Fact-checked by Grok 2 weeks ago

Rutile

Rutile is a naturally occurring mineral form of titanium dioxide (TiO₂), characterized by its tetragonal crystal system and serving as one of the principal sources of titanium worldwide.^[1] It typically appears as prismatic, often striated crystals with an adamantine to metallic luster, exhibiting colors ranging from reddish-brown and golden-yellow to black due to trace impurities such as iron or niobium.^[1] With a Mohs hardness of 6 to 6.5 and a specific gravity of approximately 4.23, rutile is a dense, brittle accessory mineral that resists weathering, making it common in heavy mineral sands and placer deposits.^[1] Rutile forms through magmatic differentiation, metamorphic processes, and hydrothermal activity, often associating with minerals like ilmenite, zircon, magnetite, and hematite in igneous rocks such as granites and syenites, as well as in metamorphic rocks like schists, gneisses, and eclogites.^[1] It is also found in sedimentary environments, including beach sands and ancient placer deposits, where its durability allows concentration in economic heavy mineral assemblages.^[2] Major global deposits occur in Australia, South Africa, Sierra Leone, India, Brazil, and Ukraine, contributing to over half of the world's titanium production from coastal heavy mineral sands.^[2] The mineral's high refractive index (nω = 2.605–2.613, nε = 2.899–2.901) and strong dispersion make it exceptionally valuable for industrial applications, particularly as a raw material for producing titanium dioxide pigment, which provides opacity and brightness in paints, plastics, paper, and ceramics.^[2] Approximately 95% of mined rutile is used for pigment manufacture via the chloride process, while the remainder supports titanium metal production for aerospace, medical implants, and welding electrodes due to titanium's strength, lightness, and corrosion resistance.^[2] Additionally, synthetic rutile and its photocatalytic properties find niche uses in optics, environmental remediation, and as inclusions in gemstones like rutilated quartz.^[1]

Description

Composition and Formula

Rutile is an oxide mineral with the chemical formula TiO₂, in which titanium exists in the +4 oxidation state and oxygen in the -2 oxidation state.^[3] This composition makes rutile the most common naturally occurring polymorph of titanium dioxide.^[4] The molecular weight of TiO₂ is 79.866 g/mol, with titanium accounting for 59.93% and oxygen for 40.07% of the mass.^[3] Natural rutile frequently incorporates impurities that substitute for titanium in the crystal lattice, including iron (up to 10 wt% as Fe²⁺ replacing Ti⁴⁺, often reported as Fe₂O₃ or FeO equivalents), niobium (Nb⁵⁺ or Nb⁴⁺), tantalum (Ta⁵⁺), and chromium (Cr³⁺).^[5]^[6] These substitutions can alter the mineral's color—such as producing red-brown hues from iron or darker tones from niobium and tantalum—and influence other properties like density.^[4] The density of pure rutile is 4.23 g/cm³ (measured) or 4.25 g/cm³ (calculated), but natural samples vary from 4.20 to 4.35 g/cm³ due to the presence of impurities, with higher values associated with elevated niobium and tantalum content.^[4] For example, a sample from Graves Mountain, Georgia, USA, with 2.62 wt% Fe₂O₃ exhibited a density of 4.23 g/cm³.^[4]

Etymology and History

The name "rutile" derives from the Latin word rutilus, meaning "reddish" or "glowing red," a reference to the mineral's characteristic deep red streak or luster observed in many specimens.^[1] This etymology was established when German geologist Abraham Gottlob Werner formally named the mineral in 1803, assigning the term to what was previously known under various local names, such as "red schorl," a reddish variety of tourmaline-like material.^[7] Werner's description, based on specimens from Horcajuelo de la Sierra in Spain, marked the first systematic identification of rutile as a distinct mineral species.^[8] In the late 18th century, prior to Werner's naming, the mineral's significance emerged through chemical analysis. German chemist Martin Heinrich Klaproth isolated titanium oxide (TiO₂) from rutile samples in 1795, recognizing it as a new element and naming it titanium after the mythological Titans, thereby establishing rutile as a key source of this metal.^[9] Building on this, Swedish chemist Jöns Jacob Berzelius conducted further analyses in 1825, successfully isolating impure metallic titanium from rutile through a reduction process, confirming its composition and advancing understanding of its potential as a metallic resource.^[10] These early 19th-century developments shifted focus from rutile's ornamental uses to its role as a primary titanium ore. The 20th century saw rutile's industrial importance surge after the 1940s, driven by demand for titanium metal in aerospace and military applications during and following World War II.^[11] The Kroll process, developed in the 1940s, enabled large-scale production of titanium sponge from rutile, leading to a boom in extraction and processing that transformed the mineral from a niche geological curiosity into a cornerstone of modern materials science.^[12] This era's innovations built directly on the foundational chemical insights of Klaproth and Berzelius, with rutile remaining the preferred high-grade ore for titanium dioxide pigments and alloys.^[13]

Properties

Physical and Optical Properties

Rutile exhibits a range of colors, typically reddish-brown, red, or black, with rarer pale yellow, violet, or bluish hues; these variations often result from iron impurities, where higher iron content imparts darker tones such as black.^[14] The streak is pale brown to light yellow, and the luster is adamantine to submetallic, contributing to its striking appearance in both crystalline and massive forms.^[4] Crystals commonly display a prismatic or acicular habit, elongated along the c-axis with vertical striations, forming slender needles up to 25 cm in length.^[4] Mechanically, rutile has a hardness of 6–6.5 on the Mohs scale, with Vickers hardness values ranging from 894 to 974 kg/mm² under a 100 g load, making it moderately resistant to scratching.^[4] Its specific gravity is 4.23 (measured), increasing slightly with niobium-tantalum content, and calculated at 4.25, reflecting its dense titanium dioxide composition.^[4] Cleavage is good on {110}, moderate on {100}, and trace on {111}, while the fracture is subconchoidal to uneven; the mineral is brittle overall.^[4] Rutile melts at 1843°C.^[15] Optically, rutile is uniaxial positive with exceptionally high refractive indices of nω = 2.605–2.613 and nε = 2.899–2.901, among the highest for natural minerals, enabling its use in optical applications.^[4] It displays strong birefringence of 0.287–0.300 and extreme dispersion of 0.28, producing vivid fire effects that exceed those of diamond.^[16] These anisotropic properties arise from its tetragonal crystal structure.^[4] Rutile is also photosensitive and shows distinct pleochroism in colors like red, brown, and yellow.^[4]

Chemical Properties

Rutile, titanium dioxide (TiO₂), is characterized by its exceptional chemical stability, rendering it insoluble in water, most acids, and bases at room temperature, though it dissolves in hot concentrated sulfuric acid and hydrofluoric acid (HF).^[17]^[18] This inertness stems from the strong Ti-O bonds in its structure, which resist typical hydrolytic or acidic attack under ambient conditions, making rutile suitable for durable applications where chemical resistance is paramount.^[19] Under specific conditions, rutile exhibits targeted reactivity; it reacts with HF to produce titanium tetrafluoride (TiF₄) and water via the equation:

\text{TiO}_2 + 4\text{HF} \rightarrow \text{TiF}_4 + 2\text{H}_2\text{O}

^[20] Additionally, in the Kroll process, rutile serves as a primary feedstock, first converted to TiCl₄ and then reduced to metallic titanium using magnesium at high temperatures (approximately 800–900°C) in an inert atmosphere, highlighting its role in industrial titanium production despite requiring elevated thermal conditions for reduction.^[21] The bonding in rutile is predominantly ionic with significant partial covalent character due to the electronegativity difference between titanium and oxygen, contributing to its overall stability.^[19] Electronically, rutile functions as a wide-bandgap semiconductor with a band gap of approximately 3.0 eV, which limits its electrical conductivity but enables applications in photocatalysis and optics where UV activation is involved.^[22] Thermally, rutile maintains structural integrity up to around 1,600°C, beyond which it approaches its melting point of about 1,843°C without significant phase transitions, while preserving the stable Ti⁴⁺ oxidation state characteristic of its composition.^[15]

Crystal Structure

Rutile, the most common polymorph of titanium dioxide (TiO₂), adopts a tetragonal crystal system with the space group P4₂/mnm (No. 136). The primitive unit cell contains two formula units, with lattice parameters a = b = 4.593 Å and c = 2.959 Å, resulting in a c/a ratio of approximately 0.644 that underscores its structural anisotropy.^[23] This arrangement forms a three-dimensional framework where titanium (Ti⁴⁺) and oxygen (O²⁻) ions are packed efficiently, contributing to rutile's high density of 4.25 g/cm³ among TiO₂ phases. In the rutile structure, each Ti atom is octahedrally coordinated by six O atoms, forming slightly distorted TiO₆ octahedra with Ti–O bond lengths of about 1.95 Å (four equatorial bonds) and 1.98 Å (two axial bonds); these octahedra share edges along the c-axis and corners in the basal plane. Conversely, each O atom is coordinated in a trigonal planar geometry to three Ti atoms, with O–Ti–O angles reflecting the directional bonding preferences.^[24] This coordination polyhedra network exemplifies ionic-covalent bonding in transition metal oxides, where the octahedral Ti sites dominate the electronic properties. Rutile serves as the archetypal structure for TiO₂ polymorphs and is the most thermodynamically stable phase under ambient pressure and temperature conditions, with an enthalpy of formation lower than that of its metastable counterparts.^[25] Compared to anatase, which shares a tetragonal symmetry but features a larger indirect band gap of ~3.2 eV (versus rutile's ~3.0 eV direct band gap), and brookite, which has an orthorhombic structure with even higher energy, rutile's stability arises from its denser packing and lower free energy. In synthetic routes involving high pressure and temperature, rutile is preferentially formed over anatase or brookite, as the latter two transform into rutile above ~600–700°C or under elevated pressures exceeding 2 GPa.^[26]^[27] The characteristic growth habit of rutile crystals is prismatic or acicular elongation along the c-axis, driven by the lower surface energy of the {110} facets that bound the sides, which minimizes the total interfacial energy during crystallization. This anisotropic growth is evident in both natural and synthetic rutile, often resulting in needle-like morphologies that align with the tetragonal symmetry.^[28]

Occurrence and Formation

Geological Settings

Rutile commonly forms in metamorphic environments through regional metamorphism, where it occurs as an accessory mineral in rocks such as gneisses and schists.^[29] This process involves the recrystallization of pre-existing titanium-bearing minerals under elevated temperatures and pressures typical of medium- to high-grade metamorphism.^[30] Additionally, rutile develops via contact metamorphism in skarns, where it precipitates from metasomatic fluids interacting with carbonate or silicate host rocks near igneous intrusions.^[29] In igneous settings, rutile originates as an accessory phase in granitic pegmatites, where it crystallizes from late-stage, volatile-rich magmas.^[1] It also appears in alkalic complexes and ultramafic rocks, including kimberlites, often as inclusions or disseminated grains within mafic to ultramafic lithologies derived from deep mantle sources.^[29]^[31] These igneous occurrences highlight rutile's stability in silica-undersaturated to oversaturated melts at high temperatures. Rutile acts as an accessory mineral in high-pressure metamorphic rocks like eclogites, contributing to the mineral assemblage in subduction-related settings.^[1] It is also concentrated in placer deposits as heavy mineral sands, formed through the mechanical and chemical weathering of primary metamorphic or igneous sources, followed by sedimentary transport and sorting.^[29] Commonly associated with ilmenite, zircon, and magnetite, rutile typically forms at temperatures of 500–800 °C and moderate pressures of 0.5–2 GPa, conditions that favor the stabilization of its titanium dioxide structure.^[32]^[30] Recent studies since 2021 have advanced the use of rutile as a geothermometer through Zr-in-rutile thermometry, which correlates zirconium substitution in rutile with crystallization temperatures, enabling precise reconstruction of metamorphic conditions in granulite- and eclogite-facies terrains.^[33] For instance, applications in Grenvillian anorthosite pathways have yielded temperatures around 760 °C, demonstrating the method's reliability for tracing thermal histories without pressure dependence.^[33] This technique has been particularly valuable in ultrahigh-temperature metamorphism studies, refining estimates of peak conditions in ancient orogenic belts.^[34]

Major Deposits

Rutile deposits are primarily concentrated in heavy mineral sands and metamorphic rock formations, with major economic sources occurring in beach placer and alluvial settings as well as hard-rock ilmenite-rutile associations.^[35] Global production of rutile concentrates was approximately 560,000 metric tons in 2023, decreasing to 450,000 metric tons in 2024.^[36] World reserves are estimated at more than 46 million metric tons, sufficient to meet demand for over a century at current rates.^[36] Australia is the leading producer, accounting for about 36% of global output in 2023 with 200,000 metric tons and maintaining similar production of 200,000 metric tons in 2024, primarily from the Murray Basin in southeastern Australia, where extensive heavy mineral sands host high-grade rutile resources totaling over 35 million metric tons in reserves.^[35]^[36] Sierra Leone follows as a key supplier, contributing 110,000 metric tons or roughly 20% of the 2023 total from the Sierra Rutile mine, a hard-rock operation in the country's southwest that taps into metamorphic deposits with 2.9 million metric tons of reserves, though production declined to 60,000 metric tons in 2024.^[35]^[36] South Africa produced 100,000 metric tons in 2023 and 2024, mainly from beach sand deposits at Richards Bay Minerals along the KwaZulu-Natal coast, a major placer site yielding rutile alongside ilmenite and zircon.^[35]^[36]^[37] Other significant producers include Ukraine (50,000 metric tons in 2023, declining to 10,000 metric tons in 2024 due to geopolitical disruptions affecting mining in the Dnipropetrovsk and Zhytomyr regions), India (13,000 metric tons in 2023, increasing slightly to 12,000 metric tons in 2024 from coastal sands in Kerala and Odisha), and Kenya (58,000 metric tons in 2023, decreasing to 40,000 metric tons in 2024).^[35]^[36]^[38]^[39] Demand for rutile has grown post-2020, driven by titanium's role in lightweight components for electric vehicles, with projections indicating sustained growth through 2025.^[40] Alluvial and beach sand mining for rutile, prevalent in sites like Richards Bay and Indian coasts, has raised concerns over coastal ecosystem degradation, including habitat loss and sedimentation from dredging operations.^[41]

Production

Natural Extraction

Rutile is primarily extracted from heavy mineral sands deposits through surface mining techniques tailored to the deposit type. For placer deposits in beach and dune environments, which account for the majority of natural rutile production, suction dredging or mechanical scraping is commonly employed to remove overburden and collect the mineral-bearing sands.^[42] These methods involve floating dredges that suction material from shallow water or dry land scrapers that excavate layers of sand, as seen in operations along coastal regions. In contrast, hard-rock rutile deposits, though less common, are mined using open-pit methods where explosives and heavy machinery extract ore from weathered igneous or metamorphic sources.^[43] For example, Sierra Leone hosts significant rutile-rich deposits mined via dredging in the Moyamba and Bonthe districts.^[44] As of 2025, global rutile production is dominated by natural sources (approximately 66% share), with synthetic rutile growing at 3–4% annually; total market value reached about USD 1.8 billion in 2024.^[45] Following extraction, the raw sands undergo concentration to isolate rutile from associated minerals like ilmenite and zircon. Gravity separation, often using spirals or shaking tables, exploits the high density of rutile (specific gravity 4.2–4.3) to separate it from lighter quartz and feldspar gangue.^[43] Subsequent magnetic separation removes ferromagnetic minerals such as magnetite, while electrostatic separation differentiates rutile's conductive properties from non-conductive ilmenite, achieving concentrates with 90–95% heavy minerals.^[46] These processes yield rutile at typically 1–5% of the raw sand volume, depending on deposit grade.^[43] Ilmenite, often co-occurring with rutile, can be upgraded to synthetic rutile (92–95% TiO₂) through processes like the Becher process, which involves reduction and oxidation to remove iron, as detailed in the Synthetic Production subsection. Direct TiO₂ pigment production from ilmenite uses sulfate or chloride processes separately. Natural rutile extraction faces challenges including high energy consumption in separation stages—gravity and electrostatic methods require significant electricity for pumps and dryers—and effective management of tailings, which consist of silica-rich waste and potentially radioactive monazite byproducts.^[47] Tailings disposal often involves pond storage or dry stacking to mitigate environmental risks like groundwater contamination. Post-2020 advancements in automated sensor-based sorting, using X-ray transmission and hyperspectral imaging, have improved recovery efficiency by up to 20–30% in heavy mineral circuits, reducing waste and operational costs.^[48]

Synthetic Production

Synthetic rutile is primarily produced through industrial processes that upgrade ilmenite ore, a common natural source containing approximately 40-65% TiO₂, into higher-grade titanium dioxide. The Becher process, developed in the early 1960s, involves an initial reduction step where ilmenite is heated with carbon (such as coal) in a rotary kiln at around 1,200°C to convert iron oxides to metallic iron and form titanium suboxides like Ti₂O₃.^[49]^[50] This is followed by aerial oxidation of the reduced material at approximately 1,200°C, which reoxidizes the titanium suboxides to rutile (TiO₂) while forming iron oxides that can be separated magnetically or by leaching, yielding synthetic rutile with 92-95% TiO₂ content.^[49]^[51] Another key industrial method is the chloride process, which produces high-purity rutile suitable for pigments. In this gas-phase reaction, purified titanium tetrachloride (TiCl₄), derived from chlorination of rutile or ilmenite feedstocks, is oxidized with oxygen at temperatures between 900°C and 1,400°C in a fluidized-bed reactor, directly forming fine rutile particles and regenerating chlorine gas for recycling.^[52]^[53] This process has been widely adopted since the 1960s for its efficiency in producing uniform, pigment-grade TiO₂.^[52] For laboratory-scale production, particularly of rutile nanoparticles, sol-gel and hydrothermal methods enable precise control over particle size and morphology. In sol-gel synthesis, titanium precursors like titanium isopropoxide are hydrolyzed and condensed to form a gel, which is then calcined to yield rutile-phase nanoparticles typically 10-50 nm in size.^[54] Hydrothermal synthesis involves treating titanium salts under high pressure and temperature (150-250°C) in water, promoting direct rutile formation without high-temperature calcination.^[55] These nanoparticles can be doped with metals such as ruthenium or tin during synthesis to create colored variants, including synthetic "titania" gemstones used in jewelry for their optical effects.^[56]^[57] Certain high-purity synthetic TiO₂ forms, such as those from the chloride process or laboratory synthesis, can exceed 99.5% TiO₂, offering advantages in consistency for optical applications like lenses and substrates, while industrial synthetic rutile provides 92–95% TiO₂.^[58] These high-purity forms have been utilized in optics since the 1950s, enabling advancements in birefringent materials and epitaxial growth.^[59] Recent advances in the 2020s focus on green synthesis to enhance sustainability and reduce energy consumption. Microwave-assisted methods, such as roasting titanium slag followed by acid leaching, accelerate rutile formation at lower temperatures (around 600-800°C) compared to conventional heating, minimizing energy use and emissions while maintaining high yields.^[60] These approaches, often combined with bio-extracts for nanoparticle doping, promote eco-friendly scalability for photocatalytic and environmental applications.^[61]

Applications

Pigment and Coating Uses

Rutile, the most stable polymorph of titanium dioxide (TiO₂), serves as a premier white pigment in paints, plastics, and coatings due to its exceptional opacity, brightness, and ability to scatter visible light effectively.^[62] This light-scattering property arises from rutile's high refractive index of approximately 2.7, which enables superior hiding power and whiteness even at lower concentrations.^[62] In paint formulations, rutile pigments typically contain over 90% TiO₂, ensuring optimal brightness and color stability without introducing unwanted hues.^[63] Compared to the anatase form of TiO₂, rutile is preferred for exterior coatings because of its greater durability and resistance to chalking, a degradation process where the paint surface powders under UV exposure.^[64] Rutile absorbs more UV radiation in the 350–400 nm range, reducing photocatalytic activity that leads to binder breakdown in anatase-based paints.^[64] This makes rutile ideal for long-lasting outdoor applications, such as architectural paints and automotive finishes, where weather resistance is critical.^[65] Globally, approximately 90% of TiO₂ production is dedicated to pigment applications, with paints and coatings accounting for the largest share.^[66] In 2023, the titanium dioxide market, dominated by pigment uses, was valued at about $20.4 billion.^[67] To enhance performance in these formulations, rutile particles are often surface-treated with layers of alumina (Al₂O₃) and silica (SiO₂), which improve dispersibility by reducing inter-particle attraction and preventing agglomeration in liquid media.^[68] These treatments also boost compatibility with resins, leading to smoother application and better film integrity.^[69] The widespread adoption of rutile TiO₂ as a pigment marked a significant historical shift, particularly after the 1940s, when it largely replaced toxic lead-based whites in industrial and artistic paints due to its relative non-toxicity and superior optical properties.^[70] As of 2025, regulatory scrutiny continues, with the EU having banned nano-TiO₂ in food since 2022, though pigment uses remain approved following the annulment of a carcinogenic label for inhalable powders.^[71]^[72] Synthetic production methods developed during this period enabled high-purity rutile forms, ensuring consistent color and performance across batches.^[73]

Industrial and Metallurgical Uses

Rutile is extensively used in the production of welding electrodes, where it serves as a key component in coatings that enhance arc stability and produce a protective slag during the welding process. These rutile-coated electrodes, also known as E6013 types, facilitate smooth operation and are suitable for general-purpose welding on mild steel, accounting for a significant portion of the global stick welding electrode market due to their ease of use and versatility.^[74]^[75]^[76] In ceramics and refractories, rutile's high melting point of approximately 1850°C contributes to its role in manufacturing durable tiles, crucibles, and other heat-resistant materials that withstand extreme temperatures. It also functions as a flux in glassmaking, lowering the melting temperature of silica and improving the overall process efficiency in producing glass products.^[74]^[77] The primary metallurgical application of rutile is in titanium metal production via the Kroll process, where rutile (TiO₂) is first converted to titanium tetrachloride and then reduced using magnesium to yield titanium sponge. A key step involves the reduction reaction:

\text{TiCl}_4 + 2\text{Mg} \rightarrow \text{Ti} + 2\text{MgCl}_2

conducted at temperatures of 800–900°C under inert conditions to produce high-purity titanium for various alloys. This process remains the dominant industrial method, with rutile supplying about 5% of global titanium ore feedstock.^[78]^[79]^[80] Additional industrial uses include rutile as a support material for catalysts in chemical reactions, leveraging its stability and surface properties, and as a filler in paper production to enhance opacity and print quality without significantly increasing weight.^[81]^[82] Global demand for rutile has grown at an annual rate of approximately 5% since 2020, driven by expanding applications in aerospace components and medical implants that require lightweight, corrosion-resistant titanium alloys.^[45]^[83]^[84]

Advanced Technological Uses

Rutile titanium dioxide (TiO₂) serves as an n-type semiconductor primarily due to oxygen vacancies acting as shallow donors, with electron mobility in single-crystal form reaching approximately 1 cm²/V·s, though values can vary to around 0.5 cm²/V·s at room temperature owing to strong electron-phonon interactions forming small polarons.^[85]^[86] This property enables its application in dye-sensitized solar cells (DSSCs), where rutile nanostructures such as nanorods or microspheres facilitate efficient electron transport and dye adsorption, achieving power conversion efficiencies up to 2.64% in optimized double-layered configurations.^[87]^[88] Additionally, doped rutile TiO₂ varistors, often incorporating tantalum or niobium, exhibit nonlinear current-voltage characteristics suitable for surge protection, with breakdown voltages as low as those in zinc oxide-based devices but with superior dielectric performance.^[89]^[90] In photocatalysis, rutile TiO₂ (band gap ~3.0 eV) absorbs UV light to generate electron-hole (e⁻/h⁺) pairs through band gap excitation, where photogenerated electrons in the conduction band reduce species like O₂ to superoxide radicals, while holes in the valence band oxidize water or pollutants to hydroxyl radicals, enabling degradation of organic contaminants such as methylene blue.^[91]^[92] Doping with non-metals like nitrogen or sulfur extends activity into the visible spectrum by introducing mid-gap states that narrow the effective band gap to ~2.4-2.8 eV, enhancing pollutant degradation rates under solar irradiation without compromising the charge separation efficiency inherent to rutile's crystal structure.^[93]^[94] Rutile's high refractive index (n ≈ 2.6-2.9) and dispersion (0.28, exceeding diamond's 0.044) contribute to its optical applications, particularly in creating asterism—the star-like effect in sapphires—through aligned needle-like inclusions that scatter light into six-ray patterns when cut en cabochon.^[95] Synthetic rutile, produced via flame fusion, was historically marketed as "Titania" diamond simulants in the late 1940s, with doped variants (e.g., chromium for color) mimicking diamond's fire while offering flawless clarity, though strontium titanate later surpassed it due to closer refractive indices.^[96] Recent post-2020 research on Fe-doped rutile TiO₂ has demonstrated room-temperature ferromagnetism in dilute concentrations (up to 5 at%), arising from Fe³⁺ substitution at Ti sites inducing spin polarization and carrier-mediated exchange, positioning it as a candidate dilute magnetic semiconductor for spintronic devices like magnetoresistive sensors.^[97]^[98] In nanotechnology, rutile TiO₂ nanowires, synthesized via thermal oxidation or hydrothermal methods, enable high-sensitivity sensors by providing large surface-to-volume ratios for gas adsorption, exhibiting rapid response times (<10 s) to UV light or H₂S at operating temperatures around 300-400°C.^[99]^[100] These nanostructures also support environmental remediation, where their photocatalytic properties degrade persistent pollutants like dyes and heavy metals in wastewater, with nanocomposites enhancing retention and activity in saturated porous media for soil and water cleanup.^[101]^[102]

References

[1]
Rutile: Mineral information, data and localities.
Rutile is one of the five forms of titanium dioxide, TiO 2 , found in nature. Sellaite (magnesium fluoride, MgF 2 ) also has a rutile-type structure.
[2]
[PDF] Titanium—Light, Strong, and White - USGS Publications Warehouse
Ninety percent of the world's titanium is accounted for by ilmenite, but because rutile has a very high index of refraction, it is the most desirable mineral ...
[3]
https://webbook.nist.gov/cgi/cbook.cgi?ID=C1317802
[4]
[PDF] Rutile TiO2 - Handbook of Mineralogy
Mineral Group: Rutile group. Occurrence: A common high-temperature, high-pressure accessory mineral in igneous rocks, anorthosite, and granite pegmatite; in ...
[5]
[PDF] Geochemistry of Niobium and Tantalum
Monazite-bearing granites containing ilmenite and rutile commonly contain niobium and tantalum in accessory biotite, whereas allanite-bearing granites ...
[6]
[PDF] Oxides
The only exception to this rule is found in the species rutile (TiO2), where Fe2+, Fe3+, Nb4+, and Ta5+ com- monly substitute (Figure 21.6). Although ionic.<|control11|><|separator|>
[7]
[PDF] Rutile and its applications in earth sciences
Substitution of Ti4+ in the rutile crystal lattice is based on the ionic radius and ionic charge of the substituted cation (Fig. 8). Cathodoluminescence (CL) ...
[8]
https://www.irocks.com/rutile-mineral-of-many-uses
[9]
Early discoveries about titanium – timeline - Science Learning Hub
1795 – Titanium named. Martin Heinrich Klaproth, a chemist working in Germany, independently isolates a white oxide from a Hungarian mineral known as rutile.
[10]
When Titanium Was Discovered - Stanford Advanced Materials
Jul 24, 2025 · Martin Heinrich Klaproth: in 1795, German chemist Klaproth discovered this oxide when analyzing the red rutile produced in Hungary. He ...
[11]
A Brief History of Titanium | Refractory Metals and Alloys
In 1948, the United States used the magnesium reduction method to produce 2 tons of sponge titanium, and the industrial production of titanium began.
[12]
The Story of Titanium - by Brian Potter - Construction Physics
Jul 7, 2023 · You can get a sense of the development of the titanium industry by reading reports on industrial symposiums held in the 1940s, 50s, and 60s.
[13]
A History Of Titanium - Brian D. Colwell
Jul 1, 2025 · Titanium's history spans over 230 years, from its discovery in black sand in 1791, named in 1795, to its current use in aerospace and medicine.
[14]
https://www.gemselect.com/other-info/all-about-rutile.php
[15]
Rutile TiO2 | An Introduction to the Rock-Forming Minerals
Jan 1, 2013 · Rutile is a widespread accessory mineral in metamorphic rocks and in granite pegmatites. It is a common detrital mineral in sediments, and occurs as acicular ...
[16]
Rutile Value, Price, and Jewelry Information
Apr 26, 2022 · Rutile also lends its name to the rutile mineral group. The only ... Etymology. From the Latin rutilus for red, in allusion to the color ...
[17]
Samples Containing Titanium - Sample Preparation Guides
Ti0 is soluble in HCl, HF and sulfuric acids. ... The anatase and rutile forms are soluble in concentrated sulfuric acid, HF, and HF mineral acid combinations.
[18]
Nano titanium oxide (nano-TiO2): A review of synthesis methods ...
Titanium oxide (TiO2) is not soluble in water and organic acids and dilute alkaline solutions, but is soluble in hot sulfuric acid and HF. Titanium oxide (TiO2) ...
[19]
[PDF] Ionic-covalent transition in titanium oxides
Rutile has been the subject of great interest precisely because it is an insulator with a wide band gap, about. 3.0-3.3 eV, but becomes a semiconductor when ...
[20]
Chemical Equation Balancer - TiO2 + HF = TiF4 + H2O - ChemicalAid
Word Equation. Titanium Dioxide + Hydrogen Fluoride = Titanium Tetrafluoride + Water. TiO2 + HF = TiF4 + H2O is a Double Displacement (Metathesis) reaction ...
[21]
Titanium Extraction Metallurgy Developments and Control of ...
The Kroll process of magnesio-thermic reduction of TiCl4 to produce titanium sponge is represented by the following chemical reaction. TiCl4+2Mg=Ti+2MgCl ...
[22]
Probing the Electronic Structure and Band Gap Evolution of Titanium ...
Photocatalysis makes use of the semiconducting properties of TiO2, which has an inherent band gap of 3.0 eV for rutile and 3.2 eV for anatase. 5,6 However, the ...
[23]
Titanium Dioxide TiO 2 Evaporation Process Notes
It is white in appearance with a density of 4.26 g/cc, a melting point of 1,830°C, and a vapor pressure of 10-4 Torr at ~1,300°C. The largest commercial ...
[24]
[PDF] Study of Structural and Electronic Properties of Rutile Titanium ...
Feb 1, 2025 · Crystal parameters are a = 4.594 Å, c = 2.959 Å for rutile, a = 3.785 Å, c = 9.514 Å for anatase and a = 5.456 Å, b = 9.182 Å, c = 5.143 Å for ...
[25]
mp-2657: TiO2 (Tetragonal, P4_2/mnm, 136) - Materials Project
TiO₂ is Rutile structured and crystallizes in the tetragonal P4₂/mnm space group. Ti⁴⁺ is bonded to six equivalent O²⁻ atoms to form a mixture of corner and ...Missing: impurities | Show results with:impurities
[26]
Stability of rutile-type TiO2 under high pressure - ResearchGate
Aug 7, 2025 · TiO 2 has three polymorphs at ambient conditions: rutile, anatase, and brookite with rutile being the most stable polymorph. Figure 1 shows ...
[27]
Brookite vs. rutile vs. anatase: What`s behind their various ...
Rutile is the polymorph with the narrowest band gap of ~3.0 eV, but mostly expresses up to an order of magnitude lower photocatalytic activity than anatase [13] ...
[28]
Review of the anatase to rutile phase transformation
Dec 8, 2010 · While rutile is the stable phase, both anatase and brookite are metastable; the latter is difficult to synthesise and so is seldom studied [8].
[29]
Growth Habit of Rutile and ??-Al2O3 Crystals - ResearchGate
Jun 25, 2025 · This explains why rutile frequently forms in a prismatic or acicular growth habit extended along the c-axis [63] . The divergence of surface ...
[30]
Rutile: The titanium mineral in white paint and star ruby - Geology.com
Rutile occurs as an accessory mineral in plutonic igneous rocks such as granite and in deep-source igneous rocks such as peridotite and lamproite. In ...
[31]
Rutile and its applications in earth sciences - ScienceDirect.com
Rutile has a wide range of applications in earth sciences. It is a major host mineral for Nb, Ta and other high field strength elements.
[32]
[PDF] Rutile as a Kimberlite Indicator Mineral: Minor and Trace Element ...
Thus, rutile can now be used as a new indicator mineral in kimberlite exploration in the same manner that other upper mantle minerals, such as pyrope garnet,.Missing: kimberlites | Show results with:kimberlites
[33]
Rutile Mineral Chemistry and Zr-in-Rutile Thermometry in ... - MDPI
Under the SEM and optical microscope, most rutile grains are euhedral, only partially angular, subangular, and subrounded in shape (Figure 3). Various degrees ...
[34]
Rutile Ages and Thermometry Along a Grenville Anorthosite Pathway
Feb 18, 2023 · The average Zr-in-rutile temperature was 761°C, ranging from 789°C to 734°C. Although no clear relationship was identified between grain age and ...
[35]
Thermal regime of the lower crust in the eastern Khondalite Belt ...
Aug 1, 2022 · Zr-in-rutile thermometry is valid to estimate the near-peak UHT metamorphic temperatures. •. Large-scale Zr-in-rutile thermometry mapping to ...<|control11|><|separator|>
[36]
[PDF] titanium mineral concentrates - Mineral Commodity Summaries 2024
World resources of anatase, ilmenite, and rutile total more than 2 billion tons. Substitutes: Ilmenite, leucoxene, rutile, slag, and synthetic rutile compete as ...
[37]
https://www.riotinto.com/en/operations/africa/richards-bay-minerals
[38]
Richards Bay Minerals | Global - Rio Tinto
RBM mines the vast mineral rich sands of the northern KwaZulu-Natal province and produces predominantly zircon, rutile, iron and slag – materials used in ...
[39]
[PDF] The Mineral Industry of Ukraine in 2020-2021
Feb 4, 2025 · Ukraine was the 3d-ranked producer of rutile (15.7% of world output); the 5th-ranked producer of titanium sponge (2.2%; not including United ...
[40]
Ukraine's CES Says Country Can Benefit From US Investment in ...
Feb 7, 2025 · In 2024, Ukraine significantly reduced titanium production to 120,000 tons of ilmenite concentrate and 10,000 tons of rutile concentrate, ...
[41]
Richard's Bay Heavy Minerals Sand Dune Mining, South Africa
Feb 24, 2025 · Richards Bay Minerals (RBM), established in 1977, stands as South Africa's largest producer of heavy mineral sands, extracting ilmenite, rutile ...
[42]
Heavy Minerals | Florida Department of Environmental Protection
Aug 14, 2025 · Two mining methods are used: suction dredging and auxiliary mining. Suction Dredging: An electrically powered suction dredge floats within a ...
[43]
[PDF] Deposit model for heavy-mineral sands in coastal environments
The principal economic minerals in the majority of heavy-mineral sands operations are the titanium minerals, mainly ilmenite, rutile, and leucoxene, as well as ...<|control11|><|separator|>
[44]
Sierra Rutile - Iluka Resources
A subsidiary of Iluka Resources, operates world-class mineral sands assets in Sierra Leone. The company produces high quality rutile, ilmenite and zircon.
[45]
Physical beneficiation of heavy minerals – Part 2: A state of the art ...
Electrostatic concentration is a physical separation technique usually employed on HMs with the aid of electrostatic fields, where electrical forces tend to act ...
[46]
[PDF] Titanium | 2018 Minerals Yearbook - USGS Publications Warehouse
Sep 15, 2020 · Rutile, naturally occurring TiO2, has the highest TiO2 content but ... The leading uses of TiO2 pigment, based on TiO2 pigment ...
[47]
[PDF] Pilot-Scale Demonstration of Ilmenite Processing Technology
May 24, 2017 · Wet classification then separates the iron oxide. The synthetic rutile produced by Becher Process contains approximately 93% TiO2. Most of ...
[48]
An investigation of environmental impacts of ilmenite and rutile ...
Sep 20, 2018 · This paper presents life-cycle environmental impacts and health hazards of the ilmenite and rutile processing routes which are very little exploredMissing: challenges | Show results with:challenges
[49]
Improving Sustainability and Efficiency in Ore Sorting with Sensors
Nov 27, 2023 · Efficiency Gains: Higher Recovery Rates and Cost-Savings. Automated sensor-based ore sorting substantially enhances productivity and efficiency, ...Missing: heavy | Show results with:heavy
[50]
[PDF] Some Electrochemical Aspects of the Becher Process - CORE
The Becher process is used to upgrade ilmenite (~60% TiO2) to synthetic rutile (92-95%. TiO2). Reduced ilmenite (FeTiO2) is an intermediate mineral product ...
[51]
Preparation of synthetic rutile from reduced ilmenite through the ...
An improved Becher process for the production of synthetic rutile was proposed. •. Catalysts significantly enhanced the aeration process. •. Magnetite can be ...
[52]
Becher Process - Engineering Heritage Australia
Dec 29, 2023 · Bob Becher invented what became known as the Becher Process, a process for converting ilmenite to synthetic rutile which contains between 88 and 95% TiO2.
[53]
Titanium dioxide - The Essential Chemical Industry
The rutile is fed into a heated bed together with a source of carbon, usually coke. Chlorine is fed into the bed and the reaction takes place to form titanium( ...
[54]
[PDF] Chloride Process
Pure titanium tetrachloride reacts with hot oxygen to create titanium dioxide and chlorine. The chlorine is reused in the chlorination while.
[55]
Synthesis of Rutile (α-TiO2) Nanocrystals with Controlled Size and ...
A new methodology was developed to synthesize uniform rutile (α-TiO2) nanocrystals by the thermohydrolysis of titanium(IV) chloride in hydrochloric ...
[56]
Mesoporous rutile TiO2: Synthesis, characterization and ...
Pure rutile phase of TiO2(R-TiO2) nanocrystals were synthesized through a low temperature sol-gel synthesis route by tuning the chemical process.
[57]
Synthesis and Characterization of Ru Doped TiO2 Nanoparticles by ...
Nov 9, 2010 · The object of this study was to prepare Ru doped TiO2 nanoparticles by a combination of sol-gel and hydrothermal methods. Experimental. Titanium ...
[58]
Effect of tin dioxide doping on rutile phase formation in sol-gel ...
Nanocrystalline titania powders with and without tin dioxide dopant were prepared by a sol-gel method. The development of the microstructure in these ...Missing: gemstones | Show results with:gemstones
[59]
Chloride Process Titanium Dioxide - Inter-China Chemical
It is a chemical procedure used to separate high purity titanium dioxide from its rutile and ilmenite ore sources.
[60]
Titanium Dioxide (Rutile) - SHINKOSHA Crystals for a bright future
Titanium Dioxide (Rutile) TiO2. Rutile is attracting attention not only as a birefringent material for optics but also as a substrate for epitaxial growth.
[61]
Synthesis of rutile TiO2 powder by microwave-enhanced roasting ...
In this paper, the preparation of rutile TiO2 powder from titanium slag by microwave-assisted activation roasting followed by hydrochloric acid leaching was ...Missing: 2020s | Show results with:2020s
[62]
Green Synthesis of Silver-Incorporated Rutile TiO2 for Enhanced ...
This study highlights the potential of Ag/TiO2 synthesized via green methods as a high-performance photocatalyst for the effective remediation of pharmaceutical ...
[63]
Titanium Dioxide - TiO2 Pigment for Paints, Coatings & Inks
Jul 8, 2025 · Titanium dioxide is by far the most suited white pigment because of its high refractive index and lack of visible light absorption.
[64]
[PDF] List of Grades Worldwide
The titanium dioxide content and density of ... It results in very bright white paints with a neutral tone and outstanding opacity and tinting strength.
[65]
[PDF] Titanium Dioxide for Coatings - Ti-Pure
Rutile TiO2 pigments are preferred because they scatter light more efficiently, are more stable and are more durable than anatase pigments. Titanium dioxide ...
[66]
Titanium Dioxide - NCBI Bookshelf - NCBI - NIH
Typically, the composition of rutile is 95% titanium dioxide, the remaining 5% being silicon, chromium, vanadium, aluminium and iron oxides (Lynd & Lefond, ...
[67]
TITANIUM - Mining Engineering Online - Official Publication of SME
Approximately 90 percent of titanium is consumed in the form of titanium dioxide (TiO2), a white pigment in paints, paper and plastics. TiO2 pigment is ...
[68]
Titanium Dioxide Market Size, Share & Trends Report, 2030
The global titanium dioxide market size was estimated at USD 20.43 billion in 2023 and is projected to reach USD 31.79 billionn by 2030, growing at a CAGR ...
[69]
Tailoring TiO2 Treatment Chemistry To Achieve Desired ...
Feb 22, 2000 · The hydrous alumina particles on the pigment surface reduce the particle-particle attractive forces and improve dispersibility. The alumina also ...
[70]
TiO2 Applications as a Function of Controlled Surface Treatment
Rutile TiO2 particles must be coated with protective layers of SiO2 and Al2O3 through wet chemistry processes in order to decrease their photoactivity, increase ...
[71]
Luminescence of coprecipitated titanium white pigments - NIH
May 17, 2019 · Titanium white (TiO2) was introduced as a pigment in the early 20th century and by mid-century was as popular as lead or zinc whites. Although ...
[72]
Pigments through the Ages - History - Titanium Dioxide Whites
Titanium White is truly the white of the 20th century. Although the titanium pigment, titanium dioxide was discovered in 1821, it was not until 1916 that modern ...Missing: shift 1940s
[73]
Rutile - Digitalfire
Rutile is considered an impure form of titanium whereas ilmenite is considered as FeTiO3. Grades of rutile are sometimes named after one of the impurities.Missing: molecular | Show results with:molecular
[74]
Stick Welding Electrode Market Size, Growth, Trends 2035
Rutile stick welding electrodes remain the largest segment, while cellulosic electrodes are experiencing the fastest growth due to their versatility. The rising ...<|separator|>
[75]
https://www.marketresearchfuture.com/reports/stick-welding-electrode-market-27461
[76]
Modern fluxing materials and analysis of their impact on silicate ...
Flux materials enhance the energy efficiency of ceramic and glass-ceramic materials production. Traditional fluxes like feldspars and alkaline carbonates ...Missing: rutile | Show results with:rutile
[77]
extraction of titanium - Chemguide
Titanium is extracted from its ore, rutile - TiO2. It is first converted into titanium(IV) chloride, which is then reduced to titanium using either magnesium or ...<|control11|><|separator|>
[78]
Titanium: An Overview of Resources and Production Methods - MDPI
The expensive and energy-consuming Kroll process produces titanium metal commercially, which is highly matured and optimized. Titanium's strong affinity for ...Missing: TiO2 HF
[79]
Titanium Production Processes - Kyocera SGS Europe
The Kroll Process Regardless of the final usage titanium must first be removed from its ore and turned into pure titanium. This is done by processing titanium ...
[80]
Recent Developments in the Synthesis of Supported Catalysts
The gold uptake increases with the surface area of the support (anatase, rutile, P-25) and is complete above 200 m2 g-1; adsorption of the gold precursor at pH ...
[81]
Application of Titanium Dioxide in the Paper Industry
Jul 24, 2025 · The opacity of the paper using titanium dioxide is 10 times higher than that of other materials, and the weight can be reduced by 15% to 30%.
[82]
Rutile Market Size, Share, Growth and Statistics - 2035 - Fact.MR
Rutile market will hit $4.54 billion by 2025 and grow at a 5.2% CAGR to reach USD 7.43 billion by 2035, United States expected 4.8% CAGR by 2035.
[83]
Titanium Ore Mining Market Insights 2025, Analysis and Forecast to ...
Apr 13, 2025 · Titanium Metal: Expected to grow at a CAGR of 4% to 7%, this segment leverages titanium's unique properties for aerospace, medical implants, and ...<|control11|><|separator|>
[84]
Rising Demand For Medical Implants Driving Growth Of The Market
Sep 10, 2025 · The progress observed in the historic phase is due to the expansion of the aerospace sector, surging demand for titanium dioxide pigments, ...
[85]
Local field effects on electron transport in nanostructured TiO2 ...
The mobilities reported here for single-crystal rutile (1 cm2/(V s)) and porous TiO2 (10(-2) cm2/(V s)) therefore represent upper limits for electron transport ...Missing: cm²/ | Show results with:cm²/
[86]
[PDF] Ultrafast scattering of electrons in TiO2 - Stanford University
The anomalous high scattering rates result in a low room temperature electron mobility of ~0.5 cm2/Vs, which sets the intrinsic limit for device performance ...Missing: cm²/ | Show results with:cm²/
[87]
Photovoltaic Effects of Dye-Sensitized Solar Cells Using Double ...
Apr 12, 2023 · The DSSC device using double-layered SPD type TiO2 photoelectrodes displayed 1.31∼2.64% efficiency, compared to single-layered SP type TiO2 ...Introduction · Results and Discussion · Conclusions · Experimental Section
[88]
Significant enhancement of power conversion efficiency for dye ...
Mar 23, 2015 · The single–crystalline TiO2 nanorod arrays with rutile phase have attracted much attention in the dye sensitized solar cells (DSSCs) ...
[89]
Varistors based on Ta-doped TiO2 - ScienceDirect.com
Varistors based on Ta-doped TiO2 ... All the samples doped with tantalum pentoxide are single phase rutile by X-ray diffraction studies (XRD not shown).
[90]
Varistors made from TiO2 — Practicability and limits - ScienceDirect
It is possible to prepare low-voltage varistors from TiO2 by doping with acceptors and by freezing in high-temperature defect equilibria.
[91]
What Controls Photocatalytic Water Oxidation on Rutile TiO2(110 ...
The formation of OH ads • is exothermic by ∼0.94 eV and is thermodynamically possible with band gap excitation because the h is photogenerated within the TiO2( ...
[92]
Heterophase Polymorph of TiO2 (Anatase, Rutile, Brookite ... - NIH
The band gap of rutile is 3.0 eV, lower than that of anatase (3.2 eV). However, the rutile phase has not been widely studied as a photocatalyst because of its ...
[93]
Photochemical Activity of Nitrogen-Doped Rutile TiO 2 (110) in ...
TiO 2 (110) single crystals, doped with nitrogen via an NH 3 treatment at 870 K, have been found to exhibit photoactivity at photon energies down to 2.4 eV.
[94]
TiS2 transformation into S-doped and N-doped TiO2 with visible ...
We observed that the S-rutile had a much better photocatalytic activity toward adsorbed methylene blue (MB) degradation in a gas–solid system and hydroxylation ...
[95]
A Review of Optical Effects in Phenomenal Gemstones and Their ...
The presence of rutile in synthetic star sapphire was first confirmed by Frondel (1954) by chemical and XRD tests on crushed and centrifugation-separated ...
[96]
Diamond simulant - Wikipedia
Upon its commercial introduction in 1955, strontium titanate quickly replaced synthetic rutile as the most popular diamond simulant. This was due not only ...Desired and differential... · Artificial simulants · 1947–1970 · Since 1976
[97]
https://pubs.aip.org/aip/adv/article/12/2/025002/2818820/A-DFT-U-study-of-site-dependent-Fe-doped-TiO2
[98]
A DFT+U study of site dependent Fe-doped TiO2 diluted magnetic ...
Feb 1, 2022 · This article reports the crystal structure, impurity formation energy, electronic property, magnetic property, and dopant configuration site ...
[99]
(PDF) A DFT+U study of site dependent Fe-doped TiO 2 diluted ...
In this work, we investigate the structural stability, electronic,. and magnetic properties of Fe-doped TiO2using DFT and DFT+U. Furthermore, there will be a ...
[100]
Rutile TiO2 nanowire arrays interconnected with ZnO nanosheets for ...
In this work, we demonstrate a UV sensor based on vertically aligned TiO2 nanowire arrays interconnected with ZnO nanosheets. The UV light sensing performance ...
[101]
Seed-Assisted Growth of TiO2 Nanowires by Thermal Oxidation for ...
May 13, 2020 · Raman spectroscopy revealed the Rutile crystalline phase of TiO2 NWs. Gas testing measurements were carried out in the presence of a relative ...
[102]
Transport and Retention of TiO 2 Rutile Nanoparticles in Saturated ...
The mechanisms governing the transport and retention kinetics of titanium dioxide (TiO2, rutile) nanoparticle (NP) aggregates were investigated in saturated ...
[103]
Nanocomposites containing titanium dioxide for environmental ...
Structural analyses suggest that single-crystalline rutile and anatase TiO2 nanorods were constructed at high temperature, 630 °C and 560 °C, respectively, ...