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Anatase

Anatase is a metastable mineral form of titanium dioxide (TiO₂), one of three naturally occurring polymorphs alongside rutile and brookite, characterized by its tetragonal crystal structure and adamantine to metallic luster.^[1] It typically occurs as dipyramidal or tabular crystals, ranging in color from colorless and pale yellow to brown, indigo, or black, though transparent varieties may appear blue in transmitted light.^[1] With a Mohs hardness of 5.5–6 and a density of 3.79–3.97 g/cm³, anatase forms primarily as a secondary mineral through the hydrothermal alteration or weathering of primary titanium-bearing minerals like ilmenite in veins, cavities, and clefts within metamorphic and igneous rocks such as schists, gneisses, granites, and syenites.^[1]^[2]^[3] Chemically stable, anatase exhibits n-type semiconducting behavior with a wide band gap of approximately 3.2 eV, enabling strong photocatalytic activity under ultraviolet light through the generation of electron-hole pairs for redox reactions.^[4] It displays perfect cleavage on the {001} and {011} planes and is often associated with minerals like quartz, zircon, apatite, and chlorite.^[1]^[3] Named in 1801 by René Just Haüy from the Greek anatasis (extension), referring to its elongated crystal habit, anatase is less thermodynamically stable than rutile and can transform into it at elevated temperatures above 600–700°C.^[1]^[2] Beyond its geological significance, anatase TiO₂ is prized for industrial applications, particularly as a white pigment in paints, plastics, paper, inks, and cosmetics due to its high refractive index, opacity, and UV resistance, with the anatase phase offering a bluer tone and lower abrasiveness compared to rutile.^[5]^[6] Its photocatalytic properties underpin uses in environmental remediation, such as water and air purification by degrading organic pollutants and disinfecting wastewater, as well as in self-cleaning coatings, solar cells, and hydrogen production via water splitting.^[4]^[2] The discovery of its photocatalytic effect in 1972 by Akira Fujishima and Kenichi Honda has driven extensive research into nanostructured anatase for advanced materials and energy applications.^[4]

Chemical Composition and Structure

Chemical Formula and Polymorphism

Anatase is a mineral form of titanium dioxide with the chemical formula TiO_2. In this compound, titanium adopts the +4 oxidation state, and each titanium atom is octahedrally coordinated by six oxygen atoms, forming distorted TiO_6 octahedra that share edges and corners.^[7] The atomic composition consists of approximately 59.9% titanium and 40.0% oxygen by weight.^[8] Anatase represents one of three naturally occurring polymorphs of TiO_2, alongside rutile and brookite, each characterized by distinct crystal structures despite sharing the same chemical formula. While rutile is the thermodynamically stable form under most conditions, anatase is metastable at room temperature and standard pressure, typically transforming to rutile upon heating above approximately 600–700°C, depending on particle size and synthesis conditions.^[5] This phase transition is irreversible and plays a key role in the material's applications. Brookite, the third polymorph, is also metastable but less commonly encountered.^[9] In addition to these natural polymorphs, several synthetic forms of TiO_2 have been developed, including metastable phases like TiO₂(B), which exhibit unique properties for specialized uses.^[7]

Crystal Structure and Unit Cell

Anatase crystallizes in the tetragonal crystal system with space group I41/amd (No. 141). The unit cell is body-centered tetragonal, containing four formula units of TiO₂ (Z = 4), with lattice parameters a = 3.78 Å and c = 9.51 Å at room temperature.^[10] These parameters reflect the slightly elongated c-axis relative to the a-axis, contributing to the overall density of 3.89 g/cm³ for the phase.^[10] The atomic structure of anatase consists of a three-dimensional framework built from distorted TiO₆ octahedra. Each titanium atom is coordinated to six oxygen atoms, forming these octahedra that share edges to create chains aligned along the c-axis; these chains are then linked laterally by corner-sharing to form the extended network.^[11] This arrangement results in open channels parallel to the c-axis within the framework, which are a distinguishing feature compared to the more compact rutile polymorph. The distortion in the octahedra arises from the tetragonal symmetry, leading to unequal Ti–O bond lengths: the four equatorial Ti–O bonds average approximately 1.93 Å, while the two axial bonds are longer at about 1.98 Å.^[12] Anatase is thermodynamically metastable relative to rutile at bulk scales, primarily due to its higher bulk free energy, but it exhibits greater stability in nanoscale forms because of lower surface energy for its dominant facets, such as (101). This size-dependent stability reversal drives the anatase-to-rutile phase transformation upon heating or particle growth, as the diminishing surface-to-volume ratio favors the lower-energy rutile phase. The transformation typically occurs between 600–800 °C, depending on particle size and impurities.^[13]

Physical Properties

Crystal Habit and Morphology

Anatase exhibits a variety of crystal habits consistent with its tetragonal symmetry, most commonly appearing as dipyramidal crystals formed by simple tetragonal dipyramids dominated by {101} faces. These dipyramids are often acute and sharply developed, with oblique striations visible on the pyramid faces that enhance their aesthetic appeal.^[14]^[15] Less frequent habits include prismatic forms elongated along the direction with {110} or {010} faces, tabular crystals flattened parallel to {001}, and pyramidal variants. Twinning, rare on {112}, occurs and can produce pseudo-octahedral or more complex aggregated structures in both natural and synthetic samples. Morphological variations may incorporate subordinate {001} or {110} faces alongside the dominant {101}, altering the overall shape from elongated bipyramids to more equant forms.^[14]^[16] Crystal sizes range from microscopic particles in fine-grained aggregates to well-formed individuals several centimeters long, with exceptional examples reaching up to 3.75 cm. Growth conditions significantly influence habit; slower crystallization rates, as in low-temperature hydrothermal environments, favor euhedral crystals with prominent faces, while rapid growth yields irregular or aggregated morphologies. In laboratory synthesis, such as hydrothermal methods, adjustments to temperature, pH, and additives enable replication of these habits at the nanoscale, often emphasizing high percentages of reactive {101} or {001} facets.^[14]^[17]^[18]

Density, Hardness, and Cleavage

Anatase exhibits a measured density ranging from 3.79 to 3.97 g/cm³, with a calculated ideal value of 3.897 g/cm³ for pure TiO₂, reflecting its tetragonal crystal structure characterized by octahedral coordination of titanium ions.^[14] These variations in specific gravity often arise from impurities, such as iron or niobium substitutions, or from structural twinning that alters the packing efficiency within the lattice.^[19] In natural specimens, lower densities are typically associated with porous or altered samples, while higher values approach the theoretical density in well-crystallized forms.^[20] The mineral's hardness is rated at 5.5 to 6 on the Mohs scale, indicating moderate resistance to scratching that places it between apatite and orthoclase in durability.^[14] This property stems from the strength of Ti-O bonds in its framework, though it is softer than the rutile polymorph due to the more open anatase structure. Vickers hardness measurements confirm this range, yielding values of 616 to 698 kg/mm² under a 100 g load, which supports its classification as a brittle material prone to fracture under stress.^[1] Cleavage in anatase is perfect on the {001} and {011} planes, resulting in a subconchoidal to uneven fracture.^[14] This combination of cleavage and brittle tenacity contributes to its tendency to form jagged fragments when abraded, distinguishing it mechanically from denser titanium oxides.^[2]

Optical and Electronic Properties

Color, Luster, and Transparency

Anatase exhibits an adamantine to splendent luster, often appearing metallic in well-formed crystals, which contributes to its striking visual appeal in mineral specimens.^[14] The mineral typically displays a range of colors, most commonly brown, pale yellow, reddish brown, indigo, or black, though rarer varieties include pale green, pale lilac, gray, or nearly colorless.^[14] These dark hues, such as black or dark blue, arise primarily from impurities like iron, which stain the otherwise white pure TiO₂ structure and impart reddish-brown to yellow tones depending on the iron content and oxidation state.^[21]^[22] Colorless or lighter forms occur when impurities are minimal, while niobium substitution can enhance blue shades through electronic effects.^[23] Additionally, intervalence charge transfer between Ti³⁺ and Ti⁴⁺ ions in mixed-valence states produces dark blue coloration by absorbing visible light in the near-infrared to visible range.^[24] In terms of transparency, anatase is transparent in light-colored varieties but becomes translucent to nearly opaque in deeply pigmented samples, with pyramidal crystals sometimes appearing fully opaque due to total internal reflection of light.^[14] The mineral shows weak pleochroism, manifesting as subtle variations in shade when viewed from different angles, though this effect intensifies in more intensely colored specimens.^[14]

Refractive Index and Birefringence

Anatase is an optically uniaxial negative crystal, characterized by distinct ordinary and extraordinary refractive indices that give rise to significant birefringence. The ordinary refractive index n_\omega is 2.561, while the extraordinary refractive index n_\varepsilon is 2.488, yielding a birefringence magnitude \delta = |n_\varepsilon - n_\omega| = 0.073.^[25] These values, measured at the sodium D line (589 nm), reflect anatase's high optical density, making it valuable in applications requiring strong light manipulation. The material exhibits high dispersion, with the refractive index varying notably across the visible spectrum, contributing to its dispersive effects in optical systems.^[26] This dispersion arises from the electronic transitions near the bandgap energy of 3.2 eV, which limits absorption to the ultraviolet region and imparts transparency in the visible range.^[27] In mineralogical studies, refractive indices and birefringence are typically determined using immersion methods, where crystals are immersed in liquids of known refractive index to match indices under a microscope, or through analysis of thin sections in polarized light to observe interference colors indicative of birefringence strength.^[25] For synthetic anatase films, advanced techniques like spectroscopic ellipsometry provide wavelength-dependent data, confirming the anisotropic optical response.^[26]

Electronic Properties

Anatase TiO₂ is an n-type semiconductor with a direct band gap of approximately 3.2 eV, corresponding to ultraviolet light absorption. The valence band primarily consists of O 2p orbitals, while the conduction band is formed by Ti 3d orbitals, enabling efficient generation of electron-hole pairs under UV irradiation. Its photocatalytic activity stems from this wide band gap and suitable band edge positions for redox reactions. Electron mobility in single-crystal anatase is around 4–9 cm²/V·s at room temperature, influenced by phonon scattering and defect states. Doping with elements like niobium can enhance conductivity by introducing donor levels, making it suitable for applications in photoelectrodes and transparent conductors.^[28]^[4]

Occurrence and Formation

Natural Geological Settings

Anatase primarily forms as a secondary mineral resulting from the hydrothermal alteration of primary titanium-bearing minerals, such as ilmenite and titanite, within metamorphic rocks.^[29] Anatase can also form through supergene weathering of primary titanium-bearing minerals in surficial environments.^[2] This process involves the mobilization and recrystallization of titanium dioxide (TiO₂) under fluid-rich conditions that facilitate the breakdown and pseudomorphic replacement of these precursor phases.^[25] The mineral is characteristically developed in low- to medium-grade metamorphic environments, such as greenschist facies, where regional or contact metamorphism promotes the necessary fluid interactions.^[30] Additionally, anatase occurs in hydrothermal veins associated with granitic pegmatites, often filling cavities or druses derived from enclosing metamorphic or igneous host rocks.^[14] Formation typically occurs at temperatures below 500 °C and low pressures, conditions that favor the stability of anatase over other TiO₂ polymorphs like rutile.^[31] These parameters align with low- to moderate-grade metamorphic and subsolidus hydrothermal regimes, where anatase acts as an authigenic phase.^[10] Globally, anatase is widespread but most prominently documented in the Alpine regions of Europe, placer-derived metamorphic sources in Brazil, and vein systems in Norway, with rarer primary occurrences in igneous rocks such as granites.^[1]

Associated Minerals and Deposits

Anatase commonly occurs in paragenetic association with quartz, albite, muscovite, rutile, brookite, and chlorite group minerals within alpine-type fissure veins formed during low-grade metamorphism.^[1] It is also frequently found alongside adularia, clinochlore, pyrite, and calcite in these settings.^[1] In certain hydrothermal vein deposits, particularly those related to tin mineralization, anatase associates with cassiterite, ilmenite, monazite, pyrite, and chalcopyrite.^[32] Notable deposits of anatase include the Binn Valley in Valais, Switzerland, where it forms in alpine clefts; the Harts Range in the Northern Territory, Australia; and various sites in Minas Gerais, Brazil, often in metamorphic terrains.^[1] The type locality is St. Christophe-en-Oisans, Bourg d'Oisans, Isère, France, in the French Alps, where it was first described.^[1] Other significant occurrences are reported in the Swiss, French, and Italian Alps, as well as in Pakistan's Balochistan region.^[33] Anatase has limited economic significance as a source of titanium dioxide (TiO₂), as it is typically recovered only as an accessory mineral during rutile or ilmenite mining operations, with primary economic titanium minerals being ilmenite, leucoxene, and rutile.^[34] Despite this, high-purity anatase deposits are of interest as potential feedstocks for titanium pigment and metal production, though such resources remain rare.^[35] Gem-quality anatase crystals, prized for their luster and twinned forms, are sourced primarily from the Swiss Alps, particularly the Binn Valley, and from diamondiferous gravels in Minas Gerais, Brazil.^[36] Additional localities yielding fine specimens include the French Alps and Pakistan.^[37]

Synthesis and Production

Laboratory Synthesis Methods

Anatase, a metastable polymorph of titanium dioxide (TiO₂), is commonly synthesized in laboratories to produce high-purity nanocrystals for research purposes, with methods emphasizing control over particle size, morphology, and phase purity.^[38] The sol-gel method is one of the most widely used laboratory techniques for preparing anatase TiO₂, involving the hydrolysis and condensation of titanium alkoxide precursors such as titanium tetraisopropoxide (TTIP) or titanium isopropoxide in the presence of water and a catalyst like hydrochloric acid.^[39]^[40] This process forms a sol that evolves into a gel network at room temperature or slightly elevated temperatures (up to 100°C), followed by drying and calcination at 400–500°C to induce crystallization into the anatase phase while maintaining nanoscale dimensions.^[39]^[40] The resulting particles typically exhibit high surface areas (34–120 m²/g) and can achieve pure anatase phase under acidic conditions (e.g., 12 M HCl), though mixtures with brookite or rutile may form without optimization.^[39] Hydrothermal synthesis provides an effective alternative for generating anatase nanocrystals directly in aqueous media, utilizing precursors like titanium tetrachloride (TiCl₄) or titanium oxyhydroxide (TiO(OH)₂) sealed in autoclaves under autogenous pressure at 150–250°C for several hours (e.g., 12 h at 180°C).^[39]^[38] This pressure-assisted crystallization yields highly crystalline anatase particles with surface areas of 100–134 m²/g and anatase content up to 78%, often without requiring additional calcination, though post-treatment at 350°C enhances purity.^[39] The method favors the formation of uniform nanocrystals due to the controlled supersaturation in the high-temperature aqueous environment.^[40] Solvothermal synthesis extends the hydrothermal approach by employing non-aqueous organic solvents (e.g., ethanol or other alcohols) instead of water, enabling finer control over particle size (typically 10–50 nm) through solvent polarity, surfactants, and reaction parameters at similar temperatures (150–200°C).^[38]^[40] This variant is particularly useful for tailoring morphologies like nanorods or nanotubes while stabilizing the anatase phase.^[40] Phase selectivity in these syntheses is critically managed by adjusting pH (acidic conditions promote anatase) and temperature (below 600°C to prevent transition to the more stable rutile phase), as higher temperatures or neutral/basic pH can lead to mixed polymorphs.^[39]^[40] Influential reviews, such as those by Zhang and Banfield, underscore these parameters as key to achieving pure anatase for photocatalytic and electronic studies.^[40]

Industrial Production Processes

The industrial production of synthetic anatase, a polymorph of titanium dioxide (TiO₂), primarily occurs through two major commercial routes: the sulfate process and the chloride process. These methods convert titanium-bearing ores, such as ilmenite (FeTiO₃), into high-purity pigment-grade material, with the sulfate process being the dominant route for anatase due to its ability to control the crystal phase effectively. Approximately 90% of global TiO₂ production is synthetic, as natural anatase deposits are insufficient for industrial demands, and anatase accounts for roughly 25% of TiO₂ used in white pigments as of 2024 estimates.^[41]^[42] In the sulfate process, ilmenite ore is digested with concentrated sulfuric acid (H₂SO₄, typically 93-98% concentration) at temperatures around 150-200°C, forming soluble titanyl sulfate (TiOSO₄) along with iron sulfates. The iron is subsequently removed through crystallization as FeSO₄·7H₂O or reduction to metallic iron, purifying the titanyl sulfate solution. This solution undergoes hydrolysis by boiling with water or steam, precipitating metatitanic acid (TiO(OH)₂), which is filtered, washed, and then calcined in rotary kilns at 800-1000°C under controlled atmospheric conditions to form the anatase phase; higher temperatures above 1000°C favor the rutile phase instead. This batch-oriented process, accounting for about 40% of total TiO₂ production, yields anatase with high opacity suitable for pigments.^[41]^[43]^[44] The chloride process, a continuous method representing around 60% of global TiO₂ output, typically produces rutile but can be adapted for selective anatase formation. It begins with the fluid-bed chlorination of rutile or upgraded ilmenite at 900-1000°C using chlorine gas and carbon (coke) to generate titanium tetrachloride (TiCl₄), which is purified by distillation. The TiCl₄ vapor is then oxidized in a flame reactor at 900-1400°C with oxygen or air, forming TiO₂ particles; to favor anatase, seeding with anatase nuclei or addition of modifiers like silicon halides (e.g., SiCl₄) and phosphorus halides (e.g., POCl₃) during oxidation promotes the desired phase and controls morphology, though this is less common than rutile production. The resulting TiO₂ is cooled, filtered from chlorine byproducts, and further processed.^[41]^[45]^[44] Particle size and surface properties are critical for anatase's pigment applications, with commercial grades maintained at 0.2-0.3 μm diameter to optimize light scattering without agglomeration. Post-calcination milling and classification achieve this uniformity, while surface treatments—such as coating with 1-5% alumina (Al₂O₃) or silica (SiO₂) via wet or dry processes—enhance dispersibility, weather resistance, and photocatalytic stability by passivating reactive sites. These modifications are applied in fluidized bed reactors or during calcination, ensuring the final product meets specifications for opacity and durability in coatings. Global TiO₂ production reached approximately 7.5 million metric tons in 2023, projected to exceed 8 million tons by 2025, underscoring the scale of these synthetic routes.^[41]^[42]

Applications and Uses

Pigment and Coating Applications

Anatase titanium dioxide (TiO₂) serves as a key white pigment in paints and plastics, leveraging its high refractive index of approximately 2.5 to scatter visible light effectively, thereby providing superior opacity, brightness, and whiteness.^[46] This property makes it indispensable for achieving hiding power in formulations where a clean, neutral white is required, and it is incorporated into the majority of white architectural paints and plastic products for aesthetic enhancement.^[47] In plastics, anatase TiO₂ is particularly valued for its ability to maintain color stability and impart a uniform finish in applications such as packaging and consumer goods.^[48] In coating formulations, anatase is often preferred over rutile TiO₂ for matte and interior finishes due to its lower hardness (Mohs scale 5.5–6.0), which reduces abrasion during processing and allows for smoother dispersion in water-based systems.^[49] It finds extensive use in dispersion paints, road markings, and plasters where a non-glossy appearance is desired, contributing to cost-effective opacity without the higher durability demands of exterior applications.^[50] The global demand for TiO₂ pigments, including anatase variants, reached approximately 8 million metric tons annually as of 2025, driven primarily by the coatings and plastics sectors.^[51] Key advantages of anatase in these applications include its enhanced dispersibility in polymer matrices, facilitated by smaller particle sizes and surface treatments that improve compatibility and reduce agglomeration.^[52] Additionally, when properly coated to mitigate photocatalytic activity, anatase offers adequate UV stability for indoor polymers and coatings, preventing degradation in non-exposed environments.^[53] Recent environmental considerations have spurred a shift toward low-VOC (volatile organic compound) paint formulations incorporating anatase nanoparticles, which enhance binding efficiency and further reduce emissions during application and curing.^[54] These water-based systems align with regulatory standards for indoor air quality while maintaining the pigment's optical performance.^[52]

Photocatalytic and Semiconductor Uses

Anatase TiO₂ exhibits photocatalytic activity primarily due to its indirect bandgap of approximately 3.2 eV, which allows absorption of ultraviolet (UV) light to generate electron-hole pairs that drive redox reactions.^[55] Upon UV irradiation, photogenerated holes in the valence band react with water or hydroxide ions to produce hydroxyl radicals (OH•), while electrons in the conduction band reduce oxygen or protons, enabling processes such as organic pollutant degradation and hydrogen evolution.^[55] This mechanism positions anatase as a benchmark photocatalyst for environmental remediation, though its UV limitation restricts solar efficiency to about 5% of the spectrum.^[55] In pollutant degradation, anatase TiO₂ nanoparticles effectively mineralize organic contaminants like dyes and antibiotics under UV light, with OH• radicals initiating oxidative breakdown into CO₂ and H₂O; for instance, studies report up to 96% degradation of methylene blue in 150 minutes using optimized anatase structures.^[56] For water splitting, electrons reduce H⁺ to H₂ (often with sacrificial agents like methanol to scavenge holes), achieving hydrogen evolution rates enhanced by metal co-catalysts such as Pt, as demonstrated in sacrificial-free systems yielding measurable H₂ under UV.^[55] Practical applications include self-cleaning coatings, exemplified by Pilkington Activ™ glass, which features a 15 nm anatase TiO₂ layer deposited via atmospheric pressure chemical vapor deposition, promoting organic decomposition and photo-induced superhydrophilicity (contact angle dropping to 0°) for rain-assisted cleaning.^[57] Air purification filters incorporating anatase TiO₂ similarly degrade volatile organic compounds, reducing indoor pollutants through continuous UV exposure in HVAC systems.^[55] To extend activity into the visible spectrum, doping anatase TiO₂ with non-metals like nitrogen (N) or sulfur (S) narrows the bandgap by introducing mid-gap states, enabling photocatalysis under solar light. Nitrogen doping, as pioneered in early 2000s work, substitutes lattice oxygen to form Ti-O-N bonds, shifting absorption edges to ~400-500 nm and enhancing methylene blue degradation rates by factors of 2-5 compared to undoped anatase.^[58] Sulfur doping, often via hydrothermal methods, incorporates S⁶⁺ into Ti sites, achieving visible-light-driven hydrogen production and pollutant removal with rate constants up to 0.024 min⁻¹—25 times higher than pure TiO₂—while maintaining anatase phase stability up to 500°C.^[59] These modifications have been commercialized in visible-responsive coatings for broader environmental applications. As a semiconductor, anatase TiO₂ serves as the mesoporous electron acceptor in dye-sensitized solar cells (DSSCs), particularly Grätzel cells, where its high surface area (from nanocrystalline films) facilitates rapid electron injection from excited dyes into the conduction band.^[60] Initial efficiencies reached 7.1-7.9% in 1991 using Ru(II) dyes on nanoporous anatase, progressing to 10% by 1997 via optimized porosity and electrolyte mediators.^[60] Modern configurations with zinc porphyrin sensitizers and cobalt electrolytes on anatase photoanodes have achieved 12.3% power conversion efficiency under AM 1.5G illumination, benefiting from anatase's favorable band alignment for charge separation.^[60] Recent advances in the 2020s focus on anatase-graphene heterojunctions to further improve charge dynamics, where graphene sheets act as electron sinks, suppressing recombination. These 2D/2D interfaces, synthesized via solvothermal routes, enable enhanced visible-light H₂ evolution and pollutant degradation, outperforming pure anatase by leveraging graphene's conductivity for improved pollutant remediation and CO₂ reduction.^[61]

History and Nomenclature

Discovery and Etymology

Anatase was first described in 1797 by the French naturalist and mineralogist Jean-Claude de La Métherie (also known as Delamétherie) under the name "oisanite," derived from the Oisans valley in the Dauphiné region of France, where the initial specimens were collected. These samples exhibited distinctive blue-black, metallic-lustered crystals, which La Métherie analyzed and distinguished from other titanium-bearing minerals based on their physical properties and occurrence in alpine veins. His description appeared in the second edition of his work Théorie de la Terre, marking one of the earliest systematic accounts of the mineral in scientific literature.^[62] The modern name "anatase" was coined in 1801 by the French crystallographer René Just Haüy in his seminal Traité de Minéralogie. Haüy recognized the mineral's tetragonal crystal system and its characteristic elongated pyramidal forms, naming it from the Ancient Greek anátasis (ἄνατασις), meaning "stretching" or "extension," to highlight how the length of the pyramid faces exceeded that of the base relative to other tetragonal species like rutile. This etymology emphasized the mineral's unique crystal habit, often appearing as slender, dipyramidal prisms or pseudo-octahedral twins, which set it apart morphologically despite its chemical similarity to rutile (TiO₂). Haüy's classification established anatase as a distinct species, building on earlier chemical insights.^[63] Early investigations frequently conflated anatase with rutile due to their identical composition of titanium dioxide, leading to initial misidentifications in the late 18th century. The element titanium was first identified in 1791 by William Gregor from a mineral in Cornwall, England, and independently confirmed and named by German chemist Martin Heinrich Klaproth in 1795 from rutile samples from Hungary—providing the foundational chemical analysis that linked anatase to the same oxide, prompting further scrutiny of its polymorphic nature. Klaproth's work, published in Chemische Annalen, confirmed the presence of a novel "titanic acid" (TiO₂), which subsequent studies applied to anatase specimens.^[64] The polymorphic relationship between anatase, rutile, and brookite was definitively confirmed in the early 20th century through X-ray diffraction analysis. Norwegian physicist Lars Vegard first determined the crystal structure of anatase in 1916, revealing its tetragonal lattice with space group I4₁/amd and unit cell parameters a ≈ 3.78 Å, c ≈ 9.52 Å, distinct from rutile's more compact P4₂/mnm structure. This structural elucidation, detailed in Vegard's paper in the Philosophical Magazine, resolved lingering debates about whether anatase was merely a variety of rutile, affirming it as a metastable polymorph of TiO₂.^[65]

Classification and Naming Conventions

Anatase is recognized as an approved mineral species by the International Mineralogical Association (IMA), assigned the status "A - Approved" and the official three-letter symbol "Ant".^[66] As a grandfathered entry, it predates the IMA's formal establishment in 1959 and remains valid without requiring revalidation or redefinition.^[1] It falls within the oxide class of minerals (class 04 in the Dana classification system), specifically the titanium oxide subgroup, and is grouped under the rutile group alongside other TiO₂ polymorphs such as rutile and brookite. This placement emphasizes its role as a distinct structural variant of titanium dioxide rather than a unique chemical composition.^[67] In mineralogical naming conventions, "anatase" denotes the specific polymorph and serves as the accepted species name under IMA guidelines, with no required prefixes, suffixes, or modifiers for the pure end-member TiO₂.^[68] Varieties are designated descriptively based on observable traits like color or minor substitutions; for example, "blue anatase" refers to specimens displaying a metallic blue tint, often attributed to trace iron or structural defects that influence light reflection.^[1] Such varietal names aid in cataloging without altering the core species designation.^[69] Historical synonyms for anatase include "octahedrite," an earlier term coined for its pseudo-octahedral crystal forms, which was widely used before standardization but officially discarded by the IMA in favor of "anatase" to avoid confusion with unrelated minerals.^[2] Other obsolete names, such as "dauphinite" or "wiserine," have similarly been superseded.^[70] The IMA's nomenclature compendium, updated through periodic reviews including the 2010 guidelines on mineral abbreviations and the 2019 booklet, reaffirms anatase's status as a valid, unvarying end-member with no recognized compositional series or subgroups.^[71]^[68] This ensures consistent application in scientific literature and databases.

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anatase (titanium dioxide-anatase) are reported in commercial products. Density of ideal minerals: Anatase, 3.79 g/cm3; rutile, 4.13 g/cm3; brookite,. 3.99 g ...
[21]
Anatase : Properties, Formation, Uses - Geology Science
Dec 12, 2023 · Hardness: Anatase has a Mohs hardness of 5.5–6, making it a moderately hard mineral. It can scratch glass but is softer than minerals like ...
[22]
[PDF] Titanium Dioxide - IARC Publications
anatase is obtained through the processing of ilmenite, a natural iron titanate (Lynd, 1985). Rutile is a widespread accessoiy minerai found in high-grade ...
[23]
[PDF] The Removal Of Mineral Impurities From Kaolin Using Flotation
While pure anatase Ti02 is a very white pigment with a brightness of approximately 100, the anatase present in the kaolin deposits has an intense reddish-brown ...
[24]
[PDF] Synthesis and characterisation of niobium doped TiO2 ... - CORE
The as-deposited films were blue in colour and the intensity of the colour increased with niobium incorporation (Fig. ... 169 When niobium is incorporated into ...
[25]
[PDF] An experimental study of OH solubility in rutile at 500–900 °C, 0.5–2 ...
The crystal in b illustrates the dark-blue coloration associated with Ti3+-Ti4+ intervalence charge transfer during equilibration at high P and T, which.
[26]
Anatase TiO2 | An Introduction to the Rock-Forming Minerals
Jan 1, 2013 · Anatase is distinguished from rutile and brookite by its uniaxial optically negative character: compared with other minerals it has a very ...
[27]
[PDF] Optical functions of uniaxial rutile and anatase (TiO2) revisited
The [011] plane of anatase is a primary cleavage plane, making the optic axis (OA) angle θ = 68.3° with respect to the normal to this plane. For a uniaxial ...
[28]
Reconsideration of Intrinsic Band Alignments within Anatase and ...
Feb 4, 2016 · Upon introducing the direct band gap for anatase, the ECB for the indirect band gap of 3.2 eV for anatase is 0.4 eV lower than that for rutile.
[29]
(PDF) Progressive Formation of Halloysite From the Hydrothermal ...
Aug 6, 2025 · Anatase was encountered as an alteration product of both ilmenite and biotite. Ilmenite was altered to anatase and Fe oxides. The altered ...
[30]
[PDF] GEOLOGY AND RESOURCES OF TITANIUM
This paper discusses the geology of titanium, including its contents, partitioning, source rocks, deposits in anorthosite and alkalic rocks, and minerals in ...
[31]
Hydrothermal TiO2 polymorphs in a pyrite stratiform deposit
Aug 20, 2023 · In contrast, anatase and brookite form usually as authigenic minerals at low-T (<500 °C) metamorphism (Dachille et al., 1968; Triebold et al., ...
[32]
[PDF] THE CASSITERITE-ANATASE-ILMENITE-MONAZITE-SULPHIDE
A mechanistic approach to the paragenetic interpretation of mineral lodes in Cornwall. Proceedings of the Ussher Society, 6, 548-554. HALLS, C. 1994. Energy ...
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[34]
Titanium Statistics and Information | U.S. Geological Survey
Of these minerals, only ilmenite, leucoxene, and rutile have significant economic importance. As a metal, titanium is well known for corrosion resistance ...
[35]
Titanium - Resouro Strategic Metals
Titanium minerals such as ilmenite, rutile, and anatase are essential sources of titanium ... Significant deposits of anatase are rare and highly prized. Market ...
[36]
Anatase Value, Price, and Jewelry Information
May 27, 2025 · Since such a reaction has many possible applications, such as disinfecting water, cleaning oil spills, and creating solar cells, scientists have ...
[37]
https://www.gemrockauctions.com/learn/a-z-of-gemstones/anatase
[38]
Synthetic Methods for Titanium Dioxide Nanoparticles: A Review
There are various methods that can be used to synthesize TiO2 and the most commonly used methods include sol-gel process, chemical vapor deposition (CVD) and ...
[39]
Effect of the Preparation Method (Sol-Gel or Hydrothermal) and ...
Nov 9, 2018 · Since the two most commonly used methods for TiO2 preparation are sol-gel (SG) and hydrothermal (HT) synthesis, this study attempts to compare ...
[40]
Methods of Titanium Dioxide Synthesis (Review)
Sep 30, 2020 · Main methods include sol-gel, hydrothermal, solvothermal, microwave, template, electrodeposition, sonochemical, chemical and physical vapor ...
[41]
Titanium dioxide - The Essential Chemical Industry
Manufacture of titanium dioxide. There are two main processes, the Sulfate Process and the Chloride Process (Table 1) which use the two principal ores ...
[42]
Titanium Dioxide Market Size, Share, Trends & Industry Forecast ...
Jul 1, 2025 · By grade, rutile led with 78% of the titanium dioxide market share in 2024; anatase is growing fastest at a 4.5% CAGR through 2030. By process, ...
[43]
Titanium Dioxide - NCBI - NIH
In the paper industry, both anatase and rutile titanium dioxides are used to improve opacity. The total amount of pigment varies with the grade of paper but may ...Production, Use, Occurrence... · Biological Data Relevant to the...
[44]
A new method for production of titanium dioxide pigment
The two main commercial processes for producing titanium dioxide pigment are sulfate process (Barksdale, 1966) and chloride process (Winkler, 2003). The main ...
[45]
PRODUCTION OF ANATASE TiO2 BY THE CHLORIDE PROCESS
Anatase TiO2 is produced by the "chloride" process involving the vapor phase oxidation of titanium tetrachloride. A silicon halide and a phosphorus halide ...
[46]
Titanium Dioxide - TiO2 Pigment for Paints, Coatings & Inks
Jul 8, 2025 · Anatase and rutile have an identical chemical composition. However, the spatial orientation of the TiO2 units in the crystal lattice differs.
[47]
TiO₂ Solutions & Pigments for Plastics | Ti-Pure™ by Chemours
It is widely used, because it efficiently scatters visible light, thereby imparting whiteness, brightness, and opacity when incorporated into a plastic product.
[48]
Anatase and applications in other areas - G&J Resources Inc
Anatase titanium dioxide is extensively used in plastics, ink, coatings, paper, rubber, chemical fiber, chemical, ceramics, pharmaceutical, food, and some ...<|control11|><|separator|>
[49]
Paints and Coatings - Tytanpol
Anatase pigments (less durable by their nature) are used in cheap dispersion paints, in self-cleaning paints, in road marking paints. Application of rutile ...
[50]
Recent and current developments in the titanium dioxide market
Mar 25, 2022 · Demand will increase to 8 million tonnes by 2025. Artikol's forecasts for the further development of the market refer to the year 2025 ...
[51]
Optimizing the effect of TiO2 nano powder in water-based paint ...
Oct 23, 2025 · The GC-MS analysis demonstrates a significant reduction in VOC emissions in the TiO₂-enhanced paint formulations compared to the TiO₂-free ...
[52]
Environmentally Friendly UV-Protective Polyacrylate/TiO2 ... - NIH
Compared with the ex situ preparation method, in situ polymerization provides better dispersibility of TiO2 nanoparticles in PA coating film, as well as a ...
[53]
The Critical Role of Titanium Dioxide in Paints & Coatings
Non-Toxicity: Safe for residential and commercial settings, TiO₂ is also suitable for low-VOC (volatile organic compound) paints. ... use of these nanoparticles, ...
[54]
Recent Developments of TiO2-Based Photocatalysis in the ... - NIH
This review summarizes recent advances of doped TiO 2 -based photocatalysts used in hydrogen production and the degradation of organic pollutants in water.
[55]
Phase transition and bandgap modulation in TiO2 nanostructures for ...
Jun 26, 2025 · Finally, anatase X-series samples degraded MB at a maximum rate of 96.4% in 150 min, outperforming undoped TiO2 (15%) and rutile-TiO2 ...
[56]
Characterisation of the photocatalyst Pilkington Activ™: a reference film photocatalyst?
### Summary of Pilkington Activ Glass
[57]
Visible Light Responsive Nitrogen Doped Anatase TiO2 Sheets with ...
Here, we report a facile and new route for one-pot synthesis of visible light responsive nitrogen doped anatase TiO2 sheets with dominant {001} facets.Missing: NS | Show results with:NS
[58]
In situ hydrothermal synthesis of visible light active sulfur doped TiO ...
Dec 28, 2024 · The catalyst calcined at 400 °C revealed the highest photocatalytic activity, with a rate constant of 0.02408 min−1, approximately 25 times ...
[59]
Dye-Sensitized Solar Cells: Fundamentals and Current Status - PMC
In 1993, Grätzel et al. reported 9.6% efficiency of cells, and then in 1997, they achieved 10% at the National Renewable Energy Laboratory (NREL). The ...
[60]
Graphene coupled TiO2 photocatalysts for environmental applications
This study briefly reviews the fundamental mechanism and interfacial charge-transfer dynamics in TiO 2 /graphene nanocomposites.Graphene Coupled Tio... · 6.2. Tio/graphene... · 7. Environmental...
[61]
Théorie de la terre, par Jean Claude Delamétherie. Tome premier ...
Jan 10, 2016 · Théorie de la terre, par Jean Claude Delamétherie. Tome premier cinquième. Publication date: 1797. Usage: Public Domain Mark 1.0 Creative ...
[62]
Traite de mineralogie, tome second : Hauy, Rene Just, 1743-1822
Jul 24, 2015 · Publication date: 1801. Topics: Mineralogy. Publisher: Chez Louis. Collection: gialibrary; additional_collections. Language: French.
[63]
[PDF] Titanium—Light, Strong, and White - USGS Publications Warehouse
In 1795, the German chemist Martin Klaproth named the oxide “titanium” after the Greek Titans, a mythical race of immortal giants with incredible strength and ...
[64]
Full article: LV. Results of crystal analysis.—III.
Apr 8, 2009 · 1. (1) The crystalline structure of xenotime Y(PO4) and anatase (TiO2) has been determined.2. (2) Tile lattice of xenotime is not of the ...
[65]
Titanium dioxide | TiO2 | CID 26042 - PubChem
Titanium dioxide is a titanium oxide with the formula TiO2. A naturally occurring oxide sourced from ilmenite, rutile and anatase, it has a wide range of ...
[66]
Rutile: Mineral information, data and localities.
The element titanium was described by Klaproth (1795) from a specimen of hungarischen rother schörl (Hungarian red schorl) from what is today's Slovakia.
[67]
[PDF] A COMPENDIUM OF IMA-APPROVED MINERAL NOMENCLATURE
Oct 6, 2009 · This document is a compendium of IMA-approved mineral nomenclature, a compilation of recommendations from the Commission on New Minerals and ...
[68]
https://mineralogy-ima.org/docs/IMA-Nomenclature-e-Booklet-2019.pdf
[69]
Anatase : ClassicGems.net
... Anatase ... Crystal Habit: Crystals typically acute dipyramidal, often highly modified; obtuse pyramidal or tabular; less commonly prismatic, to 3.75 cm. Twinning ...
[70]
Abbreviations for names of rock-forming minerals - GeoScienceWorld
Jan 1, 2010 · Kretz abbreviations are 2–3 letters and use uppercase first letters for minerals and lower case letters throughout for mineral components (e.g., ...Missing: conventions | Show results with:conventions