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Titanium Oxide (TiO2) is an important material having a lot of vital properties and applications such as the production of titanium metal, titanium oxide nanoparticles, etc. It has two important types which are rutile titanium dioxide and anatase titanium dioxide. The key difference among them is in their appearance. Anatase Titanium Dioxide is colorless, whereas Rutile Titanium Dioxide is usually found in dark red appearance. Rutile titanium dioxide is optically positive, whereas Anatase titanium dioxide is optically negative. This articles discusses the main differences between the two types of Titanium Dioxide and also describes their applications.
Rutile Titanium Dioxide Nanoparticles
As already mentioned, Rutile Titanium Dioxide appears in dark red color and it has high stability. Moreover, it is the most commonly found type of Titanium Dioxide and is usually found in metamorphic and igneous rocks, which are subjected to high-pressure and high-temperature conditions.
While talking about the rutile&#;s crystalline structure, it has a tetragonal unit cell having oxygen anions and titanium cations. The coordination number of titanium cations (Ti+4) is 6, while the coordination number of oxygen anion (O2-) is 3. Some vital properties of rutile titanium dioxide nanoparticles are given below:
Greater dispersion
Higher birefringence
Greater refractive index (RI) at visible wavelengths
It has a lot of useful applications, the main ones are the manufacturing of metallic titanium and titanium dioxide pigments. Moreover, in fine form, it is used for manufacturing plastics, papers, and paints. The finely pulverized form of titanium dioxide is white in color. Furthermore, the nanoparticles of rutile titanium dioxide have the ability to absorb UV rays and are transparent to visible light. That is the reason that they are used in the manufacturing of cosmetics.
Anatase Titanium Dioxide Nanoparticles
The nanoparticles of Anatase titanium dioxide are found in colorless or yellow color. The natural form of Anatase titanium dioxide contains a lot of impurities which makes it dark.
The crystalline structure of Anatase titanium dioxide is tetragonal and are different from rutile titanium dioxide. The appearance of Anatase titanium dioxide is metallic. It can also be synthesized to be used in the manufacturing of semiconductors.
9 Differences between Rutile and Anatase Titanium Dioxide Nanoparticles
The 9 main differences between the two types of Titanium Dioxide are given below:
1.Appearances of Rutile and Anatase TiO2 Nanoparticles
Rutile titanium dioxide is a component that contains mainly TiO2 with a dark red appearance, whereas Anatase titanium dioxide has colorless to blue appearance.
2.Colors of Rutile and Anatase TiO2 Nanoparticles
Rutile titanium dioxide has dark red color and the finely pulverized rutile titanium dioxide has a bright white color, whereas Anatase titanium dioxide has a dark color in the presence of impurities, but its pure form is colorless or white.
3.Optical activity of Anatase and Rutile Titanium Dioxide Nanoparticles
Rutile titanium dioxide is optically positive, whereas Anatase titanium dioxide is optically negative.
4.Occurrences of Anatase and Rutile TiO2 Nanoparticles
Rutile is a type of titanium dioxide that is found naturally in huge quantity as compared to anatase titanium dioxide.
5.UV absorptions of Anatase and Rutile Titanium Oxide Nanoparticles
Ultraviolent absorption by rutile titanium dioxide is great, whereas ultraviolet absorption by anatase titanium dioxide is low.
6.Hardness of Rutile and Anatase Titanium Dioxide Nanoparticles
The hardness of Rutile titanium dioxide is great, whereas Anatase titanium dioxide is not that much hard.
7.Specific gravity of two types of TiO2 Nanoparticles
The density of Rutile titanium dioxide is high, whereas the density of the anatase titanium dioxide is low.
8.Different crystal structures of two types TiO2 Nanoparticles
The anatase and rutile titanium oxide crystal structures consist of interconnected TiO2 octahedra. The difference between the two is that the degree of distortion of the octahedron is different for both.
9.Price Differences between Anatase and Rutile TiO2 Nanoparticles
Due to the relatively high price of rutile titanium dioxide, it is often used in high-end products. Rutile titanium dioxide is not only used in the production of high-quality water-based printing materials such as paints, inks and plastic woodwork. On the other hand, Anatase titanium dioxide is less expensive than rutile titanium dioxide and is mainly involved in the production of plastics, printing inks, printing inks, and coatings.
Since the price of rutile titanium dioxide is relatively high, there are many counterfeit products on the market, including the following ones:
(a) Packaging of domestic titanium dioxide on imported titanium dioxide.
(b) Impregnation of the rutile with anatase titanium dioxide or incorporating a portion of anatase titanium dioxide in the rutile type.
(c) Mixing filling materials such as calcium carbonate, lithopone and barium sulfate in rutile type titanium dioxide or anatase titanium dioxide.
The differences between the main chemical and physical properties of Rutile and Anatase Titanium Dioxide are shown in the table below:
Sr. No
Rutile Titanium Dioxide
Anatase Titanium Dioxide
1
Square crystal system
Crystal cone shape
2
Relative density (8 - 3.9)
Relative density (4.2 &#; 4.3)
3
Refractive index (2.52)
Refractive index (2.71)
4
Mo hardness 5.5 - 6
Mo hardness 6 &#; 7
Production methods of Rutile and Anatase titanium Dioxide Nanoparticles
Titanium Oxide can be obtained through two processes: the sulfate process and the chloride process, which use the two main minerals, ilmenite and rutile, they are particularly abundant in Australia and South Africa.
1)Sulfate Process in the production of TiO2 Nanoparticles
The sulfate process involves three phases:
1) Mineral Dissolution
2) Hydrate Titanium dioxide formation
3) Anhydrous titanium dioxide formation
The mineral used in this process is the ilmenite FeTiO3. After grinding, it is treated with sulfuric acid with the formation of a mixture of sulfates, titanyl sulfate, iron (II) sulfate and iron sulfate (III).
FeTiO3 (s) + 2H2SO4 (aq) &#; TiOSO4 (aq) + FeSO4 (aq) + 2H2O (l)
Before extraction of titanium dioxide, the ferric ion is converted to a ferrous ion using iron filings:
2Fe3+ (aq) + Fe (s) &#; 3Fe2+ (aq)
Any solids present are removed by filtration after sedimentation. The solution is cooled and the iron (II) sulphate crystals precipitate which, in turn, are removed by filtration.
The residual solution consists of titanyl sulfate so the next step involves the production of hydrated titanium dioxide according to the reaction:
TiOSO4 (aq) + H2O (l) &#; TiO2 (s) + H2SO4 (aq)
The hydrated form of titanium dioxide is brought to a temperature of about 800 °C to which it loses its hydration water.
2)Chloride Process in the production of Titanium Dioxide Nanoparticles
The chloride process involves the transformation of rutile to titanium chloride (IV) and the subsequent oxidation of the latter. Rutile is heated to 900 °C in the presence of chlorine and coke with the formation of titanium chloride (IV) which is a volatile compound. The latter is heated in the presence of oxygen at °C.
TiCl4 (g) + O2 (g) &#; TiO2 (s) + 2Cl2 (g)
Applications of Titanium Dioxide Nanoparticles
Titanium dioxide not only provides hiding power but also acts as an ultraviolet shielding agent. Titanium dioxide is divided into two types: anatase and rutile. Anatase titanium dioxide and rutile titanium dioxide have different structures and have different applications. For example, Anatase titanium dioxide is used for interior wall cladding because it is easy to pulverize and rutile is often used for exterior wall cladding due to its aging resistance. Given below are the main applications of the two types of Titanium Dioxide.
8 Uses of Anatase Titanium Dioxide Nanoparticles
Anatase Titanium dioxide is extensively used in plastics, ink, coatings, paper, rubber, chemical fiber, chemical, ceramics, pharmaceutical, food, and some further industries. The main uses of Anatase titanium dioxide are stated below:
1. Anatase titanium dioxide has a good photocatalytic effect and is widely used in photocatalysts and air purifiers.
2. Anatase titanium dioxide due to the huge specific surface has been broadly used in solar cells, environmental purification, photocatalysis, catalyst media, gas sensors, and lithium batteries.
3. Anatase titanium dioxide is used in papermaking, it can play the role of fluorescence and brightening and increase the whiteness of the paper. In the field of printing, the thicknesses of coatings of less than 100 millimeters are required, which is why very fine titanium dioxide pigments are used. Fillers such as chalk, talc or kaolin are used for the paper industry. Titanium dioxide pigments are used for making a very white paper and should be opaque and very thin. It is also applied as a coating to make "artistic" paper.
4. It is also used in the manufacturing of ink. It is an indispensable white pigment in advanced inks.
5. Anatase Titanium dioxide has also applications in the textile and chemical fiber industry. They remove the greasy appearance on fibers caused by the translucent properties of the resin.
6. Anatase Titanium dioxide is used as a dye in the rubber industry and it also has reinforcing, anti-aging and filling effects.
7. Other areas of application of Anatase titanium dioxide include the ceramic industry, the manufacturing of white cement and the coloring of rubber or linoleum.
8. In addition to being a pigment, titanium dioxide is used as a catalyst, as a protector of the skin against UV rays in some cosmetic creams. In nanoparticle form, it is used in sunscreens, food dyes, self-cleaning surfaces, and dyes.
7 Uses of Rutile Titanium Dioxide Nanoparticles
Its applications cover all industries as we can see in the following examples:
1. RutileTitanium dioxide is non-toxic, with strong photocatalytic action and excellent transparency, therefore, it is used in coatings and products for air purification in indoor environments.
2. RutileTitanium dioxide has antibacterial functions due to their photocatalytic property which can abolish bacteria or overpower their reproduction.
3. RutileTitanium dioxide also improves the mechanical properties of particles through dispersion.
4. RutileTitanium dioxide can be used in various military fields.
5.Titanium dioxide pigments are also employed as ultraviolet absorbers in products for, cosmetic powders, soaps, tanning, cigarette paper, creams, toothpaste, and the cosmetic industry.
6. Rutile Titanium dioxide is used universally in the paints and coatings industry, and it has replaced any other white pigment in the market.
7. Rutile Titanium dioxide is also used to color plastic items such as toys, electronics, cars, furniture, packaging, and so on. The pigment of titanium dioxide absorbs part of the UV radiation protecting its content.
Conclusion
Rutile and anatase Titanium Dioxide nanoparticles are 2 mineralogical types of titanium dioxide. The key difference among the two is their appearance as Rutile Titanium Dioxide is usually found in dark red appearance, whereas anatase titanium dioxide is colorless. They have very important applications in different industries, particularly in the paint industry.
Titanium dioxide, also known as titanium(IV) oxide or titania , is the inorganic compound derived from titanium with the chemical formula TiO
2. When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI .[4] 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 exceeded 9 million tonnes.[5][6][7] 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.[8]
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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.[9] This is distinct from the crystalline forms in which Ti coordinates to 6 oxygen atoms.
Structure of anatase. Together with rutile and brookite, one of the three major polymorphs of TiO2.[
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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.[10]
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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.[11][12][13] 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 600&#;800 °C (1,110&#;1,470 °F).[14]
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.[22] 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)[23] and bulk modulus (~300 GPa).[24][25]
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.[26]
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Industrial key players in the production of titanium dioxide -The largest TiO
2 pigment processors are Chemours, Venator, Kronos [de], and Tronox.[27][28] Major paint and coating company end users for pigment grade titanium dioxide include Akzo Nobel, PPG Industries, Sherwin Williams, BASF, Kansai Paints and Valspar.[29] Global TiO
2 pigment demand for was 5.3 Mt with annual growth expected to be about 3&#;4%.[30]
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.[31]
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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.
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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.[32] The resulting synthetic rutile is further processed according to the specifications of the end user, i.e. pigment grade or otherwise.[33]
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.[34]
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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.
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For specialty applications, TiO2 films are prepared by various specialized chemistries.[35] Sol-gel routes involve the hydrolysis of titanium alkoxides such as titanium ethoxide:
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:
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First mass-produced in ,[36] 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.[37] 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.[38] Approximately 4.6 million tons of pigmentary TiO2 are used annually worldwide, and this number is expected to increase as use continues to rise.[39]
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 it was present in two-thirds of toothpastes on the French market.[40] In food, it is commonly found in products like ice creams, chocolates, all types of candy, creamers, desserts, marshmallows, chewing gum, pastries, spreads, dressings, cakes, and many other foods.[41] 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.
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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".
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.[42] 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[43] One example of a pearlescent pigment is Iriodin, based on mica coated with titanium dioxide or iron (III) oxide.[44]
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.
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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.[45] Sometimes these UV blockers are combined with iron oxide pigments in sunscreen to increase visible light protection.[46]
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.[47]
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)[48] 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.[39] 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. [49] 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.[50] 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[51] and having a higher UV absorption.[52] In 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,[53] 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%.[54]
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.[50]
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.[54] Coating TiO2 with alumina, silica, zircon or various polymers can minimize avobenzone degradation[55] and enhance UV absorption by adding an additional light diffraction mechanism.[52]
TiO
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.[56]
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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.[57]
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Relevant patent families describing titanium dioxide production from ilmenite, &#;. Academic and public institutions having significant patent activity in titanium dioxide production.Between and , 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.[58] 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.[58]
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.[58]
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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,[59][60] although the {101} planes are thermodynamically more stable and thus more prominent in most synthesised and natural anatase,[61] 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.[62] 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.[63] 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 [64] and published in .[65] The process on the surface of the titanium dioxide was called the Honda-Fujishima effect [ja].[64] 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.[66] 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.[67] Visible-light-active nanosized anatase and rutile has been developed for photocatalytic applications.[68][69]
In Fujishima and his group discovered the superhydrophilicity phenomenon for titanium dioxide coated glass exposed to sun light.[64] 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[70] or paints, could reduce concentrations of airborne pollutants such as volatile organic compounds and nitrogen oxides.[71] A TiO2-containing cement has been produced.[72]
Using TiO2 as a photocatalyst, attempts have been made to mineralize pollutants (to convert into CO2 and H2O) in waste water.[73][74][75] The photocatalytic destruction of organic matter could also be exploited in coatings with antimicrobial applications.[76]
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Although nanosized anatase TiO2 does not absorb visible light, it does strongly absorb ultraviolet (UV) radiation (hv), leading to the formation of hydroxyl radicals.[77] 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.[78]
&#;
H+ &#; H2O2 + O2&#;
OH&#; + h+vb &#; HO&#;[
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Titanium oxide nanotubes, SEM image 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.Anatase can be converted into non-carbon nanotubes and nanowires.[79] Hollow TiO2 nanofibers can be also prepared by coating carbon nanofibers by first applying titanium butoxide.[80]
SEM (top) and TEM (bottom) images of chiral TiO2 nanofibers[80][
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As of , titanium dioxide has been regarded as "completely nontoxic".[4] 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. 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.[81]
The European Union removed the authorization to use titanium dioxide (E 171) in foods, effective 7 February , with a six months grace period.[82]
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.[83][84]
The US National Institute for Occupational Safety and Health recommends two separate exposure limits. NIOSH recommends that fine TiO
2 particles be set at an exposure limit of 2.4 mg/m3, while ultrafine TiO
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.[85]
As of May , following the European Union ban, the U.S. states California and New York were considering banning the use of titanium dioxide in foods.[86]
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Titanium dioxide (TiO&#;) is mostly introduced into the environment as nanoparticles via wastewater treatment plants.[87] 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.[87] 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.[87] 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.[88][89]
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TiO2 whitener in food was banned in France from , due to uncertainty about safe quantities for human consumption.[90]
In , 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 . 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".[91] In , 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.[92] Health Canada similarly reviewed the available evidence in and decided not to change their position on titanium dioxide as a food additive.[93]
As of , the Food and Drug Administration (FDA) in the United States permits titanium dioxide as a food additive. It is commonly used to increase whiteness and opacity in dairy products (lowfat milk, cream, ice cream, yogurt, etc), candies, frostings, fillings, and many other foods. The FDA permits the product's ingredients list to identify titanium dioxide as "color added" or "artificial colors" and does not require that titanium dioxide be explicitly named[94][95][96] despite growing scientific concerns.[97] In , 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.[98]
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Due to the potential that long-term ingestion of titanium dioxide may be toxic, particularly to cells and functions of the gastrointestinal tract, preliminary research as of was assessing its possible role in disease development, such as inflammatory bowel disease and colorectal cancer.[99]
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Companies such as Dunkin' Donuts dropped titanium dioxide from their merchandise in after public pressure.[100] Andrew Maynard, director of Risk Science Center at the University of Michigan, rejected the supposed danger from use of titanium dioxide in food. He says that the titanium dioxide used by Dunkin' Brands and many other food producers is not a new material, and it is not a nanomaterial either. Nanoparticles are typically smaller than 100 nanometres in diameter, yet most of the particles in food-grade titanium dioxide are much larger.[101] Still, size distribution analyses showed that batches of food-grade TiO&#; always include a nano-sized fraction as inevitable byproduct of the manufacturing processes.[102]
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This article incorporates text from a free content work. Licensed under CC-BY. Text taken from Production of titanium and titanium dioxide from ilmenite and related applications&#;, WIPO.
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For more information, please visit Enamel Grade Titanium Dioxide.