Titanium dioxide

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Titanium dioxide
Titanium(IV) oxide
IUPAC name Titanium dioxide
Titanium(IV) oxide
Other names Titania
CAS number 13463-67-7
PubChem 26042
KEGG C13409
RTECS number XR2775000
ChemSpider 24256
Molecular formula TiO2
Molar mass 79.866 g/mol
Appearance White solid
Density 4.23 g/cm3
Melting point

1843 °C

Boiling point

2972 °C

Refractive index (nD) 2.488 (anatase)
2.583 (brookite)
2.609 (rutile)
EU classification Not listed
NFPA 704
NFPA 704
Flash point Non-flammable
Related compounds
Other cations Zirconium dioxide
Hafnium dioxide
Related titanium oxides Titanium(II) oxide
Titanium(III) oxide
Titanium(III,IV) oxide
Related compounds Titanic acid
 Plantilla:Cross(what is this?)  (verify)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO2. When used as a pigment, it is called titanium white, Pigment White 6, or CI 77891. Generally it comes in two different forms, rutile and anatase. It has a wide range of applications, from paint to sunscreen to food colouring. When used as a food colouring, it has E number E171.

OccurrenceEditar sección

Titanium dioxide occurs in nature as well-known minerals rutile, anatase and brookite, and additionally as two high pressure forms, a monoclinic baddeleyite-like form and an orthorhombic α-PbO2-like form, both found recently at the Ries crater in Bavaria.[1][2] The most common form is rutile,[3] which is also the equilibrium phase at all temperatures.[4] The metastable anatase and brookite phases both convert to rutile upon heating.[3][5] Rutile, anatase and brookite all contain six coordinated titanium.

Titanium dioxide has eight modifications – in addition to rutile, anatase and brookite there are three metastable forms produced synthetically (monoclinic, tetragonal and orthorombic), and five high pressure forms (α-PbO2-like, baddeleyite-like, cotunnite-like, orthorhombic OI, and cubic phases):

Form Crystal system Synthesis
rutile tetragonal
anatase tetragonal
brookite orthorhombic
TiO2(B)[6] monoclinic Hydrolysis of K2Ti4O9 followed by heating
TiO2(H), hollandite-like form[7] tetragonal Oxidation of the related potassium titanate bronze, K0.25TiO2
TiO2(R), ramsdellite-like form[8] orthorhombic Oxidation of the related lithium titanate bronze Li0.5TiO2
TiO2(II)-(α-PbO2-like form)[9] orthorhombic
baddeleyite-like form, (7 coordinated Ti)[10] monoclinic
TiO2 -OI[11] orthorhombic
cubic form[12] cubic P > 40 GPa, T > 1600 °C
TiO2 -OII, cotunnite(PbCl2)-like[13] orthorhombic P > 40 GPa, T > 700 °C

The cotunnite-type phase was claimed by L. Dubrovinsky and co-authors to be the hardest known oxide with the Vickers hardness of 38 GPa and the bulk modulus of 431 GPa (i.e. close to diamond's value of 446 GPa) at atmospheric pressure.[13] However, later studies came to different conclusions with much lower values for both the hardness (7–20 GPa, which makes it softer than common oxides like corundum Al2O3 and rutile TiO2) [14] and bulk modulus (~300 GPa) .[15][16]

The naturally occurring oxides can be mined and serve as a source for commercial titanium. The metal can also be mined from other minerals such as ilmenite or leucoxene ores, or one of the purest forms, rutile beach sand. Star sapphires and rubies get their asterism from rutile impurities present in them.[17]

Titanium dioxide (B) is found as a mineral in magmatic rocks and hydrothermal veins, as well as weathering rims on perovskite. TiO2 also forms lamellae in other minerals [18]

Spectral lines from titanium oxide are prominent in class M stars, which are cool enough to allow molecules of this chemical to form.

ProductionEditar sección

Crude titanium dioxide is purified via converting to titanium tetrachloride in the chloride process. In this process, the crude ore (containing at least 70% TiO2) is reduced with carbon, oxidized with chlorine to give titanium tetrachloride; i.e., carbothermal chlorination. This titanium tetrachloride is distilled, and re-oxidized in a pure oxygen flame or plasma at 1500–2000 K to give pure titanium dioxide while also regenerating chlorine.[19] Aluminium chloride is often added to the process as a rutile promotor; the product is mostly anatase in its absence.

Another widely used process utilizes ilmenite as the titanium dioxide source, which is digested in sulfuric acid. The by-product iron(II) sulfate is crystallized and filtered-off to yield only the titanium salt in the digestion solution, which is processed further to give pure titanium dioxide. Another method for upgrading ilmenite is called the Becher Process. One method for the production of titanium dioxide with relevance to nanotechnology is solvothermal Synthesis of titanium dioxide.

Titanium oxide nanotubes, SEM image.
KidomaAñadida por Kidoma

NanotubesEditar sección

Anatase can be converted by hydrothermal synthesis to delaminated anatase inorganic nanotubes[20] and titanate nanoribbons which are of potential interest as catalytic supports and photocatalysts. In the synthesis, anatase is mixed with 10 M sodium hydroxide and heated at 130 °C for 72 hours. The reaction product is washed with dilute hydrochloric acid and heated at 400 °C for another 15 hours. The yield of nanotubes is quantitative and the tubes have an outer diameter of 10 to 20 nm and an inner diameter of 5 to 8 nm and have a length of 1 μm. A higher reaction temperature (170 °C) and less reaction volume gives the corresponding nanowires.[21]

Another process for synthesizing TiO2 is through Anodization in an electrolytic solution. When anodized in a 0.5 weight percent HF solution for 20 minutes, well-aligned titanium oxide nanotube arrays can be fabricated an average tube diameter of 60 nm and length of 250 nm. Based on X-ray Diffraction, nanotubes grown through anodization are amorphous. [22]

ApplicationsEditar sección

PigmentEditar sección

Titanium dioxide is the most widely used white pigment because of its brightness and very high refractive index (n = 2.7), in which it is surpassed only by a few other materials. Approximately 4 million tons of pigmentary TiO2 are consumed annually worldwide. When deposited as a thin film, its refractive index and colour make it an excellent reflective optical coating for dielectric mirrors and some gemstones like "mystic fire topaz". TiO2 is also an effective opacifier in powder form, where it is employed as a pigment to provide whiteness and opacity to products such as paints, coatings, plastics, papers, inks, foods, medicines (i.e. pills and tablets) as well as most toothpastes. In paint, it is often referred to offhandedly as "the perfect white", "the whitest white", or other similar terms. Opacity is improved by optimal sizing of the titanium dioxide particles.

In ceramic glazes titanium dioxide acts as an opacifier and seeds crystal formation.

Titanium dioxide is often used to whiten skimmed milk; this has been shown statistically to increase skimmed milk's palatability.[23]

Titanium dioxide is used to mark the white lines on the tennis courts of the All England Lawn Tennis and Croquet Club, best known as the venue for the annual grand slam tennis tournament The Championships, Wimbledon.[24]

The exterior of the Saturn V rocket was painted with titanium dioxide; this later allowed astronomers to determine that J002E3 was the S-IVB stage from Apollo 12 and not an asteroid.

Sunscreen and UV absorberEditar sección

In cosmetic and skin care products, titanium dioxide is used as a pigment, sunscreen and a thickener. It is also used as a tattoo pigment and in styptic pencils. Titanium dioxide is produced in varying particle sizes, oil and water dispersible, and with varying coatings for the cosmetic industry. This pigment is used extensively in plastics and other applications for its UV resistant properties where it acts as a UV absorber, efficiently transforming destructive UV light energy into heat.

Titanium dioxide is found in almost every sunscreen with a physical blocker because of its high refractive index, its strong UV light absorbing capabilities and its resistance to discolouration under ultraviolet light. This advantage enhances its stability and ability to protect the skin from ultraviolet light. Sunscreens designed for infants or people with sensitive skin are often based on titanium dioxide and/or zinc oxide, as these mineral UV blockers are believed to cause less skin irritation than other UV absorbing chemicals. The titanium dioxide particles used in sunscreens have to be coated with silica or alumina, because titanium dioxide creates radicals in the photocatalytic reaction. These radicals are carcinogenic, and could damage the skin.

PhotocatalystEditar sección

Titanium dioxide nanofiber spiral
TiO fibers and spirals.
KidomaAñadida por Kidoma

Titanium dioxide, particularly in the anatase form, is a photocatalyst under ultraviolet (UV) light. Recently it has been found that titanium dioxide, when spiked with nitrogen ions or doped with metal oxide like tungsten trioxide, is also a photocatalyst under either visible or UV light.[25] The strong oxidative potential of the positive holes oxidizes water to create hydroxyl radicals. It can also oxidize oxygen or organic materials directly. Titanium dioxide is thus added to paints, cements, windows, tiles, or other products for its sterilizing, deodorizing and anti-fouling properties and is used as a hydrolysis catalyst. It is also used in dye-sensitized solar cells, which are a type of chemical solar cell (also known as a Graetzel cell).

The photocatalytic properties of titanium dioxide were discovered by Akira Fujishima in 1967[26] and published in 1972.[27] The process on the surface of the titanium dioxide was called the Honda-Fujishima effect.[26] Titanium dioxide has potential for use in energy production: as a photocatalyst, it can carry out hydrolysis; i.e., break water into hydrogen and oxygen. Were the hydrogen collected, it could be used as a fuel. The efficiency of this process can be greatly improved by doping the oxide with carbon.[28] Further efficiency and durability has been obtained by introducing disorder to the lattice structure of the surface layer of titanium dioxide nanocrystals, permitting infrared absorption.[29]

Titanium dioxide can also produce electricity when in nanoparticle form. Research suggests that by using these nanoparticles to form the pixels of a screen, they generate electricity when transparent and under the influence of light. If subjected to electricity on the other hand, the nanoparticles blacken, forming the basic characteristics of a LCD screen. According to creator Zoran Radivojevic, Nokia has already built a functional 200-by-200-pixel monochromatic screen which is energetically self-sufficient.

In 1995 Fujishima and his group discovered the superhydrophilicity phenomenon for titanium dioxide coated glass exposed to sun light.[26] This resulted in the development of self-cleaning glass and anti-fogging coatings.

TiO2 incorporated into outdoor building materials, such as paving stones in noxer blocks or paints, can substantially reduce concentrations of airborne pollutants such as volatile organic compounds and nitrogen oxides.[30]

A photocatalytic cement that uses titanium dioxide as a primary component, produced by Italcementi Group, was included in Time's Top 50 Inventions of 2008.[31]

TiO2 offers great potential as an industrial technology for detoxification or remediation of wastewater due to several factors.

  1. The process occurs under ambient conditions very slowly; direct UV light exposure increases the rate of reaction.
  2. The formation of photocyclized intermediate products, unlike direct photolysis techniques, is avoided.
  3. Oxidation of the substrates to CO2 is complete.
  4. The photocatalyst is inexpensive and has a high turnover.
  5. TiO2 can be supported on suitable reactor substrates.

Electronic data storage mediumEditar sección

In 2010, researchers at the University of Tokyo, Japan have created a 25 terabyte titanium oxide-based disc.[32]

Other applicationsEditar sección

Synthetic single crystals of TiO2

Health and safetyEditar sección

Plantilla:POV-check Titanium dioxide is incompatible with strong reducing agents and strong acids.[38] Violent or incandescent reactions occur with molten metals that are very electropositive, e.g. aluminium, calcium, magnesium, potassium, sodium, zinc and lithium.[39]

Titanium dioxide accounts for 70% of the total production volume of pigments worldwide. It is widely used to provide whiteness and opacity to products such as paints, plastics, papers, inks, foods, and toothpastes. It is also used in cosmetic and skin care products, and it is present in almost every sunblock, where it helps protect the skin from ultraviolet light.

Many sunscreens use nanoparticle titanium dioxide (along with nanoparticle zinc oxide) which does get absorbed into the skin.[40][41] The effects on human health are not yet well understood.[42]

Titanium dioxide dust, when inhaled, has been classified by the International Agency for Research on Cancer (IARC) as an IARC Group 2B carcinogen possibly carcinogenic to humans.[43] The findings of the IARC are based on the discovery that high concentrations of pigment-grade (powdered) and ultrafine titanium dioxide dust caused respiratory tract cancer in rats exposed by inhalation and intratracheal instillation.[44] The series of biological events or steps that produce the rat lung cancers (e.g. particle deposition, impaired lung clearance, cell injury, fibrosis, mutations and ultimately cancer) have also been seen in people working in dusty environments. Therefore, the observations of cancer in animals were considered, by IARC, as relevant to people doing jobs with exposures to titanium dioxide dust. For example, titanium dioxide production workers may be exposed to high dust concentrations during packing, milling, site cleaning and maintenance, if there are insufficient dust control measures in place. However, the human studies conducted so far do not suggest an association between occupational exposure to titanium dioxide and an increased risk for cancer. The safety of the use of nano-particle sized titanium dioxide, which can penetrate the body and reach internal organs, has been criticized.[45] Studies have also found that titanium dioxide nanoparticles cause genetic damage in mice.[46]

See alsoEditar sección

ReferencesEditar sección

  1. El, Goresy; Chen, M; Dubrovinsky, L; Gillet, P; Graup, G (2001). "An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater.". Science 293 (5534): 1467–70. doi:10.1126/science.1062342. PMID 11520981. 
  2. El Goresy, Ahmed; Chen, Ming; Gillet, Philippe; Dubrovinsky, Leonid; Graup, GüNther; Ahuja, Rajeev (2001). "A natural shock-induced dense polymorph of rutile with α-PbO2 structure in the suevite from the Ries crater in Germany". Earth and Planetary Science Letters 192 (4): 485. doi:10.1016/S0012-821X(01)00480-0. 
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  4. Jamieson J, Olinger B (1969). "Pressure Temperature Studies of Anatase, Brookite, Rutile and TiO2 II: A discussion". Mineralogical Notes 54: 1477. 
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  7. Latroche, M; Brohan, L; Marchand, R; Tournoux, (1989). "New hollandite oxides: TiO2(H) and K0.06TiO2". Journal of Solid State Chemistry 81 (1): 78–82. doi:10.1016/0022-4596(89)90204-1. 
  8. J. Akimoto, Y. Gotoh, Y. Oosawa, N. Nonose, T. Kumagai, K. Aoki, H. Takei (1994). "Topotactic Oxidation of Ramsdellite-Type Li0.5TiO2, a New Polymorph of Titanium Dioxide: TiO2(R)". Journal of Solid State Chemistry 113 (1): 27–36. doi:10.1006/jssc.1994.1337. 
  9. P. Y. Simons, F. Dachille (1967). "The structure of TiO2II, a high-pressure phase of TiO2". Acta Crystallographica 23 (2): 334–336. doi:10.1107/S0365110X67002713. 
  10. Sato H. , Endo S, Sugiyama M, Kikegawa T, Shimomura O, Kusaba K (1991). "Baddeleyite-Type High-Pressure Phase of TiO2". Science 251 (4995): 786–788. doi:10.1126/science.251.4995.786. PMID 17775458. 
  11. Dubrovinskaia N A, Dubrovinsky L S., Ahuja R, Prokopenko V B., Dmitriev V., Weber H.-P., Osorio-Guillen J. M., Johansson B (2001). "Experimental and Theoretical Identification of a New High-Pressure TiO2 Polymorph". Phys. Rev. Lett. 87 (27 Pt 1): 275501. doi:10.1103/PhysRevLett.87.275501. PMID 11800890. 
  12. Mattesini M, de Almeida J. S., Dubrovinsky L., Dubrovinskaia L, Johansson B., Ahuja R. (2004). "High-pressure and high-temperature synthesis of the cubic TiO2 polymorph". Phys. Rev. B 70 (21): 212101. doi:10.1103/PhysRevB.70.212101. 
  13. 13,0 13,1 Dubrovinsky, LS; Dubrovinskaia, NA; Swamy, V; Muscat, J; Harrison, NM; Ahuja, R; Holm, B; Johansson, B (2001). "Materials science: The hardest known oxide". Nature 410 (6829): 653–654. doi:10.1038/35070650. PMID 11287944. 
  14. Oganov A.R., Lyakhov A.O. (2010). "Towards the theory of hardness of materials". J. of Superhard Materials 32 (3): 143–147. doi:10.3103/S1063457610030019. 
  15. Y. Al-Khatatbeh, K. K. M. Lee and B. Kiefer (2009). "High-pressure behavior of TiO2 as determined by experiment and theory". Phys. Rev. B 79 (13): 134114. doi:10.1103/PhysRevB.79.134114. 
  16. Nishio-Hamane D., Shimizu A., Nakahira R., Niwa K., Sano-Furukawa A., Okada T., Yagi T., Kikegawa T. (2010). "The stability and equation of state for the cotunnite phase of TiO2 up to 70 GPa". Phys. Chem. Minerals 37 (3): 129–136. doi:10.1007/s00269-009-0316-0. 
  17. Emsley, John (2001). Nature's Building Blocks: An A–Z Guide to the Elements. Oxford: Oxford University Press. pp.  451–53. ISBN 0-19-850341-5. 
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  19. Titanium Dioxide Manufacturing Processes. Millennium Inorganic Chemicals. Archived from the original on 2007-08-14. Retrieved on 2007-09-05.
  20. Mogilevsky, Gregory; Chen, Qiang; Kleinhammes, Alfred; Wu, Yue (2008). "The structure of multilayered titania nanotubes based on delaminated anatase". Chemical Physics Letters 460 (4–6): 517–520. doi:10.1016/j.cplett.2008.06.063. 
  21. Graham Armstrong, A. Robert Armstrong, Jesús Canales and Peter G. Bruce (2005). "Nanotubes with the TiO2-B structure". Chemical Communications (19): 2454–6. doi:10.1039/B501883H. PMID 15886768. 
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  40. "Manufactured Nanomaterials and Sunscreens: Top Reasons for Precaution", August 19, 2009. URL consultato il April 12, 2010.
  41. "Nano-tech sunscreen presents potential health risk", ABC News, December 18, 2008. URL consultato il April 12, 2010.
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  45. "Suncream may be linked to Alzheimer's disease, say experts", Daily Mail, 24 August 2009. URL consultato il 2009-08-25.
  46. "Nanoparticles Used in Common Household Items Cause Genetic Damage in Mice", 17 November 2009. URL consultato il 2009-11-17.

External linksEditar sección

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