• • • Hafnium is a with symbol Hf and 72. Download Driver Philips Pcvc720k/00 Windows 7. A, silvery gray,, hafnium chemically resembles and is found in many zirconium. Its existence was in 1869, though it was not identified until 1923, by Coster and Hevesy, making it the last element to be discovered. Hafnium is named after Hafnia, the name for, where it was discovered. Hafnium is used in filaments and electrodes. Some fabrication processes use its oxide for at 45 nm and smaller feature lengths.
The Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom. ASTM Manual on Zirconium and Hafnium.
Some used for special applications contain hafnium in combination with,,. Hafnium's large cross-section makes it a good material for absorption in in, but at the same time requires that it be removed from the neutron-transparent corrosion-resistant used in. Pieces of Hafnium Hafnium is a shiny, silvery, that is -resistant and chemically similar to zirconium (due to its having the same number of, being in the same group, but also to; the expected expansion of atomic radii from period 5 to 6 is almost exactly cancelled out by the ). 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, with zirconium having about one-half the density of hafnium. The most notable properties of hafnium are its high thermal and that the nuclei of several different hafnium isotopes readily absorb two or more 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 cladding of their. Chemical characteristics [ ]. Hafnium dioxide Hafnium reacts in air to form a that inhibits further. The metal is not readily attacked by acids but can be oxidized with 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.
The metal is resistant to concentrated. 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 in solvents are the major differences in the chemistry of these twin elements. Isotopes [ ].
Zircon crystal (2×2 cm) from Tocantins, Hafnium is estimated to make up about 5.8 of the 's upper by mass. It does not exist as a free element on Earth, but is found combined in with zirconium in natural compounds such as, ZrSiO 4, 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 (Hf,Zr)SiO 4, 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 is,, particularly in and, and intrusions, particularly the Crown Polymetallic Deposit at, Western Australia. A potential source of hafnium is trachyte tuffs containing rare zircon-hafnium silicates or armstrongite, at in, Australia. Hafnium reserves have been infamously estimated to last under 10 years by one source if the world population increases and demand grows.
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, a 1 cm cube, and an oxided hafnium ebeam remelted ingot (left to right) The of the titanium ores and yield most of the mined zirconium, and therefore also most of 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.
Hafnium oxidized ingots which exhibit effects. The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate. The methods first used — 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 or, as in the. HfCl 4 + 2 Mg (1100 °C) → 2 MgCl 2 + Hf Further purification is effected by a developed by: In a closed vessel, hafnium reacts with at temperatures of 500 °C, forming; 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 I 2 (500 °C) → HfI 4 HfI 4 (1700 °C) → Hf + 2 I 2 Chemical compounds [ ] Due to the the of hafnium(IV) (0.78 angstroms) is almost the same as that of (IV) (0.79 ). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties.
Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form in the oxidation state of +4. React with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with,,,,, and. Some compounds of hafnium in lower oxidation states are known. 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 such as hafnocene dichloride and tetrabenzylhafnium. The white (HfO 2), with a melting point of 2812 °C and a boiling point of roughly 5100 °C, is very similar to, but slightly more basic. Is the most 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 ( Ta 4HfC 5) possesses the highest melting point of any currently known compound, 4215 °C.
Recent supercomputer simulations suggest a hafnium alloy with a melting point of 4400 K. 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, had implicitly 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 and placed (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 done by in 1914 showed a direct dependency between and. This led to the nuclear charge, or of an element, being used to ascertain its place within the periodic table. With this method, Moseley determined the number of 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. Asserted that he found element 72 in the in 1907 and published his results on celtium in 1911. Neither the spectra nor the chemical behavior he claimed matched with the element found later, and therefore his claim was turned down after a long-standing controversy. 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 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 Moseley, and the chemical arguments of. 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, and 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 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.
Today, the of the uses in its a stylized image of the hafnium atom. Hafnium was separated from zirconium through repeated recrystallization of the double or fluorides by and von Hevesey. And were the first to prepare metallic hafnium by passing hafnium tetraiodide vapor over a heated 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 () and 61 () are radioactive elements and are only present in trace amounts in the environment, thus making elements 75 () and 72 (hafnium) the last two unknown non-radioactive elements.
Since rhenium was discovered in 1908, hafnium was the 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 for.
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 and.) Excellent mechanical properties and exceptional corrosion-resistance properties allow its use in the harsh environment of. The German research reactor uses hafnium as a neutron absorber. It is also common in military reactors, particularity in US naval reactors, but seldom found in civilian ones, the first core of the (a conversion of a naval reactor) being a notable exception.
Hafnium-containing rocket nozzle of the Apollo Lunar Module in the lower right corner Hafnium is used in with,,,, and other metals. An alloy used for thruster nozzles, for example the main engine of the, is C103 which consists of 89% niobium, 10% hafnium and 1% titanium. Small additions of hafnium increase the adherence of protective oxide scales on nickel-based alloys. It improves thereby the 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 [ ] Hafnium-based compounds are employed in insulators in the 45 nm generation of from, and others. Hafnium oxide-based compounds are practical, allowing reduction of the gate leakage current which improves performance at such scales.
Isotope geochemistry [ ] Isotopes of hafnium and (along with ) are also used in and applications, in. It is often used as a tracer of isotopic evolution of through time.
This is because 176Lu decays to 176Hf with a of approximately 37 billion years. In most geologic materials, is the dominant host of hafnium (>10,000 ppm) and is often the focus of hafnium studies in. Hafnium is readily substituted into the zircon, 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 ', i.e. The time at which it was derived from a given isotopic reservoir such as the, 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. Is another mineral that contains appreciable amounts of hafnium to act as a geochronometer.
The high and variable Lu/Hf ratios found in garnet make it useful for dating events. 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. Hafnium is also used as the electrode in because of its ability to shed electrons into air. The high energy content of 178m2Hf was the concern of a -funded program in the US. This program determined that the possibility of using a of hafnium (the above-mentioned 178m2Hf) to construct high-yield weapons with X-ray triggering mechanisms—an application of —was infeasible because of its expense. Precautions [ ] Care needs to be taken when hafnium because it is —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. People can be exposed to hafnium in the workplace by breathing it in, swallowing it, skin contact, and eye contact.
The (OSHA) has set the legal limit () for exposure to hafnium and hafnium compounds in the workplace as TWA 0.5 mg/m 3 over an 8-hour workday. The (NIOSH) has set the same (REL). At levels of 50 mg/m 3, hafnium is. See also [ ].
The uses of zirconium and high zirconium alloys, such as zircaloy-2, zircaloy-4 and zirconium-2.5 wt.% niobium, in nuclear reactor components are well known. Zirconium and high zirconium alloys being especially useful because of zirconium's low absorption of neutrons.
Zirconium is found in ores which also contain hafnium values. The hafnium, which has a moderate absorption capacity for neutrons must be essentially completely removed from mixtures with zirconium, if the zirconium, and its alloys are to be useful in nuclear reactor systems. Nuclear specifications for zirconium and high zirconium alloys generally require that the hafnium impurity content be kept at or below 100 ppm. The hafnium, in its commercially pure state is also useful in specific portions of a nuclear reactor system, where absorption of neutrons is desired. Commercial purity hafnium generally contains about 4 wt.% zirconium.
Thus, zirconium and high zirconium alloys are useful as cladding materials, while hafnium is useful in control elements. Amerie Because I Love It Vol 1 Zip Lock. The separation of hafnium values from zirconium is one of the more difficult steps in purifying zirconium. These elements are very similar in their physical and chemical properties such as ion size, solubility, reaction chemistry, and the like. Existing commercial processes use solvent extraction of thiocyanate complexes of thee metals to produce zirconium having the aforementioned low hafnium impurity level. Problems exist however because of known competing reactions that lead to decomposition of the thiocyanate.
The proceeding commercial process is summarized in J. Schemel, 'ASTM Manual on Zirconium and Hafnium,' ASTM Special Technical Publication 639, (1977), pages 56 to 59. Other processes for separation of zirconium from hafnium values are discussed in U.S.
Patent Specification No. 3,127,236, which treats a mixture of insoluble compounds such as phosphates or hydroxides with oxalic acid to form oxalato complexes and fractionally precipitates the zirconium and hafnium values from the solution of the complexes, and in U.S. 3,069,232 which uses a saturated solution of ammonium sulfate instead of sulfuric acid to extract hafnium values from the organic phase of a preferrential solvent extraction process for hafnium using a thiocyanate complex. In a recent patent, U.S. Patent Specification No.
4,389,292 (corresponding to EP-A-0067036), which is a co-invention of one of the co-inventors herein, the 9'ZR isotopic content of zirconium is altered by raising a zirconium chelate ligand, such as a tetraoxalatozirconate, from a ground state to an activated state in the presence of a scavenger that reacts with the activated ligand, and separating the reacted ligand. Activation of the zirconium compound, i.e. The breaking of a bond in the compound which can either recombine or react with the scavenger, is effected either with the use of heat or the use of light. The zirconium or a hafnium chelate complexes used in the present process are those which provide absorption spectra over a range of wavelengths that will enable excitation of one of the complexes while the other complex remains stable and in solution. A general formula for the chelate ligands usable in the present invention may be expressed as ML 4, wherein M is zirconium or hafnium, and L is an organic ligand. The preferred organic ligands are formed from ions derived from beta diketones which are of a formula.
The mixture of the zirconium and hafnium chelate ligands is dissolved in a solvent which will provide a medium for irradiation by a light source. The preferred solvent, due to economics, ease with which it may be used, and the fact that it will not absorb light in the wavelengths required for activation of one of the complexes, is water. Other solvents, in particular systems, and for use with particular complexes, for example, methanol, acetone, benzene, toluene, xylene, dimethyl formamide (DMF) or tetra methyl formamide (TMF), and the like, may also be used.
The excitation of one of the complexes, in order to separate the same from the other stable complex, is effected by irradiation, with a light source, of the complexes in solution. The wavelength of the light used for excitation should be within the range of 300-700 nm and preferably from 400 to 700 nm. A particular optimum wavelength within this range would be chosen by determining the absorption spectra of the particular zirconium and hafnium complex and using a wavelength which provides a distinct variance in the absorption characteristics of the complexes. The separation of the excited complex from the stable complex, which will remain in the solution, is effected by a scavenger, which may also be the solvent used in the formation of the solution of the complexes. For example, in aqueous solutions, the water may also act as the scavenger, forming hydroxides, or other compounds, with the excited complex that will cause formation of a precipitate. Other scavengers, such as oxalates, oxine, ethylene diamine tetraacetic acid (EDTA) or sulfate ions (S0 4=), or the like, may be added to the system to enter into photochemical reactions with the excited complex to produce a product with other properties that will enable ready separation from the stable complex which remains in solution.
For instance, ligand exchange might be used to produce a product that could be efficiently separated from the solution containing the stable complex by solvent extraction, or a charged complex could be formed that could be removed by ion exchange. The amount of scavenger present should be at least a stoichiometric amount necessary to react with the excited complex. The irradiation of the solution, with the light of the wavelength specified, is carried out for a period of time sufficient to react the one complex with the scavenger and cause separation thereof from the solution.
As an illustration, the accompanying drawing graphically shoes the optical transmission spectra of zirconium tetra acetylacetonate (a) and hafnium tetra acetylacetonate (b) illustrating the range of wavelength between 350 nm and 550 nm where the hafnium complex can be preferentially excited to a photochemically active state. Both complexes have a strong absorbance starting at about 350 nm, and peaks at 287 nm (not shown) due to the absorption by the acetylacetonate ligand. The hafnium acetylacetonate has a significant absorption band at longer wavelengths (350-550 nm) while the zirconium acetylacetonate has no significant absorbance in the 350 nm-550 nm range. Thus, it is possible to excite hafnium acetylacetonate in a solution without exciting the zirconium acetylacetonate by using light at a wavelength, within the above range, and most preferably within the range of from 400 to 500 nm.
While the illustration in the drawing is to a chelate ligand of the hafnium and zirconium which will provide excitation and separation of the hafnium complex, it would also be useful to select an organic ligand such that the zirconium complex could be selectively excited and undergo subsequent chemical reaction with a scavenger and separation from a solution that would retain a stable hafnium complex. In such a process, purified zirconium would be recovered as the separated product while the purified hafnium would remain in the solution. A saturated aqueous solution of a reagent grade tetra acetylacetonate complex of zirconium (10.1 grams/liter) was prepared.
The freshly prepared solution, at about 24°C, having an initial pH of 4.8, after irradiation with light from the argon ion laser at a wavelength of 488 nm for a period of four hours showed no precipitates. The pH of this solution was then 4.6. After a total of about 6 hours irradiation, only a slight clouding of the solution was present with no precipitate settling.