Tantalum

Tantalum
73Ta
Nb ↑ Ta ↓ Db Periodic table hafnium ← tantalum → tungsten
Appearance
gray blue
General properties
Name, symbol, number	tantalum, Ta, 73
Pronunciation	/ ˈ t æ n t əl ə m / TAN-təl-əm; previously / t æ n ˈ t æ l i ə m / tan-TAL-ee-əm
Element category	transition metal
Group, period, block	5, 6, d
Standard atomic weight	180.94788
Electron configuration	[Xe] 4f14 5d3 6s2 2, 8, 18, 32, 11, 2
History
Discovery	Anders Gustaf Ekeberg (1802)
Recognized as a distinct element by	Heinrich Rose (1844)
Physical properties
Phase	solid
Density (near r.t.)	16.69 g·cm−3
Liquid density at m.p.	15 g·cm−3
Melting point	3290 K, 3017 °C, 5463 °F
Boiling point	5731 K, 5458 °C, 9856 °F
Heat of fusion	36.57 kJ·mol−1
Heat of vaporization	732.8 kJ·mol−1
Molar heat capacity	25.36 J·mol−1·K−1
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 3297 3597 3957 4395 4939 5634
Atomic properties
Oxidation states	5, 4, 3, 2, -1 (mildly acidic oxide)
Electronegativity	1.5 (Pauling scale)
Ionization energies	1st: 761 kJ·mol−1
	2nd: 1500 kJ·mol−1
Atomic radius	146 pm
Covalent radius	170±8 pm
Miscellanea
Crystal structure	body-centered cubic α-Ta
	tetragonal β-Ta
Magnetic ordering	paramagnetic
Electrical resistivity	(20 °C) 131 nΩ·m
Thermal conductivity	57.5 W·m−1·K−1
Thermal expansion	(25 °C) 6.3 µm·m−1·K−1
Speed of sound (thin rod)	(20 °C) 3400 m·s−1
Young's modulus	186 GPa
Shear modulus	69 GPa
Bulk modulus	200 GPa
Poisson ratio	0.34
Mohs hardness	6.5
Vickers hardness	873 MPa
Brinell hardness	800 MPa
CAS registry number	7440-25-7
Most stable isotopes
Main article: Isotopes of tantalum
iso NA half-life DM DE ( MeV) DP 177Ta syn 56.56 h ε 1.166 177Hf 178Ta syn 2.36 h ε 1.910 178Hf 179Ta syn 1.82 y ε 0.110 179Hf 180Ta syn 8.125 h ε 0.854 180Hf β− 0.708 180W 180 mTa 0.012% >1.2×1015 y ε 0.929 180Hf β− 0.783 180W IT 0.075 180Ta α 2.103 176Lu 181Ta 99.988% 181Ta is stable with 108 neutrons 182Ta syn 114.43 d β− 1.814 182W 183Ta syn 5.1 d β− 1.070 183W

Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as tantalium, the name comes from Tantalus, a character from Greek mythology. Tantalum is a rare, hard, blue-gray, lustrous transition metal that is highly corrosion resistant. It is part of the refractory metals group, which are widely used as minor components in alloys. The chemical inertness of tantalum makes it a valuable substance for laboratory equipment and a substitute for platinum, but its main use today is in tantalum capacitors in electronic equipment such as mobile phones, DVD players, video game systems and computers. Tantalum, always together with the chemically similar niobium, occurs in the minerals tantalite, columbite and coltan (a mix of columbite and tantalite).

History

Tantalum was discovered in Sweden in 1802 by Anders Ekeberg. One year earlier, Charles Hatchett had discovered the element columbium. In 1809, the English chemist William Hyde Wollaston compared the oxides derived from both columbium— columbite, with a density 5.918 g/cm³, and tantalum— tantalite, with a density 7.935 g/cm³, and concluded that the two oxides, despite their difference in measured density, were identical. He decided to keep the name tantalum. After Friedrich Wöhler confirmed these results, it was thought that columbium and tantalum were the same element. This conclusion was disputed in 1846 by the German chemist Heinrich Rose, who argued that there were two additional elements in the tantalite sample, and he named them after the children of Tantalus: niobium (from Niobe, the goddess of tears), and pelopium (from Pelops). The supposed element "pelopium" was later identified as a mixture of tantalum and niobium, and it was found that the niobium was identical to the columbium already discovered in 1801 by Hatchett.

The differences between tantalum and niobium were demonstrated unequivocally in 1864 by Christian Wilhelm Blomstrand, and Henri Etienne Sainte-Claire Deville, as well as by Louis J. Troost, who determined the empirical formulas of some of their compounds in 1865. Further confirmation came from the Swiss chemist Jean Charles Galissard de Marignac, in 1866, who proved that there were only two elements. These discoveries did not stop scientists from publishing articles about the so-called ilmenium until 1871. De Marignac was the first to produce the metallic form of tantalum in 1864, when he reduced tantalum chloride by heating it in an atmosphere of hydrogen. Early investigators had been only able to produce impure tantalum, and the first relatively pure ductile metal was produced by Werner von Bolton in 1903. Wires made with metallic tantalum were used for light bulb filaments until tungsten replaced it in widespread use.

The name tantalum was derived from the name of the mythological Tantalus, the father of Niobe in Greek mythology. In the story, he had been punished after death by being condemned to stand knee-deep in water with perfect fruit growing above his head, both of which eternally tantalized him. (If he bent to drink the water, it drained below the level he could reach, and if he reached for the fruit, the branches moved out of his grasp.) Ekeberg wrote "This metal I call tantalum … partly in allusion to its incapacity, when immersed in acid, to absorb any and be saturated."

For decades, the commercial technology for separating tantalum from niobium involved the fractional crystallization of potassium heptafluorotantalate away from potassium oxypentafluoroniobate monohydrate, a process that was discovered by Jean Charles Galissard de Marignac in 1866. This method has been supplanted by solvent extraction from fluoride-containing solutions of tantalum.

Characteristics

Physical properties

Tantalum is dark (blue-gray), dense, ductile, very hard, easily fabricated, and highly conductive of heat and electricity. The metal is renowned for its resistance to corrosion by acids; in fact, at temperatures below 150 °C tantalum is almost completely immune to attack by the normally aggressive aqua regia. It can be dissolved with hydrofluoric acid or acidic solutions containing the fluoride ion and sulfur trioxide, as well as with a solution of potassium hydroxide. Tantalum's high melting point of 3017 °C (boiling point 5458 °C) is exceeded only by tungsten, rhenium and osmium for metals, and carbon.

Tantalum exists in two crystalline phases, alpha and beta. The alpha phase is relatively ductile and soft; it has body-centered cubic structure ( space group Im3m, lattice constant a = 0.33058 nm), Knoop hardness 200–400 HN and electrical resistivity 15–60 µΩּcm. The beta phase is hard and brittle; its crystal symmetry is tetragonal (space group P42/mnm, a = 1.0194 nm, c = 0.5313 nm), Knoop hardness is 1000–1300 HN and electrical resistivity is relatively high at 170–210 µΩּcm. The beta phase is metastable and converts to the alpha phase upon heating to 750–775 °C. Bulk tantalum is almost entirely alpha phase, and the beta phase usually exists as thin films obtained by magnetron sputtering, chemical vapor deposition or electrochemical deposition from an eutectic molten salt solution.

Chemical properties

Tantalum forms oxides with the oxidation states +5 (Ta₂O₅) and +4 (TaO₂). The most stable oxidation state is +5, tantalum pentoxide. Tantalum pentoxide is the starting material for several tantalum compounds. The compounds are created by dissolving the pentoxide in basic hydroxide solutions or by melting it in another metal oxide. Such examples are lithium tantalate (LiTaO₃) and lanthanum tantalate (LaTaO₄). In the lithium tantalate, the tantalate ion TaO−
3 does not occur; instead, this part of the formula represents linkage of TaO7−
6 octahedra to form a three-dimensional perovskite framework; while the lanthanum tantalate contains lone TaO3−
4 tetrahedral groups.

The fluorides of tantalum can be used for its separation from niobium. Tantalum forms halogen compounds in the oxidation states of +5, +4, and +3 of the type TaX₅, TaX₄, and TaX₃, although multi core complexes and substoichiometric compounds are also known. Tantalum pentafluoride (TaF₅) is a white solid with a melting point of 97.0 °C and tantalum pentachloride (TaCl₅) is a white solid with a melting point of 247.4 °C. Tantalum pentachloride is hydrolyzed by water and reacts with additional tantalum at elevated temperatures by forming the black and highly hygroscopic tantalum tetrachloride (TaCl₄). While the trihalogen compounds can be obtained by reduction of the pentahalogenes with hydrogen, the dihalogen compounds do not exist. A tantalum-tellurium alloy forms quasicrystals. Tantalum compounds with oxidation states as low as −1 have been reported in 2008.

Similar to most other refractory metals, the hardest known compounds of tantalum are its stable nitrides and carbides. Tantalum carbide, TaC, like the more commonly used tungsten carbide, is a very hard ceramic that is used in cutting tools. Tantalum(III) nitride is used as a thin film insulator in some microelectronic fabrication processes. Chemists at the Los Alamos National Laboratory in the United States have developed a tantalum carbide- graphite composite material that is one of the hardest materials ever synthesized. Korean researchers have developed an amorphous tantalum-tungsten-copper alloy that is more flexible and two to three times stronger than commonly used steel alloys. There are two tantalum aluminides, TaAl₃ and Ta₃Al. These are stable, refractory, and reflective, and they have been proposed as coatings for use in infrared wave mirrors.

Isotopes

Natural tantalum consists of two isotopes: ^180mTa (0.012%) and ¹⁸¹Ta (99.988%). ¹⁸¹Ta is a stable isotope. ^180mTa (m denotes a metastable state) is predicted to decay in three ways: isomeric transition to the ground state of ¹⁸⁰Ta, beta decay to ¹⁸⁰W, or electron capture to ¹⁸⁰Hf. However, radioactivity of this nuclear isomer has never been observed. Only a lower limit on its half life of over 10¹⁵ years has been set. The ground state of ¹⁸⁰Ta has a half life of only 8 hours. ^180mTa is the only naturally occurring nuclear isomer (excluding radiogenic and cosmogenic short-living nuclides). It is also the rarest isotope in the Universe, taking into account the elemental abundance of tantalum and isotopic abundance of ^180mTa in the natural mixture of isotopes (and again excluding radiogenic and cosmogenic short-living nuclides).

Tantalum has been examined theoretically as a " salting" material for nuclear weapons (cobalt is the better-known hypothetical salting material). An external shell of ¹⁸¹Ta would be irradiated by the intensive high-energy neutron flux from a hypothetical exploding nuclear weapon. This would transmute the tantalum into the radioactive isotope ¹⁸²Ta, which has a half-life of 114.4 days and produces gamma rays with approximately 1.12 million electron-volts (MeV) of energy apiece, which would significantly increase the radioactivity of the nuclear fallout from the explosion for several months. Such "salted" weapons have never been built or tested, as far as is publicly known, and certainly never used as weapons.

Occurrence

Tantalum is estimated to make up about 1  ppm or 2  ppm of the Earth's crust by weight. There are many species of tantalum minerals, only some of which are so far being used by industry as raw materials: tantalite, microlite, wodginite, euxenite, polycrase. Tantalite (Fe, Mn)Ta₂O₆ is the most important mineral for tantalum extraction. Tantalite has the same mineral structure as columbite (Fe, Mn) (Ta, Nb)₂O₆; when there is more Ta than Nb it is called tantalite and when there is more Nb than Ta is it called columbite (or niobite). The high density of tantalite and other tantalum containing minerals makes the use of gravitational separation the best method. Other minerals include samarskite and fergusonite.

The primary mining of tantalum is in Australia, where the largest producer, Global Advanced Metals, formerly known as Talison Minerals, operates two mines in Western Australia, Greenbushes in the Southwest and Wodgina in the Pilbara region. The Wodgina mine was reopened in January 2011 after mining at the site was suspended in late-2008 due to the global financial crisis. Less than a year after it reopened, Global Advanced Metals announced that due to again "... softening tantalum demand ...", and other factors, tantalum mining operations were to cease at the end of February 2012. Wodgina produces a primary tantalum concentrate which is further upgraded at the Greenbushes operation before being sold to customers. Whereas the large-scale producers of niobium are in Brazil and Canada, the ore there also yields a small percentage of tantalum. Some other countries such as China, Ethiopia, and Mozambique mine ores with a higher percentage of tantalum, and they produce a significant percentage of the world's output of it. Tantalum is also produced in Thailand and Malaysia as a by-product of the tin mining there. During gravitational separation of the ores from placer deposits, not only is Cassiterite (SnO₂) found, but a small percentage of tantalite also included. The slag from the tin smelters then contains economically useful amounts of tantalum, which is leached from the slag. Future sources of supply of tantalum, in order of estimated size, are being explored in Saudi Arabia, Egypt, Greenland, China, Mozambique, Canada, Australia, the United States, Finland, and Brazil.

Coltan, the industrial name for a columbite– tantalite mineral from which columbium (i.e. niobium) and tantalum are extracted, can also be found in Central Africa, which is why tantalum is being linked to warfare in the Democratic Republic of the Congo (formerly Zaire). According to an October 23, 2003 United Nations report, the smuggling and exportation of coltan has helped fuel the war in the Congo, a crisis that has resulted in approximately 5.4 million deaths since 1998 – making it the world’s deadliest documented conflict since World War II. Ethical questions have been raised about responsible corporate behaviour, human rights, and endangering wildlife, due to the exploitation of resources such as coltan in the armed conflict regions of the Congo Basin. However, although important for the local economy in Congo, the contribution of coltan mining in Congo to the world supply of tantalum is usually small. The United States Geological Survey reports in its yearbook that this region produced a little less than 1% of the world's tantalum output in 2002–2006, peaking at 10% in 2000 and 2008.

It is estimated that there is less than 50 years left of Tantalum resources, based on extraction at current rates, demonstrating the need for increased recycling.

Production and fabrication

Several steps are involved in the extraction of tantalum from tantalite. First, the mineral is crushed and concentrated by gravity separation. This is generally carried out near the mine site. Further processing by chemical separation is usually done by treating the ores with a mixture of hydrofluoric acid and sulfuric acid at over 90 °C. These reagents dissolve the tantalum and niobium oxides to give complex fluorides, which can be separated from impurities and from each other:

Ta₂O₅ + 14 HF → 2 H₂[TaF₇] + 5 H₂O

Nb₂O₅ + 10 HF → 2 H₂[NbOF₅] + 3 H₂O

The first industrial-scale separation, developed by de Marignac, used the difference in solubility between the complex niobium and tantalum fluorides K₂[NbOF₅]•H₂O (potassium oxypentafluoroniobate monohydrate) and K₂[TaF₇] ( potassium heptafluorotantalate) in water. Newer processes use the liquid extraction of the fluorides from aqueous solution by organic solvents such as cyclohexanone. The complex niobium and tantalum fluorides are extracted separately from the organic solvent with water, and either precipitated by the addition of potassium fluoride to produce a potassium fluoride complex, or precipitated with ammonia as the pentoxide:

H₂[TaF₇] + 2 KF → K₂[TaF₇]↓ + 2 HF

2 H₂[TaF₇] + 14 NH₄OH → Ta₂O₅↓ + 14 NH₄F + 9 H₂O

The purified K₂[TaF₇] is generally treated by reduction with molten sodium to produce a coarse tantalum powder.

In terms of fabrication, all welding of tantalum must be done in an inert atmosphere of argon or helium in order to shield it from contamination with atmospheric gases. Tantalum is not solderable. Grinding tantalum is difficult, especially so for annealed tantalum. In the annealed condition, tantalum is extremely ductile and can be readily formed as metal sheets.

Applications

Electronics

The major use for tantalum, as the metal powder, is in the production of electronic components, mainly capacitors and some high-power resistors. Tantalum electrolytic capacitors exploit the tendency of tantalum to form a protective oxide surface layer, using tantalum powder, pressed into a pellet shape, as one "plate" of the capacitor, the oxide as the dielectric, and an electrolytic solution or conductive solid as the other "plate". Because the dielectric layer can be very thin (thinner than the similar layer in, for instance, an aluminium electrolytic capacitor), a high capacitance can be achieved in a small volume. Because of the size and weight advantages, tantalum capacitors are attractive for portable telephones, personal computers, and automotive electronics.

Alloys

Tantalum is also used to produce a variety of alloys that have high melting points, are strong and have good ductility. Alloyed with other metals, it is also used in making carbide tools for metalworking equipment and in the production of superalloys for jet engine components, chemical process equipment, nuclear reactors, and missile parts. Because of its ductility, tantalum can be drawn into fine wires or filaments, which are used for evaporating metals such as aluminium. Since it resists attack by body fluids and is nonirritating, tantalum is widely used in making surgical instruments and implants. For example, porous tantalum coatings are used in the construction of orthopedic implants due to tantalum's ability to form a direct bond to hard tissue.

Tantalum is inert against most acids except hydrofluoric acid and hot sulfuric acid, also hot alkaline solutions cause tantalum to corrode. This property makes it an ideal metal for chemical reaction vessels and pipes for corrosive liquids. Heat exchanging coils for the steam heating of hydrochloric acid are made from tantalum. Tantalum was extensively used in the production of ultra high frequency electron tubes for radio transmitters. The tantalum is capable of capturing oxygen and nitrogen by forming nitrides and oxides and therefore helps to sustain the high vacuum needed for the tubes.

Other uses

The high melting point and oxidation resistance lead to the use of the metal in the production of vacuum furnace parts. Tantalum is extremely inert and is therefore formed into a variety of corrosion resistants parts, such as thermowells, valve bodies, and tantalum fasteners. Due to its high density, shaped charge and explosively formed penetrator liners have been constructed from tantalum. Tantalum greatly increases the armor penetration capabilities of a shaped charge due to its high density and high melting point. It is also occasionally used in precious watches e.g. from Audemars Piguet, Hublot, Montblanc, Omega, and Panerai. Tantalum is also highly bioinert and is used as an orthopedic implant material. The elasticity of tantalum makes it a great material for hip replacements to avoid stress shielding. The oxide is used to make special high refractive index glass for camera lenses.

Precautions

Compounds containing tantalum are rarely encountered in the laboratory. The metal is highly biocompatible and is used for body implants and coatings, therefore attention may be focused on other elements or the physical nature of the chemical compound. A single study is the only reference in literature linking tantalum to local sarcomas. The study was quoted in IARC Monograph vol. 74 which includes the following "Note to the reader": "Inclusion of an agent in the Monographs does not imply that it is a carcinogen, only that the published data have been examined."