Hafnium

Hafnium

Overview
Hafnium is a chemical element
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

 with the symbol Hf and atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

 72. A lustrous
Lustre (mineralogy)
Lustre is a description of the way light interacts with the surface of a crystal, rock, or mineral. The word lustre traces its origins back to the Latin word lux, meaning "light", and generally implies radiance, gloss, or brilliance....

, silvery gray, tetravalent
Tetravalence
In chemistry, a tetravalence is the state of an atom with four electrons available for covalent chemical bonding in its valence . An example is methane : the tetravalent carbon atom forms a covalent bond with four hydrogen atoms...

 transition metal
Transition metal
The term transition metal has two possible meanings:*The IUPAC definition states that a transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell." Group 12 elements are not transition metals in this definition.*Some...

, hafnium chemically resembles zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

 and is found in zirconium mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...

s. Its existence was predicted by Dmitri Mendeleev
Mendeleev's predicted elements
Professor Dmitri Mendeleev published the first Periodic Table of the Atomic Elements in 1869 based on properties which appeared with some regularity as he laid out the elements from lightest to heaviest....

 in 1869. Hafnium was the penultimate stable isotope
Stable isotope
Stable isotopes are chemical isotopes that may or may not be radioactive, but if radioactive, have half-lives too long to be measured.Only 90 nuclides from the first 40 elements are energetically stable to any kind of decay save proton decay, in theory...

 element to be discovered (rhenium
Rhenium
Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-white, heavy, third-row transition metal in group 7 of the periodic table. With an average concentration of 1 part per billion , rhenium is one of the rarest elements in the Earth's crust. The free element has...

 was identified two years later). Hafnium is named for Hafnia, the Latin
Latin
Latin is an Italic language originally spoken in Latium and Ancient Rome. It, along with most European languages, is a descendant of the ancient Proto-Indo-European language. Although it is considered a dead language, a number of scholars and members of the Christian clergy speak it fluently, and...

 name for "Copenhagen
Copenhagen
Copenhagen is the capital and largest city of Denmark, with an urban population of 1,199,224 and a metropolitan population of 1,930,260 . With the completion of the transnational Øresund Bridge in 2000, Copenhagen has become the centre of the increasingly integrating Øresund Region...

", where it was discovered.

Hafnium is used in filaments and electrodes.
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Encyclopedia
Hafnium is a chemical element
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

 with the symbol Hf and atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

 72. A lustrous
Lustre (mineralogy)
Lustre is a description of the way light interacts with the surface of a crystal, rock, or mineral. The word lustre traces its origins back to the Latin word lux, meaning "light", and generally implies radiance, gloss, or brilliance....

, silvery gray, tetravalent
Tetravalence
In chemistry, a tetravalence is the state of an atom with four electrons available for covalent chemical bonding in its valence . An example is methane : the tetravalent carbon atom forms a covalent bond with four hydrogen atoms...

 transition metal
Transition metal
The term transition metal has two possible meanings:*The IUPAC definition states that a transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell." Group 12 elements are not transition metals in this definition.*Some...

, hafnium chemically resembles zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

 and is found in zirconium mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...

s. Its existence was predicted by Dmitri Mendeleev
Mendeleev's predicted elements
Professor Dmitri Mendeleev published the first Periodic Table of the Atomic Elements in 1869 based on properties which appeared with some regularity as he laid out the elements from lightest to heaviest....

 in 1869. Hafnium was the penultimate stable isotope
Stable isotope
Stable isotopes are chemical isotopes that may or may not be radioactive, but if radioactive, have half-lives too long to be measured.Only 90 nuclides from the first 40 elements are energetically stable to any kind of decay save proton decay, in theory...

 element to be discovered (rhenium
Rhenium
Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-white, heavy, third-row transition metal in group 7 of the periodic table. With an average concentration of 1 part per billion , rhenium is one of the rarest elements in the Earth's crust. The free element has...

 was identified two years later). Hafnium is named for Hafnia, the Latin
Latin
Latin is an Italic language originally spoken in Latium and Ancient Rome. It, along with most European languages, is a descendant of the ancient Proto-Indo-European language. Although it is considered a dead language, a number of scholars and members of the Christian clergy speak it fluently, and...

 name for "Copenhagen
Copenhagen
Copenhagen is the capital and largest city of Denmark, with an urban population of 1,199,224 and a metropolitan population of 1,930,260 . With the completion of the transnational Øresund Bridge in 2000, Copenhagen has become the centre of the increasingly integrating Øresund Region...

", where it was discovered.

Hafnium is used in filaments and electrodes. Some semiconductor
Semiconductor
A semiconductor is a material with electrical conductivity due to electron flow intermediate in magnitude between that of a conductor and an insulator. This means a conductivity roughly in the range of 103 to 10−8 siemens per centimeter...

 fabrication processes use its oxide for integrated circuits at 45 nm and smaller feature lengths. Some superalloy
Superalloy
A superalloy, or high-performance alloy, is an alloy that exhibits excellent mechanical strength and creep resistance at high temperatures, good surface stability, and corrosion and oxidation resistance. Superalloys typically have a matrix with an austenitic face-centered cubic crystal structure. ...

s used for special applications contain hafnium in combination with niobium
Niobium
Niobium or columbium , is a chemical element with the symbol Nb and atomic number 41. It's a soft, grey, ductile transition metal, which is often found in the pyrochlore mineral, the main commercial source for niobium, and columbite...

, titanium
Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....

, or tungsten
Tungsten
Tungsten , also known as wolfram , is a chemical element with the chemical symbol W and atomic number 74.A hard, rare metal under standard conditions when uncombined, tungsten is found naturally on Earth only in chemical compounds. It was identified as a new element in 1781, and first isolated as...

.

Hafnium's large neutron capture
Neutron capture
Neutron capture is a kind of nuclear reaction in which an atomic nucleus collides with one or more neutrons and they merge to form a heavier nucleus. Since neutrons have no electric charge they can enter a nucleus more easily than positively charged protons, which are repelled...

 cross-section makes it a good material for neutron
Neutron
The neutron is a subatomic hadron particle which has the symbol or , no net electric charge and a mass slightly larger than that of a proton. With the exception of hydrogen, nuclei of atoms consist of protons and neutrons, which are therefore collectively referred to as nucleons. The number of...

 absorption in control rod
Control rod
A control rod is a rod made of chemical elements capable of absorbing many neutrons without fissioning themselves. They are used in nuclear reactors to control the rate of fission of uranium and plutonium...

s in nuclear power plant
Nuclear power plant
A nuclear power plant is a thermal power station in which the heat source is one or more nuclear reactors. As in a conventional thermal power station the heat is used to generate steam which drives a steam turbine connected to a generator which produces electricity.Nuclear power plants are usually...

s, but at the same time requires that it be removed from the neutron-transparent corrosion-resistant zirconium alloys used in nuclear reactors.

Physical characteristics



Hafnium is a shiny, silvery, ductile
Ductility
In materials science, ductility is a solid material's ability to deform under tensile stress; this is often characterized by the material's ability to be stretched into a wire. Malleability, a similar property, is a material's ability to deform under compressive stress; this is often characterized...

 metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...

 that is corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

-resistant and chemically similar to zirconium (due to its having the same number of valence electron
Valence electron
In chemistry, valence electrons are the electrons of an atom that can participate in the formation of chemical bonds with other atoms. Valence electrons are the "own" electrons, present in the free neutral atom, that combine with valence electrons of other atoms to form chemical bonds. In a single...

s 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.

A notable physical difference between these metals is their density
Density
The mass density or density of a material is defined as its mass per unit volume. The symbol most often used for density is ρ . In some cases , density is also defined as its weight per unit volume; although, this quantity is more properly called specific weight...

, with zirconium having about one-half the density of hafnium. The most notable nuclear
Nuclear physics
Nuclear physics is the field of physics that studies the building blocks and interactions of atomic nuclei. The most commonly known applications of nuclear physics are nuclear power generation and nuclear weapons technology, but the research has provided application in many fields, including those...

 properties of hafnium are its high thermal neutron-capture cross-section
Neutron capture
Neutron capture is a kind of nuclear reaction in which an atomic nucleus collides with one or more neutrons and they merge to form a heavier nucleus. Since neutrons have no electric charge they can enter a nucleus more easily than positively charged protons, which are repelled...

 and that the nuclei of several different hafnium isotopes readily absorb two or more neutron
Neutron
The neutron is a subatomic hadron particle which has the symbol or , no net electric charge and a mass slightly larger than that of a proton. With the exception of hydrogen, nuclei of atoms consist of protons and neutrons, which are therefore collectively referred to as nucleons. The number of...

s apiece. 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




Hafnium reacts in air to form a protective film
Passivation
Passivation is the process of making a material "passive", and thus less reactive with surrounding air, water, or other gases or liquids. The goal is to inhibit corrosion, whether for structural or cosmetic reasons. Passivation of metals is usually achieved by the deposition of a layer of oxide...

 that inhibits further corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

. The metal is not readily attacked by acids but can be oxidized with halogens or it can be burnt in air. Like its sister metal zirconium, finely divided hafnium can ignite spontaneously in air—similar to that obtained in Dragon's Breath
Dragon's Breath
A Dragon's Breath usually refers to a zirconium-based pyrotechnic shotgun round. When the round is fired, sparks and occasionally flames shoot out to about 15 m , beyond 15 metres, the round's already limited effectiveness is drastically reduced....

. The metal is resistant to concentrated alkali
Alkali
In chemistry, an alkali is a basic, ionic salt of an alkali metal or alkaline earth metal element. Some authors also define an alkali as a base that dissolves in water. A solution of a soluble base has a pH greater than 7. The adjective alkaline is commonly used in English as a synonym for base,...

s.

The chemistry of hafnium and zirconium is so similar that the two cannot be separated on the basis of differing chemical reactions. The melting points and boiling points of the compounds and the solubility
Solubility
Solubility is the property of a solid, liquid, or gaseous chemical substance called solute to dissolve in a solid, liquid, or gaseous solvent to form a homogeneous solution of the solute in the solvent. The solubility of a substance fundamentally depends on the used solvent as well as on...

 in solvents are the major differences in the chemistry of these twin elements.

Isotopes



At least 34 isotopes of hafnium have been observed, ranging in mass number from 153 to 186. The five stable isotopes are in the range of 176 to 180. The radioactive isotopes' half-lives
Half-life
Half-life, abbreviated t½, is the period of time it takes for the amount of a substance undergoing decay to decrease by half. The name was originally used to describe a characteristic of unstable atoms , but it may apply to any quantity which follows a set-rate decay.The original term, dating to...

 range from only 400 ms
SI prefix
The International System of Units specifies a set of unit prefixes known as SI prefixes or metric prefixes. An SI prefix is a name that precedes a basic unit of measure to indicate a decadic multiple or fraction of the unit. Each prefix has a unique symbol that is prepended to the unit symbol...

 for 153Hf, to 2.0 petayears (1015 years) for the most stable one, 174Hf.

The nuclear isomer
Nuclear isomer
A nuclear isomer is a metastable state of an atomic nucleus caused by the excitation of one or more of its nucleons . "Metastable" refers to the fact that these excited states have half-lives more than 100 to 1000 times the half-lives of the other possible excited nuclear states...

 178m2Hf was at the center of a controversy for several years regarding its potential use as a weapon.

Occurrence


Hafnium is estimated to make up about 5.8 ppm of the Earth
Earth
Earth is the third planet from the Sun, and the densest and fifth-largest of the eight planets in the Solar System. It is also the largest of the Solar System's four terrestrial planets...

's upper crust
Crust (geology)
In geology, the crust is the outermost solid shell of a rocky planet or natural satellite, which is chemically distinct from the underlying mantle...

 by weight. It does not exist as a free element in nature, but is found combined in solid solution
Solid solution
A solid solution is a solid-state solution of one or more solutes in a solvent. Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase...

 for zirconium in natural zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

 compounds such as zircon
Zircon
Zircon is a mineral belonging to the group of nesosilicates. Its chemical name is zirconium silicate and its corresponding chemical formula is ZrSiO4. A common empirical formula showing some of the range of substitution in zircon is 1–x4x–y...

, 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. An old (obsolete) name for a variety of zircon containing unusually high Hf content is alvite.

A major source of zircon (and hence hafnium) ores are heavy mineral sands ore deposits
Heavy mineral sands ore deposits
Heavy mineral sands are a class of ore deposit which is an important source of zirconium, titanium, thorium, tungsten, rare earth elements, the industrial minerals diamond, sapphire, garnet, and occasionally precious metals or gemstones....

, pegmatite
Pegmatite
A pegmatite is a very crystalline, intrusive igneous rock composed of interlocking crystals usually larger than 2.5 cm in size; such rocks are referred to as pegmatitic....

s particularly in Brazil and Malawi
Malawi
The Republic of Malawi is a landlocked country in southeast Africa that was formerly known as Nyasaland. It is bordered by Zambia to the northwest, Tanzania to the northeast, and Mozambique on the east, south and west. The country is separated from Tanzania and Mozambique by Lake Malawi. Its size...

, and carbonatite
Carbonatite
Carbonatites are intrusive or extrusive igneous rocks defined by mineralogic composition consisting of greater than 50 percent carbonate minerals. Carbonatites may be confused with marble, and may require geochemical verification....

 intrusions particularly the Crown Polymetallic Deposit at Mount Weld
Mount Weld
Mount Weld is a mountain and a mine site in Western Australia, located about 30 km south of Laverton and 120 km east of Leonora. It ranks as one of the richest major rare earth deposits in the world....

, Western Australia. A potential source of hafnium is trachyte tuffs containing rare zircon-hafnium silicates eudialyte
Eudialyte
Eudialyte, whose name derives from the Greek phrase Εὖ διάλυτος eu dialytos, meaning "well decomposable", is a somewhat rare, red silicate mineral, which forms in alkaline igneous rocks, such as nepheline syenites...

 or armstrongite, at Dubbo in New South Wales
New South Wales
New South Wales is a state of :Australia, located in the east of the country. It is bordered by Queensland, Victoria and South Australia to the north, south and west respectively. To the east, the state is bordered by the Tasman Sea, which forms part of the Pacific Ocean. New South Wales...

, Australia.

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

Production


The heavy mineral sands ore deposits
Heavy mineral sands ore deposits
Heavy mineral sands are a class of ore deposit which is an important source of zirconium, titanium, thorium, tungsten, rare earth elements, the industrial minerals diamond, sapphire, garnet, and occasionally precious metals or gemstones....

 of the titanium ores ilmenite
Ilmenite
Ilmenite is a weakly magnetic titanium-iron oxide mineral which is iron-black or steel-gray. It is a crystalline iron titanium oxide . It crystallizes in the trigonal system, and it has the same crystal structure as corundum and hematite....

 and rutile
Rutile
Rutile is a mineral composed primarily of titanium dioxide, TiO2.Rutile is the most common natural form of TiO2. Two rarer polymorphs of TiO2 are known:...

 yield most of the mined zirconium, and therefore also most the hafnium.

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.
The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate. The methods first used — fractional crystallization
Fractional crystallization (chemistry)
In chemistry, fractional crystallization is a method of refining substances based on differences in solubility. If a mixture of two or more substances in solution is allowed to crystallize, for example by allowing the temperature of the solution to decrease, the precipitate will contain more of...

 of ammonium fluoride salts or the fractionated distillation of the chloride — 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. 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. The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium
Magnesium
Magnesium is a chemical element with the symbol Mg, atomic number 12, and common oxidation number +2. It is an alkaline earth metal and the eighth most abundant element in the Earth's crust and ninth in the known universe as a whole...

 or sodium
Sodium
Sodium is a chemical element with the symbol Na and atomic number 11. It is a soft, silvery-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is 23Na. It is an abundant element that exists in numerous minerals, most commonly as sodium chloride...

, as in the Kroll process
Kroll process
Kroll Process is a pyrometallurgical industrial process used to produce metallic titanium. It was invented by William J. Kroll in Luxembourg. After moving to the United States, Kroll further developed the method for the production of zirconium...

.
HfCl4 + 2 Mg (1100 °C) → 2 MgCl2 + Hf


Further purification is effected by a chemical transport reaction
Chemical transport reaction
In chemistry, a chemical transport reaction describes a process for purification and crystallization of non-volatile solids. The process is also responsible for certain aspects of mineral growth from the effluent of volcanoes. The technique is distinct from chemical vapor deposition, which...

 developed by Arkel and de Boer
Crystal bar process
The crystal bar process was developed by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925. This process was the first industrial process for the commercial production of pure ductile metallic zirconium. It is used in the production of small quantities of ultra-pure titanium and zirconium...

: In a closed vessel, hafnium reacts with iodine
Iodine
Iodine is a chemical element with the symbol I and atomic number 53. The name is pronounced , , or . The name is from the , meaning violet or purple, due to the color of elemental iodine vapor....

 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.
Hf + 2 I2 (500 °C) → HfI4
HfI4 (1700 °C) → Hf + 2 I2

Chemical compounds


Hafnium and zirconium form nearly identical series of chemical compounds.
Hafnium tends to form inorganic compounds
Inorganic chemistry
Inorganic chemistry is the branch of chemistry concerned with the properties and behavior of inorganic compounds. This field covers all chemical compounds except the myriad organic compounds , which are the subjects of organic chemistry...

 in the oxidation state of +4. Halogen
Halogen
The halogens or halogen elements are a series of nonmetal elements from Group 17 IUPAC Style of the periodic table, comprising fluorine , chlorine , bromine , iodine , and astatine...

s react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

, nitrogen
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

, carbon
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...

, boron
Boron
Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the...

, sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...

, and silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...

. Due to the lanthanide contraction
Lanthanide contraction
Lanthanide contraction is a term used in chemistry to describe the decrease in ionic radii of the elements in the lanthanide series from atomic number 58, Cerium to 71, Lutetium, which results in smaller than otherwise expected ionic radii for the subsequent elements starting with 72, Hafnium...

 of the elements in the sixth period
Period 6 element
A period 6 element is one of the chemical elements in the sixth row of the periodic table of the elements, including the lanthanides...

, zirconium and hafnium have nearly identical ionic radii
Ionic radius
Ionic radius, rion, is the radius of an atom's ion. Although neither atoms nor ions have sharp boundaries, it is important to treat them as if they are hard spheres with radii such that the sum of ionic radii of the cation and anion gives the distance between the ions in a crystal lattice...

. The ionic radius of Zr4+ is 0.79 angstrom
Ångström
The angstrom or ångström, is a unit of length equal to 1/10,000,000,000 of a meter . Its symbol is the Swedish letter Å....

 and that of Hf4+ is 0.78 angstrom.

Hafnium(IV) chloride
Hafnium(IV) chloride
Hafnium chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It functions as a Lewis acid and catalyst for certain alkylation and isomerism reactions...

 and hafnium(IV) iodide have some applications in the production and purification of hafnium metal. They are volatile solids with polymeric structures. These tetrachlorides are precursors to various organohafnium compounds
Organozirconium chemistry
Organozirconium compounds are organometallic compounds containing a carbon to zirconium chemical bond. Organozirconium chemistry is the corresponding science exploring properties, structure and reactivity of these compounds. In general organozirconium compounds are stable and non-toxic...

 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. Hafnium carbide is the most refractory
Refraction (metallurgy)
In metallurgy, refraction is a property of metals that indicates their ability to withstand heat. Metals with a high degree of refraction are referred to as refractory. These metals derive their high melting points from their strong intermolecular forces...

 binary compound
Binary compound
A binary compound is a chemical compound that contains exactly two different elements. Examples of binary ionic compounds include calcium chloride , sodium fluoride , and magnesium oxide , whilst examples of binary covalent compounds include water , carbon monoxide , and sulfur hexafluoride...

 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. 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
Tantalum hafnium carbide
Tantalum hafnium carbide is a refractory chemical compound with a general formula TaxHf1-xCy, which can be considered as a solid solution of tantalum carbide and hafnium carbide...

  possesses the highest melting point of any currently known compound, 4215 °C.

History



In his report on The Periodic Law of the Chemical Elements, in 1869, Dmitri Mendeleev
Dmitri Mendeleev
Dmitri Ivanovich Mendeleev , was a Russian chemist and inventor. He is credited as being the creator of the first version of the periodic table of elements...

 had implicitly predicted the existence
Mendeleev's predicted elements
Professor Dmitri Mendeleev published the first Periodic Table of the Atomic Elements in 1869 based on properties which appeared with some regularity as he laid out the elements from lightest to heaviest....

 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 mass
Atomic mass
The atomic mass is the mass of a specific isotope, most often expressed in unified atomic mass units. The atomic mass is the total mass of protons, neutrons and electrons in a single atom....

es and placed lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

 (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.

The X-ray spectroscopy
X-ray spectroscopy
X-ray spectroscopy is a gathering name for several spectroscopic techniques for characterization of materials by using x-ray excitation.-Characteristic X-ray Spectroscopy:...

 done by Henry Moseley
Henry Moseley
Henry Gwyn Jeffreys Moseley was an English physicist. Moseley's outstanding contribution to the science of physics was the justification from physical laws of the previous empirical and chemical concept of the atomic number. This stemmed from his development of Moseley's law in X-ray spectra...

 in 1914 showed a direct dependency between spectral line
Spectral line
A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from a deficiency or excess of photons in a narrow frequency range, compared with the nearby frequencies.- Types of line spectra :...

 and effective nuclear charge
Effective nuclear charge
The effective nuclear charge is the net positive charge experienced by an electron in a multi-electron atom. The term "effective" is used because the shielding effect of negatively charged electrons prevents higher orbital electrons from experiencing the full nuclear charge by the repelling effect...

. This led to the nuclear charge, or atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

 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.

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. Georges Urbain
Georges Urbain
Georges Urbain - French chemist, professor of Sorbonne. He studied at the elite École supérieure de physique et de chimie industrielles de la ville de Paris . He discovered the element Lutetium in 1907.-References:...

 asserted that he found element 72 in the rare earth element
Rare earth element
As defined by IUPAC, rare earth elements or rare earth metals are a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides plus scandium and yttrium...

s in 1907 and published his results on celtium in 1911. 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. 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. By early 1923, several physicists and chemists such as Niels Bohr
Niels Bohr
Niels Henrik David Bohr was a Danish physicist who made foundational contributions to understanding atomic structure and quantum mechanics, for which he received the Nobel Prize in Physics in 1922. Bohr mentored and collaborated with many of the top physicists of the century at his institute in...

 and Charles R. Bury 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
Friedrich Paneth
Friedrich Adolf Paneth was an Austrian-born British chemist. Fleeing the Nazis, he escaped to Britain and became a British citizen in 1939 but returned as director of the Max Planck Institute for Chemistry in 1953....

.
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
Dirk Coster
Dirk Coster , was a Dutch physicist. He was a Professor of Physics and Meteorology at the University of Groningen....

 and Georg von Hevesy were motivated to search for the new element in zirconium ores. Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev. It was ultimately found in zircon
Zircon
Zircon is a mineral belonging to the group of nesosilicates. Its chemical name is zirconium silicate and its corresponding chemical formula is ZrSiO4. A common empirical formula showing some of the range of substitution in zircon is 1–x4x–y...

 in Norway through X-ray spectroscopy analysis. 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
Niels Bohr
Niels Henrik David Bohr was a Danish physicist who made foundational contributions to understanding atomic structure and quantum mechanics, for which he received the Nobel Prize in Physics in 1922. Bohr mentored and collaborated with many of the top physicists of the century at his institute in...

. Today, the Faculty of Science
University of Copenhagen Faculty of Science
The Faculty of Science at the University of Copenhagen consists of both mathematical and natural sciences, and is divided into 11 institutes including the Natural History Museum of Denmark...

 of the University of Copenhagen
University of Copenhagen
The University of Copenhagen is the oldest and largest university and research institution in Denmark. Founded in 1479, it has more than 37,000 students, the majority of whom are female , and more than 7,000 employees. The university has several campuses located in and around Copenhagen, with the...

 uses in its seal
Seal (device)
A seal can be a figure impressed in wax, clay, or some other medium, or embossed on paper, with the purpose of authenticating a document ; but the term can also mean the device for making such impressions, being essentially a mould with the mirror image of the design carved in sunken- relief or...

 a stylized image of the hafnium atom.

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium
Ammonium
The ammonium cation is a positively charged polyatomic cation with the chemical formula NH. It is formed by the protonation of ammonia...

 or potassium
Potassium
Potassium is the chemical element with the symbol K and atomic number 19. Elemental potassium is a soft silvery-white alkali metal that oxidizes rapidly in air and is very reactive with water, generating sufficient heat to ignite the hydrogen emitted in the reaction.Potassium and sodium are...

 fluorides by Valdemar Thal Jantzen and von Hevesey. Anton Eduard van Arkel
Anton Eduard van Arkel
Anton Eduard van Arkel, was a Dutch chemist.-See also:*Crystal bar process*Hafnium*Jan Hendrik de Boer*Titanium*Van Arkel-Ketelaar triangle-References:...

 and Jan Hendrik de Boer
Jan Hendrik de Boer
Jan Hendrik de Boer was a Dutch physicist and chemist.De Boer was born in Ruinen, now De Wolden, and died in 's-Gravenzande...

 were the first to prepare metallic hafnium by passing hafnium tetra-iodide vapor over a heated tungsten
Tungsten
Tungsten , also known as wolfram , is a chemical element with the chemical symbol W and atomic number 74.A hard, rare metal under standard conditions when uncombined, tungsten is found naturally on Earth only in chemical compounds. It was identified as a new element in 1781, and first isolated as...

 filament in 1924. This process for differential purification of zirconium and hafnium is still in use today.

In 1923, four predicted elements were still missing from the periodic table: 43 (technetium
Technetium
Technetium is the chemical element with atomic number 43 and symbol Tc. It is the lowest atomic number element without any stable isotopes; every form of it is radioactive. Nearly all technetium is produced synthetically and only minute amounts are found in nature...

) and 61 (promethium
Promethium
Promethium is a chemical element with the symbol Pm and atomic number 61. It is notable for being the only exclusively radioactive element besides technetium that is followed by chemical elements with stable isotopes.- Prediction :...

) are radioactive elements and are only present in trace amounts in the environment, thus making elements 75 (rhenium
Rhenium
Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-white, heavy, third-row transition metal in group 7 of the periodic table. With an average concentration of 1 part per billion , rhenium is one of the rarest elements in the Earth's crust. The free element has...

) and 72 (hafnium) the last two unknown non-radioactive elements. Since rhenium was discovered in 1925, 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.

Most of the hafnium produced is used in the production of control rod
Control rod
A control rod is a rod made of chemical elements capable of absorbing many neutrons without fissioning themselves. They are used in nuclear reactors to control the rate of fission of uranium and plutonium...

s for nuclear reactor
Nuclear reactor
A nuclear reactor is a device to initiate and control a sustained nuclear chain reaction. Most commonly they are used for generating electricity and for the propulsion of ships. Usually heat from nuclear fission is passed to a working fluid , which runs through turbines that power either ship's...

s.

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
Cadmium
Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, bluish-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Similar to zinc, it prefers oxidation state +2 in most of its compounds and similar to mercury it shows a low...

 and boron
Boron
Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the...

.) Excellent mechanical properties and exceptional corrosion-resistance properties allow its use in the harsh environment of a pressurized water reactor
Pressurized water reactor
Pressurized water reactors constitute a large majority of all western nuclear power plants and are one of three types of light water reactor , the other types being boiling water reactors and supercritical water reactors...

s. The German research reactor FRM II
Forschungsreaktor München II
The Forschungs-Neutronenquelle Heinz Maier-Leibnitz is the leading German research reactor. It serves as a neutron source, and is officially named Forschungs-Neutronenquelle Heinz Maier-Leibnitz in honor of the physicist Heinz Maier-Leibnitz who had conducted a highly successful research program...

 uses hafnium as a neutron absorber.

Alloys



Hafnium is used in iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

, titanium, niobium
Niobium
Niobium or columbium , is a chemical element with the symbol Nb and atomic number 41. It's a soft, grey, ductile transition metal, which is often found in the pyrochlore mineral, the main commercial source for niobium, and columbite...

, tantalum
Tantalum
Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as tantalium, the name comes from Tantalus, a character in Greek mythology. Tantalum is a rare, hard, blue-gray, lustrous transition metal that is highly corrosion resistant. It is part of the refractory...

, and other metal alloy
Alloy
An alloy is a mixture or metallic solid solution composed of two or more elements. Complete solid solution alloys give single solid phase microstructure, while partial solutions give two or more phases that may or may not be homogeneous in distribution, depending on thermal history...

s. An alloy used for liquid rocket
Liquid rocket
A liquid-propellant rocket or a liquid rocket is a rocket engine that uses propellants in liquid form. Liquids are desirable because their reasonably high density allows the volume of the propellant tanks to be relatively low, and it is possible to use lightweight pumps to pump the propellant from...

 thruster nozzles, for example the main engine of the Apollo Lunar Module
Apollo Lunar Module
The Apollo Lunar Module was the lander portion of the Apollo spacecraft built for the US Apollo program by Grumman to carry a crew of two from lunar orbit to the surface and back...

s is C103, which consists of 89% niobium
Niobium
Niobium or columbium , is a chemical element with the symbol Nb and atomic number 41. It's a soft, grey, ductile transition metal, which is often found in the pyrochlore mineral, the main commercial source for niobium, and columbite...

, 10% hafnium and 1% titanium
Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....

.

Small additions of hafnium increase the adherence of protective oxide scales on nickel based alloys. It improves thereby the corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

 resistance especially under cyclic temperature conditions that tend to break oxide scales by inducing thermal stresses between the bulk material and the oxide layer.

Microprocessors


The electronics industry discovered that hafnium-based compound can be employed in gate insulators in the 45 nm generation of integrated circuits from Intel, IBM
IBM
International Business Machines Corporation or IBM is an American multinational technology and consulting corporation headquartered in Armonk, New York, United States. IBM manufactures and sells computer hardware and software, and it offers infrastructure, hosting and consulting services in areas...

 and others. Hafnium oxide-based compounds are practical high-k dielectric
High-k Dielectric
The term high-κ dielectric refers to a material with a high dielectric constant κ used in semiconductor manufacturing processes which replaces the silicon dioxide gate dielectric...

s, allowing reduction of the gate leakage current which improves performance at such scales.

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
Plasma cutting
Plasma cutting is a process that is used to cut steel and other metals of different thicknesses using a plasma torch...

 because of its ability to shed electrons into air.

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
Nuclear isomer
A nuclear isomer is a metastable state of an atomic nucleus caused by the excitation of one or more of its nucleons . "Metastable" refers to the fact that these excited states have half-lives more than 100 to 1000 times the half-lives of the other possible excited nuclear states...

 of hafnium (the above mentioned 178m2Hf) to construct high yield weapons with X-ray triggering mechanisms—an application of induced gamma emission
Induced gamma emission
In physics, induced gamma emission refers to the process of fluorescent emission of gamma rays from excited nuclei, usually involving a specific nuclear isomer. It is analogous to conventional fluorescence, which is defined as the emission of a photon by an excited electron in an atom or molecule...

, was infeasible because of its expense. See Hafnium controversy.

See also

  • Nuclear isomer
    Nuclear isomer
    A nuclear isomer is a metastable state of an atomic nucleus caused by the excitation of one or more of its nucleons . "Metastable" refers to the fact that these excited states have half-lives more than 100 to 1000 times the half-lives of the other possible excited nuclear states...

  • Induced gamma emission
    Induced gamma emission
    In physics, induced gamma emission refers to the process of fluorescent emission of gamma rays from excited nuclei, usually involving a specific nuclear isomer. It is analogous to conventional fluorescence, which is defined as the emission of a photon by an excited electron in an atom or molecule...

  • Zircon
    Zircon
    Zircon is a mineral belonging to the group of nesosilicates. Its chemical name is zirconium silicate and its corresponding chemical formula is ZrSiO4. A common empirical formula showing some of the range of substitution in zircon is 1–x4x–y...

  • Zirconium
    Zirconium
    Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...



External links