Rare Earths Oxide (REO)

Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. Lanthanum is traditionally counted among the rare earth elements. Like most other rare earth elements, the usual oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.

Lanthanum usually occurs together with cerium and the other rare earth elements. Lanthanum was first found by the Swedish chemist Carl Gustaf Mosander in 1839 as an impurity in cerium nitrate – hence the name lanthanum, from the Ancient Greek λανθάνειν (lanthanein), meaning ‘to lie hidden’. Although it is classified as a rare earth element, lanthanum is the 28th most abundant element in the Earth’s crust, almost three times as abundant as lead. In minerals such as monazite and bastnäsite, lanthanum composes about a quarter of the lanthanide content.[6] It is extracted from those minerals by a process of such complexity that pure lanthanum metal was not isolated until 1923.

Lanthanum compounds have numerous applications as catalysts, additives in glass, carbon arc lamps for studio lights and projectors, ignition elements in lighters and torches, electron cathodes, scintillators, gas tungsten arc welding electrodes, and other things. Lanthanum carbonate is used as a phosphate binder in cases of high levels of phosphate in the blood seen with kidney failure.

Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 oxidation state characteristic of the series, it also has a stable +4 state that does not oxidize water. It is also considered one of the rare-earth elements. Cerium has no known biological role in humans but is not particularly toxic, except with intense or continued exposure.

Despite always occurring in combination with the other rare-earth elements in minerals such as those of the monazite and bastnäsite groups, cerium is easy to extract from its ores, as it can be distinguished among the lanthanides by its unique ability to be oxidized to the +4 state in aqueous solution. It is the most common of the lanthanides, followed by neodymium, lanthanum, and praseodymium. It is the 25th-most abundant element, making up 66 ppm of the Earth’s crust, half as much as chlorine and five times as much as lead.

Cerium was the first of the lanthanides to be discovered, in Bastnäs, Sweden, by Jöns Jakob Berzelius and Wilhelm Hisinger in 1803, and independently by Martin Heinrich Klaproth in Germany in the same year. In 1839 Carl Gustaf Mosander became the first to isolate the metal. Today, cerium and its compounds have a variety of uses: for example, cerium(IV) oxide is used to polish glass and is an important part of catalytic converters. Cerium metal is used in ferrocerium lighters for its pyrophoric properties. Cerium-doped YAG phosphor is used in conjunction with blue light-emitting diodes to produce white light in most commercial white LED light sources.

Praseodymium is a chemical element with the symbol Pr and the atomic number 59. It is the third member of the lanthanide series and is traditionally considered to be one of the rare-earth metals. It is a soft, silvery, malleable and ductile metal, valued for its magnetic, electrical, chemical, and optical properties. It is too reactive to be found in native form, and pure praseodymium metal slowly develops a green oxide coating when exposed to air.

Praseodymium always occurs naturally together with the other rare-earth metals. It is the sixth-most abundant rare-earth element and fourth-most abundant lanthanide, making up 9.1 parts per million of the Earth’s crust, an abundance similar to that of boron. In 1841, Swedish chemist Carl Gustav Mosander extracted a rare-earth oxide residue he called didymium from a residue he called “lanthana”, in turn separated from cerium salts. In 1885, the Austrian chemist Baron Carl Auer von Welsbach separated didymium into two elements that gave salts of different colours, which he named praseodymium and neodymium. The name praseodymium comes from the Ancient Greek πράσινος (prasinos), meaning ‘leek-green’, and δίδυμος (didymos) ‘twin’.

Like most rare-earth elements, praseodymium most readily forms the +3 oxidation state, which is the only stable state in aqueous solution, although the +4 oxidation state is known in some solid compounds and, uniquely among the lanthanides, the +5 oxidation state is attainable in matrix-isolation conditions. The 0, +1, and +2 oxidation states are rarely found. Aqueous praseodymium ions are yellowish-green, and similarly, praseodymium results in various shades of yellow-green when incorporated into glasses. Many of praseodymium’s industrial uses involve its ability to filter yellow light from light sources.

Neodymium is a chemical element with the symbol Nd and atomic number 60. It is the fourth member of the lanthanide series and is considered to be one of the rare-earth metals. It is a hard, slightly malleable, silvery metal that quickly tarnishes in air and moisture. When oxidized, neodymium reacts quickly to produce pink, purple/blue and yellow compounds in the +2, +3 and +4 oxidation states. It is generally regarded as having one of the most complex spectra of the elements. Neodymium was discovered in 1885 by the Austrian chemist Carl Auer von Welsbach, who also discovered praseodymium. It is present in significant quantities in the minerals monazite and bastnäsite. Neodymium is not found naturally in metallic form or unmixed with other lanthanides, and it is usually refined for general use. Neodymium is fairly common—about as common as cobalt, nickel, or copper—and is widely distributed in the Earth’s crust. Most of the world’s commercial neodymium is mined in China, as with many other rare-earth metals.

Neodymium compounds were first commercially used as glass dyes in 1927 and remain a popular additive. The color of neodymium compounds comes from the Nd3+ ion and is often a reddish-purple, but changes with the type of lighting, because of the interaction of the sharp light absorption bands of neodymium with ambient light enriched with the sharp visible emission bands of mercury, trivalent europium or terbium. Neodymium-doped glasses are used in lasers that emit infrared with wavelengths between 1047 and 1062 nanometers. These lasers have been used in extremely high-power applications, such as experiments in inertial confinement fusion. Neodymium is also used with various other substrate crystals, such as yttrium aluminium garnet in the Nd:YAG laser.

Neodymium is used in the alloys used to make high-strength neodymium magnets—a type of powerful permanent magnet. These magnets are widely used in products like microphones, professional loudspeakers, in-ear headphones, high-performance hobby DC electric motors, and computer hard disks, where low magnet mass (or volume) or strong magnetic fields are required. Larger neodymium magnets are used in electric motors with a high power-to-weight ratio (e.g., in hybrid cars) and generators (e.g., aircraft and wind turbine electric generators).

Samarium is a chemical element with the symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually assumes the oxidation state +3. Compounds of samarium(II) are also known, most notably the monoxide SmO, monochalcogenides SmS, SmSe and SmTe, as well as samarium(II) iodide. The last compound is a common reducing agent in chemical synthesis. Samarium has no significant biological role but is only slightly toxic.

Samarium was discovered in 1879 by French chemist Paul-Émile Lecoq de Boisbaudran and named after the mineral samarskite from which it was isolated. The mineral itself was named after a Russian mine official, Colonel Vassili Samarsky-Bykhovets, who thus became the first person to have a chemical element named after him, albeit indirectly. Though classified as a rare-earth element, samarium is the 40th most abundant element in Earth’s crust and more common than metals such as tin. Samarium occurs in concentration up to 2.8% in several minerals including cerite, gadolinite, samarskite, monazite and bastnäsite, the last two being the most common commercial sources of the element. These minerals are mostly found in China, the United States, Brazil, India, Sri Lanka and Australia; China is by far the world leader in samarium mining and production.

The main commercial application of samarium is in samarium–cobalt magnets, which have permanent magnetization second only to neodymium magnets; however, samarium compounds can withstand significantly higher temperatures, above 700 °C (1,292 °F), without losing their magnetic properties, due to the alloy’s higher Curie point. The radioisotope samarium-153 is the active component of the drug samarium (¹⁵³Sm) lexidronam (Quadramet), which kills cancer cells in lung cancer, prostate cancer, breast cancer and osteosarcoma. Another isotope, samarium-149, is a strong neutron absorber and so is added to control rods of nuclear reactors. It also forms as a decay product during the reactor operation and is one of the important factors considered in the reactor design and operation. Other uses of samarium include catalysis of chemical reactions, radioactive dating and X-ray lasers.

Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lanthanide, as it can be dented with a fingernail and easily cut with a knife. When oxidation is removed a shiny-white metal is visible. Europium was isolated in 1901 and is named after the continent of Europe.[6] Being a typical member of the lanthanide series, europium usually assumes the oxidation state +3, but the oxidation state +2 is also common. All europium compounds with oxidation state +2 are slightly reducing. Europium has no significant biological role and is relatively non-toxic compared to other heavy metals. Most applications of europium exploit the phosphorescence of europium compounds. Europium is one of the rarest of the rare-earth elements on Earth.

Gadolinium is a chemical element with the symbol Gd and atomic number 64. Gadolinium is a silvery-white metal when oxidation is removed. It is only slightly malleable and is a ductile rare-earth element. Gadolinium reacts with atmospheric oxygen or moisture slowly to form a black coating. Gadolinium below its Curie point of 20 °C (68 °F) is ferromagnetic, with an attraction to a magnetic field higher than that of nickel. Above this temperature it is the most paramagnetic element. It is found in nature only in an oxidized form. When separated, it usually has impurities of the other rare-earths because of their similar chemical properties.

Gadolinium was discovered in 1880 by Jean Charles de Marignac, who detected its oxide by using spectroscopy. It is named after the mineral gadolinite, one of the minerals in which gadolinium is found, itself named for the Finnish chemist Johan Gadolin. Pure gadolinium was first isolated by the chemist Paul-Émile Lecoq de Boisbaudran around 1886.

Gadolinium possesses unusual metallurgical properties, to the extent that as little as 1% of gadolinium can significantly improve the workability and resistance to oxidation at high temperatures of iron, chromium, and related metals. Gadolinium as a metal or a salt absorbs neutrons and is, therefore, used sometimes for shielding in neutron radiography and in nuclear reactors.

Like most of the rare earths, gadolinium forms trivalent ions with fluorescent properties, and salts of gadolinium(III) are used as phosphors in various applications.

Gadolinium(III) ions in water-soluble salts are highly toxic to mammals. However, chelated gadolinium(III) compounds prevent the gadolinium(III) from being exposed to the organism and the majority is excreted by healthy[4] kidneys before it can deposit in tissues. Because of its paramagnetic properties, solutions of chelated organic gadolinium complexes are used as intravenously administered gadolinium-based MRI contrast agents in medical magnetic resonance imaging. Varying amounts deposit in tissues of the brain, cardiac muscle, kidney, other organs and the skin, mainly depending on kidney function, structure of the chelates (linear or macrocyclic) and the dose administered.

Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white, rare earth metal that is malleable, and ductile. The ninth member of the lanthanide series, terbium is a fairly electropositive metal that reacts with water, evolving hydrogen gas. Terbium is never found in nature as a free element, but it is contained in many minerals, including cerite, gadolinite, monazite, xenotime and euxenite.

Swedish chemist Carl Gustaf Mosander discovered terbium as a chemical element in 1843. He detected it as an impurity in yttrium oxide, Y2O3. Yttrium and terbium, as well as erbium and ytterbium, are named after the village of Ytterby in Sweden. Terbium was not isolated in pure form until the advent of ion exchange techniques.

Terbium is used to dope calcium fluoride, calcium tungstate and strontium molybdate in solid-state devices, and as a crystal stabilizer of fuel cells that operate at elevated temperatures. As a component of Terfenol-D (an alloy that expands and contracts when exposed to magnetic fields more than any other alloy), terbium is of use in actuators, in naval sonar systems and in sensors.

Most of the world’s terbium supply is used in green phosphors. Terbium oxide is in fluorescent lamps and television and monitor cathode ray tubes (CRTs). Terbium green phosphors are combined with divalent europium blue phosphors and trivalent europium red phosphors to provide trichromatic lighting technology, a high-efficiency white light used for standard illumination in indoor lighting.

Dysprosium is the chemical element with the symbol Dy and atomic number 66. It is a rare-earth element in the lanthanide series with a metallic silver luster. Dysprosium is never found in nature as a free element, though, like other lanthanides, it is found in various minerals, such as xenotime. Naturally occurring dysprosium is composed of seven isotopes, the most abundant of which is ¹⁶⁴Dy.

Dysprosium was first identified in 1886 by Paul Émile Lecoq de Boisbaudran, but it was not isolated in pure form until the development of ion-exchange techniques in the 1950s. Dysprosium has relatively few applications where it cannot be replaced by other chemical elements. It is used for its high thermal neutron absorption cross-section in making control rods in nuclear reactors, for its high magnetic susceptibility (χ_v ≈ 5.44×10⁻³) in data-storage applications, and as a component of Terfenol-D (a magnetostrictive material). Soluble dysprosium salts are mildly toxic, while the insoluble salts are considered non-toxic.

Holmium is a chemical element with the symbol Ho and atomic number 67. It is a rare-earth element and the eleventh member of the lanthanide series. It is a relatively soft, silvery, fairly corrosion-resistant and malleable metal. Like a lot of other lanthanides, holmium is too reactive to be found in native form, as pure holmium slowly forms a yellowish oxide coating when exposed to air. When isolated, holmium is relatively stable in dry air at room temperature. However, it reacts with water and corrodes readily, and also burns in air when heated.

In nature, holmium occurs together with the other rare-earth metals (like thulium). It is a relatively rare lanthanide, making up 1.4 parts per million of the Earth’s crust, an abundance similar to tungsten. Holmium was discovered through isolation by Swedish chemist Per Theodor Cleve and independently by Jacques-Louis Soret and Marc Delafontaine, who observed it spectroscopically in 1878. Its oxide was first isolated from rare-earth ores by Cleve in 1878. The element’s name comes from Holmia, the Latin name for the city of Stockholm.

Like many other lanthanides, holmium is found in the minerals monazite and gadolinite and is usually commercially extracted from monazite using ion-exchange techniques. Its compounds in nature and in nearly all of its laboratory chemistry are trivalently oxidized, containing Ho(III) ions. Trivalent holmium ions have fluorescent properties similar to many other rare-earth ions (while yielding their own set of unique emission light lines), and thus are used in the same way as some other rare earths in certain laser and glass-colorant applications.

Holmium has the highest magnetic permeability of any element and is thus used for the polepieces of the strongest static magnets. Because holmium strongly absorbs neutrons, it is also used as a burnable poison in nuclear reactors.

Erbium is a chemical element with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements. It is a lanthanide, a rare-earth element, originally found in the gadolinite mine in Ytterby, Sweden, which is the source of the element’s name.

Erbium’s principal uses involve its pink-colored Er3+ ions, which have optical fluorescent properties particularly useful in certain laser applications. Erbium-doped glasses or crystals can be used as optical amplification media, where Er3+ ions are optically pumped at around 980 or 1480 nm and then radiate light at 1530 nm in stimulated emission. This process results in an unusually mechanically simple laser optical amplifier for signals transmitted by fiber optics. The 1550 nm wavelength is especially important for optical communications because standard single mode optical fibers have minimal loss at this particular wavelength.

In addition to optical fiber amplifier-lasers, a large variety of medical applications (i.e. dermatology, dentistry) rely on the erbium ion’s 2940 nm emission (see Er:YAG laser) when lit at another wavelength, which is highly absorbed in water in tissues, making its effect very superficial. Such shallow tissue deposition of laser energy is helpful in laser surgery, and for the efficient production of steam which produces enamel ablation by common types of dental laser.

Thulium is a chemical element with the symbol Tm and atomic number 69. It is the thirteenth and third-last element in the lanthanide series. Like the other lanthanides, the most common oxidation state is +3, seen in its oxide, halides and other compounds; however, the +2 oxidation state can also be stable. In aqueous solution, like compounds of other late lanthanides, soluble thulium compounds form coordination complexes with nine water molecules.

In 1879, the Swedish chemist Per Teodor Cleve separated from the rare earth oxide erbia another two previously unknown components, which he called holmia and thulia; these were the oxides of holmium and thulium, respectively. A relatively pure sample of thulium metal was first obtained in 1911.

Thulium is the second-least abundant of the lanthanides, after radioactively unstable promethium which is only found in trace quantities on Earth. It is an easily workable metal with a bright silvery-gray luster. It is fairly soft and slowly tarnishes in air. Despite its high price and rarity, thulium is used as the radiation source in portable X-ray devices, and in some solid-state lasers. It has no significant biological role and is not particularly toxic.

Ytterbium is a chemical element with the symbol Yb and atomic number 70. It is the fourteenth and penultimate element in the lanthanide series, which is the basis of the relative stability of its +2 oxidation state. However, like the other lanthanides, its most common oxidation state is +3, as in its oxide, halides, and other compounds. In aqueous solution, like compounds of other late lanthanides, soluble ytterbium compounds form complexes with nine water molecules. Because of its closed-shell electron configuration, its density and melting and boiling points differ significantly from those of most other lanthanides.

In 1878, the Swiss chemist Jean Charles Galissard de Marignac separated from the rare earth “erbia” another independent component, which he called “ytterbia”, for Ytterby, the village in Sweden near where he found the new component of erbium. He suspected that ytterbia was a compound of a new element that he called “ytterbium” (in total, four elements were named after the village, the others being yttrium, terbium, and erbium). In 1907, the new earth “lutecia” was separated from ytterbia, from which the element “lutecium” (now lutetium) was extracted by Georges Urbain, Carl Auer von Welsbach, and Charles James. After some discussion, Marignac’s name “ytterbium” was retained. A relatively pure sample of the metal was not obtained until 1953. At present, ytterbium is mainly used as a dopant of stainless steel or active laser media, and less often as a gamma ray source.

Natural ytterbium is a mixture of seven stable isotopes, which altogether are present at concentrations of 0.3 parts per million. This element is mined in China, the United States, Brazil, and India in form of the minerals monazite, euxenite, and xenotime. The ytterbium concentration is low because it is found only among many other rare-earth elements; moreover, it is among the least abundant. Once extracted and prepared, ytterbium is somewhat hazardous as an eye and skin irritant. The metal is a fire and explosion hazard.

Lutetium is a chemical element with the symbol Lu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted among the rare earths. Lutetium is generally considered the first element of the 6th-period transition metals by those who study the matter, although there has been some dispute on this point.

Lutetium was independently discovered in 1907 by French scientist Georges Urbain, Austrian mineralogist Baron Carl Auer von Welsbach, and American chemist Charles James. All of these researchers found lutetium as an impurity in the mineral ytterbia, which was previously thought to consist entirely of ytterbium. The dispute on the priority of the discovery occurred shortly after, with Urbain and Welsbach accusing each other of publishing results influenced by the published research of the other; the naming honor went to Urbain, as he had published his results earlier. He chose the name lutecium for the new element, but in 1949 the spelling was changed to lutetium. In 1909, the priority was finally granted to Urbain and his names were adopted as official ones; however, the name cassiopeium (or later cassiopium) for element 71 proposed by Welsbach was used by many German scientists until the 1950s.

Lutetium is not a particularly abundant element, although it is significantly more common than silver in the earth’s crust. It has few specific uses. Lutetium-176 is a relatively abundant (2.5%) radioactive isotope with a half-life of about 38 billion years, used to determine the age of minerals and meteorites. Lutetium usually occurs in association with the element yttrium[6] and is sometimes used in metal alloys and as a catalyst in various chemical reactions. ¹⁷⁷Lu-DOTA-TATE is used for radionuclide therapy (see Nuclear medicine) on neuroendocrine tumours. Lutetium has the highest Brinell hardness of any lanthanide, at 890–1300 MPa.

Yttrium is a chemical element with the symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a “rare-earth element”. Yttrium is almost always found in combination with lanthanide elements in rare-earth minerals, and is never found in nature as a free element. ⁸⁹Y is the only stable isotope, and the only isotope found in the Earth’s crust.

The most important uses of yttrium are LEDs and phosphors, particularly the red phosphors in television set cathode ray tube displays. Yttrium is also used in the production of electrodes, electrolytes, electronic filters, lasers, superconductors, various medical applications, and tracing various materials to enhance their properties.

Yttrium has no known biological role. Exposure to yttrium compounds can cause lung disease in humans.

The element is named after ytterbite, a mineral first identified in 1787 by the chemist Arrhenius. He named the mineral after the village of Ytterby, in Sweden, where it had been discovered. When one of the chemicals in ytterbite was later found to be the previously unidentified element, yttrium, the element was then named after the mineral.