Rare earths, metallic

Simple metals like alkalis, or ones with only s and p valence electrons, can often be described by a free electron gas model, whereas transition metals and rare earth metals which have d and f valence electrons camiot. Transition metal and rare earth metals do not have energy band structures which resemble free electron models. The fonned bonds from d and f states often have some strong covalent character. This character strongly modulates the free-electron-like bands. 

Scandium is a silver-white metal which develops a slightly yellowish or pinkish cast upon exposure to air. A relatively soft element, scandium resembles yttrium and the rare-earth metals more than it resembles aluminum or titanium. 

Lanthanum is silvery white, malleable, ductile, and soft enough to be cut with a knife. It is one of the most reactive of the rare-earth metals. It oxidizes rapidly when exposed to air. Cold water attacks lanthanum slowly, while hot water attacks it much more rapidly. 

Cerium is the most abundant so-called rare-earths metal. It is found in a number of minerals including ahanite (also known as orthite), monazite, bastnasite, cerhe, and samarskite. Monazite and bastnasite are presently the two more important sources of cerium. 

Large deposits of monazite (found on the beaches of Travancore, India and in river sands in Brazil), ahanite (in the western United States), and bastnasite (in Southern California) will supply cerium, thorium, and the other rare-earth metals for many years to come. 

Cerium is an iron-gray lustrous metal. It is malleable, and oxidizes very readily at room temperature, especially in moist air. Except for europium, cerium is the most reactive of the rare-earth metals. It decomposes slowly in cold water and rapidly in hot water. 

As with other rare-earth metals, except for lanthanum, europium ignites in air at about 150 to I8O0C. Europium is about as hard as lead and is quite ductile. It is the most reactive of the rare-earth metals, quickly oxidizing in air. It resembles calcium in its reaction with water. Bastnasite and monazite are the principal ores containing europium. 

Europium is one of the rarest and most costly of the rare-earth metals. It is priced about about 7500/kg. 

The element occurs along with other rare-earth elements in a variety of minerals. Monazite and bastnasite are the two principal commercial sources of the rare-earth metals. It was prepared in relatively pure form in 1931. 

Praseodymium is soft, silvery, malleable, and ductile. It is somewhat more resistant to corrosion in air than europium, lanthanum, cerium, or neodymium, but it does develop a green oxide coating that spalls off when exposed to air. As with other rare-earth metals, it should be kept under a light mineral oil or sealed in plastic. 

Gr. neos, new, and didymos, twin) In 1841, Mosander, extracted from cerite a new rose-colored oxide, which he believed contained a new element. He named the element didymium, as it was an inseparable twin brother of lanthanum. In 1885 von Welsbach separated didymium into two new elemental components, neodymia and praseodymia, by repeated fractionation of ammonium didymium nitrate. While the free metal is in misch metal, long known and used as a pyrophoric alloy for light flints, the element was not isolated in relatively pure form until 1925. Neodymium is present in misch metal to the extent of about 18%. It is present in the minerals monazite and bastnasite, which are principal sources of rare-earth metals. 

The metal has a bright silvery metallic luster. Neodymium is one of the more reactive rare-earth metals and quickly tarnishes in air, forming an oxide that spalls off and exposes metal to oxidation. The metal, therefore, should be kept under light mineral oil or sealed in a plastic material. Neodymium exists in two allotropic forms, with a transformation from a double hexagonal to a body-centered cubic structure taking place at 863oC. 

From gadolinite, a mineral named for Gadolin, a Finnish chemist. The rare earth metal is obtained from the mineral gadolinite. Gadolinia, the oxide of gadolinium, was separated by Marignac in 1880 and Lecoq de Boisbaudran independently isolated it from Mosander s yttria in 1886. 

Gadolinium is found in several other minerals, including monazite and bastnasite, both of which are commercially important. With the development of ion-exchange and solvent extraction techniques, the availability and prices of gadolinium and the other rare-earth metals have greatly improved. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. 

As with other related rare-earth metals, gadolinium is silvery white, has a metallic luster, and is malleable and ductile. At room temperature, gadolinium crystallizes in the hexagonal, close-packed alpha form. Upon heating to 1235oG, alpha gadolinium transforms into the beta form, which has a body-centered cubic structure. 

Rare-earth metals Rare-earth phosphors Rare earths... 

FeTi can also be modified with rare-earth metals, Ni, or Mn (15). AB alloys where A is a rare-earth metal or mischmetal, Ca, or Th, and B is Co or Ni have also been used. LaNi has shown special promise (16). 

The arc and spark spectra of the individual lanthanides are exceedingly complex. Thousands of emission lines are observed. For the trivalent rare-earth ions in soUds, the absorption spectra are much better understood. However, the crystal fields of the neighboring atoms remove the degeneracy of some states and several levels exist where only one did before. Many of these crystal field levels exist very close to a base level. As the soUd is heated, a number of the lower levels become occupied. Some physical properties of rare-earth metals are thus very sensitive to temperature (7). 

It is easy to reduce anhydrous rare-earth hatides to the metal by reaction of mote electropositive metals such as calcium, lithium, sodium, potassium, and aluminum. Electrolytic reduction is an alternative in the production of the light lanthanide metals, including didymium, a Nd—Pt mixture. The rare-earth metals have a great affinity for oxygen, sulfur, nitrogen, carbon, silicon, boron, phosphoms, and hydrogen at elevated temperature and remove these elements from most other metals. 

Fused Salt Electrolysis. Only light RE metals (La to Nd) can be produced by molten salt electrolysis because these have a relatively low melting point compared to those of medium and heavy RE metals. Deposition of an alloy with another metal, Zn for example, is an alternative. The feed is a mixture of anhydrous RE chlorides and fluorides. The materials from which the electrolysis cell is constmcted are of great importance because of the high reactivity of the rare-earth metals. Molybdenum, tungsten, tantalum, or alternatively iron with ceramic or graphite linings are used as cmcible materials. Carbon is frequently used as an anode material. 

At the beginning of the twentieth century, the incandescent mantle, utilising the candoluminescence of a mixture of thorium (95% weight) and cerium oxides was developed. The pyrophoricity of rare-earth metals led to the invention of the lighter flint made through the alloying of iron and mischmetal. Since that time, numerous other appHcations have developed to coincide with the availabiUty of the rare-earth compounds on an industrial scale and having a controlled purity. 

Metallurgy. The strong affinity for oxygen and sulfur makes the rare-earth metals useflil in metallurgy (qv). Mischmetal acts as a trap for these Group 16 (VIA) elements, which are usually detrimental to the properties of steel (qv) or cast iron (qv). Resistance to high temperature oxidation and thermomechanical properties of several metals and alloys are thus significantly improved by the addition of small amounts of mischmetal or its siUcide (16,17). 

R. J. Elliott, ed.. Magnetic Properties of the Rare Earth Metals, Plenum Press, London, 1972. 

Gmelin Mandbuch derAnorganische Chemie, System No. 39, Rare Earth Metals, 8th ed., Spriager-Vedag, Berlin. 

AHoy M16630 (ZE63A) which contains rare-earth metals and zinc, is designed to take advantage of a newer he at-treatment technique involving inward diffusion of hydrogen and formation of zirconium hydride [7704-99-6]. The alloy is heated in hydrogen at 480°C for 10, 24, or 72 hours for 6.3,... 

Oil field uses are primarily imidazolines for surfactant and corrosion inhibition (see Petroleum). Besides the lubrication market for metal salts, the miscellaneous market is comprised of free acids used ia concrete additives, motor oil lubricants, and asphalt-paving applications (47) (see Asphalt Lubrication AND lubricants). Naphthenic acid has also been studied ia ore flotation for recovery of rare-earth metals (48) (see Flotation Lanthanides). 

Although there are several hundred biaary nitrides, only a relative few ternary bimetallic metal nitrides are known (6). A group of ternaries of the composition where M is an alkah, alkaline-earth, or a rare-earth metal and M is a transition or post-transition metal, have been synthesized (6). 

Group 3 (IIIB) and Inner Transition-Metal Perchlorates. The rare-earth metal perchlorates of yttrium and lanthanum have been reported (53). Tetravalent cerium perchlorate [14338-93-3] 06(0.04)4, and uranium perchlorate have also been identified (54). 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

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