Mischmetall
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Mischmetal (from – "mixed metal") is an
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
of
rare-earth element The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set o ...
s. It is also called cerium mischmetal, or rare-earth mischmetal. A typical composition includes approximately 55% 
cerium Cerium is a chemical element; it has Chemical symbol, symbol Ce and atomic number 58. It is a hardness, soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it ...
, 25% 
lanthanum Lanthanum is a chemical element; it has 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 bet ...
, and 15~18% 
neodymium Neodymium is a chemical element; it has Symbol (chemistry), 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 element, rare-earth metals. It is a hard (physics), hard, sli ...
, with traces of other rare earth metals totaling 95% 
lanthanides The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 Metal, metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium ...
, plus 5% iron. Its most common use is in the
pyrophoric A substance is pyrophoric (from , , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolithium compounds and triethylb ...
ferrocerium Ferrocerium (also known in Europe as Auermetall) is a synthetic pyrophoric alloy of mischmetal (cerium, lanthanum, neodymium, other trace lanthanides and some iron – about 95% lanthanides and 5% iron) hardened by blending in oxides ...
"flint" ignition device of many
lighter A lighter is a portable device which uses mechanical or electrical means to create a controlled flame, and can be used to ignite a variety of flammable items, such as cigarettes, butane gas, fireworks, candles, or campfires. A lighter typic ...
s and torches. Because an alloy of only rare-earth elements would be too soft to give good sparks, it is blended with
iron oxide An iron oxide is a chemical compound composed of iron and oxygen. Several iron oxides are recognized. Often they are non-stoichiometric. Ferric oxyhydroxides are a related class of compounds, perhaps the best known of which is rust. Iron ...
and
magnesium oxide Magnesium oxide (MgO), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg2+ ions and O2− ions ...
to form a harder material known as ferrocerium. In chemical formulae it is commonly abbreviated as Mm, e.g. MmNi5.


History

Carl Auer von Welsbach Carl Auer von Welsbach (1 September 1858 – 4 August 1929), who received the Austrian noble title of Freiherr Auer von Welsbach in 1901, was an Austrian scientist and inventor, who separated didymium into the elements neodymium and praseody ...
was the discoverer of neodymium and
praseodymium Praseodymium is a chemical element; it has symbol Pr and atomic number 59. It is the third member of the lanthanide series and is considered one of the rare-earth metals. It is a soft, silvery, malleable and ductile metal, valued for its magnetic ...
, and co-discoverer of
lutetium Lutetium is a chemical element; it has 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 am ...
. He was also the inventor of the
gas mantle A Coleman white gas lantern mantle glowing at full brightness An incandescent gas mantle, gas mantle or Welsbach mantle is a device for generating bright white light when heated by a flame. The name refers to its original heat source in gas li ...
(using
thorium Thorium is a chemical element; it has symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive grey when it is exposed to air, forming thorium dioxide; it is moderately soft, malleable, and ha ...
) and of the
rare-earth The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set of ...
industry. After extracting thorium from
monazite Monazite is a primarily reddish-brown phosphate mineral that contains rare-earth elements. Due to variability in composition, monazite is considered a group of minerals. The most common species of the group is monazite-(Ce), that is, the cerium ...
sand, many
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...
s remained, for which there was no commercial use. He sought applications for the rare earths. Among his first discoveries/inventions was mischmetal.


Preparation

Historically, mischmetal was prepared from
monazite Monazite is a primarily reddish-brown phosphate mineral that contains rare-earth elements. Due to variability in composition, monazite is considered a group of minerals. The most common species of the group is monazite-(Ce), that is, the cerium ...
, an
anhydrous A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achie ...
phosphate Phosphates are the naturally occurring form of the element phosphorus. In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthop ...
of the light lanthanides and thorium. The ore was
cracked Cracked may refer to: Television * ''Cracked'' (British TV series), a 2008 British comedy-drama television series that aired on STV * ''Cracked'' (Canadian TV series), a 2013 Canadian crime drama series that aired on CBC * "Cracked", a Season 8 ( ...
by reaction at high temperature with either concentrated
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
or
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
. Thorium was removed by taking advantage of its weaker
basicity In chemistry, there are three definitions in common use of the word "base": ''Arrhenius bases'', ''Brønsted bases'', and ''Lewis bases''. All definitions agree that bases are substances that react with acids, as originally proposed by Guilla ...
relative to the trivalent lanthanides, its daughter
radium Radium is a chemical element; it has chemical symbol, symbol Ra and atomic number 88. It is the sixth element in alkaline earth metal, group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, ...
was precipitated out using entrainment in
barium sulfate Barium sulfate (or sulphate) is the inorganic compound with the chemical formula Ba SO4. It is a white crystalline solid that is odorless and insoluble in water. It occurs in nature as the mineral barite, which is the main commercial source of ...
, and the remaining lanthanides were converted to their
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
s. The resulting "rare-earth chloride" (
hexahydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
), sometimes known as "lanthanide chloride", was the major commodity chemical of the rare-earth industry. By careful heating, preferably with
ammonium chloride Ammonium chloride is an inorganic chemical compound with the chemical formula , also written as . It is an ammonium salt of hydrogen chloride. It consists of ammonium cations and chloride anions . It is a white crystalline salt (chemistry), sal ...
or in an atmosphere of
hydrogen chloride The Chemical compound, compound hydrogen chloride has the chemical formula and as such is a hydrogen halide. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hyd ...
, the hexahydrate could be dehydrated to provide the anhydrous
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
.
Electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
of the molten anhydrous chloride (admixed with other anhydrous
halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fl ...
to improve the melt behavior) led to the formation of molten mischmetal, which would then be cast into
ingot An ingot is a piece of relatively pure material, usually metal, that is Casting, cast into a shape suitable for further processing. In steelmaking, it is the first step among semi-finished casting products. Ingots usually require a second procedu ...
s. Any
samarium Samarium is a chemical element; it has 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 has the oxidation state +3. Compounds of s ...
content of the ore tended not to be reduced to the metal, but accumulated in the molten halide, from which it could later be profitably isolated. Monazite-derived mischmetal typically was about 48% cerium, 25% lanthanum, 17% neodymium, and 5% praseodymium, with the balance being the other lanthanides. When
bastnäsite The mineral bastnäsite (or bastnaesite) is one of a family of three fluorocarbonate minerals, which includes bastnäsite-(cerium, Ce) with a formula of (Ce, La)CO3F, bastnäsite-(lanthanum, La) with a formula of (La, Ce)CO3F, and bastnäsite-(yt ...
started being processed for rare-earth content in about 1965, it too was converted to a version of rare-earth chloride and on to mischmetal. This version was higher in lanthanum and lower in neodymium. , the high demand for neodymium has made it profitable to remove all of the heavier lanthanides and neodymium (and sometimes all of the praseodymium as well) from the natural-abundance lanthanide mixture for separate sale and to include only La-Ce-Pr or La-Ce in the most economical forms of mischmetal. The light lanthanides are so similar in their metallurgical properties, that any application for which the original composition would have been suitable, would be equally well served by these truncated mixtures. The traditional "rare-earth chloride", as a commodity chemical, was also used to extract the individual rare earths by companies that did not wish to process the ores directly. , mischmetal is typically priced at less than 10
USD The United States dollar (symbol: $; currency code: USD) is the official currency of the United States and several other countries. The Coinage Act of 1792 introduced the U.S. dollar at par with the Spanish silver dollar, divided it int ...
per kilogram, and the underlying rare-earth chloride mixtures are typically less than US$5/kg.


Use

Mischmetal is used in the preparation of virtually all rare-earth elements. This is because such elements are nearly identical in most chemical processes, meaning that ordinary extraction processes do not distinguish them. Highly specialized processes, such as those developed by
Carl Auer von Welsbach Carl Auer von Welsbach (1 September 1858 – 4 August 1929), who received the Austrian noble title of Freiherr Auer von Welsbach in 1901, was an Austrian scientist and inventor, who separated didymium into the elements neodymium and praseody ...
, exploit subtle differences in
solubility In chemistry, solubility is the ability of a chemical substance, substance, the solute, to form a solution (chemistry), solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form su ...
to separate mischmetal into its constituent elements, with each step producing only an incremental change in composition. Such processes later informed
Marie Curie Maria Salomea Skłodowska-Curie (; ; 7 November 1867 – 4 July 1934), known simply as Marie Curie ( ; ), was a Polish and naturalised-French physicist and chemist who conducted pioneering research on radioactivity. She was List of female ...
in her search for new elements.


Zinc-aluminium galvanising

Traces of a cerium and lanthanum mischmetal are sometimes added to the
Galfan Roll of modern agricultural barbed wire Barbed wire, also known as barb wire or bob wire (in the Southern and Southwestern United States), is a type of steel fencing wire constructed with sharp edges or points arranged at intervals along the ...
galvanising Galvanization ( also spelled galvanisation) is the process of applying a protective zinc coating to steel or iron, to prevent rusting. The most common method is hot-dip galvanizing, in which the parts are coated by submerging them in a bath of ...
process for steel wire. This is a zinc and 5-10% aluminium coating, with traces of mischmetal.


References

* R. J. Callow, "The Industrial Chemistry of the Lanthanons, Yttrium, Thorium and Uranium", Pergamon Press, 1967. * * F. H. Spedding and A. H. Daane, editors, "The Rare Earths", John Wiley & Sons, 1961.


External links


The Wooden Periodic Table Table - Mischmetal

Misch metal
// Encyclopædia Britannica * Ryan Wojes

{{Webarchive, url=https://web.archive.org/web/20151117031511/http://metals.about.com/od/properties/a/What-Is-Mischmetal.htm , date=2015-11-17 // About.com
Мишметалл
// Переведённая статья Rare earth alloys Cerium compounds Lanthanum compounds