Hafnium

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Not to be confused with the compound hydrogen fluoride, formula HF.
Hafnium, 72Hf
Hafnium
Pronunciation/ˈhæfniəm/ ​(HAF-nee-əm)
Appearancesteel gray
Standard atomic weight Ar°(Hf)
Hafnium 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
Zr
↑
Hf
↓
Rf
lutetium ← hafnium → tantalum
kJ/mol
Heat of vaporization648 kJ/mol
Molar heat capacity25.73 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 2689 2954 3277 3679 4194 4876
Atomic properties
Oxidation statescommon: +4
−2,
Discovery and first isolation
Dirk Coster and George de Hevesy (1922)
Isotopes of hafnium
Main isotopes[10] Decay
abun­dance half-life (t1/2) mode pro­duct
172Hf synth 1.87 y ε
172Lu
174Hf 0.16% 3.8×1016 y[11] α
170Yb
176Hf 5.26%
stable
177Hf 18.6% stable
178Hf 27.3% stable
178m2Hf synth 31 y
IT
 		178Hf
179Hf 13.6% stable
180Hf 35.1% stable
182Hf synth 8.9×106 y
β−
182Ta
 Category: Hafnium
| references

Hafnium is a

tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though it was not identified until 1922, by Dirk Coster and George de Hevesy. Hafnium is named after Hafnia, the Latin name for Copenhagen
, where it was discovered.

Hafnium is used in filaments and electrodes. Some semiconductor fabrication processes use its oxide for integrated circuits at 45 nanometers and smaller feature lengths. Some superalloys used for special applications contain hafnium in combination with niobium, titanium, or tungsten.

Hafnium's large

zirconium alloys used in nuclear reactors
.

Characteristics

Physical characteristics

Pieces of hafnium

Hafnium is a shiny, silvery, ductile metal that is corrosion-resistant and chemically similar to zirconium[12] in that they have the same number of valence electrons and are in the same group. Also, their relativistic effects are similar: The expected expansion of atomic radii from period 5 to 6 is almost exactly canceled out by the lanthanide contraction. Hafnium changes from its alpha form, a hexagonal close-packed lattice, to its beta form, a body-centered cubic lattice, at 2,388 K (2,115 °C; 3,839 °F).[13] The physical properties of hafnium metal samples are markedly affected by zirconium impurities, especially the nuclear properties, as these two elements are among the most difficult to separate because of their chemical similarity.[12]

A notable physical difference between these metals is their

nuclear fuel rods
.

Chemical characteristics

See also: § Chemical compounds
Hafnium dioxide (HfO2)

Hafnium reacts in air to form a protective film that inhibits further corrosion. Despite this, the metal is attacked by hydrofluoric acid and concentrated sulfuric acid, and can be oxidized with halogens or burnt in air. Like its sister metal zirconium, finely divided hafnium can ignite spontaneously in air. The metal is resistant to concentrated alkalis.

As a consequence of lanthanide contraction, the chemistry of hafnium and zirconium is so similar that the two cannot be separated based on differing chemical reactions. The melting and boiling points of the compounds and the solubility in solvents are the major differences in the chemistry of these twin elements.[14]

Isotopes

Main article: Isotopes of hafnium

At least 40 isotopes of hafnium have been observed, ranging in

primordial 174Hf.[15][18]

The extinct radionuclide 182Hf has a half-life of 8.9±0.1 million years, and is an important tracker isotope for the formation of planetary cores.[19] The nuclear isomer 178m2Hf was at the center of a controversy for several years regarding its potential use as a weapon.

Occurrence

Zircon crystal (2×2 cm) from Tocantins, Brazil

Hafnium is estimated to make up about between 3.0 and 4.8

ppm of the Earth's upper crust by mass.[20]: 5  [21] It does not exist as a free element on Earth, but is found combined in solid solution with zirconium in natural zirconium compounds such as zircon, ZrSiO4, which usually has about 1–4% of the Zr replaced by Hf. Rarely, the Hf/Zr ratio increases during crystallization to give the isostructural mineral hafnon (Hf,Zr)SiO4, with atomic Hf > Zr.[22] An obsolete name for a variety of zircon containing unusually high Hf content is alvite.[23]

A major source of zircon (and hence hafnium) ores is

Mount Weld, Western Australia. A potential source of hafnium is trachyte tuffs containing rare zircon-hafnium silicates eudialyte or armstrongite, at Dubbo in New South Wales, Australia.[24]

Production

Melted tip of a hafnium consumable electrode used in an electron beam remelting furnace, a 1 cm cube, and an oxidized hafnium electron beam-remelted ingot (left to right)

The heavy mineral sands ore deposits of the titanium ores ilmenite and rutile yield most of the mined zirconium, and therefore also most of the hafnium.[25]

Zirconium is a good nuclear fuel-rod cladding metal, with the desirable properties of a very low neutron capture cross section and good chemical stability at high temperatures. However, because of hafnium's neutron-absorbing properties, hafnium impurities in zirconium would cause it to be far less useful for nuclear reactor applications. Thus, a nearly complete separation of zirconium and hafnium is necessary for their use in nuclear power. The production of hafnium-free zirconium is the main source of hafnium.[12]

Hafnium oxidized ingots which exhibit thin-film optical effects

The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate.[26] The methods first used—fractional crystallization of ammonium fluoride salts[27] or the fractional distillation of the chloride[28]—have not proven suitable for an industrial-scale production. After zirconium was chosen as a material for nuclear reactor programs in the 1940s, a separation method had to be developed. Liquid–liquid extraction processes with a wide variety of solvents were developed and are still used for producing hafnium.[29] About half of all hafnium metal manufactured is produced as a by-product of zirconium refinement. The end product of the separation is hafnium(IV) chloride.[30] The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium or sodium, as in the Kroll process.[31]

Further purification is effected by a

Arkel and de Boer: In a closed vessel, hafnium reacts with iodine at temperatures of 500 °C (900 °F), forming hafnium(IV) iodide; at a tungsten filament of 1,700 °C (3,100 °F) the reverse reaction happens preferentially, and the chemically bound iodine and hafnium dissociate into the native elements. The hafnium forms a solid coating at the tungsten filament, and the iodine can react with additional hafnium, resulting in a steady iodine turnover and ensuring the chemical equilibrium remains in favor of hafnium production.[14][32]

Chemical compounds

Main article: Hafnium compounds

Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms).[33] Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties.[33] Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides.[33] At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon.[33] Some hafnium compounds in lower oxidation states are known.[34]

organohafnium compounds
such as hafnocene dichloride and tetrabenzylhafnium.

The white

binary compound known, with a melting point over 3,890 °C (4,163 K; 7,034 °F), and hafnium nitride is the most refractory of all known metal nitrides, with a melting point of 3,310 °C (3,583 K; 5,990 °F).[33] This has led to proposals that hafnium or its carbides might be useful as construction materials that are subjected to very high temperatures. The mixed carbide tantalum hafnium carbide (Ta
4HfC
5) possesses the highest melting point of any currently known compound, 4,263 K (3,990 °C; 7,214 °F).[35] Recent supercomputer simulations suggest a hafnium alloy with a melting point of 4,400 K (4,127 °C; 7,460 °F).[36]

History

Photographic recording of the characteristic X-ray emission lines of some elements

Hafnium's existence was predicted by Dmitri Mendeleev in 1869. In his report on The Periodic Law of the Chemical Elements, in 1869, Dmitri Mendeleev had implicitly predicted the existence of a heavier analog of titanium and zirconium. At the time of his formulation in 1871, Mendeleev believed that the elements were ordered by their atomic masses and placed lanthanum (element 57) in the spot below zirconium. The exact placement of the elements and the location of missing elements was done by determining the specific weight of the elements and comparing the chemical and physical properties.[37]

The

lanthanides and showed the gaps in the atomic number sequence at numbers 43, 61, 72, and 75.[38]

The discovery of the gaps led to an extensive search for the missing elements. In 1914, several people claimed the discovery after Henry Moseley predicted the gap in the periodic table for the then-undiscovered element 72.

rare earth elements in 1907 and published his results on celtium in 1911.[40] Neither the spectra nor the chemical behavior he claimed matched with the element found later, and therefore his claim was turned down after a long-standing controversy.[41] The controversy was partly because the chemists favored the chemical techniques which led to the discovery of celtium, while the physicists relied on the use of the new X-ray spectroscopy method that proved that the substances discovered by Urbain did not contain element 72.[41] In 1921, Charles R. Bury[42][43] suggested that element 72 should resemble zirconium and therefore was not part of the rare earth elements group. By early 1923, Niels Bohr and others agreed with Bury.[44][45] These suggestions were based on Bohr's theories of the atom which were identical to chemist Charles Bury,[42] the X-ray spectroscopy of Moseley, and the chemical arguments of Friedrich Paneth.[46][47]

Encouraged by these suggestions and by the reappearance in 1922 of Urbain's claims that element 72 was a rare earth element discovered in 1911,

Georg von Hevesy were motivated to search for the new element in zirconium ores.[48] Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev.[49][50][51] It was ultimately found in zircon in Norway through X-ray spectroscopy analysis.[52] The place where the discovery took place led to the element being named for the Latin name for "Copenhagen", Hafnia, the home town of Niels Bohr.[53][54][55] Today, the Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom.[56]

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium or potassium fluorides by Valdemar Thal Jantzen and von Hevesey.[27] Anton Eduard van Arkel and Jan Hendrik de Boer were the first to prepare metallic hafnium by passing hafnium tetraiodide vapor over a heated tungsten filament in 1924.[28][32] This process for differential purification of zirconium and hafnium is still in use today.[12]

Hafnium was one of the last two

stable elements to be discovered. The element rhenium was found in 1908 by Masataka Ogawa, though its atomic number was misidentified at the time, and it was not generally recognised by the scientific community until its rediscovery by Walter Noddack, Ida Noddack, and Otto Berg in 1925. This makes it somewhat difficult to say if hafnium or rhenium was discovered last.[57]

In 1923, six predicted elements were still missing from the periodic table: 43 (technetium), 61 (promethium), 85 (astatine), and 87 (francium) are radioactive elements and are only present in trace amounts in the environment,[58] thus making elements 75 (rhenium) and 72 (hafnium) the last two unknown non-radioactive elements.

Applications

Most of the hafnium produced is used in the manufacture of control rods for nuclear reactors.[29]

Hafnium has limited technical applications due to a few factors. First, it's very similar to zirconium, a more abundant element that can be used in most cases. Second, pure hafnium wasn't widely available until the late 1950s, when it became a byproduct of the nuclear industry's need for hafnium-free zirconium. Additionally, hafnium is rare and difficult to separate from other elements, making it expensive. After the Fukushima disaster reduced the demand for hafnium-free zirconium, the price of hafnium increased significantly from around $500–$600/kg ($227-$272/lb) in 2014 to around $1000/kg ($454/lb) in 2015.[59]

Nuclear reactors

The nuclei of several hafnium isotopes can each absorb multiple neutrons. This makes hafnium a good material for nuclear reactors' control rods. Its neutron capture cross section (Capture Resonance Integral Io ≈ 2000 barns)

FRM II uses hafnium as a neutron absorber.[61] It is also common in military reactors, particularly in US naval submarine reactors, to slow reactor rates that are too high.[62][63] It is seldom found in civilian reactors, the first core of the Shippingport Atomic Power Station (a conversion of a naval reactor) being a notable exception.[64]

Alloys

Hafnium-containing rocket nozzle of the Apollo Lunar Module in the lower right corner

Hafnium is used in alloys with iron, titanium, niobium, tantalum, and other metals. An alloy used for liquid-rocket thruster nozzles, for example the main engine of the Apollo Lunar Modules, is C103 which consists of 89% niobium, 10% hafnium and 1% titanium.[65]

Small additions of hafnium increase the adherence of protective oxide scales on nickel-based alloys. It thereby improves the corrosion resistance, especially under cyclic temperature conditions that tend to break oxide scales, by inducing thermal stresses between the bulk material and the oxide layer.[66][67][68]

Microprocessors

Hafnium-based compounds are employed in

high-k dielectrics, allowing reduction of the gate leakage current which improves performance at such scales.[71][72][73]

Isotope geochemistry

Isotopes of hafnium and

lutetium-hafnium dating. It is often used as a tracer of isotopic evolution of Earth's mantle through time.[74] This is because 176Lu decays to 176Hf with a half-life of approximately 37 billion years.[75][76][77]

In most geologic materials,

depleted mantle
, these "ages" do not carry the same geologic significance as do other geochronological techniques as the results often yield isotopic mixtures and thus provide an average age of the material from which it was derived.

Garnet is another mineral that contains appreciable amounts of hafnium to act as a geochronometer. The high and variable Lu/Hf ratios found in garnet make it useful for dating metamorphic events.[79]

Other uses

Due to its heat resistance and its affinity to oxygen and nitrogen, hafnium is a good scavenger for oxygen and nitrogen in gas-filled and

incandescent lamps. Hafnium is also used as the electrode in plasma cutting because of its ability to shed electrons into the air.[80]

The high energy content of 178m2Hf was the concern of a DARPA-funded program in the US. This program eventually concluded that using the above-mentioned 178m2Hf nuclear isomer of hafnium to construct high-yield weapons with X-ray triggering mechanisms—an application of induced gamma emission—was infeasible because of its expense. See hafnium controversy.

Hafnium metallocene compounds can be prepared from hafnium tetrachloride and various cyclopentadiene-type ligand species. Perhaps the simplest hafnium metallocene is hafnocene dichloride. Hafnium metallocenes are part of a large collection of Group 4 transition metal metallocene catalysts [81] that are used worldwide in the production of polyolefin resins like polyethylene and polypropylene.

A pyridyl-amidohafnium catalyst can be used for the controlled iso-selective polymerization of propylene which can then be combined with polyethylene to make a much tougher recycled plastic.[82]

Hafnium diselenide is studied in spintronics thanks to its charge density wave and superconductivity.[83]

Precautions

Care needs to be taken when

pyrophoric—fine particles can spontaneously combust when exposed to air. Compounds that contain this metal are rarely encountered by most people. The pure metal is not considered toxic, but hafnium compounds should be handled as if they were toxic because the ionic forms of metals are normally at greatest risk for toxicity, and limited animal testing has been done for hafnium compounds.[84]

People can be exposed to hafnium in the workplace by breathing, swallowing, skin, and eye contact. The

immediately dangerous to life and health.[85]

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