Astm Manual On Zirconium And Hafnium Chloride

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Zirconium(IV) chloride, also known as zirconium tetrachloride, (Zr Cl 4) is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

  1. Astm Manual On Zirconium And Hafnium Chloride Acid
Ship out in 2 business day, And Fast shipping, Free Tracking number will be provided after the shipment.Hardcover Pages Number: 393 Language: English Publisher: Metallurgical Industry Press; 1st edition (January 1. 1999). Book is non-ferrous metal extraction Metallurgy Handbook of rare metals and Volume book. focusing summarized zirconium. hafnium. niobium. tantalum. vanadium and five kinds of metal extraction principle of the metallurgical process. production processes and process equipment. secondary metal recycling information. At the same time the above-mentioned metals and their compounds related to the metallurgical process. the nature and uses of mineral resources and technology in recent years of economic data. The book is engaged in rare metals and scientific research. production. design. teaching staff and senior students of institutions of higher learning of non-ferrous metallurgy. graduate students. are also available in other metals. metallurgy. scientific and technical personnel and production management reference. Contents: Classification Section III of the metallurgical method of Section II of the physical and chemical properties of the zirconium and hafnium production of raw materials and extraction methods. the fifth chapter of the zirconium and hafnium metallurgical first chapter. section I. zirconium and hafnium and its compounds of zirconium and hafnium zirconium and hafnium concentrate raw materials dealing with the second chapter of zirconium hafnium separation technology section I of the organic solvent extraction separation of zirconium and hafnium Section II complexation step-by-step fluoride crystallization separation of zirconium and hafnium Section III distillation (distillation) Separation of zirconium and hafnium section IV of zirconium and hafnium tetrachloride vapor with alkali metal chlorine selective reaction and the double salt of the compounds from the solution of separation section V of the zirconium and hafnium zirconium and hafnium chloride selective reduction of Chapter III of the replacement of zirconium and hafnium separation in the molten zinc and molten salt system of sub-section VI of anti-zirconium and hafnium metal zirconium and hafnium system Deng section zirconia chlorination system to take chloride hafnium zirconium Section II metal thermal reduction method in section III of the production of zirconium metal zirconium fluoride potassium system molten salt electrolysis method in section IV of the production of zirconium metal powder production methods dense and high Preparation of pure zirconium and hafnium first section of metal zirconium iodide refining Section II arc and electron beam melting zirconium Section III high-purity and dense hafnium system to take the main references of the first chapter of the tantalum and niobium metallurgy tantalum and niobium and its compounds the nature of the first section of the nature of the Section III Section II of the nature of the uses first section of tantalum and niobium tantalum. niobium important compounds. tantalum and niobium and its compounds the use of mineral raw materials of the second chapter of tantalum and niobium enrichment methods. tantalum and niobium mineral resources and their section III of the standard distribution of Section II of tantalum and niobium concentrate ores of tantalum and niobium enrichment method for the separation of Chapter III of tantalum and niobium and its compounds. preparation of the acid decomposition of the production process of the first section of tantalum and niobium metal and its compounds Section II Section III tantalum and niobium compounds in organic solvent extraction section IV Preparation of Chapter IV of the hydrometallurgical process in section VI Section 5 tantalum and niobium compounds preparation of tantalum and niobium concentrates decomposition method in section VII of the separation of tantalum and niobium tantalum niobium compounds to restore the first section of tantalum an. Bookseller Inventory # MO4801
Hafnium, 72Hf
General properties
Name, symbolhafnium, Hf
Appearancesteel gray
Pronunciation/ˈhæfniəm/
HAF-nee-əm
Hafnium in the periodic table
Zr

Hf

Rf
lutetium ← hafnium → tantalum
Atomic number(Z)72
Group, blockgroup 4, d-block
Periodperiod 6
Element categorytransition metal
Standard atomic weight(±)(Ar)178.49(2)[1]
Electron configuration[Xe] 4f14 5d2 6s2
per shell
2, 8, 18, 32, 10, 2
Physical properties
Phasesolid
Melting point2506 K ​(2233 °C, ​4051 °F)
Boiling point4876 K ​(4603 °C, ​8317 °F)
Densitynear r.t.13.31 g/cm3
when liquid, at m.p.12 g/cm3
Heat of fusion27.2 kJ/mol
Heat of vaporization648 kJ/mol
Molar heat capacity25.73 J/(mol·K)
vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)268929543277367941944876
Atomic properties
Oxidation states4, 3, 2, 1, −2 ​(an amphoteric oxide)
ElectronegativityPauling scale: 1.3
Ionization energies1st: 658.5 kJ/mol
2nd: 1440 kJ/mol
3rd: 2250 kJ/mol
Atomic radiusempirical: 159 pm
Covalent radius175±10 pm
Miscellanea
Crystal structure​hexagonal close-packed (hcp)
Speed of soundthin rod3010 m/s (at 20 °C)
Thermal expansion5.9 µm/(m·K) (at 25 °C)
Thermal conductivity23.0 W/(m·K)
Electrical resistivity331 nΩ·m (at 20 °C)
Magnetic orderingparamagnetic[2]
Young's modulus78 GPa
Shear modulus30 GPa
Bulk modulus110 GPa
Poisson ratio0.37
Mohs hardness5.5
Vickers hardness1520–2060 MPa
Brinell hardness1450–2100 MPa
CAS Number7440-58-6
History
Namingafter Hafnia. Latin for: Copenhagen, where it was discovered
PredictionDmitri Mendeleev(1869)
Discovery and first isolationDirk Coster and George de Hevesy (1922)
Most stable isotopes of hafnium
isoNAhalf-lifeDMDE(MeV)DP
172Hfsyn1.87 yε0.350172Lu
174Hf0.162%2×1015 yα2.495170Yb
176Hf5.206%(α)2.2550172Yb
177Hf18.606%(α)2.2449173Yb
178Hf27.297%(α)2.0832174Yb
178m2Hfsyn31 yIT2.446178Hf
179Hf13.629%(α)1.8065175Yb
180Hf35.1%(α)1.2828176Yb
182Hftrace8.9×106 yβ0.373182Ta
Decay modes in parentheses are predicted, but have not yet been observed
· references

Hafnium is a chemical element with symbolHf and atomic number 72. A lustrous, silvery gray, tetravalenttransition metal, hafnium chemically resembles zirconium and is found in zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though it was not identified until 1923, making it the penultimate stable element to be discovered (rhenium was identified two years later). Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered.[3][4]

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.

  • 1Characteristics
  • 5Applications

Characteristics

Physical characteristics

Hafnium bits

Hafnium is a shiny, silvery, ductilemetal that is corrosion-resistant and chemically similar to zirconium[5] (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.[5]

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.[5] 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

See also: Category:Hafnium compounds.
Hafnium dioxide

Hafnium reacts in air to form a protective film that inhibits further corrosion. 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, producing an effect similar to that obtained in Dragon's Breath.[6] The metal is resistant to concentrated alkalis.

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 in solvents are the major differences in the chemistry of these twin elements.[7]

Isotopes

At least 34 isotopes of hafnium have been observed, ranging in mass number from 153 to 186.[8][9] The five stable isotopes are in the range of 176 to 180. The radioactive isotopes' half-lives range from only 400 ms for 153Hf,[9] to 2.0 petayears (1015 years) for the most stable one, 174Hf.[8]

The nuclear isomer178m2Hf 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
Astm manual on zirconium and hafnium chloride acid

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.[10] An old (obsolete) name for a variety of zircon containing unusually high Hf content is alvite.[11]

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.[12]

Hafnium reserves have been infamously estimated to last under 10 years by one source if the world population increases and demand grows.[13] In reality, since hafnium occurs with zirconium, hafnium can always be a byproduct of zirconium extraction to the extent that the low demand requires.

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.[14]

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.[5]

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.[15] The methods first used — fractional crystallization of ammonium fluoride salts[16] or the fractionated distillation of the chloride[17] — 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.[18] 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.[19] The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium or sodium, as in the Kroll process.[20]

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.[7][21]

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

Chemical compounds

Hafnium and zirconium form nearly identical series of chemical compounds.[22] Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides.[22] At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon.[22] 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.[22]

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.[7] These tetrachlorides are precursors to various organohafnium compounds such as hafnocene dichloride and tetrabenzylhafnium.

Astm Manual On Zirconium And Hafnium Chloride Acid

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.[7]Hafnium carbide is the most refractorybinary 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.[22] 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
4
HfC
5
) possesses the highest melting point of any currently known compound, 4215 °C.[23] Recent supercomputer simulations suggest a hafnium alloy with a melting point of 4400 K.[24]

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.[25]

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.[26]

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.[27]Georges Urbain asserted that he found element 72 in the rare earth elements in 1907 and published his results on celtium in 1911.[28] 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.[29] 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.[29] By early 1923, several physicists and chemists such as Niels Bohr[30] and Charles R. Bury[31] 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.[32][33]

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.[34] Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev.[35][36] It was ultimately found in zircon in Norway through X-ray spectroscopy analysis.[37] 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.[38] Today, the Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom.[39]

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium or potassium fluorides by Valdemar Thal Jantzen and von Hevesey.[16]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.[17][21] This process for differential purification of zirconium and hafnium is still in use today.[5]

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,[40] thus making elements 75 (rhenium) and 72 (hafnium) the last two unknown non-radioactive elements. Since rhenium was discovered in 1925,[41] 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.[5]

Most of the hafnium produced is used in the production of control rods for nuclear reactors.[18]

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.[18] The German research reactor FRM II uses hafnium as a neutron absorber.[42] It is also common in military reactors, particularity in US naval reactors,[43] 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.[44]

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.[45]

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.[46][47][48]

Microprocessors

Hafnium-based compounds are employed in gate insulators in the 45 nm generation of integrated circuits from Intel, IBM and others.[49][50] Hafnium oxide-based compounds are practical high-k dielectrics, allowing reduction of the gate leakage current which improves performance at such scales.[51][52]

Isotope geochemistry

Isotopes of hafnium and lutetium (along with ytterbium) are also utilized in isotope geochemistry and geochronological applications. It is often used as a tracer of isotopic evolution of Earth’s mantle through time.[53] This is because 176Lu decay to 176Hf with a half-life of approximately 37 billion years.[54][55][56]

In most geologic materials, zircon is the dominant host of hafnium (>10,000 ppm) and is often the focus of hafnium studies in geology.[57] Hafnium is readily substituted into the zircon crystal lattice, and is therefore very resistant to hafnium mobility and contamination. Zircon also has an extremely low Lu/Hf ratio, making any correction for initial lutetium minimal. Although the Lu/Hf system can be used to calculate a 'model age', i.e. Zen pinball thd rapidshare downloader pc. the time at which it was derived from a given isotopic reservoir such as the 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. Given the high and variable Lu/Hf ratios found in garnet make it useful for dating metamorphic events.[58]

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.[59]

The high energy content of 178m2Hf was the concern of a DARPA-funded program in the US. This program determined that 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

Care needs to be taken when machining hafnium because it is 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.[60]

People can be exposed to hafnium in the workplace by breathing it in, swallowing it, skin contact, and eye contact. The Occupational Safety and Health Administration (OSHA) has set the legal limit (Permissible exposure limit) for exposure to hafnium and hafnium compounds in the workplace as TWA 0.5 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set the same recommended exposure limit (REL). At levels of 50 mg/m3, hafnium is immediately dangerous to life and health.[61]

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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)
Periodic table(Large cells)
123456789101112131415161718
1HHe
2LiBeBCNOFNe
3NaMgAlSiPSClAr
4KCaScTiVCrMnFeCoNiCuZnGaGeAsSeBrKr
5RbSrYZrNbMoTcRuRhPdAgCdInSnSbTe I Xe
6CsBaLaCePrNdPmSmEuGdTbDyHoErTmYbLuHfTaWReOsIrPtAuHgTlPbBiPoAtRn
7FrRaAcThPaUNpPuAmCmBkCfEsFmMdNoLrRfDbSgBhHsMtDsRgCnUutFlUupLvUusUuo
Alkali metalAlkaline earth metalLan­thanideActinideTransition metalPost-​transition metalMetalloidPolyatomic nonmetalDiatomic nonmetalNoble gasUnknown
chemical
properties
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