Titanium

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Titanium,  ₂₂Ti

Titanium
Pronunciation	/tɪˈteɪniəm, taɪ-/ ​(tih-TAY-nee-əm, ty-)
Appearance	silvery grey-white metallic
Standard atomic weight Ar, std(Ti)	47.867(1)
Titanium in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson – ↑ Ti ↓ Zr scandium ← titanium → vanadium
Atomic number (Z)	22
Group	group 4
Period	period 4
Block	d-block
Element category	transition metal
Electron configuration	[Ar] 3d2 4s2
Electrons per shell	2, 8, 10, 2
Physical properties
Phase at STP	solid
Melting point	1941 K ​(1668 °C, ​3034 °F)
Boiling point	3560 K ​(3287 °C, ​5949 °F)
Density (near r.t.)	4.506 g/cm3
when liquid (at m.p.)	4.11 g/cm3
Heat of fusion	14.15 kJ/mol
Heat of vaporization	425 kJ/mol
Molar heat capacity	25.060 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 1982 2171 (2403) 2692 3064 3558
Atomic properties
Oxidation states	−2, −1, +1, +2, +3, +4 (an amphoteric oxide)
Electronegativity	Pauling scale: 1.54
Ionization energies	1st: 658.8 kJ/mol 2nd: 1309.8 kJ/mol 3rd: 2652.5 kJ/mol
Atomic radius	empirical: 147 pm
Covalent radius	160±8 pm
Spectral lines of titanium
Other properties
Natural occurrence	primordial
Crystal structure	​hexagonal close-packed (hcp)
Speed of sound thin rod	5090 m/s (at r.t.)
Thermal expansion	8.6 µm/(m·K) (at 25 °C)
Thermal conductivity	21.9 W/(m·K)
Electrical resistivity	420 nΩ·m (at 20 °C)
Magnetic ordering	paramagnetic
Magnetic susceptibility	+153.0·10−6 cm3/mol (293 K)
Young's modulus	116 GPa
Shear modulus	44 GPa
Bulk modulus	110 GPa
Poisson ratio	0.32
Mohs hardness	6.0
Vickers hardness	830–3420 MPa
Brinell hardness	716–2770 MPa
CAS Number	7440-32-6
History
Discovery	William Gregor (1791)
First isolation	Jöns Jakob Berzelius (1825)
Named by	Martin Heinrich Klaproth (1795)
Main isotopes of titanium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct 44Ti syn 63 y ε 44Sc γ – 46Ti 8.25% stable 47Ti 7.44% stable 48Ti 73.72% stable 49Ti 5.41% stable 50Ti 5.18% stable

Titanium is a chemical element with symbol Ti and atomic number 22. It is a lustrous transition metal with a silver color, low density, and high strength. Titanium is resistant to corrosion in sea water, aqua regia, and chlorine.

Titanium was discovered in Cornwall, Great Britain, by William Gregor in 1791, and was named by Martin Heinrich Klaproth after the Titans of Greek mythology. The element occurs within a number of mineral deposits, principally rutile and ilmenite, which are widely distributed in the Earth's crust and lithosphere, and it is found in almost all living things, water bodies, rocks, and soils. The metal is extracted from its principal mineral ores by the Kroll and Hunter processes. The most common compound, titanium dioxide, is a popular photocatalyst and is used in the manufacture of white pigments. Other compounds include titanium tetrachloride (TiCl₄), a component of smoke screens and catalysts; and titanium trichloride (TiCl₃), which is used as a catalyst in the production of polypropylene.

Titanium can be alloyed with iron, aluminium, vanadium, and molybdenum, among other elements, to produce strong, lightweight alloys for aerospace (jet engines, missiles, and spacecraft), military, industrial processes (chemicals and petrochemicals, desalination plants, pulp, and paper), automotive, agri-food, medical prostheses, orthopedic implants, dental and endodontic instruments and files, dental implants, sporting goods, jewelry, mobile phones, and other applications.

The two most useful properties of the metal are corrosion resistance and strength-to-density ratio, the highest of any metallic element. In its unalloyed condition, titanium is as strong as some steels, but less dense. There are two allotropic forms and five naturally occurring isotopes of this element, ⁴⁶Ti through ⁵⁰Ti, with ⁴⁸Ti being the most abundant (73.8%). Although they have the same number of valence electrons and are in the same group in the periodic table, titanium and zirconium differ in many chemical and physical properties.

Characteristics

Physical properties

As a metal, titanium is recognized for its high strength-to-weight ratio. It is a strong metal with low density that is quite ductile (especially in an oxygen-free environment), lustrous, and metallic-white in color. The relatively high melting point (more than 1,650 °C or 3,000 °F) makes it useful as a refractory metal. It is paramagnetic and has fairly low electrical and thermal conductivity.

Commercially pure (99.2% pure) grades of titanium have ultimate tensile strength of about 434 MPa (63,000 psi), equal to that of common, low-grade steel alloys, but are less dense. Titanium is 60% denser than aluminium, but more than twice as strong as the most commonly used 6061-T6 aluminium alloy. Certain titanium alloys (e.g., Beta C) achieve tensile strengths of over 1,400 MPa (200,000 psi). However, titanium loses strength when heated above 430 °C (806 °F).

Titanium is not as hard as some grades of heat-treated steel; it is non-magnetic and a poor conductor of heat and electricity. Machining requires precautions, because the material can gall unless sharp tools and proper cooling methods are used. Like steel structures, those made from titanium have a fatigue limit that guarantees longevity in some applications.

The metal is a dimorphic allotrope of an hexagonal α form that changes into a body-centered cubic (lattice) β form at 882 °C (1,620 °F). The specific heat of the α form increases dramatically as it is heated to this transition temperature but then falls and remains fairly constant for the β form regardless of temperature.

Chemical properties

The Pourbaix diagram for titanium in pure water, perchloric acid, or sodium hydroxide

 

Like aluminium and magnesium, titanium metal and its alloys oxidize immediately upon exposure to air. Titanium readily reacts with oxygen at 1,200 °C (2,190 °F) in air, and at 610 °C (1,130 °F) in pure oxygen, forming titanium dioxide. It is, however, slow to react with water and air at ambient temperatures because it forms a passive oxide coating that protects the bulk metal from further oxidation. When it first forms, this protective layer is only 1–2 nm thick but continues to grow slowly; reaching a thickness of 25 nm in four years.

Atmospheric passivation gives titanium excellent resistance to corrosion, almost equivalent to platinum. Titanium is capable of withstanding attack by dilute sulfuric and hydrochloric acids, chloride solutions, and most organic acids. However, titanium is corroded by concentrated acids.^[18] As indicated by its negative redox potential, titanium is thermodynamically a very reactive metal that burns in normal atmosphere at lower temperatures than the melting point. Melting is possible only in an inert atmosphere or in a vacuum. At 550 °C (1,022 °F), it combines with chlorine. It also reacts with the other halogens and absorbs hydrogen.

Titanium is one of the few elements that burns in pure nitrogen gas, reacting at 800 °C (1,470 °F) to form titanium nitride, which causes embrittlement. Because of its high reactivity with oxygen, nitrogen, and some other gases, titanium filaments are applied in titanium sublimation pumps as scavengers for these gases. Such pumps inexpensively and reliably produce extremely low pressures in ultra-high vacuum systems.

Occurrence

Titanium is the ninth-most abundant element in Earth's crust (0.63% by mass) and the seventh-most abundant metal. It is present as oxides in most igneous rocks, in sediments derived from them, in living things, and natural bodies of water. Of the 801 types of igneous rocks analyzed by the United States Geological Survey, 784 contained titanium. Its proportion in soils is approximately 0.5 to 1.5%.

Common titanium-containing minerals are anatase, brookite, ilmenite, perovskite, rutile, and titanite (sphene). Akaogiite is an extremely rare mineral consisting of titanium dioxide. Of these minerals, only rutile and ilmenite have economic importance, yet even they are difficult to find in high concentrations. About 6.0 and 0.7 million tonnes of those minerals were mined in 2011, respectively. Significant titanium-bearing ilmenite deposits exist in western Australia, Canada, China, India, Mozambique, New Zealand, Norway, Sierra Leone, South Africa, and Ukraine. About 186,000 tonnes of titanium metal sponge were produced in 2011, mostly in China (60,000 t), Japan (56,000 t), Russia (40,000 t), United States (32,000 t) and Kazakhstan (20,700 t). Total reserves of titanium are estimated to exceed 600 million tonnes.

The concentration of titanium is about 4 picomolar in the ocean. At 100 °C, the concentration of titanium in water is estimated to be less than 10⁻⁷ M at pH 7. The identity of titanium species in aqueous solution remains unknown because of its low solubility and the lack of sensitive spectroscopic methods, although only the 4+ oxidation state is stable in air. No evidence exists for a biological role, although rare organisms are known to accumulate high concentrations of titanium.

Titanium is contained in meteorites, and it has been detected in the Sun and in M-type stars (the coolest type) with a surface temperature of 3,200 °C (5,790 °F). Rocks brought back from the Moon during the Apollo 17 mission are composed of 12.1% TiO₂. It is also found in coal ash, plants, and even the human body. Native titanium (pure metallic) is very rare.

Isotopes

Naturally occurring titanium is composed of 5 stable isotopes: ⁴⁶Ti, ⁴⁷Ti, ⁴⁸Ti, ⁴⁹Ti, and ⁵⁰Ti, with ⁴⁸Ti being the most abundant (73.8% natural abundance). At least 21 radioisotopes have been characterized, the most stable of which are ⁴⁴Ti with a half-life of 63 years; ⁴⁵Ti, 184.8 minutes; ⁵¹Ti, 5.76 minutes; and ⁵²Ti, 1.7 minutes. All other radioactive isotopes have half-lives less than 33 seconds, with the majority less than half a second.

The isotopes of titanium range in atomic weight from 39.99 u (⁴⁰Ti) to 57.966 u (⁵⁸Ti). The primary decay mode before the most abundant stable isotope, ⁴⁸Ti, is electron capture and the primary mode after is beta emission. The primary decay products before ⁴⁸Ti are element 21 (scandium) isotopes and the primary products after are element 23 (vanadium) isotopes.

Titanium becomes radioactive upon bombardment with deuterons, emitting mainly positrons and hard gamma rays.

Compounds

TiN-coated drill bit

 

The +4 oxidation state dominates titanium chemistry, but compounds in the +3 oxidation state are also common. Commonly, titanium adopts an octahedral coordination geometry in its complexes, but tetrahedral TiCl₄ is a notable exception. Because of its high oxidation state, titanium(IV) compounds exhibit a high degree of covalent bonding. Unlike most other transition metals, simple aquo Ti(IV) complexes are unknown.

Oxides, sulfides, and alkoxides

The most important oxide is TiO₂, which exists in three important polymorphs; anatase, brookite, and rutile. All of these are white diamagnetic solids, although mineral samples can appear dark (see rutile). They adopt polymeric structures in which Ti is surrounded by six oxide ligands that link to other Ti centers. 

The term titanates usually refers to titanium(IV) compounds, as represented by barium titanate (BaTiO₃). With a perovskite structure, this material exhibits piezoelectric properties and is used as a transducer in the interconversion of sound and electricity. Many minerals are titanates, e.g. ilmenite (FeTiO₃). Star sapphires and rubies get their asterism (star-forming shine) from the presence of titanium dioxide impurities.

A variety of reduced oxides (suboxides) of titanium are known, mainly reduced stoichiometries of titanium dioxide obtained by atmospheric plasma spraying.Ti₃O₅, described as a Ti(IV)-Ti(III) species, is a purple semiconductor produced by reduction of TiO₂ with hydrogen at high temperatures, and is used industrially when surfaces need to be vapour-coated with titanium dioxide: it evaporates as pure TiO, whereas TiO₂ evaporates as a mixture of oxides and deposits coatings with variable refractive index. Also known is Ti₂O₃, with the corundum structure, and TiO, with the rock salt structure, although often nonstoichiometric.

The alkoxides of titanium(IV), prepared by reacting TiCl₄ with alcohols, are colourless compounds that convert to the dioxide on reaction with water. They are industrially useful for depositing solid TiO₂ via the sol-gel process. Titanium isopropoxide is used in the synthesis of chiral organic compounds via the Sharpless epoxidation. 

Titanium forms a variety of sulfides, but only TiS₂ has attracted significant interest. It adopts a layered structure and was used as a cathode in the development of lithium batteries. Because Ti(IV) is a "hard cation", the sulfides of titanium are unstable and tend to hydrolyze to the oxide with release of hydrogen sulfide.

Nitrides and carbides

Titanium nitride (TiN) is a member of a family of refractory transition metal nitrides and exhibits properties similar to both covalent compounds including; thermodynamic stability, extreme hardness, thermal/electrical conductivity, and a high melting point. TiN has a hardness equivalent to sapphire and carborundum (9.0 on the Mohs Scale), and is often used to coat cutting tools, such as drill bits. It is also used as a gold-colored decorative finish and as a barrier metal in semiconductor fabrication. Titanium carbide, which is also very hard, is found in cutting tools and coatings.

Titanium(III) compounds are characteristically violet, illustrated by this aqueous solution of titanium trichloride.

Halides

Titanium tetrachloride (titanium(IV) chloride, TiCl₄) is a colorless volatile liquid (commercial samples are yellowish) that, in air, hydrolyzes with spectacular emission of white clouds. Via the Kroll process, TiCl₄ is produced in the conversion of titanium ores to titanium dioxide, e.g., for use in white paint. It is widely used in organic chemistry as a Lewis acid, for example in the Mukaiyama aldol condensation. In the van Arkel process, titanium tetraiodide (TiI₄) is generated in the production of high purity titanium metal. 

Titanium(III) and titanium(II) also form stable chlorides. A notable example is titanium(III) chloride (TiCl₃), which is used as a catalyst for production of polyolefins and a reducing agent in organic chemistry.

Organometallic complexes

Owing to the important role of titanium compounds as polymerization catalyst, compounds with Ti-C bonds have been intensively studied. The most common organotitanium complex is titanocene dichloride ((C₅H₅)₂TiCl₂). Related compounds include Tebbe's reagent and Petasis reagent. Titanium forms carbonyl complexes, e.g. (C₅H₅)₂Ti(CO)₂.

Anticancer therapy

Following the success of platinum-based chemotherapy, titanium(IV) complexes were among the first non-platinum compounds to be tested for cancer treatment. The advantage of titanium compounds lies in their high efficacy and low toxicity. In biological environments, hydrolysis leads to the safe and inert titanium dioxide. Despite these advantages the first candidate compounds failed clinical trials. Further development resulted in the creation of potentially effective, selective, and stable titanium-based drugs. Their mode of action is not yet well understood.

History

Martin Heinrich Klaproth named titanium for the Titans of Greek mythology

 

Titanium was discovered in 1791 by the clergyman and amateur geologist, William Gregor, as an inclusion of a mineral in Cornwall, Great Britain. Gregor recognized the presence of a new element in ilmenite when he found black sand by a stream and noticed the sand was attracted by a magnet. Analyzing the sand, he determined the presence of two metal oxides: iron oxide (explaining the attraction to the magnet) and 45.25% of a white metallic oxide he could not identify. Realizing that the unidentified oxide contained a metal that did not match any known element, Gregor reported his findings to the Royal Geological Society of Cornwall and in the German science journal Crell's Annalen.

Around the same time, Franz-Joseph Müller von Reichenstein produced a similar substance, but could not identify it. The oxide was independently rediscovered in 1795 by Prussian chemist Martin Heinrich Klaproth in rutile from Boinik (German name Bajmócska), a village in Hungary (now Bojničky in Slovakia). Klaproth found that it contained a new element and named it for the Titans of Greek mythology. After hearing about Gregor's earlier discovery, he obtained a sample of manaccanite and confirmed that it contained titanium. 

The currently known processes for extracting titanium from its various ores are laborious and costly; it is not possible to reduce the ore by heating with carbon (as in iron smelting) because titanium combines with the carbon to produce titanium carbide. Pure metallic titanium (99.9%) was first prepared in 1910 by Matthew A. Hunter at Rensselaer Polytechnic Institute by heating TiCl₄ with sodium at 700–800 °C under great pressure in a batch process known as the Hunter process. Titanium metal was not used outside the laboratory until 1932 when William Justin Kroll proved that it can be produced by reducing titanium tetrachloride (TiCl₄) with calcium. Eight years later he refined this process with magnesium and even sodium in what became known as the Kroll process. Although research continues into more efficient and cheaper processes (e.g., FFC Cambridge, Armstrong), the Kroll process is still used for commercial production.

Titanium sponge, made by the Kroll process

 

Titanium of very high purity was made in small quantities when Anton Eduard van Arkel and Jan Hendrik de Boer discovered the iodide, or crystal bar, process in 1925, by reacting with iodine and decomposing the formed vapours over a hot filament to pure metal.

In the 1950s and 1960s, the Soviet Union pioneered the use of titanium in military and submarine applications (Alfa class and Mike class) as part of programs related to the Cold War. Starting in the early 1950s, titanium came into use extensively in military aviation, particularly in high-performance jets, starting with aircraft such as the F-100 Super Sabre and Lockheed A-12 and SR-71.

Recognizing the strategic importance of titanium, the U.S. Department of Defense supported early efforts of commercialization.

Throughout the period of the Cold War, titanium was considered a strategic material by the U.S. government, and a large stockpile of titanium sponge was maintained by the Defense National Stockpile Center, which was finally depleted in the 2000s. According to 2006 data, the world's largest producer, Russian-based VSMPO-AVISMA, was estimated to account for about 29% of the world market share. As of 2015, titanium sponge metal was produced in seven countries: China, Japan, Russia, Kazakhstan, the US, Ukraine, and India. (in order of output).

In 2006, the U.S. Defense Advanced Research Projects Agency (DARPA) awarded $5.7 million to a two-company consortium to develop a new process for making titanium metal powder. Under heat and pressure, the powder can be used to create strong, lightweight items ranging from armour plating to components for the aerospace, transport, and chemical processing industries.

Production and fabrication

Titanium (mineral concentrate)

 

Basic titanium products: plate, tube, rods, and powder

 

The processing of titanium metal occurs in four major steps: reduction of titanium ore into "sponge", a porous form; melting of sponge, or sponge plus a master alloy to form an ingot; primary fabrication, where an ingot is converted into general mill products such as billet, bar, plate, sheet, strip, and tube; and secondary fabrication of finished shapes from mill products. 

Because it cannot be readily produced by reduction of its dioxide, titanium metal is obtained by reduction of TiCl₄ with magnesium metal in the Kroll process. The complexity of this batch production in the Kroll process explains the relatively high market value of titanium, despite the Kroll process being less expensive than the Hunter process. To produce the TiCl₄ required by the Kroll process, the dioxide is subjected to carbothermic reduction in the presence of chlorine. In this process, the chlorine gas is passed over a red-hot mixture of rutile or ilmenite in the presence of carbon. After extensive purification by fractional distillation, the TiCl₄ is reduced with 800 °C molten magnesium in an argon atmosphere. Titanium metal can be further purified by the van Arkel–de Boer process, which involves thermal decomposition of titanium tetraiodide. 

A more recently developed batch production method, the FFC Cambridge process, consumes titanium dioxide powder (a refined form of rutile) as feedstock and produces titanium metal, either powder or sponge. The process involves fewer steps than the Kroll process and takes less time. If mixed oxide powders are used, the product is an alloy. 

Common titanium alloys are made by reduction. For example, cuprotitanium (rutile with copper added is reduced), ferrocarbon titanium (ilmenite reduced with coke in an electric furnace), and manganotitanium (rutile with manganese or manganese oxides) are reduced.

2 FeTiO₃ + 7 Cl₂ + 6 C → 2 TiCl₄ + 2 FeCl₃ + 6 CO (900 °C)

TiCl₄ + 2 Mg → 2 MgCl₂ + Ti (1,100 °C)

About fifty grades of titanium and titanium alloys are designed and currently used, although only a couple of dozen are readily available commercially. The ASTM International recognizes 31 grades of titanium metal and alloys, of which grades one through four are commercially pure (unalloyed). Those four vary in tensile strength as a function of oxygen content, with grade 1 being the most ductile (lowest tensile strength with an oxygen content of 0.18%), and grade 4 the least ductile (highest tensile strength with an oxygen content of 0.40%). The remaining grades are alloys, each designed for specific properties of ductility, strength, hardness, electrical resistivity, creep resistance, specific corrosion resistance, and combinations thereof.

In addition to the ASTM specifications, titanium alloys are also produced to meet aerospace and military specifications (SAE-AMS, MIL-T), ISO standards, and country-specific specifications, as well as proprietary end-user specifications for aerospace, military, medical, and industrial applications.

Titanium powder is manufactured using a flow production process known as the Armstrong process that is similar to the batch production Hunter process. A stream of titanium tetrachloride gas is added to a stream of molten sodium metal; the products (sodium chloride salt and titanium particles) is filtered from the extra sodium. Titanium is then separated from the salt by water washing. Both sodium and chlorine are recycled to produce and process more titanium tetrachloride.

All welding of titanium must be done in an inert atmosphere of argon or helium to shield it from contamination with atmospheric gases (oxygen, nitrogen, and hydrogen). Contamination causes a variety of conditions, such as embrittlement, which reduce the integrity of the assembly welds and lead to joint failure. 

Commercially pure flat product (sheet, plate) can be formed readily, but processing must take into account the fact that the metal has a "memory" and tends to spring back. This is especially true of certain high-strength alloys. Titanium cannot be soldered without first pre-plating it in a metal that is solderable. The metal can be machined with the same equipment and the same processes as stainless steel.

Applications

A titanium cylinder of "grade 2" quality

 

Titanium is used in steel as an alloying element (ferro-titanium) to reduce grain size and as a deoxidizer, and in stainless steel to reduce carbon content. Titanium is often alloyed with aluminium (to refine grain size), vanadium, copper (to harden), iron, manganese, molybdenum, and other metals. Titanium mill products (sheet, plate, bar, wire, forgings, castings) find application in industrial, aerospace, recreational, and emerging markets. Powdered titanium is used in pyrotechnics as a source of bright-burning particles.

Pigments, additives, and coatings

Titanium dioxide is the most commonly used compound of titanium

 

About 95% of all titanium ore is destined for refinement into titanium dioxide (TiO
₂), an intensely white permanent pigment used in paints, paper, toothpaste, and plastics. It is also used in cement, in gemstones, as an optical opacifier in paper, and a strengthening agent in graphite composite fishing rods and golf clubs. 

TiO
₂ pigment is chemically inert, resists fading in sunlight, and is very opaque: it imparts a pure and brilliant white colour to the brown or grey chemicals that form the majority of household plastics. In nature, this compound is found in the minerals anatase, brookite, and rutile. Paint made with titanium dioxide does well in severe temperatures and marine environments. Pure titanium dioxide has a very high index of refraction and an optical dispersion higher than diamond. In addition to being a very important pigment, titanium dioxide is also used in sunscreens.

Aerospace and marine

Because titanium alloys have high tensile strength to density ratio, high corrosion resistance, fatigue resistance, high crack resistance, and ability to withstand moderately high temperatures without creeping, they are used in aircraft, armour plating, naval ships, spacecraft, and missiles. For these applications, titanium is alloyed with aluminium, zirconium, nickel, vanadium, and other elements to manufacture a variety of components including critical structural parts, fire walls, landing gear, exhaust ducts (helicopters), and hydraulic systems. In fact, about two thirds of all titanium metal produced is used in aircraft engines and frames. The titanium 6AL-4V alloy accounts for almost 50% of all alloys used in aircraft applications.

The Lockheed A-12 and its development the SR-71 "Blackbird" were two of the first aircraft frames where titanium was used, paving the way for much wider use in modern military and commercial aircraft. An estimated 59 metric tons (130,000 pounds) are used in the Boeing 777, 45 in the Boeing 747, 18 in the Boeing 737, 32 in the Airbus A340, 18 in the Airbus A330, and 12 in the Airbus A320. The Airbus A380 may use 77 metric tons, including about 11 tons in the engines. In aero engine applications, titanium is used for rotors, compressor blades, hydraulic system components, and nacelles. An early use in jet engines was for the Orenda Iroquois in the 1950s.

Because titanium is resistant to corrosion by sea water, it is used to make propeller shafts, rigging, and heat exchangers in desalination plants; heater-chillers for salt water aquariums, fishing line and leader, and divers' knives. Titanium is used in the housings and components of ocean-deployed surveillance and monitoring devices for science and the military. The former Soviet Union developed techniques for making submarines with hulls of titanium alloys forging titanium in huge vacuum tubes.

Titanium is used in the walls of the Juno spacecraft's vault to shield on-board electronics.

Industrial

High-purity (99.999%) titanium with visible crystallites

 

Welded titanium pipe and process equipment (heat exchangers, tanks, process vessels, valves) are used in the chemical and petrochemical industries primarily for corrosion resistance. Specific alloys are used in oil and gas downhole applications and nickel hydrometallurgy for their high strength (e. g.: titanium beta C alloy), corrosion resistance, or both. The pulp and paper industry uses titanium in process equipment exposed to corrosive media, such as sodium hypochlorite or wet chlorine gas (in the bleachery). Other applications include ultrasonic welding, wave soldering, and sputtering targets.

Titanium tetrachloride (TiCl₄), a colorless liquid, is important as an intermediate in the process of making TiO₂ and is also used to produce the Ziegler–Natta catalyst. Titanium tetrachloride is also used to iridize glass and, because it fumes strongly in moist air, it is used to make smoke screens.

Consumer and architectural

Titanium sealing stamps

Titanium metal is used in automotive applications, particularly in automobile and motorcycle racing where low weight and high strength and rigidity are critical. The metal is generally too expensive for the general consumer market, though some late model Corvettes have been manufactured with titanium exhausts, and a Corvette Z06's LT4 supercharged engine uses lightweight, solid titanium intake valves for greater strength and resistance to heat.

Titanium is used in many sporting goods: tennis rackets, golf clubs, lacrosse stick shafts; cricket, hockey, lacrosse, and football helmet grills, and bicycle frames and components. Although not a mainstream material for bicycle production, titanium bikes have been used by racing teams and adventure cyclists.

Titanium alloys are used in spectacle frames that are rather expensive but highly durable, long lasting, light weight, and cause no skin allergies. Many backpackers use titanium equipment, including cookware, eating utensils, lanterns, and tent stakes. Though slightly more expensive than traditional steel or aluminium alternatives, titanium products can be significantly lighter without compromising strength. Titanium horseshoes are preferred to steel by farriers because they are lighter and more durable.

Titanium cladding of Frank Gehry's Guggenheim Museum, Bilbao

 

Titanium has occasionally been used in architecture. The 42.5 m (139 ft) Monument to Yuri Gagarin, the first man to travel in space (55°42′29.7″N 37°34′57.2″E), as well as the 110 m (360 ft) Monument to the Conquerors of Space on top of the Cosmonaut Museum in Moscow are made of titanium for the metal's attractive colour and association with rocketry. The Guggenheim Museum Bilbao and the Cerritos Millennium Library were the first buildings in Europe and North America, respectively, to be sheathed in titanium panels. Titanium sheathing was used in the Frederic C. Hamilton Building in Denver, Colorado.

Because of titanium's superior strength and light weight relative to other metals (steel, stainless steel, and aluminium), and because of recent advances in metalworking techniques, its use has become more widespread in the manufacture of firearms. Primary uses include pistol frames and revolver cylinders. For the same reasons, it is used in the body of laptop computers (for example, in Apple's PowerBook line).

Some upmarket lightweight and corrosion-resistant tools, such as shovels and flashlights, are made of titanium or titanium alloys.

Jewelry

Relation between voltage and color for anodized titanium. (Cateb, 2010).

 

Because of its durability, titanium has become more popular for designer jewelry (particularly, titanium rings). Its inertness makes it a good choice for those with allergies or those who will be wearing the jewelry in environments such as swimming pools. Titanium is also alloyed with gold to produce an alloy that can be marketed as 24-karat gold because the 1% of alloyed Ti is insufficient to require a lesser mark. The resulting alloy is roughly the hardness of 14-karat gold and is more durable than pure 24-karat gold.

Titanium's durability, light weight, and dent and corrosion resistance make it useful for watch cases. Some artists work with titanium to produce sculptures, decorative objects and furniture.

Titanium may be anodized to vary the thickness of the surface oxide layer, causing optical interference fringes and a variety of bright colors. With this coloration and chemical inertness, titanium is a popular metal for body piercing.

Titanium has a minor use in dedicated non-circulating coins and medals. In 1999, Gibraltar released the world's first titanium coin for the millennium celebration. The Gold Coast Titans, an Australian rugby league team, award a medal of pure titanium to their player of the year.

Medical

Because titanium is biocompatible (non-toxic and not rejected by the body), it has many medical uses, including surgical implements and implants, such as hip balls and sockets (joint replacement) and dental implants that can stay in place for up to 20 years. The titanium is often alloyed with about 4% aluminium or 6% Al and 4% vanadium.

Medical screws and plate used for repair fracture of the wrist, scale is in centimeters.

 

Titanium has the inherent ability to osseointegrate, enabling use in dental implants that can last for over 30 years. This property is also useful for orthopedic implant applications. These benefit from titanium's lower modulus of elasticity (Young's modulus) to more closely match that of the bone that such devices are intended to repair. As a result, skeletal loads are more evenly shared between bone and implant, leading to a lower incidence of bone degradation due to stress shielding and periprosthetic bone fractures, which occur at the boundaries of orthopedic implants. However, titanium alloys' stiffness is still more than twice that of bone, so adjacent bone bears a greatly reduced load and may deteriorate.

Because titanium is non-ferromagnetic, patients with titanium implants can be safely examined with magnetic resonance imaging (convenient for long-term implants). Preparing titanium for implantation in the body involves subjecting it to a high-temperature plasma arc which removes the surface atoms, exposing fresh titanium that is instantly oxidized.

Titanium is used for the surgical instruments used in image-guided surgery, as well as wheelchairs, crutches, and any other products where high strength and low weight are desirable. 

Titanium dioxide nanoparticles are widely used in electronics and the delivery of pharmaceuticals and cosmetics.

Nuclear waste storage

Because of its corrosion resistance, containers made of titanium have been studied for the long-term storage of nuclear waste. Containers lasting more than 100,000 years are thought possible with manufacturing conditions that minimize material defects. A titanium "drip shield" could also be installed over containers of other types to enhance their longevity.

Bioremediation

The fungal species Marasmius oreades and Hypholoma capnoides can bioconvert titanium in titanium polluted soils.

Precautions

Nettles contain up to 80 parts per million of titanium.

 

Titanium is non-toxic even in large doses and does not play any natural role inside the human body. An estimated quantity of 0.8 milligrams of titanium is ingested by humans each day, but most passes through without being absorbed in the tissues. It does, however, sometimes bio-accumulate in tissues that contain silica. One study indicates a possible connection between titanium and yellow nail syndrome. An unknown mechanism in plants may use titanium to stimulate the production of carbohydrates and encourage growth. This may explain why most plants contain about 1 part per million (ppm) of titanium, food plants have about 2 ppm, and horsetail and nettle contain up to 80 ppm.

As a powder or in the form of metal shavings, titanium metal poses a significant fire hazard and, when heated in air, an explosion hazard. Water and carbon dioxide are ineffective for extinguishing a titanium fire; Class D dry powder agents must be used instead.

When used in the production or handling of chlorine, titanium should not be exposed to dry chlorine gas because it may result in a titanium–chlorine fire. Even wet chlorine presents a fire hazard when extreme weather conditions cause unexpected drying. 

Titanium can catch fire when a fresh, non-oxidized surface comes in contact with liquid oxygen. Fresh metal may be exposed when the oxidized surface is struck or scratched with a hard object, or when mechanical strain causes a crack. This poses a limitation to its use in liquid oxygen systems, such as those in the aerospace industry. Because titanium tubing impurities can cause fires when exposed to oxygen, titanium is prohibited in gaseous oxygen respiration systems. Steel tubing is used for high pressure systems (3,000 p.s.i.) and aluminium tubing for low pressure systems.

Aluminium oxide

From Wikipedia, the free encyclopedia

Aluminium oxide
(Aluminum oxide)

Identifiers
CAS Number	1344-28-1
3D model (JSmol)	Interactive image Interactive image
ChemSpider	8164808
ECHA InfoCard	100.014.265
PubChem CID	9989226
RTECS number	BD120000
UNII	LMI26O6933
InChI[show]
SMILES[show]
Properties
Chemical formula	Al2O3
Molar mass	101.960 g·mol−1
Appearance	white solid
Odor	odorless
Density	3.987g/cm3
Melting point	2,072 °C (3,762 °F; 2,345 K)
Boiling point	2,977 °C (5,391 °F; 3,250 K)
Solubility in water	insoluble
Solubility	insoluble in diethyl ether practically insoluble in ethanol
log P	0.31860
Magnetic susceptibility (χ)	−37.0×10−6 cm3/mol
Thermal conductivity	30 W·m−1·K−1
Refractive index (nD)	nω=1.768–1.772 nε=1.760–1.763 Birefringence 0.008
Structure
Crystal structure	Trigonal, hR30, space group = R3c, No. 167
Lattice constant	a = 478.5 pm, c = 1299.1 pm
Coordination geometry	octahedral
Thermochemistry
Std molar entropy (So298)	50.92 J·mol−1·K−1
Std enthalpy of formation (ΔfHo298)	−1675.7 kJ/mol
Pharmacology
ATC code	D10AX04 (WHO)
Hazards
Safety data sheet	See: data page
EU classification (DSD) (outdated)	Not listed.
NFPA 704	0 1 0
Flash point	Non-flammable
US health exposure limits (NIOSH):
PEL (Permissible)	OSHA 15 mg/m3 (Total Dust) OSHA 5 mg/m3 (Respirable Fraction) ACGIH/TLV 10 mg/m3
REL (Recommended)	none
IDLH (Immediate danger)	N.D.
Related compounds
Other anions	aluminium hydroxide
Other cations	boron trioxide gallium oxide indium oxide thallium oxide
Supplementary data page
Structure and properties	Refractive index (n), Dielectric constant (εr), etc.
Thermodynamic data	Phase behaviour solid–liquid–gas
Spectral data	UV, IR, NMR, MS

Aluminium oxide (IUPAC name) or aluminum oxide (American English) is a chemical compound of aluminium and oxygen with the chemical formula Al₂O₃. It is the most commonly occurring of several aluminium oxides, and specifically identified as aluminium(III) oxide. It is commonly called alumina and may also be called aloxide, aloxite, or alundum depending on particular forms or applications. It occurs naturally in its crystalline polymorphic phase α-Al₂O₃ as the mineral corundum, varieties of which form the precious gemstones ruby and sapphire. Al₂O₃ is significant in its use to produce aluminium metal, as an abrasive owing to its hardness, and as a refractory material owing to its high melting point.

Natural occurrence

Corundum is the most common naturally occurring crystalline form of aluminium oxide. Rubies and sapphires are gem-quality forms of corundum, which owe their characteristic colors to trace impurities. Rubies are given their characteristic deep red color and their laser qualities by traces of chromium. Sapphires come in different colors given by various other impurities, such as iron and titanium.

Properties

Aluminium oxide in its powdered form.

 

Al₂O₃ is an electrical insulator but has a relatively high thermal conductivity (30 Wm⁻¹K⁻¹) for a ceramic material. Aluminium oxide is insoluble in water. In its most commonly occurring crystalline form, called corundum or α-aluminium oxide, its hardness makes it suitable for use as an abrasive and as a component in cutting tools.

Aluminium oxide is responsible for the resistance of metallic aluminium to weathering. Metallic aluminium is very reactive with atmospheric oxygen, and a thin passivation layer of aluminium oxide (4 nm thickness) forms on any exposed aluminium surface. This layer protects the metal from further oxidation. The thickness and properties of this oxide layer can be enhanced using a process called anodising. A number of alloys, such as aluminium bronzes, exploit this property by including a proportion of aluminium in the alloy to enhance corrosion resistance. The aluminium oxide generated by anodising is typically amorphous, but discharge assisted oxidation processes such as plasma electrolytic oxidation result in a significant proportion of crystalline aluminium oxide in the coating, enhancing its hardness. 

Aluminium oxide was taken off the United States Environmental Protection Agency's chemicals lists in 1988. Aluminium oxide is on the EPA's Toxics Release Inventory list if it is a fibrous form.

Amphoteric nature

Aluminium oxide is an amphoteric substance, meaning it can react with both acids and bases, such as hydrofluoric acid and sodium hydroxide, acting as an acid with a base and a base with an acid, neutralising the other and producing a salt.

Al₂O₃ + 6 HF → 2 AlF₃ + 3 H₂O

Al₂O₃ + 2 NaOH + 3 H₂O → 2 NaAl(OH)₄ (sodium aluminate)

Structure

Corundum from Brazil, size about 2×3 cm.

 

The most common form of crystalline aluminium oxide is known as corundum, which is the thermodynamically stable form. The oxygen ions form a nearly hexagonal close-packed structure with the aluminium ions filling two-thirds of the octahedral interstices. Each Al³⁺ center is octahedral. In terms of its crystallography, corundum adopts a trigonal Bravais lattice with a space group of R3c (number 167 in the International Tables). The primitive cell contains two formula units of aluminium oxide. 

Aluminium oxide also exists in other, metastable, phases, including the cubic γ and η phases, the monoclinic θ phase, the hexagonal χ phase, the orthorhombic κ phase and the δ phase that can be tetragonal or orthorhombic. Each has a unique crystal structure and properties. Cubic γ-Al₂O₃ has important technical applications. The so-called β-Al₂O₃ proved to be NaAl₁₁O₁₇.

Molten aluminium oxide near the melting temperature is roughly 2/3 tetrahedral (i.e. 2/3 of the Al are surrounded by 4 oxygen neighbors), and 1/3 5-coordinated, with very little (<5 a="" class="mw-redirect" href="https://en.wikipedia.org/wiki/Octahedral" title="Octahedral">octahedral

Al-O present. Around 80% of the oxygen atoms are shared among three or more Al-O polyhedra, and the majority of inter-polyhedral connections are corner-sharing, with the remaining 10–20% being edge-sharing. The breakdown of octahedra upon melting is accompanied by a relatively large volume increase (~20%), the density of the liquid close to its melting point is 2.93 g/cm³. The structure of molten alumina is temperature dependent and the fraction of 5- and 6-fold aluminium increases during cooling (and supercooling), at the expense of tetrahedral AlO₄ units, approaching the local structural arrangements found in amorphous alumina.

Production

Aluminium hydroxide minerals are the main component of bauxite, the principal ore of aluminium. A mixture of the minerals comprise bauxite ore, including gibbsite (Al(OH)₃), boehmite (γ-AlO(OH)), and diaspore (α-AlO(OH)), along with impurities of iron oxides and hydroxides, quartz and clay minerals. Bauxites are found in laterites. Bauxite is purified by the Bayer process:

Al₂O₃ + H₂O + NaOH → NaAl(OH)₄

Al(OH)₃ + NaOH → NaAl(OH)₄

Except for SiO₂, the other components of bauxite do not dissolve in base. Upon filtering the basic mixture, Fe₂O₃ is removed. When the Bayer liquor is cooled, Al(OH)₃ precipitates, leaving the silicates in solution.

NaAl(OH)₄ → NaOH + Al(OH)₃

The solid Al(OH)₃ Gibbsite is then calcined (heated to over 1100 °C) to give aluminium oxide:

2 Al(OH)₃ → Al₂O₃ + 3 H₂O

The product aluminium oxide tends to be multi-phase, i.e., consisting of several phases of aluminium oxide rather than solely corundum. The production process can therefore be optimized to produce a tailored product. The type of phases present affects, for example, the solubility and pore structure of the aluminium oxide product which, in turn, affects the cost of aluminium production and pollution control.

Applications

Known as alundum (in fused form) or aloxite in the mining, ceramic, and materials science communities, aluminium oxide finds wide use. Annual world production of aluminium oxide in 2015 was approximately 115 million tonnes, over 90% of which is used in the manufacture of aluminium metal. The major uses of speciality aluminium oxides are in refractories, ceramics, polishing and abrasive applications. Large tonnages of aluminium hydroxide, from which alumina is derived, are used in the manufacture of zeolites, coating titania pigments, and as a fire retardant/smoke suppressant. 

Over 90% of the aluminium oxide, normally termed Smelter Grade Alumina (SGA), produced is consumed for the production of aluminium, usually by the Hall–Héroult process. The remainder, normally called speciality alumina is used in a wide variety of applications which reflect its inertness, temperature resistance and electrical resistance.

Fillers

Being fairly chemically inert and white, aluminium oxide is a favored filler for plastics. Aluminium oxide is a common ingredient in sunscreen and is sometimes also present in cosmetics such as blush, lipstick, and nail polish.

Glass

Many formulations of glass have aluminium oxide as an ingredient.

Catalysis

Aluminium oxide catalyses a variety of reactions that are useful industrially. In its largest scale application, aluminium oxide is the catalyst in the Claus process for converting hydrogen sulfide waste gases into elemental sulfur in refineries. It is also useful for dehydration of alcohols to alkenes.

Aluminium oxide serves as a catalyst support for many industrial catalysts, such as those used in hydrodesulfurization and some Ziegler–Natta polymerizations.

Abrasive

Aluminium oxide is used for its hardness and strength. It is widely used as an abrasive, including as a much less expensive substitute for industrial diamond. Many types of sandpaper use aluminium oxide crystals. In addition, its low heat retention and low specific heat make it widely used in grinding operations, particularly cutoff tools. As the powdery abrasive mineral aloxite, it is a major component, along with silica, of the cue tip "chalk" used in billiards. Aluminium oxide powder is used in some CD/DVD polishing and scratch-repair kits. Its polishing qualities are also behind its use in toothpaste. It is also used in microdermabrasion, both in the machine process available through dermatologists and estheticians, and as a manual dermal abrasive used according to manufacturer directions.

Paint

Aluminium oxide flakes are used in paint for reflective decorative effects, such as in the automotive or cosmetic industries.

Composite fiber

Aluminium oxide has been used in a few experimental and commercial fiber materials for high-performance applications (e.g., Fiber FP, Nextel 610, Nextel 720). Alumina nanofibers in particular have become a research field of interest.

Body armor

Some body armors utilize alumina ceramic plates, usually in combination with aramid or UHMWPE backing to achieve effectiveness against even most rifle threats. Alumina ceramic armor is readily available to most civilians in jurisdictions where it is legal, but is not considered military grade.

Abrasion protection

Aluminium oxide can be grown as a coating on aluminium by anodizing or by plasma electrolytic oxidation (see the "Properties" above). Both the hardness and abrasion-resistant characteristics of the coating originate from the high strength of aluminium oxide, yet the porous coating layer produced with conventional direct current anodizing procedures is within a 60-70 Rockwell hardness C range  which is comparable only to hardened carbon steel alloys, but considerably inferior to the hardness of natural and synthetic corundum. Instead, with plasma electrolytic oxidation, the coating is porous only on the surface oxide layer while the lower oxide layers are much more compact than with standard DC anodizing procedures and present a higher crystallinity due to the oxide layers being remelted and densified to obtain α-Al2O3 clusters with much higher coating hardness values circa 2000 Vickers hardness. 

Aluminium oxide output in 2005

 

Alumina is used to manufacture tiles which are attached inside pulverized fuel lines and flue gas ducting on coal fired power stations to protect high wear areas. They are not suitable for areas with high impact forces as these tiles are brittle and susceptible to breakage.

Electrical insulation

Aluminium oxide is an electrical insulator used as a substrate (silicon on sapphire) for integrated circuits but also as a tunnel barrier for the fabrication of superconducting devices such as single electron transistors and superconducting quantum interference devices (SQUIDs).

For its application as an electrical insulator in integrated circuits, where the conformal growth of a thin film is a prerequisite and the preferred growth mode is atomic layer deposition, Al₂O₃ films can be prepared by the chemical exchange between trimethylaluminum (Al(CH₃)₃) and H₂O:

2 Al(CH₃)₃ + 3 H₂O → Al₂O₃ + 6 CH₄

H₂O in the above reaction can be replaced by ozone (O₃) as the active oxidant and the following reaction then takes place:

2 Al(CH₃)₃ + O₃ → Al₂O₃ + 3 C₂H₆

The Al₂O₃ films prepared using O₃ show 10–100 times lower leakage current density compared with those prepared by H₂O. 

Aluminum oxide, being a dielectric with relatively large band gap, is used as an insulating barrier in capacitors.

Other

In lighting, transparent aluminium oxide is used in some sodium vapor lamps. Aluminium oxide is also used in preparation of coating suspensions in compact fluorescent lamps. 

In chemistry laboratories, aluminium oxide is a medium for chromatography, available in basic (pH 9.5), acidic (pH 4.5 when in water) and neutral formulations. 

Health and medical applications include it as a material in hip replacements and birth control pills.

It is used as a dosimeter for radiation protection and therapy applications for its optically stimulated luminescence properties.

Insulation for high-temperature furnaces is often manufactured from aluminium oxide. Sometimes the insulation has varying percentages of silica depending on the temperature rating of the material. The insulation can be made in blanket, board, brick and loose fiber forms for various application requirements. 

Small pieces of aluminium oxide are often used as boiling chips in chemistry.

It is also used to make spark plug insulators.

Using a plasma spray process and mixed with titania, it is coated onto the braking surface of some bicycle rims to provide abrasion and wear resistance.

Most ceramic eyes on fishing rods are circular rings made from aluminium oxide.