関: Hf

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a grey tetravalent metallic element that resembles zirconium chemically and is found in zirconium minerals; used in filaments for its ready emission of electrons (同)Hf, atomic number 72

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ハフニウム(金属元素;原子記号は『Hf』)
hafnium の化学記号

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/03/05 03:46:22」(JST)

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Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though hafnium was not identified until 1923, making it the penultimate stable isotope element to be discovered (rhenium was identified two years later). Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered.^[2]^[3]

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

Hafnium's large neutron capture cross-section makes it a good material for neutron absorption in control rods in nuclear power plants, but at the same time requires that it be removed from the neutron-transparent corrosion-resistant zirconium alloys used in nuclear reactors.

Characteristics

Physical characteristics

Hafnium bits

Hafnium is a shiny, silvery, ductile metal that is corrosion-resistant and chemically similar to zirconium^[4] (due to its having the same number of valence electrons and being in the same group). 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.^[4]

A notable physical difference between these metals is their density, with zirconium having about one-half the density of hafnium. The most notable nuclear properties of hafnium are its high thermal neutron-capture cross-section and that the nuclei of several different hafnium isotopes readily absorb two or more neutrons apiece.^[4] In contrast with this, zirconium is practically transparent to thermal neutrons, and it is commonly used for the metal components of nuclear reactors – especially the claddings of their nuclear fuel rods.

Chemical characteristics

Isotopes

At least 34 isotopes of hafnium have been observed, ranging in mass number from 153 to 186.^[7]^[8] The five stable isotopes are in the range of 176 to 180. The radioactive isotopes' half-lives range from only 400 ms for ¹⁵³Hf,^[8] to 2.0 petayears (10¹⁵ years) for the most stable one, ¹⁷⁴Hf.^[7]

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 5.8 ppm of the Earth's upper crust by mass. It does not exist as a free element in nature, 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.^[9] An old (obsolete) name for a variety of zircon containing unusually high Hf content is alvite.^[10]

A major source of zircon (and hence hafnium) ores is heavy mineral sands ore deposits, pegmatites particularly in Brazil and Malawi, and carbonatite intrusions particularly the Crown Polymetallic Deposit at 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.^[11]

Hafnium reserves are projected to last under 10 years if the world population increases and demand grows.^[12]

Production

Melted tip of a hafnium consumable electrode used in an ebeam remelting furnace

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.^[13]

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 for hafnium.^[4]

Hafnium oxidized ingots which exhibits thin film optical effects.

The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate.^[14] The methods first used — fractional crystallization of ammonium fluoride salts^[15] or the fractionated distillation of the chloride^[16] — have not proven suitable for an industrial-scale production. After zirconium was chosen as 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 the production of hafnium.^[17] 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.^[18] The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium or sodium, as in the Kroll process.^[19]

HfCl₄ + 2 Mg (1100 °C) → 2 MgCl₂ + Hf

Further purification is effected by a chemical transport reaction developed by Arkel and de Boer: In a closed vessel, hafnium reacts with iodine at temperatures of 500 °C, forming hafnium(IV) iodide; at a tungsten filament of 1700 °C the reverse reaction happens, and the iodine and hafnium are set free. The hafnium forms a solid coating at the tungsten filament, and the iodine can react with additional hafnium, resulting in a steady turn over.^[6]^[20]

Hf + 2 I₂ (500 °C) → HfI₄

HfI₄ (1700 °C) → Hf + 2 I₂

Chemical compounds

Hafnium and zirconium form nearly identical series of chemical compounds.^[21] Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides.^[21] At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon.^[21] Due to the lanthanide contraction of the elements in the sixth period, zirconium and hafnium have nearly identical ionic radii. The ionic radius of Zr⁴⁺ is 0.79 angstrom and that of Hf⁴⁺ is 0.78 angstrom.^[21]

Hafnium(IV) chloride and hafnium(IV) iodide have some applications in the production and purification of hafnium metal. They are volatile solids with polymeric structures.^[6] These tetrachlorides are precursors to various organohafnium compounds such as hafnocene dichloride and tetrabenzylhafnium.

The white hafnium oxide (HfO₂), with a melting point of 2812 °C and a boiling point of roughly 5100 °C, is very similar to zirconia, but slightly more basic.^[6] Hafnium carbide is the most refractory binary compound known, with a melting point over 3890 °C, and hafnium nitride is the most refractory of all known metal nitrides, with a melting point of 3310 °C.^[21] 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, 4215 °C.^[22]

History

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

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.^[23]

The X-ray spectroscopy done by Henry Moseley in 1914 showed a direct dependency between spectral line and effective nuclear charge. This led to the nuclear charge, or atomic number of an element, being used to ascertain its place within the periodic table. With this method, Moseley determined the number of lanthanides and showed the gaps in the atomic number sequence at numbers 43, 61, 72, and 75.^[24]

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.^[25] Georges Urbain asserted that he found element 72 in the rare earth elements in 1907 and published his results on celtium in 1911.^[26] Neither the spectra nor the chemical behavior matched with the element found later, and therefore his claim was turned down after a long-standing controversy.^[27] 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.^[27] By early 1923, several physicists and chemists such as Niels Bohr^[28] and Charles R. Bury^[29] suggested that element 72 should resemble zirconium and therefore was not part of the rare earth elements group. These suggestions were based on Bohr's theories of the atom, the X-ray spectroscopy of Mosley, and the chemical arguments of Friedrich Paneth.^[30]^[31]

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, Dirk Coster and Georg von Hevesy were motivated to search for the new element in zirconium ores.^[32] Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev.^[33]^[34] It was ultimately found in zircon in Norway through X-ray spectroscopy analysis.^[35] 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.^[36] Today, the Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom.^[37]

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium or potassium fluorides by Valdemar Thal Jantzen and von Hevesey.^[15] Anton Eduard van Arkel and Jan Hendrik de Boer were the first to prepare metallic hafnium by passing hafnium tetra-iodide vapor over a heated tungsten filament in 1924.^[16]^[20] This process for differential purification of zirconium and hafnium is still in use today.^[4]

In 1923, four predicted elements were still missing from the periodic table: 43 (technetium) and 61 (promethium) are radioactive elements and are only present in trace amounts in the environment,^[38] thus making elements 75 (rhenium) and 72 (hafnium) the last two unknown non-radioactive elements. Since rhenium was discovered in 1925,^[39] hafnium was the next to last element with stable isotopes to be discovered.

Applications

Several details contribute to the fact that there are only a few technical uses for hafnium: First, the close similarity between hafnium and zirconium makes it possible to use zirconium for most of the applications; second, hafnium was first available as pure metal after the use in the nuclear industry for hafnium-free zirconium in the late 1950s. Furthermore, the low abundance and difficult separation techniques necessary make it a scarce commodity.^[4]

Most of the hafnium produced is used in the production of control rods for nuclear reactors.^[17]

Nuclear reactors

The nuclei of several hafnium isotopes can each absorb multiple neutrons. This makes hafnium a good material for use in the control rods for nuclear reactors. Its neutron-capture cross-section is about 600 times that of zirconium. (Other elements that are good neutron-absorbers for control rods are cadmium and boron.) Excellent mechanical properties and exceptional corrosion-resistance properties allow its use in the harsh environment of pressurized water reactors.^[17] The German research reactor FRM II uses hafnium as a neutron absorber.^[40] It is also common in military reactors, particularity in US naval reactors,^[41] but seldom found in civilian ones, the first core of the Shippingport Atomic Power Station (a conversion of a naval reactor) being a notable exception.^[42]

Alloys

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

Hafnium is used in iron, titanium, niobium, tantalum, and other metal alloys. 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.^[43]

Small additions of hafnium increase the adherence of protective oxide scales on nickel-based alloys. It improves thereby 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.^[44]^[45]^[46]

Microprocessors

The electronics industry discovered that hafnium-based compounds can be employed in gate insulators in the 45 nm generation of integrated circuits from Intel, IBM and others.^[47]^[48] Hafnium oxide-based compounds are practical high-k dielectrics, allowing reduction of the gate leakage current which improves performance at such scales.^[49]^[50]

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 air.^[51]

The high energy content of ^178m2Hf was the concern of a DARPA funded program in the US. This program determined the possibility of using a nuclear isomer of hafnium (the above-mentioned ^178m2Hf) 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.

Precautions

Dragon's Breath at night

Care needs to be taken when machining hafnium because, like its sister metal zirconium, when hafnium is divided into fine particles, it is pyrophoric and can ignite spontaneously in air—similar to that obtained in Dragon's Breath. 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.^[52]

References

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External links

Hafnium at Los Alamos National Laboratory's periodic table of the elements
Hafnium at The Periodic Table of Videos (University of Nottingham)
Hafnium Technical & Safety Data
NLM Hazardous Substances Databank – Hafnium, elemental
Intel Shifts from Silicon to Lift Chip Performance
Hafnium-based Intel 45nm Process Technology
CDC - NIOSH Pocket Guide to Chemical Hazards

English Journal

Synthesis, Characterization, and Lactide Polymerization Activity of Group 4 Metal Complexes Containing Two Bis(phenolate) Ligands.

Sauer A, Buffet JC, Spaniol TP, Nagae H, Mashima K, Okuda J.SourceInstitute of Inorganic Chemistry, RWTH Aachen University , Landoltweg 1, D-52056 Aachen, Germany.
Inorganic chemistry.Inorg Chem.2012 May 9. [Epub ahead of print]
A series of group 4 metal complexes Zr-(1)(2), Zr-(2)(2), Zr-(3)(2), Zr-(4)(2), Zr-(5)(2), Hf-(1)(2), and Hf-(4)(2) containing two bridged bis(phenolate) ligands of the (OSSO)-type were prepared by the reaction of the corresponding bis(phenol) and group 4 metal precursor MX(4) (X = O(i)Pr, CH(2)Ph)
PMID 22571415

Low-voltage bendable pentacene thin-film transistor with stainless steel substrate and polystyrene-coated hafnium silicate dielectric.

Yun DJ, Lee S, Yong K, Rhee SW.SourceSamsung Advanced Institute of Technology , PO Box 111, Suwon 440-600, Republic of Korea.
ACS applied materials & interfaces.ACS Appl Mater Interfaces.2012 Apr 25;4(4):2025-32. Epub 2012 Apr 10.
The hafnium silicate and aluminum oxide high-k dielectrics were deposited on stainless steel substrate using atomic layer deposition process and octadecyltrichlorosilane (OTS) and polystyrene (PS) were treated improve crystallinity of pentacene grown on them. Besides, the effects of the pentacene de
PMID 22462593

Photoelectron spectroscopy of the molecular anions, ZrO(-), HfO(-), HfHO(-), and HfO(2)H(-).

Li X, Zheng W, Buonaugurio A, Buytendyk A, Bowen K, Balasubramanian K.SourceDepartments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, Maryland 21218, USA.
The Journal of chemical physics.J Chem Phys.2012 Apr 21;136(15):154306.
Negative ion photoelectron spectra of ZrO(-), HfO(-), HfHO(-), and HfO(2)H(-) are reported. Even though zirconium- and hafnium-containing molecules typically exhibit similar chemistries, the negative ion photoelectron spectral profiles of ZrO(-) and HfO(-) are dramatically different from one another
PMID 22519325

Japanese Journal

四極構造の真空トランジスタを用いた周波数混合実験(電子管と真空ナノエレクトロニクス及びその評価技術)

安友佳樹,大上航,後藤康仁,辻博司
電子情報通信学会技術研究報告. ED, 電子デバイス 111(248), 5-8, 2011-10-13
ゲート電極一体型の窒化ハフニウムフィールドエミッタアレイ(HfN-FEA)、コレクタ電極に加え、制御電極からなる四極構造真空トランジスタを構成し、周波数混合実験を行った。まずコレクタ電流の制御電極電庄に対する依存性を測定した。その結果エミッタ電圧が-60Vのとき制御電極電圧-40V〜-50Vにおいてコレクタ電流を線形に制御できる領域があることが明らかになった。この部分について考察を行い、周波数混合 …
NAID 110008899876

Atomic layer coating of hafnium oxide on carbon nanotubes for high-performance field emitters

Song Young Il,Yang Cheol-Min,Kwac Lee Ku,Kim Hong Gun,Kim Yoong Ahm
APPLIED PHYSICS LETTERS 99(15), 153115, 2011-10-10
… Carbon nanotubes coated with hafnium oxide exhibit excellent electron emission characteristics, including a low turn-on voltage, a high field enhancement factor, and exceptional current stability. … Their enhanced emission performance was attributed to a decrease in the work function and an increase in the electron density of states at the carbon nanotube Fermi level closest to the conduction band minimum of hafnium oxide. …
NAID 80022059628

ハフニウム酸化物への元素添加効果 : 第一原理計算による検討(ゲート絶縁薄膜,容量膜,機能膜及びメモリ技術)

中山利紀,川崎裕,丸泉琢也
電子情報通信学会技術研究報告. SDM, シリコン材料・デバイス 111(114), 75-80, 2011-06-27
MOSデバイス高誘電率ゲート絶縁膜として、ハフニウム酸化物(HfO_2)が期待されている。一方、同酸化物については、酸素欠損、ハフニウム欠損などの欠陥が、ゲート絶縁膜信頼性に影響する事が知られており、元素添加による改善が試みられている。本研究では、ランタン、アルミニウム、マグネシウムの添加効果について、第一原理計算により比較したので報告する。
NAID 110008800859

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「Hf」

Hafnium, ₇₂Hf
General properties
Name, symbol	hafnium, Hf
Pronunciation	/ˈhæfniəm/; HAF-nee-əm
Appearance	steel gray
Hafnium in the periodic table
	lutetium ← hafnium → tantalum
Atomic number	72
Standard atomic weight (±)	178.49(2)
Element category	transition metal
Group, block	group 4, d-block
Period	period 6
Electron configuration	[Xe] 4f14 5d2 6s2
per shell	2, 8, 18, 32, 10, 2
Physical properties
Phase	solid
Melting point	2506 K (2233 °C, 4051 °F)
Boiling point	4876 K (4603 °C, 8317 °F)
Density near r.t.	13.31 g·cm−3
when liquid, at m.p.	12 g·cm−3
Heat of fusion	27.2 kJ·mol−1
Heat of vaporization	648 kJ·mol−1
Molar heat capacity	25.73 J·mol−1·K−1
Atomic properties
Oxidation states	4, 3, 2 (an amphoteric oxide)
Electronegativity	Pauling scale: 1.3
Ionization energies	1st: 658.5 kJ·mol−1; 2nd: 1440 kJ·mol−1; 3rd: 2250 kJ·mol−1
Atomic radius	empirical: 159 pm
Covalent radius	175±10 pm
Miscellanea
Crystal structure	hexagonal close-packed (hcp)
Speed of sound thin rod	3010 m·s−1 (at 20 °C)
Thermal expansion	5.9 µm·m−1·K−1 (at 25 °C)
Thermal conductivity	23.0 W·m−1·K−1
Electrical resistivity	331 nΩ·m (at 20 °C)
Magnetic ordering	paramagnetic
Young's modulus	78 GPa
Shear modulus	30 GPa
Bulk modulus	110 GPa
Poisson ratio	0.37
Mohs hardness	5.5
Vickers hardness	1520–2060 MPa
Brinell hardness	1450–2100 MPa
CAS Registry Number	7440-58-6
History
Naming	after Hafnia. Latin for: Copenhagen, where it was discovered
Prediction	Dmitri Mendeleev (1869)
Discovery and first isolation	Dirk Coster and George de Hevesy (1922)
Most stable isotopes
	Main article: Isotopes of hafnium
	Decay modes in parentheses are predicted, but have not yet been observed
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ハフニウム

関: hafnium

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