers have been demonstrated as possibly
manufactured in this way [81].
Market potential
The growing demand for energy storage as intermittent power sources become more
prominent in the energy mix will likely fuel the growth in this sector. The market
for such fuel cells is currently approximately 60 000 units sold worldwide every year
although it is growing [82]. These units go from portable personal ones to cells providing
megawatts of power. The amount of Zirconium potentially used in such application
depends on the type of cell, but the cathode represents approximately 1% of the mass of
a fuel cell (see e.g. [83]). Thus assuming an average mass of 500 kg for fuel cell, which
is typical for an automotive application, only approximately 300t of Zirconium might be
used for this application. The other applications would not grow significantly the market
for Zr, as they are in effect an alternative over existing manufacturing technologies for
mature applications.
4.2 Solar cells

Context
The drive to increase the share of renewable energy in electric production has led to
an explosion in the market for solar cells. The enormous growth in that market has
in turn fueled the development of better or more versatile cells. A promising solar
cell technology is the dye sensitised cell. There are two technologies which have been
4.2 Solar cells 53
5000
Number of references for 'Zirconium solar cell'
0 1000 2000 3000 4000
1980 1990 2010 2000 2020
Year
Figure 4.2: Growth in the number of citation on Zr applications in solar cell technology
topic over time. This graph has been generated by querying Google scholar for papers
published each year corresponding to the search string ‘zirconium solar cell’.
developed based on the same physical basis. One uses a liquid electrolyte, and can
be used in architecture as coloured glass windows which double as solar panels, and
Perovskite (any material with the same type of crystal structure as calcium titanium oxide
(CaTiO3 )) solid-state cells which can be deposited as thin films on flexible surfaces,
allowing for many other applications. Both these technologies currently typically use
titanium dioxide as the semiconductor. For it to be efficient, it needs to be doped with
Zirconium. Research indicates that 1% doping provides optimal band properties in terms
of power conversion, but values ranging up to 5% are commonly reported [84].
F -doped SnO glass

Perovskite Perovskite
Semiconductor TiO2
Zr-doped
Semiconductor TiO2
Semiconductor ZrO2
Electrolyte
Semiconductor ZrO2
Pt coat
F -doped SnO glass F -doped SnO glass F -doped SnO glass
A B C
Figure 4.3: Dye-sensitised solar cells. A uses liquid electrolytes, B and C are Perovskite
type cells, with C the latest proposed printable solar cell using only ZrO2 as semiconduc-
tor.
Perovskite solar cells are the most promising due to the flexibility they offer notably for
wearable applications, but in general as a surface treatment transforming any cladding
54 Emerging R&D – highlights
into a solar panel. Printable perovskite solar cells use mesoporous TiO2 and ZrO2
layers which are infiltrated by the Perovskite and the die. This layered arrangement is
advantageous for large scale production and has been shown to be both efficient and
stable [85]. More recent development suggest using only Zr could be not only cheaper
but more efficient [86].
Market potential
Currently, the market is dominated by production of Si-based solar modules, and thin
films represent only about 11% of the market. Solar cells producing approximately 50
GW of electricity are installed every year. Assuming 11% as a typical load factor, an
efficiency of 20%, and an input from the sun of 1 kW, this represents 2.27 billion m2 . If
the share of thin films stays the same, and the technology moves to using ZrO2 films
exclusively, this amounts to 25,000 t of ZrO2 . This number is expected to double by
2050, following the projections for solar power growth from the International Energy
Agency.
4.3 Shape memory alloys

Number of references for 'Zirconium shape memory alloy'
4000
3000
2000
1000
0
1980 1990 2010 2000 2020
Year
Figure 4.4: Growth in the number of citation on Zr applications on shape memory alloys
over time. This graph has been generated by querying Google scholar for papers
published each year corresponding to the search string ‘zirconium shape memory’.
Context
Ceramics containing zirconia undergo an martensitic transformation when their tem-
perature is raised. This transformation changes the volume of the material, making it
possible to macroscopically reconfigure its shape.
Shape memory alloys (SMA) are used most commonly in fastening mechanisms: the
4.3 Shape memory alloys 55
cooled piece is put into place, and snaps to its final shape at ambient temperature,
locking into place. This is used in aerospace applications, but also in medical settings:
shape memory allows the placing and deployment of stents using minimally invasive
procedures [87]. For this later purpose Ti-Zr alloyed with Nb or Mo and Sn alloys are
the most common [88]. The amount of material involved in this market is small however,
only a couple tonnes. In general, research is focussed on substituting Ti with Zr in
existing alloys and understanding the role of Zr [89]. This work is driven by economic
considerations, but the new alloys are also lighter, which is useful in certain applications.
Although actuators seem like a natural use for shape memory alloys, in reality the
temperature control required, in particular the cooling phase, makes them relatively
impractical, and few industrial application have emerged.
Recently, superelastic zirconia has been shown to be capable of very high actuation
stresses in micro-applications, making it an excellent material for such [90]. As an
indication of this trend reviewed here [91], shape memory alloy automotive parts have
entered service (this was used as a marketing highlight in the Corvette Stingray from
2014)
Market potential
Traditionally, SMAs are more commonly used in the aerospace industry, albeit for the
purpose of fastening. The potential Zr market for aerospace actuators is perhaps only 1-
2,000 tonnes, assuming 1% of the aircraft mass is actuators, and deliveries of about 1,600
airliners yearly. By contrast, there is a growing number of actuators in cars. Assuming
that a fraction of them would use SMA rather than electrical motors, potentially as
much as 100g of zirconium per car could be required. As the yearly production of cars
approaches 60 million, and this number is expected to rise as the world develops, the
potential demand for zirconium in this instance is as high as 6 Mt. This is an upper
bound which is unlikely to be reached, but underscores the large potential of this market.
Inside locks
clutch drive
Headlight settings
Mirror settings
Dashboard actuators
Door lock
Trunk lock
brakes
Figure 4.5: Some of the automotive actuators which could use SMA technology.
5 — Emerging R&D
This section initially presents the results of a thorough literature survey designed to
discover the current research and development trends in the world of zirconium and
zirconium compounds. This survey focused not only on identifying new material science
developments, but also paid special attention to new application trends for zirconium
and zirconium based materials. In the third revision, it consisted of the review of
abstracts retrieved from Google Scholar search engine after looking for the keywords
‘zircon’ (45,000 results, classified 2,880), ‘zirconia’ (62,900 results, 5,200 classified),
and ‘zirconium’ (72,600 results, 3,300 classified), restricting the search to the last seven
years (from 2008 to 2015). The search included both scholarly articles and patents. Only
the material deemed relevant to each category was considered and cited in the sections
below, accounting for a total number of 532 references. This analysis is based on R&D
publications and therefore the market applicability is not yet known.
The section was updated with the top publications from 2015–2018, classified according
to the previous scheme. The 250 most relevant publications as returned by scopus were
looked at for each year, corresponding approximately to the top 10 % of all academic
publications on the topic of Zirconium during that period. A number of new subsections
have been added, reflecting the emergence of new possible applications. In total 172
new references were added in the fourth revision of the handbook.
The next subsections explore the relevant literature for several application areas. These
are listed in Tables 5.1 and 5.2, that also identifies the new application areas and those
that are already served by zirconium chemicals.
Metal-organic frameworks are a very active area of research [92], with Zr-based MOFs
attracting the most interest. Most Zr-MOFs feature Zr6 O8 clusters as nodes, coordinated
to carboxylate-terminated organic linkers. They offer the possibility of flexibly generat-
ing a wide range of organic catalysts [93]. They have a wide range of properties, and are
in particular photosensitive [94]. Their efficient synthesis is becoming better understood,
increasing their attractiveness [95, 96]. They now appear in all areas of research, and
understanding their production as well as their stability in a range of environments and
58 Emerging R&D
Organic catalysis
Other
Nuclear industry
Ceramic surfaces
Bioconjugation
Advanced ceramics
Water, food and biological applications
TiO2 coatings Nanoparticles, nanopowders,
Proton Exchange Membranes nanocrystals and composites
Implants
Radioactive applications
Gas catalysis Inorganic catalysis
Refractories
Luminescence and emission
Foils and thin films Zirconia and zirconium metal
dental implants
Self assemblies, organic templates, Composite and alloy
and hybrid materials fabrication technologies
Coating technologies Remediation applications
Ultra−High temperature and
high−wear applications
Figure 5.1: Sources used used for the 2019 update of the yearbook. Articles having
received more than 10 citations a year, by topic.
temperatures is continuously being refined [97]. The latest developments look at the
production of MOFs whose porosity changes with the environment [98] and in producing
a greater range of microstructures [99].
5.1 Advanced coatings and functional materials

5.1.1 Paper
Glyoxal has been traditionally used for paper coating crosslinking and colouring. How-
ever, zirconium compounds such as ammonium zirconium carbonate (AZC) and Potas-
sium zirconium carbonate (PZC) have been proposed and successfully used for the
same function [100] . Zirconium chelates have also been used as insolubilisers for
coating binders for paper and starch, as well as for substitution of AZC [101, 102]. The
colouration, viscosity and surface properties that these zirconium compounds confer to
the paper coatings are advantageous for its manufacturing and other applications such as
high speed inkjet printing [103].
5.1.2 Plastics
Zirconia particles have been proposed as constituents of elastomers in the fabrication of
gloves; their properties allow not only a durable interaction but also alter the strength
and flexibility properties of the material [104]. Anti-bacterial properties have also been
introduced into gloves and other apparel by zirconium phosphate [105]. The use of
advanced zirconium compounds coatings is not limited to the formulation of plastics
or elastomers, they are also key elements for their fabrication: zirconium oxide and
zirconium alloys are used in latex forming moulds for improving durability in their
Table 5.1: Newly served application areas by zirconium chemicals.
Section Application areas
5.8.1 Water, food and biological applications

5.8.2 Remediation applications
5.8.4 Gas storage and adsorption
5.8.5 Sorption for catalysis
5.9.1 High temperature and pressure sensing
5.9.2 Gas sensing
5.9.3 Relative humidity sensing
5.9.5 Food applications
5.9.5 DNA sensing
5.9.5 Proteins sensing
5.10.1 Nanotubes and ordered arrays
5.10.2 Foils and thin films
5.10.3 Surface modification
5.10.4 Nanofibres
5.10.5 Self assemblies, organic templates, and hybrid materials
5.10.6 Nanofluids
5.10.7 Nanoparticles, nanopowders, nanocrystals and composites
5.11.1 Waveguides, fibres and optical substrates
5.11.2 Nanostructured colour and dyeing
5.11.3 Luminescence and emission
5.12.1 Memory devices
5.12.2 Electrical gates and transistors
5.12.3 Superionic conductivity
5.1.2 Plastics
5.1.3 Wood
5.1.4 Fabrics and textiles
5.1.5 Glass
5.1.9 Smart coatings with enhanced properties
5.1.10 Coating technologies
5.2.1 Ceramics with tunable properties
5.2.2 Ultra-High temperature, high-wear and other extreme applications x
5.3.3 3D printing consumables and photo-polymerisable ceramics
5.4 Griding media and grinding technologies
5.5.3 Biodegradation
5.5.6 Bioimaging
5.6.1 Crystal growth control
fabrication [106]. Another property conferred to elastomers and hybrid materials by

zirconium is thermal stability. For example, zirconium propoxide has been used to
improve silicone hybrids such as PDMS and other siloxanes [107]. Polyurethane is used
in several applications, from shoe soles to packaging, and zirconia nanoparticles have
been used to incorporate chemical inertness, thermal stability, high refractive index and
high hardness [108].
5.1.3 Wood
Radiation curable coatings in the wood flooring industry have been modified by the
use of alumina and zirconia acrylate composites [109]. Although the particles did not
show any improvement in the polymerizability of the coatings, their use led to improved
weathering performance and better fire protection for wooden claddings due to their
refractory properties [109–111]. Zirconium and other nanoparticles have also been
proposed to improve the strength and waterproofing of wooden materials [112, 113].
60 Emerging R&D
Table 5.2: Already served application areas by zirconium chemicals.
Section Application areas
5.6.3 Esterification, transesterification, acetylation and ketonisation

5.6.3 Enantioselective and Regioselective reactions
5.6.3 Synthesis of specialty compounds
5.6.3 Fuels and biofuels
5.6.3 Biocatalysis
5.7.1 Proton exchange membranes
5.7.2 Hydrogen storage
5.7.3 Ion transport and conductivity in zirconia
5.7.4 Solid oxide fuel cells
5.8.3 Radioactive applications
5.9.3 Relative Humidity Sensing
5.9.4 Biosensing
5.1.1 Paper
5.1.7 Gems
5.1.8 Ceramic surfaces
5.2.2 Ultra-High temperature, high-wear and other extreme applications
5.2.3 Dental implants
5.2.4 Composite and alloy fabrication technologies
5.3 Casting and moulding
5.3.1 Enhanced modulus refractories
5.3.2 Injection moulding ceramics
5.5.1 Implants
5.5.2 Dental parts
5.5.3 Biocompatibility
5.5.3 Osseointegration
5.5.4 Bioconjugation
5.5.5 Drug delivery and pharmaceutical formulations
5.6.1 Redox reactions
5.6.2 Hydrogen production
5.6.2 Gas oxidation and reduction
5.6.1 Redox reactions
5.6.2 Gas purification
5.1.4 Fabrics and textiles

Zirconium dioxide nanoparticles have been used to confer functional properties to linen,
cotton and other fabrics. Among these properties are UV protection and antibacterial
protection [114, 115]. Similarly, these materials have been used for the treatment of
wounds [115, 116]. Zirconium oxychloride and zirconium phosphates have been used in
wool and polyester fabrics to improve the limiting oxygen limit, thus improving flame
retardancy [117, 118]. Salts of zirconium have long been used in waterproof textiles
and, with the rise of nanotechnology, nanostructures with improved water repellency
properties have emerged for their use in fabrics and textiles [119, 120]. Following
these developments, it was found that α-zirconium phosphate compounds increased the
thermal stability and flame retardancy of various polymers [121, 122].
5.1.5 Glass
Zirconium’s nature has allowed its wide use in coating and functionalisation of glass.
Bending stress and toughness improvements have been reported as a result of addition
of zirconia nanoparticles to glass mixtures before sintering [123]. Thermal and chemical
resistant glasses have also been fabricated with the presence of zircon and zirconia
particles in the glass mixtures [124]. Other uses include super-hydrophobic zirconium
compounds in anti-icing coatings on glass surfaces [120], zirconium oxide particles as
dopants for porosity in photon active glass [125], and Y-PSZ to alter the crystallisation
behaviour of certain glass [126].
5.1.6 Concrete
Zirconium compounds have been used to confer additional properties to concrete mix-
tures. For example, fibre reinforced concrete requires the fibres to be stiffer than the
concrete matrix and resistant to the alkaline concrete paste [127]. Glass fibres containing
zircon (16%) are alkali resistant and have been used in reinforced concrete because of
their high tensile strength (2-4 GPa) and elastic modulus (70-80 GPa) [127–129]. High
performance concrete has indirectly benefited from the zircon industry: by-products
such as micro-silica and fumed-silica from the zirconium industry are used for novel
high-performance concrete applications [130, 131]. Zirconium compounds have been
used in the past as colourants for cement and concrete mixtures [132], and new im-
provements on zircon pigments colouration are under development to improve colour or
reduce toxicity [133, 134]. For cold climate applications, asphalt joints can be replaced
with Zr tungstate, making roads more durable [135].
5.1.7 Gems
Current developments in the modification of gemstones are directed to alter the colour
or optical properties of zircon or zirconium compounds [136, 137]; for example, treating
the gemstones under gaseous atmospheres at certain temperatures could result in colour
improvement or changes in its crystal structure [138, 139].
5.1.8 Ceramic surfaces

Zirconium compounds can be used as an integral part of ceramic materials, as shown in
3.3, but also as coatings, for example zircon is widely used as a glaze opacifier [140] or
means of functionalising surfaces. These can be applied to ceramics used in a range of
applications, from dental to piezoelectric (See Section 3.3 and 5.2) [141, 142], and also
to influence their optical properties [143].
5.1.9 Smart coatings with enhanced properties

Zirconium compounds are used in multi-purpose coatings looking to improve the heat
resistance, abrasion resistance, thermal barrier or stability, or durability of many ma-
terials. Zirconium nitride, for example, has been used as a heat-treatable material to
produce scratch resistance surfaces of zirconium oxide [144]. Rare earth zirconates
such as Gd2 Zr2 O7 in pyrochlore phase are also under evaluation for thermal barrier
coatings [145]. Other uses of zirconium compounds include thermal barrier applications
for manufacturing specialty chemicals, steel, aluminium, or other alloys [146–148].
Zirconia-based films have also been used for corrosion protection in mild [149] and
stainless steel [150]. In addition, zirconia can be used to emulate the microstructure of
ceramic finishings on materials such as magnesium [151]. The type of microstructures
62 Emerging R&D
produced by zirconia may also confer superior mechanical and thermal properties, as
well as porosity, that in combination improve the overall finishing of the coated mate-
rial [152, 153]. Chemical properties can also be enhanced by the presence of zirconium
compounds in coatings. For example: abrasion resistance can be conferred to diverse
materials by coating them with an alloy of zirconium silicate and nickel [154]; the me-
chanical properties of oxide dispersion strengthened ferritic steels containing aluminium
can be enhanced by adding zirconium [155]; the corrosion resistance of an aerospace
aluminium alloy was also shown to be improved with a zirconium-cerium conversion
coating [156, 157]; similarly, improved refractory properties in other casting materials
can be enhanced by zircon coatings which can also affect the thickness of the casting
skin of metals [158–160].
5.1.10 Coating technologies

Novel coatings are accompanied by innovative coating technologies that suit partic-
ular applications. For example, turbine blades may be coated by suspension plasma
spraying with yttria stabilised zirconia (YZT), resembling EB-PVD layers [161–163].
This technique has been used to modify the microstructure of the blades in order to
improve their thermal stability, as well as improving their reliability and manufacturing
reproducibility [161]. It has also been used for the incorporation of nickel dopants
directly on ceramic composites [164]. Air plasma sprayed zirconium diboride coatings
can be used to increase emissivity of surfaces of hypersonic vehicles [165]. Other
industrial applications include the use of plasma sprayed magnesia stabilised zirconia for
thermal barrier coatings [166]. Additional techniques used for ceramic glazing, corro-
sion resistance, and fabrication of ceramic coatings are sol-gel processes, photocatalytic
curing processes, and electrolytic oxidation of zirconia [167–170], some enabling new
colours with enhanced properties [171, 172]. Mullite-based coatings from alumina and
zircon powder have been achieved by plasma spraying and laser remelting, where the
laser remelting reduces porosity and increases the coatings’ hardness [173]. In addition,
stainless steel has been coated with thin films of zirconium oxynitride to enhance its
corrosion resistance [174]. A process to coat steel plate was described in [175]. Coat-
ing technologies are of particular importance for the purpose of accident-resistance in
nuclear reactors [176–178].
5.2 Advanced ceramics

The addition of zirconium compounds and nanoparticles to ceramics can lead to novel
properties for specific applications. Similarly, the addition of chemical compounds to
traditional zirconium ceramics has also proven useful to alter and enhance their physical
and chemical properties [179–181]. There are several examples of these enhancements
in literature, as described in the sections below.
5.2.1 Ceramics with tunable properties

Zirconium dielectric and piezoelectric properties have been incorporated into ceramics,
transforming them into responsive materials. Barium zirconium titanate ceramics have
5.2 Advanced ceramics 63
been used as tunable dielectric ceramics whose dielectric constant changes as a function
of temperature [182, 183]. Other composite ceramics such as lead zinc niobate–lead
zirconium titanate are also known to change dielectric and piezoelectric properties [184].
5.2.2 Ultra-High temperature, high-wear and extreme applications
Ceramic composites and alloys containing zirconium have recently been proposed for
aerospace, automobile, and military applications which require material performance at
extreme temperature. It has been shown that SiC ceramic composites with ZrB2 , ZrC and
other zirconium compounds offer useful characteristics for high temperature applications
such as improved thermal shock resistance [185–188]. Zirconium carbide, in particular,
is commonly used for high-temperature applications and coatings for nuclear particle
fuels, and has been modified with additives to improve its sinterability and cavitation
resistance even further [189] In general, there is active research in protective coatings
for Zr-based alloys [190], as well as fabrication using alloys such as MoTiZr [191].
The infiltration of melts with ZrC composites has found applicability in rocket nozzles
for aerospace vehicles [192, 193]. Similarly, the use of nicalon- reinforced zirconium
phosphate composites has been proposed for defensive missiles to survive high speed
aerodynamic heating or spatial applications [194, 195]. Further developments show
that fibre reinforced ceramic composites such as carbon fibre reinforced ZrB2 −SiC or
ZrC could demonstrate further improvements for ultra-high temperature applications
and result in a remarkable improvement of the mechanical properties of the composites
[185, 186, 196, 197]. The latter can also be used as a protective coating [198]. It is also
suggested that the use of higher purity materials, in the case of zirconium diboride-silicon
carbide-boron carbide ceramics, could lead to significant improvements in ultra-high
temperature strength [199]. The production process to obtain fully dense ceramics is also
being optimised [200], as well as the preparation of the required powders [201], and other
production routes which maximise properties [202] Ceramics from pure ZrC have been
produced by plasma spark sintering [203]. Al, Si and other alloys used in automobile
components (e.g. brakes), aircraft, marine vessels, and other industrial machines, are
exposed to high temperatures and wear, thus their reinforcement with zircon particles has
been extensively studied in recent scientific literature [204–212] Recent work suggests as
much as 12% reinforcement is optimal [213]. Radiation-hardened electrical components
can be produced using PVA-PEG-PVP-ZrO2 nanocomposites [214].
5.2.3 Dental implants
Advanced ceramics have also been intensively developed for dental applications, not
only due to their strength and resistance to temperature, microfracture and fatigue, but
also due to their biocompatibility [215–221]. Zirconium compounds are used mainly as
structural ceramic materials for dental implants and ceramic crowns. Additionally, they
have also been used in the veneering of dental parts [222–227]. These applications and
current R&D are further discussed in §5.5.2.
64 Emerging R&D
5.2.4 Composite and alloy fabrication technologies

As the demand for novel alloys and ceramic composites grows, the techniques for
developing such materials improve. Research and development regarding the fabri-
cation of zirconium alloys and composites includes microwave sintering and sol-gel
techniques. These techniques have demonstrated capacity for producing composite
materials, including metal matrix composites, and reports in literature show success in
improving their properties [228–232]. An example is the use of tetragonal zirconia to
reinforce glass-ceramics composites, which result in a significant improvement of their
mechanical properties [233]. Phase composition and crystal structure of zircon-type
composite ceramics have also been studied, revealing possible applications in microwave
devices and low temperature co-fired ceramic technology [234].
5.3 Casting and moulding

The use of zircon, zirconia and zirconium compounds in casting and moulding represents
an application in continuous development and optimisation (see Section 3.1) where re-
search is carried out to fulfil particular process requirements. Some of these requirements
include hydraulic cement casting, high manganese steel casting, inclusions removal,
casting skin control in iron melts, and crucible and porosity control when casting TiAl
alloy turbine blades [159, 160, 235–239]. A study has explored the effect of processing
technique and TiO2 addition on alumina-zircon refractory materials, showing that fired
bricks processed by the gelcasting technique have improved properties compared to
those that underwent a semi-dry pressing process. These bricks also had similar proper-
ties to those currently used in lining the basin of electric glass melting furnaces, which
are fusion-cast [240]. Other examples include, zirconium hydride used in liquid phase
metal foam processing techniques [241] and the addition of zirconium to a magnesium-
zinc-calcium alloy has shown to delay texture weakening during rolling [242]. Other
materials have also been used in combination with zircon to improve its melting or
solubility properties [243].
5.3.1 Enhanced modulus refractories

One focus of research in casting applications is the modification of rheological properties
of castable refractories. Casting moulds encounter several challenges to accommodate
castable materials and casting technologies: sometimes they need to behave as elastic
materials but also preserve certain microstructure. The use of zircon sands and other
zirconites has been shown to improve these characteristics [244, 245]. In addition, their
use as fillers has found success in anti-corrosion applications [246].
5.3.2 Injection moulding ceramics

The alteration of rheological properties in inorganic materials by the addition of zirco-
nium compounds has found applications in certain industrial processes. The manufacture
of plastic materials commonly employs injection moulding to mass-produce consumer
goods. This process can also be applied to ceramics as long as the rheological properties
5.4 Grinding media and grinding technologies 65
of the ceramic adapt to the injection systems for fast moulding techniques. Thus, the
addition of zircon or zirconia to ceramics pastes is fundamental for their use in injection
moulding [247–250]. Recent development focus on environmentally-friendly production
routes [251].
5.3.3 3D printing consumables and photo-polymerisable ceramics

A novel application derived from the appearance of mouldable ceramics and cements
is their use for 3D printing. Zirconium compounds can be used in combination with
ceramics, hybrid plastic-ceramics, or metal alloys for 3D printing applications [252,253].
The incorporation of organic compounds and polymers in ceramic and cement mixtures
has led to innovation in polymerisable and photo-polymerisable ceramic materials which
use zirconium compounds as additives [254, 255]. Zirconium compounds are also
preferential materials used by selective laser sintering technologies [256].
5.4 Grinding media and grinding technologies

The durability and hardness of zirconium compounds are often exploited for grinding
in current state of the art applications, while novel compositions and technologies are
constantly being developed. Sintering zircon based particles with other compounds
allows control over the hardness and wear rate of grinding media [257, 258]. Precision
grinding is also possible by carefully controlling the grinding temperature of nano-
zirconia ceramics [259].
5.5 Biomedical applications

5.5.1 Implants
The properties of zirconia have found use in the biomedical sciences mainly for the
production of durable implantable materials. On the one hand, having high strength and
fracture toughness allows zirconia to be used as a structural substitute for bones, hips or
dental parts; on the other hand, its ionic conductivity and low thermal conductivity allow
its acceptance in living tissue. A drawback of its use when exposed to water vapour
for long periods of time (decades) is that it experiences low-temperature degradation
and aging. However, this can be overcome by alloying the material, particularly with
alumina [37, 260–262]. Thus, research about its use in orthopaedics and arthroplasty
(i.e. surgical modification of joints) is carried out continuously. However, it is still
not clear to what extent zirconium implants can be an alternative to titanium implants
[263], although recent studies suggest that zirconia particles are less bioactive than
titanium particles [264]. In addition, the conventional and early loading of titanium-
zirconium alloy implants have also been explored, demonstrating that these implants
have a comparable biomechanical outcome to conventional titanium implants [265].
Zirconia (and other zirconium compounds) have been used for the reconstruction of hips,
hip joints, femoral heads, and knees, amongst other body implants [37, 260, 261, 266].
Novel zirconium alloys and composites are currently proposed in the scientific literature
66 Emerging R&D
as biocompatible materials for implants due to their combination of corrosion resistance,

bearing resistance, and mechanical properties [267–269]. One example is the use of
zirconia and polydimethylsiloxane hybrid coatings to promote tissue-implant integration
[270]. Alloys of magnesium, zirconium and strontium have also been investigated for
use as biodegradable orthopedic implants [271]. Whilst yttria-stabilized zirconia foil
could have applications in the fabrication of ultrathin implantable devices [272]. MOFs
can be used to generate singlet oxygen, which is toxic to cells; this has potential as
targeted cancer therapy [273].
5.5.2 Dental parts
Dental parts have a strong aesthetic connotation but must also be biocompatible and
provide resistance and durability to the mouth environment. The properties of zirconium
compounds allow its use in dental implants that show less biofilm formation [274, 275],
and in dental veneering [222, 276]. Veneering is a cosmetic treatment in which a thin
layer of material is deposited on the surface of teeth. This material has to undergo
thermal cycles during its application and must possess high shear bond strength to stay
in place, as well as to match the colour and brightness of the teeth. The strength and
durability of zirconia for veneering has been extensively studied in recent scientific
literature [223–225, 227, 277]. The colour of the veneering is important for aesthetic
purposes and the addition of particles for colouration has also been studied as a factor
influencing the shear strength and durability [226]. Similarly, the application of adhesives
and surface treatments are an important factor influencing the shear strength [278–280].
Zirconia ceramics are used not only for covering the surface of teeth, but also to fix
partial dentures or for dental reconstructions [222, 281–283]. Titanium/zirconium alloys
have been used as implants in the molar region of the mandible, and after 1 year of
function these show similar results to pure titanium implants [284]. The advances
in moulding techniques for zirconia ceramics presented in Section 5.3 having also
proven applicability in dentistry with computer aided design and manufacturing of fixed
dentures [218,285,286], the first cohort studies of pure ceramic implants have concluded
successfully [287].
5.5.3 Biocompatibility
It is important to evaluate the permanence of dental fixtures and other implanted ceramics
in the body, thus extensive clinical research is continuously conducted to evaluate their
impact in human subjects. New zirconium based materials are tested with in vivo or in
vitro animal studies to show their positive compatibility and some suggesting that the
biocompatibility of zirconia is greater than titanium [264, 288–294]. The acceptance or
rejection of the material by the living tissue or cells is an important research question,
as well as the effects of the material on the molecular mechanisms of the cells. Factors
that may influence this are not only biochemical, they can also include the physical
structures and surfaces [295]. There are several studies investigating how organisms
respond to zirconium based materials, what structures are built in response to them,
and how the findings can be used to benefit future applications. For example, it was
observed that in adult pigs, collagen fibres in connective tissue oriented around zirconia
5.5 Biomedical applications 67
implants, providing some adhesion to the tissue [296]. Zirconium has also been used
with protamine sulfate to trace haematopoietic progenitor cells (HPCs) when intrabone
injected in order to maximise marrow retention of HPCs [297]. It is also important to
evaluate the impact of the biological environment on the implants and composites. It was
recently shown, for example, that saliva affects the bonding of zirconia implants [298].
Efforts were then directed towards finding reliable zirconia bonding agents for implants,
and novel silane-based zirconia primers have been proposed and investigated for this
purpose [299, 300]. Mechanical solutions are also proposed so that zirconia abutments,
crowns and posts can be safely fixed [301, 302].
Osseointegration
The largest biomedical application of zirconium compounds, particularly zirconia al-

loys and composites, is their use as bone replacements. Current research efforts are
aimed at understanding the material properties that best suit this application. The chem-
ical composition of the implants plays a key role in the acceptance, but also in the
durability and strength as discussed before. The aim is to achieve successful osseoin-
tegration, which has already been proved for zirconia implants [303, 304]. Several
material combinations have been suggested for improving this, for example, graded
hydroxyapatite-zirconia (HA-ZrO2 ) or zirconium modified calcium-silicate ceramics
(Ca3 ZrSi2 O9 (Baghdadite)) [305–310]. Structural and surface modifications have also
been studied as important factors in the acceptance of implants by osteoblasts [311].
Zirconia toughened alumina is widely used as an orthopaedic graft material and it has
been shown that altering its structure to a porous one permits its bioactivation and
better acceptance [312, 313]. Oxidised zirconium shows promise for use as the bearing
surface for femoral heads in total hip arthroplasty, with initial studies showing lower
wear compared to cobalt-chrome, although long term analysis is still required [314]. In
addition, magnesia-stabilised zirconia is being studied for use as a femoral component in
knee arthroplasty [315]. When evaluating osseointegration in vivo, direct observations
are useful, however biochemical and genetic activity could be better indicators of cell
proliferation and give insights into which interactions the cells prefer [316, 317]. In
addition, zirconium ions seem to induce proliferation and differentiation of primary
human osteoblasts during in vitro culture [318]. An ultimate osseointegration would
be one that not only mimics the material properties and surface structures of bones and
other tissues, but also incorporates molecules that biochemically enhance the acceptance
of the implant materials. A study showed that it is possible to go down to the level
of mimicking interaction with neurotransmitters and protein interactions on zirconia
ceramics to enhance osseointegration [319]. Further experimentation shown that sol–gel-
derived Si/Zr O2 coatings could promote the osteogenic differentiation of mesenchymal
cells, opening applications in tissue engineering. Similarly, Zr-based coatings were
found as efficient as a material already employed in clinical practice to promote the
growth of osteoblasts [320].
Replacing cartilage, which is a non-regenerative tissue is an important medical applica-
tion. A Zirconium-based hydrogel has been proposed for that purpose [321].
68 Emerging R&D
Biodegradation
Understanding the biodegradation pathways of zirconium based materials is important
for the design and proposal of new composites and coatings [322]. For example, ZrN/Zr
has high corrosion resistance and has been used to coat magnesium alloys used in
biomedical implants, improving its corrosion resistance [323]. Sometimes it is desirable
that natural biodegradation occurs, and hybrids of biomaterials and zirconia nanoparticles
have been used for this purpose [324].
5.5.4 Bioconjugation
Zirconium compounds possess electrochemical properties that allow interaction with
biomolecules at the nanoscale. These interactions permit communication with the
biomolecules at the electronic level allowing electron transfer and their incorporation
into electrochemical devices. Haemoglobin and myoglobin have been directly conju-
gated with zirconium derived compounds for electrochemical studies [325, 326]. These
conjugations can be taken further to analyse the interactions of the conjugated molecules
with other ones; thus, the use of zirconium compounds can be seen as a bridge for
reading molecule interactions, which is the basis for biosensing (explored in detail in
Section 5.9.4).
5.5.5 Drug delivery and pharmaceutical formulations

The element zirconium has been proposed as an inhibitor of human smooth muscle
cell proliferation for treating various diseases [327]. Other compounds, such as silver-
carried zirconium phosphate (AgZrP), have been tested as powerful antibacterials able to
annihilate E. coli and kill up to 99.9% of S. aureus at low doses [328]. Sodium zirconium
cyclosilicate has been tested for use as a selective cation exchanger to reduce serum
potassium levels in people with hyperkalemia [329–331], as well being shown as a urgent
treatment option for severe hyperkalemia [332]. Most zirconium compounds are safe to
use in the human body due to their biocompatibility, and can be easily excreted without
negative effects. Thus, zirconium compounds can be used as delivery systems [333],
such as zirconia/polyethylene glycol [334, 335] and monodisperse zirconium metal-
organic frameworks [336]. An example of this use is the nanoencapsulation of insulin
in zirconium phosphate cages (ZrP, which has shown no cytotoxicity) and their use
as delivery systems [337]. In addition, molybdocene dichloride has been intercalated
into zirconium phosphate to develop a potential anti-cancer drug [338] with zirconium
phosphate nanoplatelets also suggested for drug delivery for cancer therapy [339].
Targetted delivery may be possible using photosensitive MOFs encapsulation [340].
5.5.6 Bioimaging
Imaging through the use of zirconium compounds is an important research area that is
finding broad applicability in the biomedical sciences. Zirconium-89 radiation has been
used as an indirect labelling system for biomolecules, particularly using chelates for its
attachment to antibodies [341–344]. This emerging technique is called Immuno-PET
(Positron Emission Tomography) and takes advantage of zirconium-89 as a positron
5.6 Catalysis 69
emitter. A specific example is where chelator-free zirconium-89 has been used to label
mesoporous silica nanoparticles to enable PET image-guided delivery of this drug for
use in nano-oncology [345]. Further development have looked at the promising safety
of the new methods [346]. Fluorescence has also been used for imaging: it has been
found that doped zirconia nanoparticles with lanthanides are fluorescent and can be
functionalized for imaging biomolecules [347]. Some doping elements, such as Eu,
Tb or Gd, have also shown magnetic properties that can be used in combination with
fluorescence for dual imaging applications [348]. Research had suggested the use of
this technique for characterising tumours and monitoring the therapy outcome in cancer
patients [349], this technique has now been applied in breast cancer treatment [350].
5.6 Catalysis
Zirconium based catalysts have been used in a large number of chemical reactions due
to the versatility and abundance of this element. It has been used as a catalyst for pollu-
tion control, automotive applications, chemical refining, and hydrocarbon reforming,
among other areas. Organic reactions catalysed by zirconium include hydrogenation,
oxidation, amination, isomerisation, and pyrolysis, among others. A famous reaction
is the zirconium-catalysed asymmetric carboalumination developed by Nobel laureate
Ei-ichi Negishi [351]. Because of its versatility to form chemical compounds, it can be
used as a strong base or strong acid, as well as in different physical forms such as slurry,
tablets, extrudate, or foams, augmenting the number of possible catalytic reactions. The
particle size, surface area, porosity and crystallinity of certain zirconium compounds
can also be modified to fulfil particular catalytic applications. Furthermore, zirconium
compounds are also used as support media for other catalysts. One emerging catalyst
is the use of mesoporous zirconium phosphonates to catalyse a cycloaddition reaction
between aziridines and CO2 as a method to fix CO2 , for use in carbon capture and
storage [352–354]. This section summarises current R&D for zirconium catalysts.
5.6.1 Inorganic catalysis

Redox reactions
Oxygen mobility in zirconium oxide particle surfaces allows for good redox properties
with thermal stability. Ceria-Zirconia oxides have been used to emulate the redox
properties of similar particles in solution [355]. Activated zirconium carbide may
also be used for oxygen reduction [356]. Zirconium-porphyrin frameworks also show
properties as precursors for oxygen reduction reaction catalysts [357]. Recently, these
have been produced as thin thilms MOFs [358]. A highly selective synthesis reaction of
hydrogen peroxide from H2 and O2 can be catalysed by zirconia doped catalysts [359].
Photoactive srilankite-type zirconium titanate hollow spheres look to be promising
candidates for photocatalyst due to higher redox potential [360]. Meerwein–Ponndorf–
Verley organic-inorganic reduction is efficiently catalysed using a Zr–phytic acid hybrid
[361]. Zirconium is emerging as a substitution for the much more expensive ruthenium
chelates in photoredox catalysis [362].
70 Emerging R&D
Crystal growth control

Crystal growth can be accelerated or slowed by zirconium based compounds. For
example, the presence of zirconium silicate has been found to produce accelerated
abnormal grain growth in rutile TiO2 [363]. On the other hand, the glass former CuZr
induced slower crystal growth rates [364]. Not only the growth rate can be influenced,
a zirconium acetate complex has been shown to have ice shaping properties similar to
those of antifreeze proteins [365].
5.6.2 Gas catalysis

Hydrogen production
The ability of zirconium compounds to catalyse redox reactions has found applications
in gas catalysis, particularly for the production of hydrogen gas for fuel cell applications
(see Section 5.7). One popular reaction that can be catalysed by zirconia is the ’water gas
shift reaction’ in which water and CO are combined to produce H2 and CO2 . Zirconia is
usually doped with gold and it is known that its crystal phase affects the performance
of the reaction [366, 367]. CeO2 −ZrO2 ceramic foam is also used to perform this
reaction [368]. Other methods for hydrogen production are based on water splitting
systems catalysed by ZrO2 in a similar fashion, making use of the semiconducting
properties of zirconia when doped with other materials such as TaNO, WO3 [369],
or when coating SiC structures for thermochemical production [370, 371]. Hydrogen
can also be obtained from other compounds by steam reforming or hydrolysis. For
example, CeO2 −ZrO2 coated metallic foam and NiAl2 O3 −ZrO2 catalysts are used for
reforming liquefied natural gas obtaining H2 gas [372–375]. Ethanol has been used
in a similar process based on nickel Ce/Zr catalysts [376, 377] and silica and zirconia
supported catalysts [378]. Hydrolysis of hydrogen rich compounds such as sodium
tetrahydroborate is achieved by sulphate-zirconia based catalysts [379–381]. In addition,
the magnetocaloric parameters of zircon-type DyCrO4 and HOCrO4 suggest they could
be used as magnetic refrigerant materials for the liquefaction of hydrogen [382].
Gas oxidation and reduction

Partial oxidation of gas molecules is important for industrial applications related to the
production and storage of gases. Carbon monoxide, methane, nitrous oxide, methanol
and hydrogen are amongst the most popular gases for this processes [383–387]. The
configuration of the catalysts used for this purpose are nickel and yttria-stabilized
zirconia, PtCe-Zr mixed oxides, molybdenum zirconium, and CuCe-Zr [383–390].
The oxidation of incomplete catalysed hydrocarbons, also known as soot oxidation, is
also catalysed by this type of zirconia based catalysts [391, 392]. Similarly, reduction
reactions can be catalysed by zirconia supported catalysts for the production of methanol
or the reduction of gases such as NO [393–395].
Gas purification
Since various gas species can be transformed or absorbed by zirconium oxide based
catalysts, these compounds can be applied for the production of pure inert gases such
as xenon and others (e.g. in car exhausts) [76, 396]. Ceria-zirconia mixed oxides has
5.6 Catalysis 71
also been used to reduce soot emissions of a diesel engine [397]. A composition of
zirconium, cerium and niobium are used as a catalyst to treat gases containing nitrogen
oxides, which are emitted from motor vehicles [398]. A three-dimensional zirconium
modified TUD-1 mesoporous material has been synthesized and successfully used as a
catalyst for the hydrodesulfurization of FCC diesel [399].
5.6.3 Organic catalysis

Esterification, transesterification, acetylation and ketonisation
It has been found that sulphated-zirconia, tungsten-zirconia, and other modified zirconia,
namely zirconium-based metal organic frameworks, can be used for homogeneous
esterification and transesterification of natural oils, lipids, triglycerides, soybean oils,
oleic acids, and waste oils [400–406]. Ketonisation of biomass derived species and
carboxylic acids can also be achieved by similar solid state zirconia catalysed reactions
[407,408]. Acetylation of glycerol and selective oxidation of cyclohexane are some other
examples of the broad range of organic reactions that can be catalysed by zirconia and
zirconium compounds [409–411]. Zirconium(IV) Phosphonate-Phosphates can be used
to select ions in solution, enhancing specificity of reaction involving hydrocarbons [412].
Enantioselective and Regioselective reactions

The advantage of using zirconium catalysts for organic chemistry is due to their enan-
tioselectivity and regioselectivity. This allows modification of chemical compounds on
specific sites and regions. Reactions that have been possible include the enantioselec-
tive alkene hydroamination, and the synthesis of amino alcohols and alkyl indoles by
regioselective ring-opening of epoxides, amongst others [413–417].
Synthesis of specialty compounds

There are many reactions that can be catalysed by zirconium compounds, most of
which are catalysed in the solid state: from acetic acid reforming to warfare agent
degradation, all can be catalysed by a zirconium derived catalyst or zirconia sup-
ported catalysts [418–421]. Some examples taken from current scientific literature
include: synthesis of dimethyl carbonate [408], hydroxylation of phenol over molyb-
dovanadophosphoric acid modified zirconia [422], total oxidation of toluene by nanos-
tructured mesoporous zirconia [423], four-component synthesis of pyranopyridine deriva-
tives [424], tetrahydropyridines [425], solvent free aza-Michael addition with sulphated
zirconia [426], bis and tris (indolyl) methanes with tungstophosphoric acid on zirco-
nia [427], hydroxy derivatives of 4-methyl coumarin [428], glycerol dehydration to
acrolein by sulphated zirconia [429], aerobic oxidation of alcohols to aldehydes by
polyoxometalate-zirconia (POM/ZrO2 ) nanocomposite [430], SBA-15 catalytic activ-
ities in sulphated zirconia [431], hydrogenation of haloaromatic nitro compounds by
hydrous zirconia supported iridium nanoparticles [432], Lewis acidic three-dimensional
mesoporous zirconium catalyst [433], and synthesis of dimethyl carbonate from urea and
methanol over ZnO−CeO2 [434], hydrolysis of nerve-agent simulants with a zirconium
based metal-organic framework [435], amide formation using a zirconium chloride
catalyst [436, 437], a low waste Heck reaction of methyl acrylate and styrene with
72 Emerging R&D
palladium nanoparticles on layered potassium α-zirconium phosphate [438, 439], AgCl-

based composite photocatalyst obtained from nanosized silver exchanged α-zirconium
phosphate as a precipitating agent [440], synthesis of xanthene derivatives promoted
by zirconium dodecylphosphonate [441], conversion of glucose, fructose and sucrose
into 5-hydroxymethyl-2-furfural with mesoporous zirconium phosphate catalyst is a
hot research topic [442–445], hydrodeoxygenation of guaiacol over ceria-zirconia cata-
lysts [446] and synthesis of 2,3-dihydroquinazolin-4(1H)-ones, which has a wide range
of biological activities, with sulphated zirconia [447]. Polypropylene oxyde can be
produced from CO2 using zirconium complexes [448]. Thioanisole can be selected for
by NPF-201, a Zr-MOF [449].
Fuels and Biofuels
One significant application in which zirconium catalysts play an important role is

organic catalysis for fuels and biofuels. Continuous research has been devoted to
the use of zirconium compounds in improving the performance of the cracking of
naphtha [450]. Synthesis of biodiesel has been achieved by zirconia supported tungstates
[451], KOH [452], acid modified zirconia [453], and sulfated zirconia [454] while
synthesis of high-octane gasoline from carbohydrates has been achieved by Pt/zirconium
phosphate [455, 456]. Zirconia supported metallic catalysts have also been used for the
reforming of gasoline, diesel, butane, propane, and ethanol, and are under continuous
research [457–461]. Synthesis of ammonia from air has been shown [462]. Size-selective
oxidation of alkanes may also be catalysed by heteropolytungstic acids incorporated in
mesoporous zirconia [463]. Zirconia catalysts have also been used for desulphurisation
of liquid fuels [464]. Cleaning biogas and upgrading to natural gas is an important
industrial process for the full utilisation of these environmentally friendly fuels. This
process can also be catalysed by zirconium compounds such as zirconium terephthalate,
zirconia-titania or zirconia-alumina catalyst supports [465–468]. Sustainable production
of biofuels is the topic of ongoing research [469]. Not only the transformation but also
the combustion of natural gas is possible by using zirconia supported catalysts [470].
Zirconium phosphate was shown to be a very effective catalyst for the production of
γ-valerolactone, a key solvent for the dissolution of biomass [471].
Biocatalysis
The flexible chemistry of zirconium compounds as catalysts has led to their application
in biochemistry. They have been used to mimic biological catalysts such as metallopor-
phyrins [472], or to achieve biochemical transformations in fewer steps, which can be
achieved for example during the dehydration of fructose to 5-hydroxymethylfurfural
by sulphated zirconia solid acid [473]. Zirconium based catalysts have also found a
niche application as immobilisation matrices for lipases to mediate enantioselective
catalysis [474–476]. Zirconium silicate can also be used in the deproteinization of
human plasma [477].
5.7 Fuel cells and batteries 73
5.7 Fuel cells and batteries

The use of zirconium for hydrogen production has been discussed in Section 5.6.2.
Hydrogen is a clean fuel that can be easily obtained from one of the most abundant
molecules in the planet: water. In addition, hydrogen can also be obtained from hydrogen
rich molecules such as uranium-zirconium hydride or borohydrides [379, 380, 478]).
Early research also suggests that zirconium acetylacetonate can be used as the electron
extracting layers in regular and inverted small molecule organic photovoltaic cells [479].
Zirconium alloys are also used in water-cooled nuclear reactors for nuclear fuel cladding
and structural components [480], but can be embrittled by hydride precipitation [481],
modelling and electron microscopy is being undertaken to develop strategies to mitigate
this aqueous oxidation in zirconium alloys and thus extend their lifetime [480]. This
section further explores current research and development trends in the fabrication and
optimisation of fuel cells using zirconium.
5.7.1 Proton Exchange Membranes

Traditional fuel cells are produced using proton exchange membranes made of poly-
anions. Nafion is a derivate of tetrafluoroethylene with sulfonic acid in its porous
matrix that allows protons to be transported from one side to the other by exchange
with water, freeing electrons in the process. Nafion-zirconia, nafion-sulphated zirconia
and nafion-zirconium phosphate composites have been formed by different methods
to improve the proton exchange performance in fuel cells [482–489]. Other cation
exchange membranes such as MS-4K resins have also been improved by modification
with hydrous zirconia [490]. It has been found that these ion transport improvements,
gas diffusivity, and proton conductivity properties in zirconia crystals can be used on
their own in the solid state and not necessarily in a wet membrane (Section 5.7.3).
5.7.2 Hydrogen storage

Hydrogen as a means of energy storage has been touted as one of the technological
solutions to global warming. Although this claim is likely oversold, much work has
been devoted to the development of safe liquefied hydrogen storage, usually using
metallic foams, which release the gas slowly in the case of a leak. These are difficult to
manufacture and shape. In this work by Lv and Huot, a TiFe foam is made more suitable
for practical large scale deployment by the addition of 4% of ZrMn2 [491].
5.7.3 Ion transport and conductivity in zirconia

For a solid oxide such as zirconia to be used in hydrogen fuel cell applications, it
is required that hydrogen and oxygen diffuse through it [492–494]. Not only is gas
diffusion important, but also the cation conductivity that generates the electric potential,
while yttria-stabilised zirconia must be able to conduct protons as well [495, 496].
Zirconium hydrogen phosphate, incorporated into the catalyst layer, has also been used
to improve the performance and durability of high temperature polymer electrolyte
membrane fuel cells [497]. These phenomena have been found to work even better in
combination with other solid oxides for high temperature applications, as developed in
74 Emerging R&D
emerging Solid Oxide Fuel Cells (SOFC) in the next section.
5.7.4 Solid Oxide Fuel Cells
There are different types of solid oxides that have been modified with zirconia or doped
zirconia for their use in fuel cells. Examples of these include various composites of lan-
thanides, gallium, magnesium, strontium, cobalt, iron, scandium, bismuth, gadolinium,
and manganese oxides, usually modified with yttria stabilized zirconia, which is also
a solid oxide [498–506]. Nickel-zirconia anodes have also been investigated for solid
oxide fuel cells, as well as ceria and zirconium thin films, highlighting the importance
of the film structure for their performance [507–513]. Micro-tubular solid fuel cells
have also been proposed which use porous zirconia [514]. Oxide ion conductivity is
a well researched phenomenon that has been transferred to other areas such as gas
sensors or the preparation of BASE (sodium ’beta’-alumina+zirconia solid electrolyte)
for Na-S-batteries [515].
5.7.5 Batteries
The thermal stability and ionic conductivity of ZrO2 make it an excellent candidate for
separators in Li-ion batteries, enhancing safety [516]. Further, there is ongoing work on
developing solid-state batteries using ZrO2 as the cathode.
5.8 Adsorption and immobilisation

Not all reactions with zirconium compounds are reversible and not all of them see
the transformation of the reactants: some of these reactions are partially reversible
or completely irreversible and may incorporate zirconium permanently, or vice versa.
Adsorption and immobilisation of different chemicals onto zirconium compounds is
then possible [517] and some applications are described in this section.
5.8.1 Water, food and biological applications
Early work shows a zirconium (IV)-based metal-organic framework membranes as

showing significant promise for use in water desalination [518]. There is a particular
interaction between zirconium compounds and proteins that has been exploited by
the food industry and other biological applications: zirconium dioxide in metallic
cages has been used to stabilise proteins of white wines [519]. Similarly, addition of
transition metals and zirconium has been found to prevent unwanted aromas [520].
This original selectivity for certain molecules has also been used for chromatographic
determination of xanthines and for the extraction and characterisation of melamine
residues in milk [521,522]. Adsorption of proteins has also been taken to the microscopic
level to absorb viruses from water with colloidal zirconia microfilters [523]. Selective
elimination of selenate and selenite has been shown [524]. Zirconia is also suggested as
a potential phase for the separation of biological samples [525].
5.8 Adsorption and immobilisation 75
5.8.2 Remediation applications
Another adsorption application for zirconium compounds is the adsorption of con-

taminants and toxic compounds. It has been shown that iron-zirconium oxides and
hydrous zirconium oxide effectively remove arsenic from water [526, 527], and that a
zirconium-based magnetic sorbent for arsenates is possible [528] as well as for mer-
cury [529]. Amongst other applications, hydrous zirconium oxide has been shown to
adsorb Cr(VI) from aqueous solutions [530, 531], as has mesoporous iron-zirconium
bimetal oxide [532]. Titanium dioxide doped with zirconium element also shows
promise for use as a heterogeneous photocatalyst to treat water pollution [533]. Zirco-
nium alginate can be used for fluoride removal [534]. Desulphuration by adsorption
has also been possible using copper supported zirconia as adsorbent [535]. Ammo-
nia, which is a common water component, and a contaminant if in excess, can be
adsorbed by aluminium-zirconium polycations [536]. Similarly, vanadium can be re-
moved from aqueous solution chitosan-zirconium (IV) composites [537], Phosphate
can be removed using ZrO2 in quaternary-ammonium Chinese reed or treated ben-
tonite [538, 539]. Removing lead (II) from an aqueous solution onto gel spheres of
zirconium hydroxide was shown [540], similarly copper (II) and cadmium (II) by ad-
sorption on nano zirconium silicate [541]. Methylene blue has been removed from waste
water by polyaniline zirconium (IV) silicophosphate nanocomposite [542, 543], and by
photoactive zirconia-titania [544] and Ce and Er doped ZrO2 [545], both showing its
potential for environmental purification applications. RhodamineB could be removed
from water by a graphene-Zr photocatalyst [546]. Research has also shown that a
hydrous zirconium oxide-based nanocomposite can be used to remove trace phosphate
from water, particularly at acidic pH [547,548]. Stable detoxifying of nerve agents using
a Zr-based MOF has been demonstrated [549–551]. Similarly, arsenic removal was
shown [552]. Emerging pollution remediation can also benefit from the photocatalysis
possibilities offered by Zr-doped TiO2 [553]. The same properties have been exploited
to degrade methyl orange [554].
5.8.3 Radioactive applications
Zirconium compounds are known for their radioactive shielding and adsorptive prop-
erties, and research is constantly carried out to optimise these processes [555, 556].
Neutron adsorption for shielding materials has been done with zirconium borohydride
and zirconium hydride [557]. Immobilising nuclear waste is also paramount and zirco-
nium phosphates have been proposed as host structures for this purpose [558]. Zircon
ceramics have also shown potential to immobilise trivalent and tetravalent actinides,
contained in high-level nuclear waste [559]. Further examples include the removal of
uranium (VI) with humic acid immobilised zirconium pillared clays, and the removal of
radioactive actinides by doping zirconia crystals [560, 561]. Evidence at nanoscale also
suggests that even radiation damaged and highly porous zircon may still be suitable to
store in nuclear waste (minor actinides) [562].
76 Emerging R&D
5.8.4 Gas storage and adsorption
The adsorption of gas molecules has been identified as a great advantage for gas storage
applications in fuels and transport. It has been shown that oxygen can be stored in
ceria-zirconia materials with alumina decorating the grain boundaries of ceria-zirconia
particles and acting as diffusion barrier [384, 563]. Similarly, it has also been shown
that hydrogen can be incorporated into crystalline zircon [492], which can be used for
adsorption applications in membranes, as discussed in Section 5.6.2. Metal-organic
frameworks containing zirconium are a growing class of materials of potential utility for
hydrogen and methane storage in vehicles [564–566]. CO2 capture is also a growing
research area due to the potentially negative consequences of an increased abundance of
this gas in the atmosphere: lithium zirconate has been proposed and researched as an
effective CO2 sorbent [567, 568], mesoporous alumina-zirconia-organosilica composites
also show promise for CO2 capture at ambient and elevated temperature [569], in
particular when organised as high effective surface nanosheets [570].
5.8.5 Sorption for catalysis
Sorption of gas molecules can be advantageous for catalytic processes that require the
presence of certain gas molecules, which can be fixed onto solid state catalysts for use
in the reactions. Examples of these are: the CO adsorption over zirconium oxide cluster
ions [571]; water adsorption into monoclinic zirconia [572]; NO, NO2 and other NOx
molecules adsorption over ceria-zirconia mixed oxides [573–576]. Acidic modulators
have been incorporated into zirconium-based metal-organic frameworks to improve
their structural integrity and thus use in gas sorption [577]. Research also shows the
potential of zirconium-based MIL-140 frameworks for CO2 adsorption, which could
have application in carbon capture technology [578].
5.8.6 Sorption of zirconium
In some cases, zirconium can be the adsorbed material rather than the sorbent. This could
be done to achieve its recovery or for doping novel materials. In a recent study, Candida
tropicalis was used to recover and remove zirconium from its aqueous solution [579].
Graphene has extraordinary conductive properties and so does zirconium; studies of its
diffusion on graphene show that it is in fact possible to combine them both for possible
applications [580].
5.9 Sensing
When the adsorption is highly reversible, it can be used for detection of the adsorbed
molecule. These adsorption mechanisms can be coupled with detection methods for
sensing. However, there are other sensing mechanisms that involve zirconium and do
not necessarily include adsorption. This section reports sensing applications in current
R&D in which zirconium compounds are used.
5.9 Sensing 77
5.9.1 High temperature and pressure
Zircon sand has been studied with various analytic techniques under several conditions,
particularly high temperatures and pressures. Raman spectroscopy has been used to
detect changes of pressure in high temperature silicate melt systems [581]. Zirconium
based electrodes perform adequately when used to measure chemicals or pH under high
temperature and in high pressure environments [582, 583].
5.9.2 Gas sensing
The electrochemistry of zirconia is affected when interactions with oxidising gases are
present, or when there is an electronic interaction with them. Thus, the electrochemical
detection of gases by zirconia is widely investigated and has built substantial knowledge
in the R&D literature [584]. Some of these investigations aim at detecting gases
in automotive exhausts [585], while stabilized zirconia and NiO electrodes have been
employed for the detection of NO2 [586], and mesoporous ceria-zirconia for the detection
of oxygen [587]. Oxygen sensors for steelmaking processes are fabricated using a MgO-
partially stabilised zirconia (MgO-PSZ) electrolyte tube [588]. The use of gas-sensors
with combined yttria-stabilised zirconia has also been suggested for detection of carbon
monoxide, hydrocarbons, nitrogen oxides, hydrogen, volatile organic compounds, and
ammonia [589–592]. UiO-66, a MOFs, can be deposited using only Zr foil as a source,
creating a sensor for dilute volatile organic compounds [593].
5.9.3 Relative humidity sensing
Sensing relative humidity reliably is difficult. A (PVA-PEG-PVP) blend as a matrix and

zirconium oxide nanoparticles as an additive was shown to vary its electrical resistivity
as a function of RH. This may lead to improved RH sensors [594].
5.9.4 Biosensing
Detection of biomolecules has also been possible with the use of zirconium com-
pounds. Ascorbic acid, uric acid, and dopamine have been detected with a phosphory-
lated zirconia-silica composite electrode and adsorbed methylene blue [595]. Zirconia
nanocomposites may also be used for vitamin B2 , B6 , and C effective detection [596],
with titania-zirconia nanocomposites utilised for urea detection [597]. Vitamin C de-
tection and phosphate content in blood serum has also been possible by nanostructured
zirconia platforms [598, 599]. Furthermore, silanized nanostructured zirconia within
a biosensing platform holds promise for the detection of oral cancer [600]. The use
of glucose oxidase/chitosan/α-zirconium phosphate ternary biocomposites have also
been suggested for biological sample estimation of glucose [601]. Zirconium sensing
platforms can be coupled with biomolecules such as enzymes for detection of specific
biochemical transformations [602]. Such is the case of ethanol oxidation by immo-
bilisation of enzymes and cofactors onto zirconium phosphate sensors [603]. Recent
developments indicate Zr-MOFs can be used in cancer clinical diagnosis [604].
78 Emerging R&D
5.9.5 Food and drink applications

ZrO2-based sorbents can be used in a quick and inexpensive analytical method to
determine the types and amounts of pesticides that may be present in milk [605].
Hydrogen peroxide can be detected using zirconium molybdate nanostructures [606].
DNA
The specificity of nanostructured zirconium based sensors can be extrapolated to a level
in which it is possible to detect complex structures or several types of molecules at the
same time. For instance, it has been possible to detect DNA hybridisation [607, 608], or
even DNA strings or genes corresponding to particular pathogens such as Mycobacterium
tuberculosis and E. coli [608–610]. Subsequent research demonstrated the fabricability
of biosensors with good performance with excellent selectivity and high stability [611].
Proteins
The detection of DNA is based on the phosphorus and phosphorylation sites, and
this can be taken even further to detect the interaction of genes and proteins or entire
proteomes. Microarrays for probing DNA-protein interactions have been fabricated
based on zirconium phosphonate [612], and zirconium phosphonate modified magnetic
nanoparticles have also been used for phosphoproteome analysis [613]. Similarly,
mapping of phosphorylation sites on protein complexes has been possible on acidified
zirconium oxide [614].
5.10 Nanomaterials, nanorods, nanostructures and nanofabrica-

tion
There is an increasing number of research groups investigating the properties and ad-
vantages of nanomaterials and nanostructures for different applications. Zirconium
compounds are not the exception and are commonly used for constructing these nanos-
tructures with novel properties.
5.10.1 Nanotubes and ordered arrays

Order at the nanoscale presents different material properties than disordered material
in the bulk. Ordered arrays can be formed by uniformly growing the material or
by degrading the mould ordering the material. For example, ordered arrays of lead
zirconium titanate have been grown on monolayers of latex nanospheres with the aim
of exploiting its ferroelectric properties [615]. Similarly, crystalline mesoporous walls
have been grown on PMMA nanosphere templates [616]. Chiral zirconia nanotubes
have been prepared with a potential of being applied in the fields of asymmetric catalysis
and chirality sensors [617]. Examples of directly grown zirconia tubes or arrays are
the anodisation of zirconium foils for in situ fabrication [618, 619]. The behaviour of
zircon-type LaVO4 nanorods has also been studied, identifying an irreversible transition
zircon to monazite phase under pressure treatment [620]. In addition, zirconium oxide
based electrocatalysts with multi-walled carbon nanotubes have been examined for use
5.10 Nanomaterials, nanorods, nanostructures and nanofabrication 79
as non-platinum cathodes for polymer electrolyte fuel cells [621].
5.10.2 Foils and thin films

Thin film structures are also common nanoconstructs that allow materials to be used in
various dimensions with different properties, along the film plane and across it. The
mechanism synthesis and characterisation of the formation of zirconium oxide thin films
has been investigated either by laser deposition or chemical deposition of the zirconium
oxide molecules [509,622,623]. Ultra-thin films are expected to have enhanced catalytic
properties [624]. It has recently been suggested a spray-coating process to manufacture
films with a mechanically robust coating that shows excellent gas barrier properties
[625]. These films can be then patterned with nanolithography to build circuits or other
useful structures [626]. Two dimensional nanomaterials such as α-zirconium phosphate
nanoplatelets have revealed to be effective as lubricant additives [627]. In addition,
lead sulfide nanoparticles embedded in a thin-film matrix of zirconium oxide have been
shown to have potential use in nanodosimetry of ionizing radiation [628].
5.10.3 Surface modification

Mesoporous walls and surfaces can be fabricated to tune the surface properties of the bulk
material and control its wettability (i.e. hydrophilicity and hydrophobicity). Engineered
nanostructures of zirconia have been constructed to control these properties, finding
use in suitable applications such as load-bearing [629]. Hollow mesoporous zirconia
nanospheres offer a promise for active corrosion protection coatings of metals and alloys
with self healing ability [630]. Surface modification of layered zirconium phosphates
can be used to tailor nanoparticles for varied specific applications [631].
5.10.4 Nanofibres
Ultra-thin fibres mixed with bulk materials have been found to strengthen the host
materials and therefore several research efforts have been directed towards the fabrication
and growth of these fibres. Particular attention has been paid to composite fibres such
as alumina-zirconium [632], zirconium carbide (produced by electrospinning) [633],
zirconium nitride (produced by nitridation of electrospun fibres) [634], and zirconia-
carbon plasma sintered composites [635]. Semiconducting nanobelts of zirconium oxide
have also been fabricated by thermal decomposition [636]. the crystalline polymorph of
CaO-doped zirconia nanofibres can be fully controlled, for tunable properties [637].
5.10.5 Self assemblies, organic templates, and hybrid materials

Nanofabrication techniques may have limitations for building complex structures of
certain zirconium compounds. Thus, researchers have approached biomimetic synthesis
or the use of organic templates or assemblies for producing such structures. The
complexity can go as far as the organism level: yeast, for example, has been used as
a biotemplate for producing mesoporous zirconium phosphate [638]. Self-assembled
triblock copolymers, hybrid polymers, metal-organic cages, or metal-organic frameworks
have also been used to produce such structures with a higher level of control and
80 Emerging R&D
stability [639–643].
5.10.6 Nanofluids
The heat resistance properties of zirconium compounds have been exploited for decades
in solid materials (see Section 3). Since nanoparticles can be included in liquid solutions
as colloids, the use and exploitation of the thermal resistance and strength of zirconium
particles has been considered for fluidic applications. Nanofluids of zirconia in water
have been tested for laminar heat transfer and viscous pressure loss in turbulent fluids,
as well as for their effect on surface wettability and critical heat flux [644–647]. Solvent-
free zirconia nanofluids have been developed as part of hybrid coatings that have the
potential to improve the efficiency of solar energy related devices [648].
5.10.7 Nanoparticles, nanopowders, nanocrystals and composites
Nanoparticles and nanopowders have proved to be useful for certain industrial applica-
tions and easy to incorporate in bulk materials due to their mass fabrication. Research
and development efforts have been directed towards the synthesis and crystallisation of
these particles and powders, particularly for zirconia. These methods include sol-gel
processes, hydrothermal methods, hot-air pyrolysis, or microwave sintering [649–654].
Nanoparticles can be functionalized or doped during the synthesis to enhance certain
properties: for example, Al2 O3 can be dispersed with zirconia for mass production of
hybrid particles; silane groups for multiple functionalisation can be also added to the
particles [655]; and hematite can be doped with zirconia for sensing enhancing [656].
Complex functionalisation of polymerisation can also be achieved during the mass
production of these particles: zirconium carbide preceramic polymers, light curable
ceramics and films, synthesis of particles on nanotubes for enhancing fracture tough-
ness, or PET-zirconium nanocomposite as fire retardants, are all examples of these
applications [657–661]. The use of yttria-stabilised zirconium dioxide nanoparticles
has been explored for the cleanup step in post-harvest pesticide residue analysis [662]
and the effect of hyperbranched polyester and zirconium slag nanoparticles on the
toughness of epoxy resin has been investigated, showing excellent impact and flexural
strength [663, 664]. Surface treatment with zirconia nanoparticles have also been shown
to improve the tensile and bonding properties of flax fibres [665]. Furthermore, cerium-
zirconium binary oxide nanoparticles have been shown to be effective for phosphate
adsorption [666]. Whereas the encapsulation of platinum nanoparticles in a zirconia
nanocage significantly increases platinum stability and activity, enhancing its use as a
catalyst in polymer electrolyte fuel cells [667]. Alternatively, graphene-based foams
can be reinforced with nanocrystalline zirconia, improving their oil adsorption capac-
ity [668]. Carbon nanotubes and carbon fibre hybrids with zirconia nanoparticles are of
particular interest due to their microstructural properties and strength [669–671]. The
uses of these hybrids extend to different application categories, as discussed in other
sections here, but the key research regarding their synthesis as mass producible particle
suspensions is going to have an impact in the future use of zirconium derivatives.
5.11 Optical materials 81
5.11 Optical materials
5.11.1 Waveguides, fibres and optical substrates
The dielectric properties of zirconium compounds have found applications based on the
direct use of the dielectric constants to guide light waves. Magneto-optical waveguides
made of cobalt ferrite nanoparticles embedded in a silica-zirconia matrix have been
successfully fabricated using the advantages of zirconia composite materials [672].
Similarly, erbium-activated silica-zirconia planar waveguides and other gratings have
been successfully used to manipulate the path of light at different frequencies and
bandwidths [673–675]. Another advantage of using hybrid zirconium materials is
the possibility of using them as optical substrates for cost effective photopatternable
organic-inorganic hybrids [676].
5.11.2 Nanostructured colour and dyeing
When the dielectric constant of a material changes in an ordered fashion at the nanoscale,
the apparent colour of the structure changes. This characteristic has been used to produce
tunable zirconia opals [677], which are photonic crystals with ordered nanostructures. A
similar effect is observed in liquid crystals, and zirconia nanoparticles have been used
to enhance their electro-optical performance and potential application in liquid crystal
devices (LCDs) [678, 679]. New developments focus on the scratch resistance of such
thin films, and important step in making them practical [680]. Sometimes the colour of
the materials is not coming from a photonic structure, but from the absorption of light
by the material itself. Zircon has a natural colouration which can be altered by ‘plasma
dissociation’ in the known Plasma Dissociated zircon (PDZ) material [681]. The ratio
of other elements in this process, and the physical conditions of the process itself, may
affect the crystallisation and, therefore, the final colouration [682–684]. These processes
and mixtures of elements with zirconium compounds can be controlled in such a way
that soluble pigments for particular applications can be produced, such as turquoise
V−ZrSiO4 [685,686]. A new development claims to significantly improve Zircon-based
heteromorphic encapsulation pigment efficiency [687].
5.11.3 Luminescence and emission
Another optical characteristic of zirconium compounds is the emission of radiation in

form of light when excited by other forms of energy. Examples of these achievements
are: green emitting phosphors based on zirconium oxide phosphate [688], luminescent
and photochemical ruthenium complex/zirconium phosphate hybrid assemblies [689],
luminescent Pr3+ doped yttria-stabilised zirconia nanopowders [690], luminescent lan-
thanide polyoxometalates based on zirconia matrices to titania [691], vapoluminiscent
and vapochromic platinum (II) complexes on layered zirconium phosphate [692], lumi-
nescence in Eu-doped nanopowders [693, 694], and even zirconia spheres with tunable
luminescence [695]. It has also been suggested that Dy3+ doped calcium zirconium
phosphate CaZr4 (PO4 )6 :Dy3+ could be a promising candidate for use in warm-white
LEDs [696], similarly blue-white light was produced from K2 ZrSi2 O7 :Eu 2+ [697].
82 Emerging R&D
5.12 Electronics and solid state devices

5.12.1 Memory devices
Zirconium nitride, zirconium oxide and other doped oxides have found applications in
the fabrication of memory cells and memory devices. For example, dielectric structures
containing zirconium oxide stacks have been used to fabricate flash memories [698],
and particular electronic effects can be observed in this type of materials by embedding
gold [699] and other elements [700]. Similarly, embedding ruthenium oxide nanocrystals
in zirconium and hafnium oxide capacitors has proved efficient for the fabrication of
electronic memories [701]. Resistive-switching memory cells can also be fabricated
using zirconium nitride [702].
5.12.2 Electrical gates and transistors

Dielectric zirconium compounds are playing an important role in the design of electrical
gate stacks, particularly zirconium oxides and germanium oxide doped zirconium oxides
[703]. The future of graphene electronics seems promising, and thus the use of zirconium
compounds. For example, zirconium oxide nanowires have been used as high dielectric
constant electric gates and have found applications for certain configurations using
graphene nanoribbons [704]. In addition, zirconium diboride shows promise for the use
in high temperature thin film electronics [705], zirconium oxide is suggested for use in
a semiconductor structure [706] and dysprosium-doped zirconium oxide thin films are
being assessed for use as dielectric in metal-insulator-metal electronic devices [707].
5.12.3 Superionic conductivity

The production of superionic conductors has represented a step towards the minia-
turisation of electronics to a level called ‘deep-sub voltage nanoelectronics’ [708].
Low-temperature superionic conductivity has been shown in strained yttria-stabilised
zirconia [709], thus zirconium compounds may play an important role in the future of
electronics.
5.13 Research trends

This section provides further insight into the potential impact of emerging research
and development areas by looking at the average number of citations per paper for all
references included in each research topic presented in Section 4 (Figure 5.2, Figure 5.3
).
A few important comments need to be made about this analysis:
• The number of citations can vary substantially with time and more recent papers
will obviously have fewer citations. Additionally, the publication type may affect
the number of citations (e.g. a book will get more citations than a patent because
of the generality of its topics). References in Section 4 of this report include
papers, patents and books from the last 7 years only.
• The number of citations per paper was extracted from a scholar search engine and
reflects all data available until 10 August 2015. However, the choice of references
included in this report was inevitably selective, based on the criteria explained in
the introduction of Section 4.
• The classification of each paper based on the maturity level of their application
and their relation to higher level research trends was performed according to the
authors’ criteria and does not necessarily represent the absolute research trends
about zirconium and its derivatives in the future. The data shown here applies
only to the references used in this study.
5.13.1 Number of citations per research topic

The average number of citations per paper for all references included in each research
topic presented in Section 4 are given in Figure 5.2
84 Emerging R&D
Waveguides, fibres and optical substrates

Memory devices
Catalysis
Bioconjugation
Luminescence and emission
Remediation applications
Gas sensing
Gas catalysis
Bioimaging
fuel cells
Sorption of zirconium
Self assemblies, organic templates, and hybrid materials
Flame retardants
Foils and thin films
Gas storage and adsorption
TiO2 coatings
Inorganic catalysis
Biomedical applications
Drug delivery and pharmaceutical formulations
Nanomaterials, nanorods, nanostructures and nanofabrication
Proton Exchange Membranes
Coating technologies
Sorption for catalysis
Nuclear industry
Organic catalysis
Electronics and solid state devices
Nanoparticles, nanopowders, nanocrystals and composites
Ceramics with tunable properties
Ceramic surfaces
Nanostructured colour and dyeing
Foundry sands and coatings
Traditional ceramics
Ultra−High temperature and high−wear applications
Fabrics and textiles
Composite and alloy fabrication technologies
Dental parts
Refractories
Water, food and biological applications
Biosensing
3D printing consumables and photo−polymerizable ceramics
Paints and inks
Radioactive applications
Electrical gates and transistors
Implants
Zirconia and zirconium metal
Adsorption and immobilisation
Ion transport and conductivity in zirconia
Smart coatings with enhanced properties
Grinding media and grinding technologies
dental implants
Nanofibres
Surface modification
Advanced ceramics
Nanotubes and ordered arrays
Biocompatibility
Shape memory alloy
Optical materials
Solid Oxide Fuel Cells
Concrete
Solar cells
Glass
0 2 4 6 8
Geometric mean number of citations per year (2015-2018)
Figure 5.2: Geometric mean number of citation of citations per research topic in the
last 4 years — All categories (X-axis: geometric mean number of citations per paper for
all references in each category).
Adsorption and immobilisation

Optical materials
Electronics and solid state devices
Refractories
Nanomaterials, nanorods, nanostructures and nanofabrication
Nuclear industry
Fuel cells and batteries
Biomedical applications
Advanced coatings and functional materials
Basic research
Sensing
Advanced ceramics
Catalysis
Casting and moulding
0 1 2 3 4
geometric mean number of citations per year
Figure 5.3: Geometric mean number of citation of citations per research topic in the
last 4 years — Main categories (X-axis: geometric mean number of citations per paper
for all references in each category).
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Technical handbook on

zirconium and zirconium

P UBLISHED BY Z IRCON I NDUSTRY A SSOCIATION

ZIRCON - ASSOCIATION . ORG

1.2 Mineralogy and deposits 10

1.3 Mining and processing 12

1.4 World production, reserves and market 18

1.5 Industry structure and consumption patterns 19

2.2 Zirconium Compounds 29

3.5 Major industrial zirconia and zirconium chemical applications 44

3.6 Minor chemical applications 49

4 Emerging R&D – highlights . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

4.2 Solar cells 52

4.3 Shape memory alloys 54

5.2 Advanced ceramics 62

5.3 Casting and moulding 64

5.4 Grinding media and grinding technologies 65

5.5 Biomedical applications 65

5.7 Fuel cells and batteries 73

5.8 Adsorption and immobilisation 74

5.10 Nanomaterials, nanorods, nanostructures and nanofabrication 78

5.11 Optical materials 81

5.12 Electronics and solid state devices 82

1.1 Zirconium, zircon and zirconia definition

1.2 Mineralogy and deposits

Mineral Chemical formula Specific Hardness ZrO2

data per country (data extracted from [6]

1.3 Mining and processing

1.3 Mining and processing 13

Various Dry Mining Process Flows

Simple Mining Unit:

Quartz Tails Solar Evap Dam

Magnetic Separation Tails Dam in mine void

Ilmenite Tails Concentrators

a secondary concentration process or mineral separation plant. Residual sand is pumped

1.3.2 Zirconia and zirconium metal

SiO2/AlSiO5 Wet Gravity

Electrostatic Zircon Leach (opt config)

(a) Fusion with calcium sulphate

1.4 World production, reserves and market

Zr mine production Zr reserves

Total 1,270 1,620 1,420 1,510 1,540 1,520 1,330 78,000

1.4.2 Market behaviour and dynamic

1.5 Industry structure and consumption patterns

FOUNDRY REFRACTORIES ABRASIVES CERAMIC GRES ZIRCONIA ZIRCONIUM CERAMIC ZIRCONIUM

Figure 1.11: Detailed structure of the zircon industry (Courtesy of TZMI).

Atomic weight 91.22

Standard state Solid at 298K (25◦ C)

CAS Registry ID 7440-67-7

Group in Periodic Table IVB

Colour Silvery white

Oxidation numbers +4, +3, +2, 0, -2

Molar volume 14.02 cm3

Melting point 1852 ± 10◦ C

Boiling point 4409◦ C

Allotropic transition 862 ± 5◦ C

Thermal expansion 6.39x10−6 / ◦ C k c-axis

Linear coefficient 5.64x10−6 / ◦ C ⊥ c-axis

Continued on next page

Table 2.1 – continued from previous page

Specific heat 0.2759 J/g-◦ C [at 25◦ C]

Molar heat capacity Zr(α)Cp = 6.83 + 1.12x10−3 T

Zr(β )Cp = 7.27(1135 − 1400K)