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Titanium

From Chemistry

22 scandiumtitaniumvanadium
-

Ti

Zr
General
Name, Symbol, Number titanium, Ti, 22
Chemical series transition metals
Group, Period, Block 4, 4, d
Appearance silvery metallic
Atomic mass 47.867(1) g/mol
Electron configuration [Ar] 3d2 4s2
Electrons per shell 2, 8, 10, 2
Physical properties
Phase solid
Density (near r.t.) 4.506 g·cm−3
Liquid density at m.p. 4.11 g·cm−3
Melting point 1941 K
(1668 °C, 3034 °F)
Boiling point 3560 K
(3287 °C, 5949 °F)
Heat of fusion 14.15 kJ·mol−1
Heat of vaporization 425 kJ·mol−1
Heat capacity (25 °C) 25.060 J·mol−1·K−1
Vapor pressure
P/Pa 1 10 100 1 k 10 k 100 k
at T/K 1982 2171 (2403) 2692 3064 3558
Atomic properties
Crystal structure hexagonal
Oxidation states 2, 3, 4
(amphoteric oxide)
Electronegativity 1.54 (Pauling scale)
Ionization energies
(more)
1st: 658.8 kJ·mol−1
2nd: 1309.8 kJ·mol−1
3rd: 2652.5 kJ·mol−1
Atomic radius 140 pm
Atomic radius (calc.) 176 pm
Covalent radius 136 pm
Miscellaneous
Magnetic ordering paramagnetic
Electrical resistivity (20 °C) 0.420 µΩ·m
Thermal conductivity (300 K) 21.9 W·m−1·K−1
Thermal expansion (25 °C) 8.6 µm·m−1·K−1
Speed of sound (thin rod) (r.t.) 5090  m·s−1
Young's modulus 116 GPa
Shear modulus 44 GPa
Bulk modulus 110 GPa
Poisson ratio 0.32
Mohs hardness 6.0
Vickers hardness 970 MPa
Brinell hardness 716 MPa
CAS registry number 7440-32-6
Selected isotopes
Main article: Isotopes of Titanium
iso NA half-life DM DE (MeV) DP
44Ti syn 63 y ε - 44Sc
γ 0.07D, 0.08D -
46Ti 8.0% Ti is stable with 24 neutrons
47Ti 7.3% Ti is stable with 25 neutrons
48Ti 73.8% Ti is stable with 26 neutrons
49Ti 5.5% Ti is stable with 27 neutrons
50Ti 5.4% Ti is stable with 28 neutrons
References

Titanium (IPA: /tʌɪˈteɪniəm/) is a chemical element; in the periodic table it has the symbol Ti and atomic number 22. It is a light, strong, lustrous, corrosion-resistant (including resistance to sea water and chlorine) transition metal with a white-silvery-metallic color.[1] Titanium can be alloyed with other elements such as iron, aluminium, vanadium, molybdenum and others, to produce strong lightweight alloys for aerospace and other demanding applications. In powdered form it can be added to other materials, such as graphite composites. Its most common compound, titanium dioxide, is used in the manufacture of white pigments.[1]

The element occurs within a number of mineral deposits, principally rutile and ilmenite, which are widely distributed in the Earth's crust. There are two allotropic forms[2] and five naturally occurring isotopes of this element; 46Ti through 50Ti with 48Ti being the most abundant (73.8%). One of the most useful properties of the metal form is that it has the highest strength-to-weight ration of any metal (in its unalloyed condition, as strong as steel, but only 60% its density).[3] Titanium's properties are chemically and physically similar to zirconium.

Contents

[edit] History

Titanium was discovered at Creed, Cornwall, in England by amateur geologist Reverend William Gregor in 1791. He recognized the presence of a new element in ilmenite, and named it menachite (alternately spelled manaccanite), after the nearby parish of Manaccan.[1] Around the same time, Franz Joseph Muller also produced a similar substance, but could not identify it.[1] The element was independently rediscovered several years later by German chemist Martin Heinrich Klaproth in rutile ore. Klaproth confirmed it as a new element and in 1795 he named it for the Titans of Greek mythology.[1]

The processes required to extract titanium from its various ores are laborious and costly. Pure metallic titanium (99.9%) was first prepared in 1910 by Matthew A. Hunter by heating TiCl4 with sodium in a steel bomb[3] at 700–800 °C in the Hunter process. Titanium metal was not used outside the laboratory until 1946 when William Justin Kroll proved that it could be commercially produced by reducing titanium tetrachloride with magnesium (Kroll process). Although research continues into more efficient and cheaper processes (FFC Cambridge, e.g.), the Kroll process still used for commercial production.[1][3]

In 1950–1960s the Soviet Union led the world in the refinement, processing, and use of titanium. In Western Europe and the US, a fledging industry existed, primarily driven by fluctuating demand side market forces. As a result, the refined titanium supply in the west was unreliable until the late 1960s.[4] Indeed, titanium for the highly successful U.S. SR-71 reconnaissance aircraft was acquired from the Soviet Union at the height of the Cold War. Throughout the period of the Cold War, titanium was considered a Strategic Material by the US government, and a large stockpile of titanium sponge was maintained by the DNSC, which was finally depleted in 2005. Today, Russia accounts for about 60% of world production.

[edit] Characteristics

Titanium is recognized for its excellent resistance to corrosion; it is almost as resistant as platinum, capable of withstanding attack by acids, moist chlorine gas, and by common salt solutions.[2] Pure titanium is not soluble in water but is soluble in concentrated acids.[5] A metallic element, it is also recognized for its high strength-to-weight ratio.[2] It is a light, strong metal with low density that, when pure, is quite ductile (especially in an oxygen-free environment),[6] lustrous, and metallic-white in colour. The relatively high melting point (over 3000 deg F) makes it useful as a refractory metal. Commercially pure grades of titanium have ultimate tensile strengths of up to 80,000psi, equal to that of high strength low alloy steels, but are 43% lighter. Titanium is 60% heavier than aluminium, but more than twice as strong as the most commonly used 6061-T6 aluminum alloy. Certain titanium alloys (Beta C, e.g.) achieve tensile strengths of close to 200,000psi. It is fairly hard (although by no means as hard as some grades of heat-treated steel) and can be tricky to machine due to the fact that it will gall if sharp tools and proper cooling methods are not used. Like those made from steel, titanium structures have a fatigue limit which guarantees longevity in some applications.

This metal forms a passive and protective oxide coating (leading to corrosion-resistance) when exposed to elevated temperatures in air, but at room temperatures it resists tarnishing.[6] It burns when heated in air 610 °C or higher (forming titanium dioxide) and is also one of the few elements that burns in pure nitrogen gas (it burns at 800 °C and forms titanium nitride).[2][7] Titanium is resistant to dilute sulfuric and hydrochloric acid, along with chlorine gas, chloride solutions, and most organic acids.[3] It is paramagnetic (weakly attracted to magnets) and has fairly low electrical conductivity and thermal conductivity.[6]

Experiments have shown that natural titanium becomes radioactive after it is bombarded with deuterons, emitting mainly positrons and hard gamma rays.[3] The metal is a dimorphic allotrope with the hexagonal alpha form changing into the cubic beta form very slowly at around 880 °C.[3] When it is red hot the metal combines with oxygen, and when it reaches 550 °C it combines with chlorine.[3] It also reacts with the other halogens and absorbs hydrogen.[1]

[edit] Occurrence

Titanium is always bonded to other elements in nature. It is the ninth-most abundant element in the Earth's crust (0.63% by mass) and the fourth-most abundant metal. It is present in most igneous rocks and in sediments derived from them (as well as in living things and natural bodies of water).[6][3] It is widely distributed and occurs primarily in the minerals anatase, brookite, ilmenite, perovskite, rutile, titanite (sphene), as well in many iron ores. Of these minerals, only rutile(app. 70% Ti) and ilmenite (app. 95% Ti) have significant economic importance, yet even they are difficult to find in high concentrations.[1] Significant titanium bearing ore deposits exist in Australia, New Zealand, Scandinavia, North America, and Malaysia. Large quantities have also been detected in the Kwale region in Kenya, deposits to which a Canadian firm, Tiomin, has mining rights.

Producer Thousands of tons  % of total
Australia 1291.0 30.6
South Africa 850.0 20.1
Canada 767.0 18.2
Norway 382.9 9.1
Ukraine 357.0 8.5
Other countries 573.1 13.5
Total world 4221.0 100.0

Data from 2003, production in thousands of tons of titanium dioxide.[8]

This metal is found in meteorites and has been detected in the sun and in M-type stars.[3] Rocks brought back from the moon during the Apollo 17 mission are composed of 12.1% TiO2.[3] Titanium is also found in coal ash, plants, and even the human body (while harmless, it is not believed to be an essential element).

By 1956 U.S. production of titanium mill products was more than 6 million kg/yr.[9]

[edit] Production by isolation

Titanium (Mineral Concentrate)

Because the metal reacts with air at high temperatures it cannot be produced by reduction of its dioxide.[2] Titanium metal is therefore produced commercially by the Kroll process, a complex and expensive batch process developed in 1946 by William Justin Kroll.[2] In the Kroll process, the oxide is first converted to chloride through carbochlorination, whereby chlorine gas is passed over red-hot rutile or ilmenite in the presence of carbon to make TiCl4.[2] This is condensed and purified by fractional distillation and then reduced with 800 °C molten magnesium in an argon atmosphere.[2]

A newer process, the FFC Cambridge Process, may replace the older Kroll process. This method uses the feedstock titanium dioxide powder (which is a refined form of rutile) to make the end product which is either a powder or sponge. If mixed oxide powders are used, the product is an alloy at a much lower cost than the conventional multi-step melting process. It is hoped that the FFC Cambridge Process will render titanium a less rare and expensive material for the aerospace industry and the luxury goods market, and will be seen in many products currently manufactured using aluminium and specialist grades of steel. In 2006, the U.S. Defense Agency 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 armor plating to components for the aerospace, transportation and chemical processing industries. [2]

Titanium was purified to ultra high purity 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 vapors over a hot filament to pure metal.

Titanium oxide is produced commercially by grinding its mineral ore and mixing it with potassium carbonate and aqueous hydrofluoric acid.[7] This yields potassium fluorotitanate (K2TiF6) which is extracted with hot water and decomposed with ammonia, producing an ammoniacal hydrated oxide. This in turn is ignited in a platinum vessel, which creates pure titanium dioxide.[7]

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.[7]

And its reactions are:

2TiFeO3 + 7Cl2 + 6C (900°C) → 2TiCl4 + 2FeCl3 + 6CO

TiCl4 + 2Mg (1100°C) → 2MgCl2 + Ti

[edit] Manufacture and fabrication

Titanium bearing ore is initially reduced using the Kroll process to produce titanium sponge, the basic feedstock for melting and pouring a titanium ingot in a VAR (Vacuum Arc Furnace). Because titanium is a reactive metal (it strongly attracts atmospheric gases), all transformation at temperature (other than cold working) must be done in vacuum or in an inert atmosphere (argon, e.g.) Once produced, the ingot is subsequently reduced and transformed through a variety of steps by forging, extruding and rolling into finished mill products. The relatively high market value of titanium, notwithstanding effects of supply and demand, is a function of the cost of the processing, which exceeds the processing costs of other metallics, and not of scarcity.

The ASTM International recognizes 31 Grades of titanium metal and alloys, of which Grades 1 through 4 are commercially pure (unalloyed) and distinguished by their varying degrees of tensile strength, as a function of oxygen content, with Grade 1 being the most ductile (lowest tensile strength), and Grade 4 the least (highest tensile strengh). The remaining grades are alloys, each designed for specific purposes, be it ductility, strength, hardness, electrical resistivity, creep resistance, resistance to corrosion from specific media, or a combination thereof. Fewer than 10 grades are readily available commercially; most are melted upon demand. The grades covered by ASTM and other alloys are also produced to meet Aerospace and Military specifications (SAE-AMS, MIL-T), ISO standards, country-specific specifications (e.g.: JIS: Japan, WL, DIN, TUV: Germany, BS: England), as well as per proprietary end-user specifications for aerospace, military, medical and industrial applications. Some of these alloys are patented and not available on the open market.

In terms of fabrication, titanium cannot be welded to any metal other than itself, unless silver brazing is used as an intermediary layer, which is cost-prohibitive. Again, due to its reactivity, welding must be done in an inert atmosphere in order to shield it from contamination with atmospheric gases. Contamination will cause a variety of conditions, such as embrittlement, which will 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.

[edit] Applications

watch with titanium cover

About 95% of titanium production is consumed in the form of titanium dioxide (TiO2), an intensely white permanent pigment with good covering power in paints, paper, toothpaste, and plastics.[10] Paints made with titanium dioxide are excellent reflectors of infrared radiation and are therefore used extensively by solar astronomers and in exterior paints.[2][3] It is also used in cement, in gemstones, as an optical opacifier in paper,[11] and a strengthening agent in graphite composite fishing rods and golf clubs. Recently, it has been put to use in air purifiers (as a filter coating), or in film used to coat windows on buildings which when exposed to UV light (either solar or man-made) and moisture in the air produces reactive redox species like hydroxyl radicals that can purify the air or keep window surfaces clean.

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.[6] Titanium is often alloyed with aluminium (to refine grain size), vanadium, copper (to harden), iron, manganese, molybdenum, and with other metals.

Applications for titanium mill products (sheet, plate, bar, wire, forgings, castings) can be found in Industrial, Aerospace, Recreational and Emerging markets.

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 downhole and nickel hydrometallurgy applications due to their high strength (titanium Beta C) or corrosion resistance or combination of both. The pulp and paper industry uses titanium in process equipment exposed to corrosive media such as chlorine (in the bleachery). Other applications include: ultrasonic welding, sputtering targets, wave soldering.

Due to excellent corrosion resistance to sea water, it is used to make propeller shafts and rigging and in the heat exchangers of desalination plants[3]; in heater-chillers for salt water aquariums, fishing line and leader, and diver knives as well. As there are substantial ore deposits in Russia, it was the principal material used in the construction of many advanced Russian submarines, including the deepest-diving military submarines to date, Alfa and Mike class, as well as Typhoon class. Titanium is used to manufacture the housings and other components of ocean-deployed surveillance and monitoring devices for scientific and military use.

Because of its high tensile strength (even at high temperatures),[2] light weight, extraordinary corrosion resistance,[3] and ability to withstand extreme temperatures, titanium alloys are used in aircraft, armour plating, naval ships, spacecraft, and missiles.[1][3]. For these applications, titanium alloyed with aluminum, vanadium, and other elements is used for a variety of components including critical structural parts, fire walls, landing gear, exhaust ducts (helicopters) and hydraulic systems. An estimated 58 tons are used in the Boeing 777, 43 in the 747, 18 in the 737, 24 in the Airbus A340, 17 in the A330 and 12 in the A320, according to the 2004 annual report of the Titanium Metals Corporation. Generally, newer models use more and widebodies use the most. The A380 may use 77 tons, including about 10 or 11 tons in the engines. In engine applications, titanium is used for rotors, turbine blades, hydraulic system components and nacelles.

Titanium is used in automotive applications, particularly in automobile or motorcycle racing, where weight reduction is critical while maintaining high strength and rigidity. The metal is generallly too expensive to make it marketable to the general consumer market, other than high end products. Late model Corvettes have been available with titanium exhausts, and racing bikes are frequently outfitted with titanium mufflers. Other automotive uses include piston rods and hardware (bolts, nuts, etc.).

selected colors achievable through anodization of titanium.[12]

Its inertness and ability to be attractively coloured makes it a popular metal for use in body piercing. Titanium may be anodized to produce various colors.[13]. A number of artists work with titanium to produce artworks: sculptures, objects and furniture that take advantage of the coloring achievable by surface treatments and heating. [14]

Use of titanium in consumer products such as sporting goods: tennis rackets, golf clubs, lacrosse stick shafts, cricket helmet grills, bicycle frames, or jewelry: wristwatches, wedding rings, and laptop computers is becoming more common. Titanium alloys are also used in spectacle frames. This results in a rather expensive, but highly durable and long lasting frame which is light in weight and causes no skin allergies. Both traditional alloys and shape memory alloys find use in this application. Many backpackers use titanium equipment, including cookware, eating utensils, lanterns and tent stakes. Though slightly more expensive than traditional steel or aluminium alternatives, these titanium products can be significantly lighter without compromising strength. However, the thermal properties of titanium cookware can cause uneven heating without a well-distributed heat source, which may make it unsuitable for some culinary applications.

Titanium has occasionally been used in architectural applications: the 150-foot (45 m) memorial to Yuri Gagarin, the first man to travel in space, in Moscow, is 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. Other construction uses of titanium sheathing include the Frederic C. Hamilton Building in (Denver, Colorado).

[edit] Medical applications

A titanium hip prosthesis, with a ceramic head and polyethylene acetabular cup.

Because it is biocompatible, titanium is used in a gamut of medical applications including surgical implements and implants, such as hip balls and sockets (joint replacement). Since titanium is non-ferromagnetic, patients with titanium implants can be safely examined with magnetic resonance imaging (convenient for long-term implants). Titanium is also used for the surgical instruments used in image-guided surgery, as well as wheelchairs, crutches, and any other product where high strength and low weight are important.

Titanium has the inherent property to osseointegrate, enabling use in dental implants. This property is also useful for orthopaedic implant applications. These benefit from titanium's lower modulus of elasticity (Young's modulus) to more closely match the MOE 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 orthopaedic implants which act as stress risers. However, titanium alloys' stiffness is still more than twice that of bone, eventually leading to joint degradation.

[edit] Compounds

The +4 oxidation state dominates in titanium chemistry, but compounds in the +3 oxidation state are also common. Because of this high oxidation state, many titanium compounds have a high degree of covalent bonding.

Although titanium metal is relatively uncommon, due to the cost of extraction, titanium dioxide (also called titanium(IV), titanium white, or even titania) is cheap, nontoxic, readily available in bulk, and very widely used as a white pigment in paint, enamel, lacquer, plastic and construction cement. TiO2 powder is chemically inert, resists fading in sunlight, and is very opaque: this allows it to impart a pure and brilliant white colour to the brown or gray chemicals that form the majority of household plastics.[1] In nature, this compound is found in the minerals anatase, brookite, and rutile.[6]

Paint made with titanium dioxide does well in severe temperatures, is somewhat self-cleaning, and stands up to marine environments.[1] Pure titanium dioxide has a very high index of refraction and an optical dispersion higher than diamond.[3] Star sapphires and rubies get their asterism from the titanium dioxide present in them. Titanates are compounds made with titanium dioxide.[2] Barium titanate has piezoelectric properties, thus making it possible to use it as a transducer in the interconversion of sound and electricity.[2] Esters of titanium are formed by the reaction of alcohols and titanium tetrachloride and are used to waterproof fabrics.[2]

Titanium nitride is often used to coat cutting tools, such as drill bits. It also finds use as a gold-coloured decorative finish, and as a barrier metal in semiconductor fabrication.

Titanium(IV) chloride (titanium tetrachloride, TiCl4, sometimes called "Tickle") is a colourless, weakly acidic liquid which is used as an intermediate in the manufacture of titanium(IV) oxide for paint. It is widely used in organic chemistry as a Lewis acid, for example in the Mukaiyama aldol condensation. Titanium also forms a lower chloride, titanium(III) chloride (TiCl3), which is used as a reducing agent.

Titanocene dichloride is an important catalyst for carbon-carbon bond formation. Titanium isopropoxide is used for Sharpless epoxidation. Other compounds include; Titanium bromide (used in metallurgy, superalloys, and high-temperature electrical wiring and coatings) and titanium carbide (found in high-temperature cutting tools and coatings).[1]

[edit] 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). Eleven radioisotopes have been characterized, with the most stable being 44Ti with a half-life of 63 years, 45Ti with a half-life of 184.8 minutes, 51Ti with a half-life of 5.76 minutes, and 52Ti with a half-life of 1.7 minutes. All of the remaining radioactive isotopes have half-lifes that are less than 33 seconds and the majority of these have half-lifes that are less than half a second.

The isotopes of titanium range in atomic weight from 39.99 amu (40Ti) to 57.966 amu (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.

[edit] Precautions

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.[1] Water and carbon dioxide-based methods to extinguish fires are ineffective on burning titanium;[1] Class D dry powder fire fighting agents must be used instead.

Salts of titanium are often considered to be relatively harmless but its chlorine compounds, such as TiCl2, TiCl3 and TiCl4, have unusual hazards. The dichloride takes the form of pyrophoric black crystals, and the tetrachloride is a volatile fuming liquid. All of titanium's chlorides are corrosive. Titanium also has a tendency to bio-accumulate in tissues that contain silica but it does not play any known biological role in humans.

[edit] See also

[edit] Notes

  1. 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 1.11 1.12 1.13 Krebs, The History and Use of Our Earth's Chemical Elements
  2. 2.00 2.01 2.02 2.03 2.04 2.05 2.06 2.07 2.08 2.09 2.10 2.11 2.12 titanium, The Columbia Electronic Encyclopedia, 6th ed
  3. 3.00 3.01 3.02 3.03 3.04 3.05 3.06 3.07 3.08 3.09 3.10 3.11 3.12 3.13 3.14 LANL.gov: Titanium
  4. Commission on Engineering and Technical Systems. Titanium: Past, Present, and Future (1983). darwin.nap.edu. Retrieved on 10 December 2006.
  5. Casillas N, Charlebois S, Smyrl WH, White HS (1994). "Pitting Corrosion of Titanium". J. Electrochem. Soc. 141 (3): pp. 636-642.
  6. 6.0 6.1 6.2 6.3 6.4 6.5 titanium, Encyclopædia Britannica 2005
  7. 7.0 7.1 7.2 7.3 titanium, Microsoft Encarta Online Encyclopedia 2005
  8. Cordellier, Serge and Didiot, Béatrice. L'état du monde 2005: annuaire économique géopolitique mondial. Paris: La Découverte, 2004.
  9. (1957). "Titanium: The Industry, Its Future, Its Equities": pp 7, 33-67.
  10. USGS Minerals Information: Titanium. Retrieved on 10 December 2006.
  11. Smook, p. 223
  12. Titanium Wedding Ring Catalog. Ringsforever.com. Retrieved on 10 December 2006.
  13. Anodized Titanium Ring Colors. Cascadia Design Studio. Retrieved on 10 December, 2006.
  14. [1]

[edit] References

[edit] External links

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