Titanium dioxide#Sulfate process
{{Short description|Chemical compound}}
{{Cs1 config|name-list-style=vanc}}
{{Use dmy dates|date=August 2021}}
{{Chembox
| Verifiedfields = sleep
| Watchedfields = changed
| verifiedrevid = 476992554
| Name = Titanium dioxide
| ImageFile = Rutile-unit-cell-3D-balls.png
| ImageCaption = Unit cell of titanium dioxide (rutile form)
{{colorbox|#d3d3d3}} Titanium {{colorbox|#ee2010}} Oxygen
| ImageSize =
| ImageName = Titanium(IV) oxide
| ImageFile1 = Titanium(IV)_oxide.jpg
| ImageSize1 =
| ImageName1 = The unit cell of rutile
| IUPACName = Titanium dioxide
Titanium(IV) oxide
| OtherNames = {{Unbulleted list|Titania|Rutile|Anatase|Brookite}}
| SystematicName =
| Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 24256
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 15FIX9V2JP
| ChEMBL_Ref = {{ebicite|changed|EBI}}
| ChEMBL = 1201136
| InChI = 1/2O.Ti/rO2Ti/c1-3-2
| InChIKey = GWEVSGVZZGPLCZ-TYTSCOISAW
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 32234
| SMILES = O=[Ti]=O
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/2O.Ti
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = GWEVSGVZZGPLCZ-UHFFFAOYSA-N
| CASNo = 13463-67-7
| CASNo_Ref = {{cascite|correct|CAS}}
| PubChem = 26042
| RTECS = XR2775000
| KEGG_Ref = {{keggcite|changed|kegg}}
| KEGG = C13409
}}
| Section2 = {{Chembox Properties
| Formula = {{chem|TiO|2}}
| MolarMass = 79.866 g/mol
| Appearance = White solid
| Odor = Odorless
| Density = {{ubl
| 4.23 g/cm3 (rutile)
| 3.78 g/cm3 (anatase)
}}
| MeltingPtC = 1843
| BoilingPtC = 2972
| Solubility = Insoluble
| BandGap = 3.21{{nbsp}}eV (anatase){{cite journal |last1=Zanatta |first1=A.R. | title= Temperature-dependent optical bandgap of TiO2 under the Anatase and Rutile phases |journal=Results Phys. |date=May 2024 |volume=60 |pages= 107653–5pp |doi=10.1016/j.rinp.2024.107653 |doi-access=free }}
| RefractIndex = {{ubl
| 2.488 (anatase)
| 2.583 (brookite)
| 2.609 (rutile)
}}
| MagSus = +5.9·10−6{{nbsp}}cm3/mol
}}
| Section3 =
| Section4 = {{Chembox Thermochemistry
| DeltaHf = −945 kJ·mol−1{{cite book |author= Zumdahl, Steven S.|title =Chemical Principles 6th Ed. |publisher= Houghton Mifflin Company |year= 2009 |isbn= 978-0-618-94690-7|page=A23}}
}}
| Section5 =
| Section6 =
| Section7 = {{Chembox Hazards
| ExternalSDS = [http://www.inchem.org/documents/icsc/icsc/eics0338.htm ICSC 0338]
| NFPA-H = 1
| NFPA-F = 0
| NFPA-R = 0
| NFPA-S =
| FlashPt = not flammable
| IDLH = Ca [5000{{nbsp}}mg/m3]{{PGCH|0617}}
}}
| Section8 = {{Chembox Related
| OtherAnions =
| OtherCations = Zirconium dioxide
Hafnium dioxide
| OtherFunction = Titanium(II) oxide
Titanium(III) oxide
Titanium(III,IV) oxide
| OtherFunction_label = Titanium oxides
| OtherCompounds = Titanic acid
}}
}}
Titanium dioxide, also known as titanium(IV) oxide or titania {{IPAc-en|t|aɪ|ˈ|t|eɪ|n|i|ə}}, is the inorganic compound derived from titanium with the chemical formula {{chem|TiO|2}}. When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891.{{Ullmann|author=Völz, Hans G. |display-authors=etal |title=Pigments, Inorganic|year=2006|doi=10.1002/14356007.a20_243.pub2}} It is a white solid that is insoluble in water, although mineral forms can appear black. As a pigment, it has a wide range of applications, including paint, sunscreen, and food coloring. When used as a food coloring, it has E number E171. World production in 2014 exceeded 9 million tonnes.[http://minerals.usgs.gov/minerals/pubs/commodity/titanium/myb1-2014-titan.pdf "Titanium"] in 2014 Minerals Yearbook. USGS{{cite web |url=http://minerals.usgs.gov/minerals/pubs/mcs/2015/mcs2015.pdf|title=Mineral Commodity Summaries, 2015|website=U.S. Geological Survey|publisher=U.S. Geological Survey 2015}}{{cite web |url=http://minerals.usgs.gov/minerals/pubs/mcs/2016/mcs2016.pdf|title=Mineral Commodity Summaries, January 2016|website=U.S. Geological Survey|publisher=U.S. Geological Survey 2016}} It has been estimated that titanium dioxide is used in two-thirds of all pigments, and pigments based on the oxide have been valued at a price of $13.2 billion.{{cite news |url=https://www.bloomberg.com/features/2018-quest-for-billion-dollar-red/|title=The Quest for the Next Billion-Dollar Color|last=Schonbrun|first=Zach|work=Bloomberg.com|access-date=2018-04-24}}
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Structure
File:Anatase crystal structure.png. Together with rutile and brookite, one of the three major polymorphs of TiO2.]]
In all three of its main dioxides, titanium exhibits octahedral geometry, being bonded to six oxide anions. The oxides in turn are bonded to three Ti centers. The overall crystal structures of rutile and anatase are tetragonal in symmetry whereas brookite is orthorhombic. The oxygen substructures are all slight distortions of close packing: in rutile, the oxide anions are arranged in distorted hexagonal close-packing, whereas they are close to cubic close-packing in anatase and to "double hexagonal close-packing" for brookite. The rutile structure is widespread for other metal dioxides and difluorides, e.g. RuO2 and ZnF2.
Molten titanium dioxide has a local structure in which each Ti is coordinated to, on average, about 5 oxygen atoms.{{Cite journal |last1=Alderman |first1=O. L. G. |last2=Skinner |first2=L. B. |last3=Benmore |first3=C. J. |last4=Tamalonis |first4=A. |last5=Weber |first5=J. K. R. |year=2014 |title=Structure of molten titanium dioxide |journal=Physical Review B |language=en |volume=90 |issue=9 |page=094204 |bibcode=2014PhRvB..90i4204A |doi=10.1103/PhysRevB.90.094204 |issn=1098-0121 |doi-access=free}} This is distinct from the crystalline forms in which Ti coordinates to 6 oxygen atoms.
Synthetic and geologic occurrence
Synthetic TiO2 is mainly produced from the mineral ilmenite. Rutile, and anatase, naturally occurring TiO2, occur widely also, e.g. rutile as a 'heavy mineral' in beach sand. Leucoxene, fine-grained anatase formed by natural alteration of ilmenite, is yet another ore. Star sapphires and rubies get their asterism from oriented inclusions of rutile needles.{{cite book |last=Emsley |first=John |title=Nature's Building Blocks: An A–Z Guide to the Elements |year=2001 |isbn=978-0-19-850341-5 |pages=451–53 |publisher=Oxford University Press |location=Oxford}}
=Mineralogy and uncommon polymorphs=
Titanium dioxide occurs in nature as the minerals rutile and anatase. Additionally two high-pressure forms are known minerals: a monoclinic baddeleyite-like form known as akaogiite, and the other has a slight monoclinic distortion of the orthorhombic α-PbO2 structure and is known as riesite. Both of which can be found at the Ries crater in Bavaria.{{cite journal |doi=10.1126/science.1062342|year=2001|title=An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater.|volume=293|issue=5534|pages=1467–70|pmid=11520981|journal=Science|author1=El, Goresy|author2=Chen, M|author3=Dubrovinsky, L|author4=Gillet, P|author5=Graup, G|bibcode=2001Sci...293.1467E|s2cid=24349901}}{{cite journal |doi=10.1016/S0012-821X(01)00480-0|title=A natural shock-induced dense polymorph of rutile with α-PbO2 structure in the suevite from the Ries crater in Germany|year=2001|author=El Goresy, Ahmed|journal=Earth and Planetary Science Letters|volume=192|pages=485|last2=Chen|first2=Ming|last3=Gillet|first3=Philippe|last4=Dubrovinsky|first4=Leonid|last5=Graup|first5=GüNther|last6=Ahuja|first6=Rajeev|bibcode=2001E&PSL.192..485E|issue=4}}[https://www.mindat.org/min-35912.html Akaogiite]. mindat.org It is mainly sourced from ilmenite, which is the most widespread 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 irreversibly to the equilibrium rutile phase upon heating above temperatures in the range {{convert|600|-|800|C|-1}}.{{cite journal |last1=Hanaor |first1=Dorian A. H. |last2=Sorrell |first2=Charles C. |title=Review of the anatase to rutile phase transformation |journal=Journal of Materials Science |date=February 2011 |volume=46 |issue=4 |pages=855–874 |doi=10.1007/s10853-010-5113-0 |bibcode=2011JMatS..46..855H |s2cid=97190202 |url=https://hal.science/hal-02308408|doi-access=free }}
Titanium dioxide has twelve known polymorphs – in addition to rutile, anatase, brookite, akaogiite and riesite, three metastable phases can be produced synthetically (monoclinic, tetragonal, and orthorhombic ramsdellite-like), and four high-pressure forms (α-PbO2-like, cotunnite-like, orthorhombic OI, and cubic phases) also exist:
The cotunnite-type phase was claimed 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 (7–20 GPa, which makes it softer than common oxides like corundum Al2O3 and rutile TiO2){{cite journal |author1=Oganov A.R. |author2=Lyakhov A.O. |title= Towards the theory of hardness of materials |year= 2010|journal= Journal of Superhard Materials |volume= 32|pages= 143–147|doi= 10.3103/S1063457610030019|issue= 3|arxiv= 1009.5477|bibcode=2010JSMat..32..143O|s2cid=119280867 }} and bulk modulus (~300 GPa).{{cite journal |author1=Al-Khatatbeh, Y. |author2=Lee, K. K. M. |author3=Kiefer, B. |title= High-pressure behavior of TiO2 as determined by experiment and theory|year= 2009|journal= Phys. Rev. B |volume= 79|page= 134114|doi=10.1103/PhysRevB.79.134114|issue= 13|bibcode= 2009PhRvB..79m4114A}}{{cite journal |author1=Nishio-Hamane D. |author2=Shimizu A. |author3=Nakahira R. |author4=Niwa K. |author5=Sano-Furukawa A. |author6=Okada T. |author7=Yagi T. |author8=Kikegawa T. |title= The stability and equation of state for the cotunnite phase of TiO2 up to 70 GPa|year= 2010|journal= Phys. Chem. Miner. |volume= 37|pages= 129–136|doi=10.1007/s00269-009-0316-0|issue= 3|bibcode= 2010PCM....37..129N|s2cid=95463163 }}
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.{{cite journal |author1= Banfield, J. F.|author2=Veblen, D. R.|author3=Smith, D. J. |title= The identification of naturally occurring TiO2 (B) by structure determination using high-resolution electron microscopy, image simulation, and distance–least–squares refinement|journal= American Mineralogist|url=http://www.minsocam.org/ammin/AM76/AM76_343.pdf |year= 1991 |volume= 76|page= 343}}
Production
File:Industrial key players in the production of titanium dioxide.png
File:Evolution production dioxyde de titane.svg
The largest {{Chem|Ti||O|2}} pigment processors are Chemours, Venator, {{Interlanguage link|Kronos International|lt=Kronos|de}}, and Tronox.{{cite press release |url=https://www.businesswire.com/news/home/20170420006437/en/Top-5-Vendors-Global-Titanium-Dioxide-Market|title=Top 5 Vendors in the Global Titanium Dioxide Market From 2017-2021: Technavio|date=2017-04-20}}{{cite web |last=Hayes|year=2011|first=Tony|title=Titanium Dioxide: A Shining Future Ahead|url=http://argex.ca/documents/Euro_Pacific_Canada_Titanium_Dioxide_August2011.pdf|publisher=Euro Pacific Canada|access-date=16 August 2012|page=5}}{{dead link|date=January 2018 |bot=InternetArchiveBot |fix-attempted=yes}} Major paint and coating company end users for pigment grade titanium dioxide include Akzo Nobel, PPG Industries, Sherwin Williams, BASF, Kansai Paints and Valspar.Hayes (2011), p. 3 Global {{Chem|Ti||O|2}} pigment demand for 2010 was 5.3 Mt with annual growth expected to be about 3–4%.Hayes (2011), p. 4
The production method depends on the feedstock. In addition to ores, other feedstocks include upgraded slag. Both the chloride process and the sulfate process (both described below) produce titanium dioxide pigment in the rutile crystal form, but the sulfate process can be adjusted to produce the anatase form. Anatase, being softer, is used in fiber and paper applications. The sulfate process is run as a batch process; the chloride process is run as a continuous process.{{Cite web|url=https://www.essentialchemicalindustry.org/chemicals/titanium-dioxide.html|title=Titanium dioxide|website=www.essentialchemicalindustry.org}}
=Chloride process=
{{Main|Chloride process}}
In chloride process, the ore is treated with chlorine and carbon to give titanium tetrachloride, a volatile liquid that is further purified by distillation. The TiCl4 is treated with oxygen to regenerate chlorine and produce the titanium dioxide.
=Sulfate process=
In the sulfate process, ilmenite is treated with sulfuric acid to extract iron(II) sulfate pentahydrate. This process requires concentrated ilmenite (45–60% TiO2) or pretreated feedstocks as a suitable source of titanium.{{cite web |url=https://patentimages.storage.googleapis.com/c6/c1/7b/20176ebf24a65c/EP0869194A1.pdf|title=Process for preparing titanium dioxide|last=Vartiainen|first=Jaana|date=7 October 1998}} The resulting synthetic rutile is further processed according to the specifications of the end user, i.e. pigment grade or otherwise.{{cite book |last=Winkler |first=Jochen |title=Titanium Dioxide |year=2003 |isbn=978-3-87870-148-4 |pages=30–31 |publisher=Vincentz Network |location=Hannover}}
Examples of plants using the sulfate process are the Sorel-Tracy plant of QIT-Fer et Titane and the Eramet Titanium & Iron smelter in Tyssedal Norway.{{Cite web |vauthors=Withers JC, Cardarelli F, Laughlin J, Loutfy RO |date= |title=Recent Improvements for Electrowinning Titanium Metal from Composite Anodes |url=http://www.francoiscardarelli.ca/PDF_Files/Article_Cardarelli_MER_Process.pdf |location=Tucson, AZ |publisher=Materials & Electrochemical Research (MER) Corporation}}
=Becher process=
{{Main|Becher process}}
The Becher process is another method for the production of synthetic rutile from ilmenite. It first oxidizes the ilmenite as a means to separate the iron component.
=Specialized methods=
For specialty applications, TiO2 films are prepared by various specialized chemistries.{{cite journal |title=Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications|author1=Chen, Xiaobo |author2=Mao, Samuel S. |journal=Chemical Reviews|year=2007|volume=107|issue=7|pages=2891–2959|doi=10.1021/cr0500535|pmid=17590053}} Sol-gel routes involve the hydrolysis of titanium alkoxides such as titanium ethoxide:
: Ti(OEt)4 + 2 H2O → TiO2 + 4 EtOH
A related approach that also relies on molecular precursors involves chemical vapor deposition. In this method, the alkoxide is volatilized and then decomposed on contact with a hot surface:
: Ti(OEt)4 → TiO2 + 2 Et2O
Applications
=Pigment=
{{Main|Titanium white}}
First mass-produced in 1916,{{cite book|title=The Secret Lives of Colour|last=St. Clair|first=Kassia|publisher=John Murray|year=2016|isbn=978-1-4736-3081-9|location=London|page=40|oclc=936144129}} 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 (see list of indices of refraction). Titanium dioxide crystal size is ideally around 220 nm (measured by electron microscope) to optimize the maximum reflection of visible light. However, abnormal grain growth is often observed in titanium dioxide, particularly in its rutile phase.{{cite journal| last1=Hanaor| first1=D. A. H. | last2=Xu| first2=W.|last3=Ferry|first3=M.|last4=Sorrell|first4=C. C. | title= Abnormal grain growth of rutile TiO2 induced by ZrSiO4| journal= Journal of Crystal Growth| year= 2012| volume=359| pages=83–91| url= https://hal.archives-ouvertes.fr/hal-02315198/document/#page=2 | doi=10.1016/j.jcrysgro.2012.08.015|arxiv=1303.2761| bibcode=2012JCrGr.359...83H | s2cid=94096447 }}
The occurrence of abnormal grain growth brings about a deviation of a small number of crystallites from the mean crystal size and modifies the physical behaviour of TiO2. The optical properties of the finished pigment are highly sensitive to purity. As little as a few parts per million (ppm) of certain metals (Cr, V, Cu, Fe, Nb) can disturb the crystal lattice so much that the effect can be detected in quality control.{{Cite book |title=Kemira pigments quality titanium dioxide |last=Anderson |first=Bruce |year=1999 |location=Savannah, Georgia |pages=39}}{{Full citation needed|date=January 2025}} Approximately 4.6 million tons of pigmentary TiO2 are used annually worldwide, and this number is expected to increase as use continues to rise.{{cite book |last=Winkler |first=Jochen |title=Titanium Dioxide |year=2003 |isbn=978-3-87870-148-4 |pages=5 |publisher=Vincentz Network |location=Hannover, Germany}}
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, supplements, medicines (i.e. pills and tablets), and most toothpastes; in 2019 it was present in two-thirds of toothpastes on the French market.{{cite news |title=Deux dentifrices sur trois contiennent du dioxyde de titane, un colorant au possible effet cancérogène|language=fr|trans-title=Two out of three toothpastes contain titanium dioxide, a possibly carcinogenic colouring material|author=Margaux de Frouville|url=https://www.bfmtv.com/sante/deux-dentifrices-sur-trois-contiennent-du-dioxyde-de-titane-un-colorant-au-possible-effet-cancerogene-1660942.html |publisher=BFMTV.com |date=28 March 2019}} In paint, it is often referred to offhandedly as "brilliant white", "the perfect white", "the whitest white", or other similar terms. Opacity is improved by optimal sizing of the titanium dioxide particles.
=Food additive=
In food, it is commonly found in ice creams, chocolates, all types of candy, creamers, desserts, marshmallows, chewing gum, pastries, spreads, dressings, cakes, some cheeses, and many other foods.{{cite web|url=https://healthknight.com/titanium-dioxide-e171-side-effects-benefits |title=Titanium Dioxide (E171) – Overview, Uses, Side Effects & More |date=10 April 2022 |publisher=HealthKnight |access-date=2022-06-09}}
=Thin films=
When deposited as a thin film, its refractive index and colour make it an excellent reflective optical coating for dielectric mirrors; it is also used in generating decorative thin films such as found in "mystic fire topaz".{{cn|date=December 2024}}
Some grades of modified titanium based pigments as used in sparkly paints, plastics, finishes and cosmetics – these are man-made pigments whose particles have two or more layers of various oxides – often titanium dioxide, iron oxide or alumina – in order to have glittering, iridescent and or pearlescent effects similar to crushed mica or guanine-based products. In addition to these effects a limited colour 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.{{cite book|author=Koleske, J. V. |title=Paint and Coating Testing Manual|url=https://books.google.com/books?id=ri6FkY2xvgcC&pg=PA232|year=1995|publisher=ASTM International|isbn=978-0-8031-2060-0|page=232}} 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{{cite book|author=Koleske, J. V. |title=Paint and Coating Testing Manual|url=https://books.google.com/books?id=ri6FkY2xvgcC&pg=PA229|year=1995|publisher=ASTM International|isbn=978-0-8031-2060-0|page=229}} One example of a pearlescent pigment is Iriodin, based on mica coated with titanium dioxide or iron (III) oxide.{{citation |url= http://pearl-effect.com/index.php?option=com_content&view=article&id=92&Itemid=62 |archive-url= https://web.archive.org/web/20120117030508/http://pearl-effect.com/index.php?option=com_content&view=article&id=92&Itemid=62 |archive-date= 17 January 2012 |title= Pearlescence with Iriodin |work= pearl-effect.com}}
The iridescent effect in these titanium oxide particles 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.
=Sunscreen and UV blocking pigments=
In cosmetic and skin care products, titanium dioxide is used as a pigment, sunscreen and a thickener. As a sunscreen, ultrafine TiO2 is used, which is notable in that combined with ultrafine zinc oxide, it is considered to be an effective sunscreen that lowers the incidence of sun burns and minimizes the premature photoaging, photocarcinogenesis and immunosuppression associated with long term excess sun exposure.{{Citation|last1=Gabros|first1=Sarah|title=Sunscreens And Photoprotection|date=2021|url=http://www.ncbi.nlm.nih.gov/books/NBK537164/|work=StatPearls|place=Treasure Island (FL)|publisher=StatPearls Publishing|pmid=30725849|access-date=2021-03-06|last2=Nessel|first2=Trevor A.|last3=Zito|first3=Patrick M.}} Sometimes these UV blockers are combined with iron oxide pigments in sunscreen to increase visible light protection.{{Cite journal|last1=Dumbuya|first1=Hawasatu|last2=Grimes|first2=Pearl E.|last3=Lynch|first3=Stephen|last4=Ji|first4=Kaili|last5=Brahmachary|first5=Manisha|last6=Zheng|first6=Qian|last7=Bouez|first7=Charbel|last8=Wangari-Talbot|first8=Janet|date=2020-07-01|title=Impact of Iron-Oxide Containing Formulations Against Visible Light-Induced Skin Pigmentation in Skin of Color Individuals|journal=Journal of Drugs in Dermatology |volume=19|issue=7|pages=712–717|doi=10.36849/JDD.2020.5032|issn=1545-9616|pmid=32726103|doi-access=free}}
Titanium dioxide and zinc oxide are generally considered to be less harmful to coral reefs than sunscreens that include chemicals such as oxybenzone, octocrylene and octinoxate.{{Cite web|title=US Virgin Islands bans sunscreens harming coral reefs|url=https://www.downtoearth.org.in/news/wildlife-biodiversity/us-virgin-islands-bans-sunscreens-harming-coral-reefs-70158|access-date=2021-03-06|website=www.downtoearth.org.in|date=April 2020 |language=en}}
Nanosized titanium dioxide is found in the majority of physical sunscreens because of 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 (particle size of 20–40 nm)Dan, Yongbo et al. [https://www.perkinelmer.com/CMSResources/Images/44-171045APP_011990_01-NexION-350D-TiO2-NPs-in-Sunscreen.pdf Measurement of Titanium Dioxide Nanoparticles in Sunscreen using Single Particle ICP-MS] {{Webarchive|url=https://web.archive.org/web/20211206180608/https://www.perkinelmer.com/CMSResources/Images/44-171045APP_011990_01-NexION-350D-TiO2-NPs-in-Sunscreen.pdf |date=6 December 2021 }}. perkinelmer.com titanium dioxide particles are primarily used in sunscreen lotion because they scatter visible light much less than titanium dioxide pigments, and can give 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. Nano-TiO2, which blocks both UV-A and UV-B radiation, is used in sunscreens and other cosmetic products.
The EU Scientific Committee on Consumer Safety considered nano sized titanium dioxide to be safe for skin applications, in concentrations of up to 25 percent based on animal testing. {{Cite web|url=https://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_o_136.pdf|title=Health_scientific_committees}} The risk assessment of different titanium dioxide nanomaterials in sunscreen is currently evolving since nano-sized TiO2 is different from the well-known micronized form.{{Cite journal|date=2010|title=Sunscreens with Titanium Dioxide (TiO2) Nano-Particles: A Societal Experiment|journal=Nanoethics|pmc=2933802|last1=Jacobs|first1=J. F.|last2=Van De Poel|first2=I.|last3=Osseweijer|first3=P.|volume=4|issue=2|pages=103–113|doi=10.1007/s11569-010-0090-y|pmid=20835397}} The rutile form is generally used in cosmetic and sunscreen products due to it not possessing any observed ability to damage the skin under normal conditions{{Cite web|last=cosmeticsdesign-europe.com|title=Scientists encourage 'safer' rutile form of TiO2 in cosmetics|url=https://www.cosmeticsdesign-europe.com/Article/2013/09/26/Scientists-encourage-safer-rutile-form-of-TiO2-in-cosmetics|access-date=2021-03-06|website=cosmeticsdesign-europe.com|date=25 September 2013 |language=en-GB}} and having a higher UV absorption.{{Cite journal|date=29 March 2006|title=Characteristics of silica-coated TiO2 and its UV absorption for sunscreen cosmetic applications|url=https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/sia.2313|journal=Wiley Analytical Science|doi=10.1002/sia.2313|via=Wiley Online Library|last1=Jaroenworaluck|first1=A.|last2=Sunsaneeyametha|first2=W.|last3=Kosachan|first3=N.|last4=Stevens|first4=R.|volume=38|issue=4|pages=473–477|s2cid=97137064 }} In 2016 Scientific Committee on Consumer Safety (SCCS) tests concluded that the use of nano titanium dioxide (95–100% rutile, ≦5% anatase) as a UV filter can be considered to not pose any risk of adverse effects in humans post-application on healthy skin,{{Cite journal |last1=Dréno |first1=B. |last2=Alexis |first2=A. |last3=Chuberre |first3=B. |last4=Marinovich |first4=M. |date=2019 |title=Safety of titanium dioxide nanoparticles in cosmetics |journal=Journal of the European Academy of Dermatology and Venereology |language=en |volume=33 |issue=S7 |pages=34–46 |doi=10.1111/jdv.15943 |issn=0926-9959 |pmid=31588611 |s2cid=203849903 |doi-access=free |hdl-access=free |hdl=2434/705700}} except in the case the application method would lead to substantial risk of inhalation (ie; powder or spray formulations). This safety opinion applied to nano TiO2 in concentrations of up to 25%.{{Cite journal|date=7 November 2016|title=OPINION ON additional coatings for Titanium Dioxide (nano form) as UV-filter in dermally applied cosmetic products|url=https://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_o_202.pdf|journal=Scientific Committee on Consumer Safety (SCCS)|publisher=European Commission|via=ec.europa.eu}}
Initial studies indicated that nano-TiO2 particles could penetrate the skin, causing concern over its use. These studies were later refuted, when it was discovered that the testing methodology couldn't differentiate between penetrated particles and particles simply trapped in hair follicles and that having a diseased or physically damaged dermis could be the true cause of insufficient barrier protection.
SCCS research found that when nanoparticles had certain photostable coatings (e.g., alumina, silica, cetyl phosphate, triethoxycaprylylsilane, manganese dioxide), the photocatalytic activity was attenuated and no notable skin penetration was observed; the sunscreen in this research was applied at amounts of 10 mg/cm2 for exposure periods of 24 hours. Coating TiO2 with alumina, silica, zircon or various polymers can minimize avobenzone degradation{{Cite journal|title=Preparation of rutile TiO2@avobenzone composites for the further enhancement of sunscreen performance|url=https://pubs.rsc.org/en/content/articlelanding/2016/ra/c6ra23282e#!divRelatedContent&articles|journal=RSC Advances|bibcode=2016RSCAd...6k1865W|via=Royal society of chemistry|last1=Wang|first1=Can|last2=Zuo|first2=Shixiang|last3=Liu|first3=Wenjie|last4=Yao|first4=Chao|last5=Li|first5=Xiazhang|last6=Li|first6=Zhongyu|year=2016|volume=6|issue=113|page=111865|doi=10.1039/C6RA23282E}} and enhance UV absorption by adding an additional light diffraction mechanism.
{{Chem|Ti|O|2}} is used extensively in plastics and other applications as a white pigment or an opacifier and for its UV resistant properties where the powder disperses light – unlike organic UV absorbers – and reduces UV damage, due mostly to the particle's high refractive index.[http://www2.dupont.com/Titanium_Technologies/en_US/tech_info/literature/Plastics/PL_B_Polymers_Light_Science.pdf Polymers, Light and the Science of TiO2] {{Webarchive|url=https://web.archive.org/web/20170329071755/http://www2.dupont.com/Titanium_Technologies/en_US/tech_info/literature/Plastics/PL_B_Polymers_Light_Science.pdf |date=29 March 2017 }}, DuPont, pp. 1–2
=Other uses of titanium dioxide=
In ceramic glazes, titanium dioxide acts as an opacifier and seeds crystal formation.
It is used as a tattoo pigment and in styptic pencils. Titanium dioxide is produced in varying particle sizes which are both oil and water dispersible, and in certain grades for the cosmetic industry. It is also a common ingredient in toothpaste.
The exterior of the Saturn V rocket was painted with titanium dioxide; this later allowed astronomers to determine that J002E3 was likely the S-IVB stage from Apollo 12 and not an asteroid.{{cite journal |bibcode= 2003DPS....35.3602J |last1= Jorgensen |first1= K. |last2= Rivkin |first2= A. |last3= Binzel |first3= R. |last4= Whitely |first4= R. |last5= Hergenrother |first5= C. |last6= Chodas |first6= P. |last7= Chesley |first7= S. |last8= Vilas |first8= F. |title= Observations of J002E3: Possible Discovery of an Apollo Rocket Body |journal= Bulletin of the American Astronomical Society |date= May 2003 |volume= 35 |page= 981}}
Titanium dioxide is an n-type semiconductor and is used in dye-sensitized solar cells.{{Cite journal |last1=Aboulouard |first1=Abdelkhalk |last2=Gultekin |first2=Burak |last3=Can |first3=Mustafa |last4=Erol |first4=Mustafa |last5=Jouaiti |first5=Ahmed |last6=Elhadadi |first6=Benachir |last7=Zafer |first7=Ceylan |last8=Demic |first8=Serafettin |date=2020-03-01 |title=Dye sensitized solar cells based on titanium dioxide nanoparticles synthesized by flame spray pyrolysis and hydrothermal sol-gel methods: a comparative study on photovoltaic performances |journal=Journal of Materials Research and Technology |volume=9 |issue=2 |pages=1569–1577 |doi=10.1016/j.jmrt.2019.11.083 |issn=2238-7854|doi-access=free }} It is also used in other electronics components such as electrodes in batteries.{{Cite journal |last1=Mahmoud |first1=Zaid H. |last2=Ajaj |first2=Yathrib |last3=Kamil Ghadir |first3=Ghadir |last4=Musaad Al-Tmimi |first4=Hayder |last5=Hameed Jasim |first5=Hamza |last6=Al-Salih |first6=Moatasem |last7=Hasen shuhata Alubiady |first7=Mahmood |last8=Muzahem Al-Ani |first8=Ahmed |last9=Salih Jumaa |first9=Sally |last10=Azat |first10=Seitkhan |last11=Fadhil Smaisim |first11=Ghassan |last12=kianfar |first12=Ehsan |date=2024-01-01 |title=Carbon-doped titanium dioxide (TiO2) as Li-ion battery electrode: Synthesis, characterization, and performance |journal=Results in Chemistry |volume=7 |pages=101422 |doi=10.1016/j.rechem.2024.101422 |issn=2211-7156|doi-access=free }}
Research
=Patenting activities=
File:Relevant patent families describing titanium dioxide production from ilmenite, 2002–2021.png
File:Public Institutions patent activity in titanium dioxide production.png
Between 2002 and 2022, there were 459 patent families that describe the production of titanium dioxide from ilmenite. The majority of these patents describe pre-treatment processes, such as using smelting and magnetic separation to increase titanium concentration in low-grade ores, leading to titanium concentrates or slags. Other patents describe processes to obtain titanium dioxide, either by a direct hydrometallurgical process or through the main industrial production processes, the sulfate process and the chloride process.{{Cite journal |date=2023 |title=Patent Landscape Report : Production of titanium and titanium dioxide from ilmenite and related applications |url=https://www.wipo.int/publications/en/details.jsp?id=4651&plang=EN |access-date=2023-11-13 |website=www.wipo.int |publisher=WIPO |doi=10.34667/tind.47029 |language=en |author1=World Intellectual Property Organization. |series=Patent Landscape Reports }} The sulfate process represents 40% of the world’s titanium dioxide production and is protected in 23% of patent families. The chloride process is only mentioned in 8% of patent families, although it provides 60% of the worldwide industrial production of titanium dioxide.
Key contributors to patents on the production of titanium dioxide are companies from China, Australia and the United States, reflecting the major contribution of these countries to industrial production. Chinese companies Pangang and Lomon Billions Groups hold major patent portfolios.
=Photocatalyst=
Nanosized titanium dioxide, particularly in the anatase form, exhibits photocatalytic activity under ultraviolet (UV) irradiation. This photoactivity is reportedly most pronounced at the {001} planes of anatase,{{cite journal |author=Liang Chu |journal=Scientific Reports |volume=5 |pages=12143 |title=Anatase TiO2 Nanoparticles with Exposed {001} Facets for Efficient Dye-Sensitized Solar Cells |doi=10.1038/srep12143 |pmid=26190140 |pmc=4507182 |bibcode=2015NatSR...512143C |year=2015}}{{cite journal |author= Li Jianming and Dongsheng Xu |title=tetragonal faceted-nanorods of anatase TiO2 single crystals with a large percentage of active {100} facets |journal= Chemical Communications |volume=46 |issue=13 |pages=2301–3 |year=2010 |doi=10.1039/b923755k |pmid=20234939}} although the {101} planes are thermodynamically more stable and thus more prominent in most synthesised and natural anatase,{{cite journal |author= M Hussein N Assadi |title= The effects of copper doping on photocatalytic activity at (101) planes of anatase TiO 2: A theoretical study |url=https://www.researchgate.net/publication/304714130 |journal= Applied Surface Science |volume= 387 |pages=682–689|year=2016|bibcode=2016ApSS..387..682A|doi=10.1016/j.apsusc.2016.06.178 |arxiv= 1811.09157|s2cid= 99834042 }} as evident by the often observed tetragonal dipyramidal growth habit. Interfaces between rutile and anatase are further considered to improve photocatalytic activity by facilitating charge carrier separation and as a result, biphasic titanium dioxide is often considered to possess enhanced functionality as a photocatalyst.{{cite journal |title=Sand Supported Mixed-Phase TiO2 Photocatalysts for Water Decontamination Applications |journal= Advanced Engineering Materials |year=2014 |volume=16|issue=2 |pages=248–254|doi=10.1002/adem.201300259 |arxiv=1404.2652 |last1= Hanaor |first1= Dorian A. H. |last2= Sorrell |first2= Charles C. |bibcode= 2014arXiv1404.2652H|s2cid= 118571942 }} It has been reported that titanium dioxide, when doped with nitrogen ions or doped with metal oxide like tungsten trioxide, exhibits excitation also under visible light.{{cite journal |author1=Kurtoglu M. E. |author2=Longenbach T. |author3=Gogotsi Y. |year= 2011|title= Preventing Sodium Poisoning of Photocatalytic TiO2 Films on Glass by Metal Doping|journal= International Journal of Applied Glass Science|volume= 2|issue= 2|pages= 108–116|doi= 10.1111/j.2041-1294.2011.00040.x}} The strong oxidative potential of the positive holes oxidizes water to create hydroxyl radicals. It can also oxidize oxygen or organic materials directly. Hence, in addition to its use as a pigment, titanium dioxide can be 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 nanosized titanium dioxide were discovered by Akira Fujishima in 1967 and published in 1972.{{cite journal |doi=10.1038/238037a0|title=Electrochemical Photolysis of Water at a Semiconductor Electrode|year=1972|journal=Nature|volume=238|pages=37–8|pmid=12635268|issue=5358|bibcode= 1972Natur.238...37F|last1=Fujishima|first1=Akira|last2=Honda|first2=Kenichi|s2cid=4251015}} The process on the surface of the titanium dioxide was called the {{ill|Honda-Fujishima effect|ja|本多-藤嶋効果}}.[https://web.archive.org/web/20050608091634/http://www.nanonet.go.jp/english/mailmag/2005/044a.html "Discovery and applications of photocatalysis – Creating a comfortable future by making use of light energy"]. Japan Nanonet Bulletin Issue 44, 12 May 2005. In thin film and nanoparticle form, titanium dioxide has the potential for use in energy production: As a photocatalyst, it can break water into hydrogen and oxygen. With 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.{{cite news |work=Advanced Ceramics Report|date=1 December 2003|url=http://www.highbeam.com/doc/1G1-110587279.html|archive-url=https://web.archive.org/web/20070204161415/http://www.highbeam.com/doc/1G1-110587279.html|url-status=dead|archive-date=4 February 2007|title=Carbon-doped titanium dioxide is an effective photocatalyst|quote=This carbon-doped titanium dioxide is highly efficient; under artificial visible light, it breaks down chlorophenol five times more efficiently than the nitrogen-doped version.}} 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.[https://www.sciencedaily.com/releases/2011/01/110128165212.htm Cheap, Clean Ways to Produce Hydrogen for Use in Fuel Cells? A Dash of Disorder Yields a Very Efficient Photocatalyst]. Sciencedaily (28 January 2011) Visible-light-active nanosized anatase and rutile has been developed for photocatalytic applications.{{cite journal |last=Karvinen|first=Saila|title=Preparation and Characterization of Mesoporous Visible-Light-Active Anatase|journal=Solid State Sciences|volume=5 2003|issue=8|pages=1159–1166|bibcode=2003SSSci...5.1159K|year=2003|doi=10.1016/S1293-2558(03)00147-X}}{{Cite journal |last1=Bian |first1=Liang |last2=Song |first2=Mianxin |last3=Zhou |first3=Tianliang |last4=Zhao |first4=Xiaoyong |last5=Dai |first5=Qingqing |date=June 2009 |title=Band gap calculation and photo catalytic activity of rare earths doped rutile TiO2 |url=https://linkinghub.elsevier.com/retrieve/pii/S1002072108602707 |journal=Journal of Rare Earths |language=en |volume=27 |issue=3 |pages=461–468 |doi=10.1016/S1002-0721(08)60270-7}}
In 1995 Fujishima and his group discovered the superhydrophilicity phenomenon for titanium dioxide coated glass exposed to sun light. This resulted in the development of self-cleaning glass and anti-fogging coatings.
Nanosized TiO2 incorporated into outdoor building materials, such as paving stones in noxer blocks[http://www.cptechcenter.org/publications/task15/task15_vol2/track12am.pdf Advanced Concrete Pavement materials] {{Webarchive|url=https://web.archive.org/web/20130620080135/http://www.cptechcenter.org/publications/task15/task15_vol2/track12am.pdf |date=20 June 2013}}, National Concrete Pavement Technology Center, Iowa State University, p. 435. or paints, could reduce concentrations of airborne pollutants such as volatile organic compounds and nitrogen oxides.Hogan, Jenny (4 February 2004) [https://www.newscientist.com/article/dn4636 "Smog-busting paint soaks up noxious gases"]. New Scientist. A TiO2-containing cement has been produced.[https://content.time.com/time/specials/packages/0,28757,1852747,00.html TIME's Best Inventions of 2008]. (31 October 2008).
Using TiO2 as a photocatalyst, attempts have been made to mineralize pollutants (to convert into CO2 and H2O) in waste water.{{cite book |last=Winkler |first=Jochen |title=Titanium Dioxide |year=2003 |isbn=978-3-87870-148-4 |pages=115–116 |publisher=Vincentz Network |location=Hannover}}{{cite journal |doi=10.1016/j.apcatb.2003.11.010|title=TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: Kinetic and mechanistic investigations|year=2004|last1=Konstantinou|first1=Ioannis K|last2=Albanis|first2=Triantafyllos A|journal=Applied Catalysis B: Environmental|volume=49|issue=1 |pages=1–14|bibcode=2004AppCB..49....1K }}{{cite journal |last1=Hanaor |first1=Dorian A. H. |last2=Sorrell |first2=Charles C. |title= Sand Supported Mixed-Phase TiO2 Photocatalysts for Water Decontamination Applications |journal= Advanced Engineering Materials |year=2014 |volume=16 |issue=2 |pages=248–254 |doi=10.1002/adem.201300259 |arxiv=1404.2652|s2cid=118571942 }} The photocatalytic destruction of organic matter could also be exploited in coatings with antimicrobial applications.{{cite journal |last1=Ramsden|first1=Jeremy J.|title=Photocatalytic antimicrobial coatings|journal=Nanotechnology Perceptions|date=2015|volume=11|issue=3|pages=146–168|doi=10.4024/N12RA15A.ntp.15.03|doi-access=free}}
==Hydroxyl radical formation==
Although nanosized anatase TiO2 does not absorb visible light, it does strongly absorb ultraviolet (UV) radiation (hv), leading to the formation of hydroxyl radicals.{{cite book|title=Kirk-Othmer Encyclopedia of Chemical Technology|last1=Jones|first1=Tony|last2=Egerton|first2=Terry A.|date=2000|publisher=John Wiley & Sons, Inc.|isbn=978-0-471-23896-6|language=en|chapter=Titanium Compounds, Inorganic|doi=10.1002/0471238961.0914151805070518.a01.pub3}} This occurs when photo-induced valence bond holes (h+vb) are trapped at the surface of TiO2 leading to the formation of trapped holes (h+tr) that cannot oxidize water.{{cite journal |last1=Hirakawa|first1=Tsutomu|last2=Nosaka|first2=Yoshio|date=23 January 2002|title=Properties of O2•-and OH• formed in TiO2 aqueous suspensions by photocatalytic reaction and the influence of H2O2 and some ions|journal=Langmuir|volume=18|issue=8|pages=3247–3254|doi=10.1021/la015685a}}
: TiO2 + hv → e− + h+vb
: h+vb → h+tr
: O2 + e− → O2•−
: O2•− + O2•−+ 2{{H+}} → H2O2 + O2
: O2•− + h+vb → O2
: O2•− + h+tr → O2
: {{OH-}} + h+vb → HO•
: e− + h+tr → recombination
: Note: Wavelength (λ)= 387 nm This reaction has been found to mineralize and decompose undesirable compounds in the environment, specifically the air and in wastewater.
=Nanotubes=
Anatase can be converted into non-carbon nanotubes and nanowires.{{cite journal |doi=10.1016/j.cplett.2008.06.063 |title=The structure of multilayered titania nanotubes based on delaminated anatase |year=2008 |last1=Mogilevsky |first1=Gregory |last2=Chen |first2=Qiang |last3=Kleinhammes |first3=Alfred |last4=Wu |first4=Yue |journal=Chemical Physics Letters |volume=460 |issue=4–6 |pages=517–520 |bibcode= 2008CPL...460..517M}} Hollow TiO2 nanofibers can be also prepared by coating carbon nanofibers by first applying titanium butoxide.{{cite journal |doi=10.1088/1468-6996/16/5/054206 |pmid=27877835 |title=Hard-templating of chiral TiO2 nanofibres with electron transition-based optical activity |journal=Science and Technology of Advanced Materials |volume=16 |issue=5 |pages=054206 |author=Wang, Cui |pmc=5070021 |year=2015 |bibcode=2015STAdM..16e4206W}}
File:Chiral TiO2 nanofibers 2.jpg|SEM (top) and TEM (bottom) images of chiral TiO2 nanofibers
File:TiO2nanotube.jpg|Titanium oxide nanotubes, SEM image
File:The army of titanium dioxide nanotubes.jpg|Nanotubes of titanium dioxide (TiO2-Nt) obtained by electrochemical synthesis. The SEM image shows an array of vertical self-ordered TiO2-Nt with closed bottom ends of tubes.
= Solubility =
Titanium dioxide is insoluble in water, organic solvents, and inorganic acids. It is slightly soluble in alkali, soluble in saturated potassium acid carbonate, and can be completely dissolved in strong sulfuric acid and hydrofluoric acid after boiling for a long time.{{Citation |last=Wu |first=Yuan |title=15 - PREPARATION OF ULTRAFINE POWDERS BY REACTION–PRECIPITATION IN IMPINGING STREAMS III: NANO TITANIA |date=2007-01-01 |work=Impinging Streams |pages=301–315 |editor-last=Wu |editor-first=Yuan |url=https://www.sciencedirect.com/science/article/abs/pii/B9780444530370500458 |access-date=2024-11-15 |place=Amsterdam |publisher=Elsevier Science B.V. |isbn=978-0-444-53037-0}}
Health and safety
Widely-occurring minerals and even gemstones are composed of TiO2. All natural titanium, comprising more than 0.5% of the Earth's crust, exists as oxides.{{cite journal |vauthors=Warheit DB, Donner EM |title=Risk assessment strategies for nanoscale and fine-sized titanium dioxide particles: Recognizing hazard and exposure issues |journal=Food Chem Toxicol |volume=85 |issue= |pages=138–47 |date=November 2015 |pmid=26362081 |doi=10.1016/j.fct.2015.07.001 |type=Review}}
=Food additive=
As of 2024, titanium dioxide is considered safe by the US FDA as a color ingredient for oral human consumption as long as it is 1% or less of the total food composition.{{cite web |title=Titanium Dioxide as a Color Additive in Foods |url=https://www.fda.gov/industry/color-additives/titanium-dioxide-color-additive-foods |publisher=US Food and Drug Administration |access-date=26 March 2025 |date=4 March 2024}} A 2021 ban by the EU EFSA has been criticized as based on errors regarding the safety of titanium dioxide (E171) particles as a food additive,{{Cite journal |last=Warheit |first=David B. |date=2024 |title=Safety of titanium dioxide (E171) as a food additive for humans |journal=Frontiers in Toxicology |volume=6 |pages=1333746 |doi=10.3389/ftox.2024.1333746|doi-access=free |issn=2673-3080 |pmc=11295244 |pmid=39100893}} and according to a 2022 review, existing evidence does not support a direct DNA damaging mechanism for titanium dioxide.{{Cite journal |last1=Kirkland |first1=David |last2=Aardema |first2=Marilyn J. |last3=Battersby |first3=Rüdiger V. |last4=Beevers |first4=Carol |last5=Burnett |first5=Karin |last6=Burzlaff |first6=Arne |last7=Czich |first7=Andreas |last8=Donner |first8=E. Maria |last9=Fowler |first9=Paul |last10=Johnston |first10=Helinor J. |last11=Krug |first11=Harald F. |last12=Pfuhler |first12=Stefan |last13=Stankowski |first13=Leon F.|display-authors=3 |date=2022-12-01 |title=A weight of evidence review of the genotoxicity of titanium dioxide (TiO2) |journal=Regulatory Toxicology and Pharmacology |volume=136 |pages=105263 |doi=10.1016/j.yrtph.2022.105263 |issn=0273-2300|doi-access=free |pmid=36228836 }}
== Government policies ==
TiO2 whitener in food was banned in France from 2020, due to uncertainty about safe quantities for human consumption.[https://www.reuters.com/article/us-france-food-additive/france-to-ban-titanium-dioxide-whitener-in-food-from-2020-idUSKCN1RT23D France to ban titanium dioxide whitener in food from 2020]. Reuters, 2019-04-17
In 2021, the European Food Safety Authority (EFSA) ruled that as a consequence of new understandings of nanoparticles, titanium dioxide could "no longer be considered safe as a food additive", and the EU health commissioner announced plans to ban its use across the EU, with discussions beginning in June 2021. EFSA concluded that genotoxicity—which could lead to carcinogenic effects—could not be ruled out, and that a "safe level for daily intake of the food additive could not be established".{{cite news |last1=Boffey |first1=Daniel |title=E171: EU watchdog says food colouring widely used in UK is unsafe |url=https://www.theguardian.com/world/2021/may/06/e171-eu-watchdog-says-food-colouring-widely-used-in-uk-is-unsafe |work=the Guardian |date=6 May 2021 |language=en}} In 2022, the UK Food Standards Agency and Food Standards Scotland announced their disagreement with the EFSA ruling, and did not follow the EU in banning titanium dioxide as a food additive.[https://www.foodsafetynews.com/2022/03/uk-disagrees-with-eu-position-on-titanium-dioxide/ 'UK disagrees with EU position on titanium dioxide']. Food Safety News, 2022-03-09 Health Canada similarly reviewed the available evidence in 2022 and decided not to change their position on titanium dioxide as a food additive.[https://www.canada.ca/en/health-canada/services/food-nutrition/reports-publications/titanium-dioxide-food-additive-science-report.html "Titanium dioxide (TiO2) as a food additive: Current science report"]. Health Canada, 2022-06-20.
The European Union removed the authorization to use titanium dioxide (E 171) in foods, effective 7 February 2022, with a six months grace period.[https://eur-lex.europa.eu/legal-content/EN/TXT/HTML/?uri=CELEX:32022R0063 'amending Annexes II and III to Regulation (EC) No 1333/2008 of the European Parliament and of the Council as regards the food additive titanium dioxide (E 171)']. Commission Regulation (EU) 2022/63, 14 January 2022
As of May 2023, following the European Union 2022 ban, the U.S. states California and New York were considering banning the use of titanium dioxide in foods.{{Cite news |last=Smith |first=Dana G. |date=April 13, 2023 |title=Two States Have Proposed Bans on Common Food Additives Linked to Health Concerns |work=The New York Times |url=https://www.nytimes.com/2023/04/13/well/eat/food-additive-ban.html |url-status=live |access-date=November 15, 2023 |archive-url=https://web.archive.org/web/20231113022102/https://www.nytimes.com/2023/04/13/well/eat/food-additive-ban.html |archive-date=November 13, 2023}}
As of 2024, the Food and Drug Administration (FDA) in the United States permits titanium dioxide as a food additive. It may be used to increase whiteness and opacity in dairy products (some cheeses, ice cream, and yogurt), candies, frostings, fillings, and many other foods. The FDA regulates the labeling of products containing titanium dioxide, allowing the product's ingredients list to identify titanium dioxide either as "color added" or "artificial colors" or "titanium dioxide;" it does not require that titanium dioxide be explicitly named. In 2023, the Consumer Healthcare Products Association, a manufacturer's trade group, defended the substance as safe at certain limits while allowing that additional studies could provide further insight, saying an immediate ban would be a "knee-jerk" reaction.{{Cite web |last=Bedigan |first=Mike |date=2024-06-12 |title=Scientists raise alarm over sunscreen ingredient being found in cakes and candies |url=https://www.independent.co.uk/life-style/health-and-families/health-news/frozen-pizza-candy-titanium-dioxide-sunscreen-foods-b2561031.html |access-date=2024-06-13 |website=The Independent |language=en}}
==Industry response==
Dunkin' Donuts dropped titanium dioxide from their merchandise in 2015 after public pressure.{{cite web |title=Dunkin' Donuts to remove titanium dioxide from donuts|url=https://money.cnn.com/2015/03/10/news/companies/dunkin-donuts-titanium-dioxide/|website=CNN Money|date=March 2015}}
==Research as an ingestible nanomaterial==
Size distribution analyses showed that batches of food-grade TiO₂, which is produced with a target particle size in the 200{{En dash}}300{{Nbsp}}nm range for optimal pigmentation qualities, include a nanoparticle-sized fraction as inevitable byproduct of the manufacturing processes.
{{Cite journal |last1=Winkler |first1=Hans Christian |last2=Notter |first2=Tina |last3=Meyer |first3=Urs |last4=Naegeli |first4=Hanspeter |date=December 2018 |title=Critical review of the safety assessment of titanium dioxide additives in food |journal=Journal of Nanobiotechnology |language=en |volume=16 |issue=1 |page=51 |doi=10.1186/s12951-018-0376-8 |issn=1477-3155 |pmc=5984422 |pmid=29859103 |doi-access=free }}
=Inhalation=
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.{{cite book|publisher= International Agency for Research on Cancer|year= 2006 |volume= 93|title=Titanium dioxide|url= http://monographs.iarc.fr/ENG/Monographs/vol93/mono93.pdf}}{{cite web |url=https://www.ccohs.ca/headlines/text186.html|title=Titanium Dioxide Classified as Possibly Carcinogenic to Humans |date= August 2006|website=Canadian Centre for Occupational Health & Safety}} The US National Institute for Occupational Safety and Health recommends two separate exposure limits. NIOSH recommends that fine {{chem|Ti|O|2}} particles be set at an exposure limit of 2.4 mg/m3, while ultrafine {{chem|Ti|O|2}} be set at an exposure limit of 0.3 mg/m3, as time-weighted average concentrations up to 10 hours a day for a 40-hour work week.{{cite web |author= National Institute for Occupational Safety and Health |title= Current Intelligence Bulletin 63: Occupational Exposure to Titanium Dioxide (NIOSH Publication No. 2011-160) |publisher= National Institute for Occupational Safety and Health |url= https://www.cdc.gov/niosh/docs/2011-160/pdfs/2011-160.pdf}}
Although no evidence points to acute toxicity, recurring concerns have been expressed about nanophase forms of these materials. Studies of workers with high exposure to TiO2 particles indicate that even at high exposure there is no adverse effect to human health.
=Environmental waste introduction=
Titanium dioxide (TiO₂) is mostly introduced into the environment as nanoparticles via wastewater treatment plants.{{cite journal |last1=Tourinho|first1=Paula S.|last2=van Gestel|first2=Cornelis A. M.|last3=Lofts|first3=Stephen|last4=Svendsen|first4=Claus|last5=Soares|first5=Amadeu M. V. M.|last6=Loureiro|first6=Susana|date=2012-08-01|title=Metal-based nanoparticles in soil: Fate, behavior, and effects on soil invertebrates|journal=Environmental Toxicology and Chemistry|language=en|volume=31|issue=8|pages=1679–1692|doi=10.1002/etc.1880|pmid=22573562|s2cid=45296995 |issn=1552-8618|doi-access=free|bibcode=2012EnvTC..31.1679T }} Cosmetic pigments including titanium dioxide enter the wastewater when the product is washed off into sinks after cosmetic use. Once in the sewage treatment plants, pigments separate into sewage sludge which can then be released into the soil when injected into the soil or distributed on its surface. 99% of these nanoparticles wind up on land rather than in aquatic environments due to their retention in sewage sludge. In the environment, titanium dioxide nanoparticles have low to negligible solubility and have been shown to be stable once particle aggregates are formed in soil and water surroundings. In the process of dissolution, water-soluble ions typically dissociate from the nanoparticle into solution when thermodynamically unstable. TiO2 dissolution increases when there are higher levels of dissolved organic matter and clay in the soil. However, aggregation is promoted by pH at the isoelectric point of TiO2 (pH= 5.8) which renders it neutral and solution ion concentrations above 4.5 mM.{{cite book|title=Kirk-Othmer Encyclopedia of Chemical Technology|last=Swiler|first=Daniel R.|date=2005|publisher=John Wiley & Sons, Inc.|isbn=978-0-471-23896-6|language=en|chapter=Pigments, Inorganic|doi=10.1002/0471238961.0914151814152215.a01.pub2}}{{cite journal |last1=Preočanin|first1=Tajana|last2=Kallay|first2=Nikola|year=2006|title=Point of Zero Charge and Surface Charge Density of TiO2 in Aqueous Electrolyte Solution as Obtained by Potentiometric Mass Titration|journal=Croatica Chemica Acta|volume=79|issue=1|pages=95–106|issn=0011-1643}}
See also
- Delustrant
- Dye-sensitized solar cell
- List of inorganic pigments
- Noxer blocks, TiO2-coated pavers that remove {{NOx}} pollutants from the air
- Suboxide
- Surface properties of transition metal oxides
- Titanium dioxide nanoparticle
Sources
{{Free-content attribution
| title = Production of titanium and titanium dioxide from ilmenite and related applications
| publisher = WIPO
| documentURL = https://www.wipo.int/edocs/pubdocs/en/wipo-pub-1077-23-en-patent-landscape-report-ilmenite.pdf
| license = CC-BY
}}
References
{{Reflist}}
External links
{{Wiktionary|titanium suboxide}}
{{Wikiquote}}
- [https://inchem.org/documents/icsc/icsc/eics0338.htm International Chemical Safety Card 0338]
- [https://www.cdc.gov/niosh/npg/npgd0617.html NIOSH Pocket Guide to Chemical Hazards]
- [https://www.ccohs.ca/headlines/text186.html "Titanium Dioxide Classified as Possibly Carcinogenic to Humans", Canadian Centre for Occupational Health and Safety, August, 2006] (if inhaled as a powder)
- [https://web.archive.org/web/20070112210620/http://www.threebond.co.jp/en/technical/technicalnews/pdf/tech62.pdf A description of TiO2 photocatalysis]
- [https://www.usgs.gov/centers/national-minerals-information-center/titanium-statistics-and-information Titanium and titanium dioxide production data (US and World)]
{{Titanium compounds}}
{{Oxides}}
{{Molecules detected in outer space}}
{{Sunscreening agents}}
{{Authority control}}
Category:Dye-sensitized solar cells
Category:IARC Group 2B carcinogens