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Titanium dioxide

Titanium dioxide
Titanium dioxide

Identifiers CAS number PubChem ChemSpider UNII KEGG ChEBI ChEMBL RTECS number Jmol-3D images 13463-67-7 26042 24256
[2] [3] [4] [1]

15FIX9V2JP C13409




CHEMBL1201136 XR2775000 Image 1 Properties


Molecular formula Molar mass Appearance Odor Density Melting point Boiling point Solubility in water Refractive index (n )

TiO 2 79.866 g/mol White solid odorless 4.23 g/cm3 1843 C 2972 C insoluble 2.488 (anatase) 2.583 (brookite) 2.609 (rutile)

Titanium dioxide

Thermochemistry Std enthalpy of formation fHo298 Standard molar entropy So298 945kJmol1

50Jmol1K1 Hazards


MSDS EU classification NFPA 704

ICSC 0338 Not listed


Flash point

Non-flammable Related compounds

Other cations Related titanium oxides

Zirconium dioxide Hafnium dioxide Titanium(II) oxide Titanium(III) oxide Titanium(III,IV) oxide Titanic acid
(verify) [10]

Related compounds

(what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25C, 100kPa)

Infobox references

Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO 2. When used as a pigment, it is called titanium white, Pigment White 6, or CI 77891. Generally it is sourced from ilmenite, 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.

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 -PbO2-like form, both found recently at the Ries crater in Bavaria.[11][12] It is mainly sourced from ilmenite ore. This is the most wide spread form of titanium dioxide-bearing ore around the world. Rutile is the next most abundant and contains around 98% titanium dioxide in the ore. The metastable anatase and brookite phases convert to rutile upon heating.[] Titanium dioxide has eight modifications in addition to rutile, anatase, and brookite three metastable phases can be produced synthetically (monoclinic, tetragonal and orthorombic), and five high pressure forms (-PbO2-like, baddeleyite-like, cotunnite-like, orthorhombic OI, and cubic phases):

Titanium dioxide

Form rutile anatase brookite TiO2(B) [13] [14] [15]

Crystal system tetragonal tetragonal orthorhombic monoclinic tetragonal orthorhombic orthorhombic [17] monoclinic orthorhombic cubic [] orthorhombic P > 40 GPa, T > 1600 C P > 40 GPa, T > 700 C


Hydrolysis of K2Ti4O9 followed by heating Oxidation of the related potassium titanate bronze, K0.25TiO2 Oxidation of the related lithium titanate bronze Li0.5TiO2

TiO2(H), hollandite-like form

TiO2(R), ramsdellite-like form TiO2(II)-(-PbO2-like form)


baddeleyite-like form, (7 coordinated Ti) TiO2 -OI [18] [19]

cubic form

TiO2 -OII, cotunnite(PbCl2)-like

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.[] However, later studies came to different conclusions with much lower values for both the hardness (720 GPa, which makes it softer than common oxides like corundum Al2O3 and rutile TiO2)[20] and bulk modulus (~300 GPa).[21][22] The oxides are commercially important ores of 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.[] 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.[23] Spectral lines from titanium oxide are prominent in class M stars, which are cool enough to allow molecules of this chemical to form.

The production method depends on the feedstock. The most common method for the production of titanium dioxide utilizes ilmenite. Ilmenite is mixed with sulfuric acid. This reacts to remove the iron oxide group in the ilmenite. The by-product iron(II) sulfate is crystallized and filtered-off to yield only the titanium salt in the digestion solution. This product is called synthetic rutile. This is further processed in a similar way to rutile to give the titanium dioxide product. Synthetic rutile and titanium slags are made especially for titanium dioxide production.[] The use of ilminite ore usually only produces pigment grade titanium dioxide. Another method for the production of synthetic rutile from ilminite utilizes the Becher Process. Rutile is the second most abundant mineral sand. Rutile found in primary rock cannot be extracted hence the deposits containing rutile sand can be mined meaning a reduced availability to the high concentration ore. Crude titanium dioxide (in the form of rutile or synthetic rutile) 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 15002000 K to give pure titanium dioxide while also regenerating chlorine.[24] Aluminium chloride is often added to the process as a rutile promotor; the product is mostly anatase in its absence.

Titanium dioxide The preferred raw material for the chloride process is natural rutile because of its high titanium dioxide content.[] One method for the production of titanium dioxide with relevance to nanotechnology is solvothermal Synthesis of titanium dioxide.

Anatase can be converted by hydrothermal synthesis to delaminated anatase inorganic nanotubes[25] and titanate nanoribbons which are of potential interest as catalytic supports and photocatalysts. In the synthesis, anatase is mixed with 10M sodium hydroxide and heated at 130C for 72 hours. The reaction product is washed with dilute hydrochloric acid and heated at 400C for another 15 hours. The yield of nanotubes is quantitative and the tubes have an outer diameter of 10 to 20nm and an inner diameter of 5 to 8nm and have a length of 1m. A higher reaction temperature (170C) and less reaction volume gives the corresponding nanowires.[26]

Titanium oxide nanotubes, SEM image.

Another process for synthesizing TiO 2 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 60nm and length of 250nm. Based on X-ray Diffraction, nanotubes grown through anodization are amorphous.[27]

The most important application areas are paints and varnishes as well as paper and plastics: They process about 80% of the world's titanium dioxide consumption. Other pigment applications like printing inks, fibers, rubber, cosmetic products and foodstuffs account for another 8%. The rest is used in other applications, for instance the production of technical pure titanium, glass and glass ceramics, electrical ceramics, catalysts, electric conductors and chemical intermediates.[28]

Titanium dioxide is the most widely used white pigment because of its brightness and very high refractive index, in which it is surpassed only by a few other materials. Approximately 4.6 million tons of pigmentary TiO2 are consumed annually worldwide, and this number is expected to increase as consumption continues to rise.[] 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. Some grades of titanium based pigments as used in sparkly paints, plastics, finishes and pearlescent cosmetics are man made pigments whose particles have two or more layers of various oxides -amongst which we have often titanium dioxide, iron oxide or alumina , in order to have glittering, iridescent and or pearlescent effects similar to a certain extent to crushed mica alone or guanine based products, but in addition to these effects a limited color change is possible in certain formulations depending on how and at which angle the finished product is illuminated and the thickness of the oxide layer in the pigment particle : one or more colours appear by reflection while the other tones appear due to interference of the transparent titanium dioxide layers.[29] These pigments are coined "interference pigments".[30] In some products, the layer of titanium dioxide is grown in conjunction with iron oxide by calcination of titanium salts (sulfates, chlorates) around 800 C[31] or other industrial deposition methods

Titanium dioxide such as chemical vapour deposition on substrates which are natural or synthetic mica platelets or even silicon dioxide crystal platelets of no more than 50 microns in diameter.[32] The iridescent effect in these titanium oxide particles (which are only partly natural ) is unlike the opaque effect obtained with usual ground titanium oxide pigment obtained by mining, in which case only a certain diameter of the particle is considered and the effect is due only to scattering. In ceramic glazes titanium dioxide acts as an opacifier and seeds crystal formation. Titanium dioxide has been shown statistically to increase skimmed milk's whiteness, increasing skimmed milk's sensory acceptance score.[33] Titanium dioxide is used to mark the white lines of some tennis courts.[34] 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 blocking pigments in the industry 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 in certain grades for the cosmetic industry. 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. Nano-scaled titanium dioxide particles are primarily used in sun screen lotion because they scatter visible light less than titanium dioxide pigments while still providing UV protection.[] 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. This pigment is used extensively in plastics and other applications not only as a white pigment or an opacifier but also for its UV resistant properties where the powder disperses the light unlike organic UV absorbers and reduces UV damage, due mostly to the extremely high refractive index of the particles.[35] Certain polymers used in coatings for concrete[36] or those used to impregnate concrete as a reinforcement are sometimes charged with titanium white pigment for UV shielding in the construction industry, but it only delays the oxidative photodegradation of the polymer in question, which is said to "chalk" as it flakes off due to lowered impact strength and may crumble after years of exposure in direct sunlight if UV stabilizers have not been included .

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.[] 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).

TiO2 fibers and spirals.

The photocatalytic properties of titanium dioxide were discovered by Akira Fujishima in 1967[37] and published in 1972.[38] The process on the surface of the titanium dioxide was called the Honda-Fujishima effect.[37] Titanium

Titanium dioxide 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.[39] 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.[40] 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.[37] 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[41] or paints, can substantially reduce concentrations of airborne pollutants such as volatile organic compounds and nitrogen oxides.[42] 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.[43] Attempts have been made to photocatalytically mineralize pollutants (to convert into CO2 and H2O) in waste water.[] TiO2 offers great potential as an industrial technology for detoxification or remediation of wastewater due to several factors:[44] 1. The process uses natural oxygen and sunlight and thus occurs under ambient conditions; it is wavelength selective and is accelerated by UV light. 2. The photocatalyst is inexpensive, readily available, non-toxic, chemically and mechanically stable, and has a high turnover. 3. The formation of photocyclized intermediate products, unlike direct photolysis techniques, is avoided. 4. Oxidation of the substrates to CO2 is complete. 5. TiO2 can be supported on suitable reactor substrates.

Electronic data storage medium

In 2010, researchers at the University of Tokyo, Japan have created a crystal form of titanium oxide with particles 5 to 20 nanometers that can be switched between two states with light. Use of the 5nm particles could theoretically lead to a 25 TB storage disc.[45]

Other applications

Titanium dioxide

Titanium dioxide in solution or suspension can be used to cleave protein that contains the amino acid proline at the site where proline is present. This breakthrough in cost-effective protein splitting took place at Arizona State University in 2006.[46] Titanium dioxide is also used as a material in the memristor, a new electronic circuit element. It can be employed for solar energy conversion based on dye, polymer, or quantum dot sensitized nanocrystalline TiO2 solar cells using conjugated polymers as solid electrolytes.[47] Synthetic single crystals and films of TiO2 are used as a semiconductor,[48] and also in Bragg-stack style dielectric mirrors due to the high refractive index of TiO2 (2.52.9).[49][50]
Synthetic single crystals of TiO2, ca. 23 mm in size, cut from a larger plate.

Health and safety

Titanium dioxide is incompatible with strong reducing agents and strong acids.[] Violent or incandescent reactions occur with molten metals that are very electropositive, e.g. aluminium, calcium, magnesium, potassium, sodium, zinc and lithium.[] 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, despite reports of potential health risks,[51] is not actually absorbed through the skin.[52] Other effects of titanium dioxide nanoparticles on human health are not well understood.[53] Nevertheless, allergy to topical application has been confirmed.[54] Titanium dioxide dust, when inhaled, has been classified by the International Agency for Research on Cancer (IARC) as an IARC Group 2B carcinogen, meaning it is possibly carcinogenic to humans.[] 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.[55] 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.[56] Studies have also found that titanium dioxide nanoparticles cause inflammatory response and genetic damage in mice.[57][58] The mechanism by which TiO 2 may cause cancer is unclear. Molecular research suggests that cell cytotoxicity due to TiO 2 results from the interaction between TiO [59] 2 nanoparticles and the lysosomal compartment, independently of the known apoptotic signalling pathways. There is some evidence the rare disease Yellow nail syndrome may be caused by titanium, either implanted for medical reasons or through eating various foods containing titanium dioxide.[]

Titanium dioxide

[1] http:/ / www. commonchemistry. org/ ChemicalDetail. aspx?ref=13463-67-7 [2] http:/ / pubchem. ncbi. nlm. nih. gov/ summary/ summary. cgi?cid=26042 [3] http:/ / www. chemspider. com/ 24256 [4] http:/ / fdasis. nlm. nih. gov/ srs/ srsdirect. jsp?regno=15FIX9V2JP [5] http:/ / www. kegg. jp/ entry/ C13409 [6] https:/ / www. ebi. ac. uk/ chebi/ searchId. do?chebiId=32234 [7] https:/ / www. ebi. ac. uk/ chembldb/ index. php/ compound/ inspect/ CHEMBL1201136 [8] http:/ / chemapps. stolaf. edu/ jmol/ jmol. php?model=O%3D%5BTi%5D%3DO [9] http:/ / www. inchem. org/ documents/ icsc/ icsc/ eics0338. htm [10] http:/ / en. wikipedia. org/ w/ index. php?title=Special:ComparePages& rev1=476992554& page2=Titanium+ dioxide [30] http:/ / www. impactcolorsinc. com/ Optique-Iridescence [32] Pearlescence with Iriodin (http:/ / pearl-effect. com/ index. php?option=com_content& view=article& id=92& Itemid=62). pearl-effect.com [34] Les, Caren B. (November 2008) Light spells doom for bacteria (http:/ / www. photonics. com/ Article. aspx?AID=35722). Photonics.com [35] Polymers, Light and the Science of TiO2 (http:/ / www2. dupont. com/ Titanium_Technologies/ en_US/ tech_info/ literature/ Plastics/ PL_B_Polymers_Light_Science. pdf), DuPont, pp. 12 [36] Fibre Cement Coating (http:/ / www. dowconstructionchemicals. com/ eu/ en/ applications/ fibercementcoat). dowconstructionchemicals.com [37] "Japan Nanonet Bulletin 44th Issue May 12, 2005: Discovery and applications of photocatalysis Creating a comfortable future by making use of light energy" (http:/ / www. nanonet. go. jp/ english/ mailmag/ 2005/ 044a. html) [40] Cheap, Clean Ways to Produce Hydrogen for Use in Fuel Cells? A Dash of Disorder Yields a Very Efficient Photocatalyst (http:/ / www. sciencedaily. com/ releases/ 2011/ 01/ 110128165212. htm). Sciencedaily (2011-01-28) [41] Advanced Concrete Pavement materials, page 435 http:/ / www. cptechcenter. org/ publications/ task15/ task15_vol2/ track12am. pdf [42] Hogan, Jenny (2004-02-04) Smog-busting paint soaks up noxious gases (http:/ / www. newscientist. com/ article/ dn4636). New Scientist. [43] TIME's Best Inventions of 2008 (http:/ / www. time. com/ time/ specials/ packages/ article/ 0,28804,1852747_1854195_1854176,00. html). (2008-10-31).

External links
International Chemical Safety Card 0338 (http://www.inchem.org/documents/icsc/icsc/eics0338.htm) "Nano-Oxides, Inc. Nano Powders, LEGIT information on Titanium Dioxide TiO2" (http://www.nano-oxides. com/pdf/TiO2_Brochure.pdf). www.nano-oxides.com. Retrieved November2008. NIOSH Pocket Guide to Chemical Hazards (http://www.cdc.gov/niosh/npg/npgd0617.html) "Fresh doubt over America map", bbc.co.uk, 30 July 2002 (http://news.bbc.co.uk/1/hi/health/2162248.stm) Titanium Dioxide Classified as Possibly Carcinogenic to Humans, 2007 (http://www.ccohs.ca/headlines/ text186.html) (if inhaled as a powder) A description of TiO2 photocatalysis (http://www.threebond.co.jp/en/technical/technicalnews/pdf/tech62. pdf) Crystal structures of the three forms of TiO2 (http://ruby.colorado.edu/~smyth/min/tio2.html) "Architecture in Italy goes green", Elisabetta Povoledo, International Herald Tribune, November 22, 2006 (http:/ /www.iht.com/articles/2006/11/22/news/smog.php) "A Concrete Step Toward Cleaner Air", Bruno Giussani, BusinessWeek.com, November 8, 2006 (http://www. businessweek.com/innovate/content/nov2006/id20061108_116412.htm?campaign_id=bier_innv.g3a. rss1109c) "Titanium Dioxide Classified as Possibly Carcinogenic to Humans", Canadian Centre for Occupational Health and Safety, August, 2006 (http://www.ccohs.ca/headlines/text186.html) Sunscreen in the Sky? Reflective Particles May Combat Warming (http://news.nationalgeographic.com/news/ 2012/05/120529-global-warming-titanium-dioxide-balloons-earth-environment-science/) Titanium and titanium dioxide production data (US and World) (http://minerals.usgs.gov/minerals/pubs/ commodity/titanium/mcs-2012-titan.pdf)

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