Skutterudite Allemagne
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Named after Skuterudåsen, a hill in Modum,
Norway Norway, officially the Kingdom of Norway, is a Nordic country in Northern Europe, the mainland territory of which comprises the western and northernmost portion of the Scandinavian Peninsula. The remote Arctic island of Jan Mayen and the ...
, skutterudite is a
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, p ...
arsenide mineral containing variable amounts of
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow ...
and
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
substituting for cobalt with the ideal formula CoAs3. Some references give the arsenic a variable formula subscript of 2–3. High nickel varieties are referred to as nickel-skutterudite, previously chloanthite. It is a
hydrothermal Hydrothermal circulation in its most general sense is the circulation of hot water (Ancient Greek ὕδωρ, ''water'',Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon. revised and augmented throughout by Sir Henry Stuart Jones. with th ...
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 Apr ...
mineral found in moderate to high temperature veins with other Ni-Co minerals. Associated minerals are
arsenopyrite Arsenopyrite ( IMA symbol: Apy) is an iron arsenic sulfide (FeAsS). It is a hard ( Mohs 5.5-6) metallic, opaque, steel grey to silver white mineral with a relatively high specific gravity of 6.1. When dissolved in nitric acid, it releases elem ...
, native
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
,
erythrite Erythrite or red cobalt is a secondary hydrated cobalt arsenate mineral with the formula . Erythrite and annabergite, chemical formula , or nickel arsenate form a complete series with the general formula . Erythrite crystallizes in the monocli ...
,
annabergite Annabergite is an arsenate mineral consisting of a hydrous nickel arsenate, Ni3(AsO4)2·8H2O, crystallizing in the monoclinic system and isomorphous with vivianite and erythrite. Crystals are minute and capillary and rarely met with, the mineral ...
,
nickeline Nickeline or niccolite is a mineral consisting primarily of nickel arsenide (NiAs). The naturally-occurring mineral contains roughly 43.9% nickel and 56.1% arsenic by mass, but composition of the mineral may vary slightly. Small quantities of ...
,
cobaltite Cobaltite is a sulfide mineral composed of cobalt, arsenic, and sulfur, Co As S. Its impurities may contain up to 10% iron and variable amounts of nickel.Klein, Cornelus and Cornrlius Hurlbut, 1996, ''Manual of Mineralogy'', 20th ed., Wiley, p. ...
, silver
sulfosalt Sulfosalt minerals are sulfide minerals with the general formula , where *A represents a metal such as copper, lead, silver, iron, and rarely mercury, zinc, vanadium *B usually represents semi-metal such as arsenic, antimony, bismuth, and rarely ...
s, native
bismuth Bismuth is a chemical element with the symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental bismuth occurs ...
, calcite,
siderite Siderite is a mineral composed of iron(II) carbonate (FeCO3). It takes its name from the Greek word σίδηρος ''sideros,'' "iron". It is a valuable iron mineral, since it is 48% iron and contains no sulfur or phosphorus. Zinc, magnesium and ...
, barite and
quartz Quartz is a hard, crystalline mineral composed of silica ( silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical ...
. It is mined as an ore of cobalt and nickel with a by-product of
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, ...
. The
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns ...
of this mineral has been found to be exhibited by several compounds with important technological uses. The mineral has a bright metallic luster, and is tin white or light steel gray in color with a black streak. The
specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water at its densest ...
is 6.5 and the
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
is 5.5–6. Its
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns ...
is isometric with cube and octahedron forms similar to that of
pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Fe S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic luster and pale brass-yellow hue giv ...
. The arsenic content gives a garlic odor when heated or crushed. Skutterudite was discovered in Skuterud Mines, Modum,
Buskerud Buskerud () is a former county and a current electoral district in Norway, bordering Akershus, Oslo, Oppland, Sogn og Fjordane, Hordaland, Telemark and Vestfold. The region extends from the Oslofjord and Drammensfjorden in the southeast to Ha ...
,
Norway Norway, officially the Kingdom of Norway, is a Nordic country in Northern Europe, the mainland territory of which comprises the western and northernmost portion of the Scandinavian Peninsula. The remote Arctic island of Jan Mayen and the ...
, in 1845. Smaltite is an alternative name for the mineral. Notable occurrences include Cobalt, Ontario, Skuterud,
Norway Norway, officially the Kingdom of Norway, is a Nordic country in Northern Europe, the mainland territory of which comprises the western and northernmost portion of the Scandinavian Peninsula. The remote Arctic island of Jan Mayen and the ...
, and
Franklin, New Jersey Franklin is a borough in Sussex County, in the U.S. state of New Jersey. As of the 2010 United States Census, the borough's population was 5,045United States The United States of America (U.S.A. or USA), commonly known as the United States (U.S. or US) or America, is a country primarily located in North America. It consists of 50 states, a federal district, five major unincorporated territori ...
. The rare arsenide minerals are classified in Dana's sulfide mineral group, even though it contains no sulfur.


Crystal structure

The crystal structure of the skutterudite mineral was determined in 1928 by Oftedahl to be cubic, belonging to
space group In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it uncha ...
Im-3 (number 204). The
unit cell In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
can be considered to consist of eight smaller cubes made up of the Co atoms. Six of these cubes are filled with (almost) square planar rings of As, each of which is oriented parallel to one of the unit cell edges. The As atoms then form
octahedra In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet a ...
with Co in the center. In crystallographic terms, the Co atoms occupy the 8c sites, while the As atoms occupy the 24g sites. The position of the Co atoms within the unit cell is fixed, while the positions of the As atoms are determined by the parameters x and y. It has been shown that for the As-rings to be fully square, these parameters must satisfy the Oftedahl relation x + y = 1/2. Any deviation from this relation yields a rectangular configuration of the As atoms; indeed, this is the case for all known compounds with this structure, and the As atoms do not form a perfect octahedron. Together with the unit cell size and the assigned space group, the aforementioned parameters fully describe the crystal structure of the material. This structure is often referred to as ''the skutterudite structure''.


Applications

Materials with a skutterudite structure are studied as a low cost thermoelectric material with low
thermal conductivity The thermal conductivity of a material is a measure of its ability to conduct heat. It is commonly denoted by k, \lambda, or \kappa. Heat transfer occurs at a lower rate in materials of low thermal conductivity than in materials of high thermal ...
. See also Thermoelectric materials#Skutterudite thermoelectrics.


References

{{Reflist * A. Kjekshus and T. Rakke. Compounds with skutterudite type crystal-structure .3. Structural data for arsenides and antimonides. Acta Chemica Scandinavica Series A 28 (1): 99-103 1974. Cobalt minerals Arsenide minerals Cubic minerals Minerals in space group 204