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Skutterudite is a
cobalt Cobalt is a chemical element; it has Symbol (chemistry), 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. ...
arsenide mineral containing variable amounts of nickel and
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
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 ore mineral found in moderate to high temperature veins with other Ni-Co minerals. Associated minerals are arsenopyrite, native
silver Silver is a chemical element; it has Symbol (chemistry), symbol Ag () and atomic number 47. A soft, whitish-gray, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. ...
, erythrite,
annabergite Annabergite is an arsenate mineral consisting of a hydrous nickel arsenate. It is considered a member of the vivianite group and known for its ability to form crystals in a characteristic apple-green color. History Annabergite has been kn ...
, nickeline, cobaltite, silver sulfosalts, native bismuth,
calcite Calcite is a Carbonate minerals, carbonate mineral and the most stable Polymorphism (materials science), polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on ...
, siderite, barite and
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The Atom, atoms are linked in a continuous framework of SiO4 silicon–oxygen Tetrahedral molecular geometry, tetrahedra, with each oxygen being shared between two tet ...
. It is mined as an ore of cobalt and nickel with a by-product of
arsenic Arsenic is a chemical element; it has Symbol (chemistry), symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is not ...
. The
crystal structure In crystallography, crystal structure is a description of ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from intrinsic nature of constituent particles to form symmetric patterns that repeat ...
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 is 6.5 and the
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to plastic deformation, such as an indentation (over an area) or a scratch (linear), induced mechanically either by Pressing (metalworking), pressing or abrasion ...
is 5.5–6. Its
crystal structure In crystallography, crystal structure is a description of ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from intrinsic nature of constituent particles to form symmetric patterns that repeat ...
is isometric with cube and octahedron forms similar to that of pyrite. The arsenic content gives a garlic odor when heated or crushed.


Origins

Skutterudite has been known since the
Middle Ages In the history of Europe, the Middle Ages or medieval period lasted approximately from the 5th to the late 15th centuries, similarly to the post-classical period of global history. It began with the fall of the Western Roman Empire and ...
, when it was used in the production of smalt. It was discovered in the Skuterud Mines, Modum,
Buskerud Buskerud () is a Counties of Norway, county and a current electoral district in Norway, bordering Akershus, Oslo, Innlandet, Vestland, Telemark and Vestfold. The region extends from the Oslofjord and Drammensfjorden in the southeast to Hardanger ...
, Norway, in 1845. Smaltite is an alternative name for the mineral. Notable occurrences include Cobalt, Ontario and Franklin, New Jersey, in the United States.


Structure

The crystal structure of the skutterudite mineral was determined in 1928 by Oftedahl to be cubic, belonging to space group Im (number 204). The unit cell of a skutterudite consists of a total of 32 atoms, arranged in eight smaller cubes composed of cobalt atoms, which form octahedra with cobalt at the center. Six of these cubes are filled with planar square rings of arsenic, each oriented parallel to one of the unit cell's edges. In its structure, at the 2''a'' Wyckoff position, there are two large structural voids—each approximately five angstroms in size—that can be filled with impurity atoms. Together with the unit cell size and the assigned space group, the parameters mentioned above fully describe the crystalline structure of the material. This structure is commonly referred to as a 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 heat conduction, conduct heat. It is commonly denoted by k, \lambda, or \kappa and is measured in W·m−1·K−1. Heat transfer occurs at a lower rate in materials of low ...
. These materials have been synthesized with a thermoelectric figure of merit (ZT) close to 1 at 800 kelvin. A relatively high dimensionless figure of merit has been observed in a polycrystalline skutterudite partially filled with ytterbium ions. The small-diameter but heavy ytterbium atoms partially occupy the voids in the CoSb3 host structure, resulting in low thermal conductivity values while the favorable electronic properties are not substantially disrupted by the addition of ytterbium.


References

{{Reflist Cobalt minerals Arsenide minerals Cubic minerals Minerals in space group 204