# Calcium hexaboride

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Names Identifiers IUPAC name Calcium hexaboride Other names Calcium boride 3D model (JSmol) ChemSpider ECHA InfoCard 100.031.374 EC Number 234-525-3 PubChem CID InChI=1S/B6.Ca/c1-2-3(1)5(1)4(1,2)6(2,3)5;/q-2;+2 Key: PXRBHCKHCRNGSE-UHFFFAOYSA-N InChI=1/B6.Ca/c1-2-3(1)5(1)4(1,2)6(2,3)5;/q-2;+2 [B-]123B45B16[B-]47B52B376.[Ca+2] CaB6 Molar mass 104.94 g/mol Appearance black powder Density 2.45 g/cm3 Melting point 2,235 °C (4,055 °F; 2,508 K) insoluble Cubic Pm3m ; Oh [1] Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). (what is   ?) Infobox references

Calcium hexaboride (sometimes calcium boride) is a compound of calcium and boron with the chemical formula CaB6. It is an important material due to its high electrical conductivity, hardness, chemical stability, and melting point. It is a black, lustrous, chemically inert powder with a low density. It has the cubic structure typical for metal hexaborides, with octahedral units of 6 boron atoms combined with calcium atoms. [2] CaB6 and lanthanum-doped CaB6 both show weak ferromagnetic properties, which is a remarkable fact because calcium and boron are neither magnetic, nor have inner 3d or 4f electronic shells, which are usually required for ferromagnetism.

Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to its heavier homologues strontium and barium. It is the fifth most abundant element in Earth's crust and the third most abundant metal, after iron and aluminium. The most common calcium compound on Earth is calcium carbonate, found in limestone and the fossilised remnants of early sea life; gypsum, anhydrite, fluorite, and apatite are also sources of calcium. The name derives from Latin calx "lime", which was obtained from heating limestone.

Boron is a chemical element with the symbol B and atomic number 5. Produced entirely by cosmic ray spallation and supernovae and not by stellar nucleosynthesis, it is a low-abundance element in the Solar system and in the Earth's crust. Boron is concentrated on Earth by the water-solubility of its more common naturally occurring compounds, the borate minerals. These are mined industrially as evaporites, such as borax and kernite. The largest known boron deposits are in Turkey, the largest producer of boron minerals.

Hardness is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. Some materials are harder than others. Macroscopic hardness is generally characterized by strong intermolecular bonds, but the behavior of solid materials under force is complex; therefore, there are different measurements of hardness: scratch hardness, indentation hardness, and rebound hardness.

## Properties

CaB6 has been investigated in the past due to a variety of peculiar physical properties, such as superconductivity, valence fluctuation and Kondo effects. [3] However, the most remarkable property of CaB6 is its ferromagnetism. It occurs at unexpectedly high temperature (600 K) and with low magnetic moment (below 0.07 ${\displaystyle \mu _{\mathrm {B} }}$ per atom). The origin of this high temperature ferromagnetism is the ferromagnetic phase of a dilute electron gas, linkage to the presumed excitonic state in calcium boride, or external impurities on the surface of the sample. The impurities might include iron and nickel, probably coming from impurities in the boron used to prepare the sample. [4]

Superconductivity is a phenomenon of exactly zero electrical resistance and expulsion of magnetic flux fields occurring in certain materials, called superconductors, when cooled below a characteristic critical temperature. It was discovered by Dutch physicist Heike Kamerlingh Onnes on April 8, 1911, in Leiden. Like ferromagnetism and atomic spectral lines, superconductivity is a quantum mechanical phenomenon. It is characterized by the Meissner effect, the complete ejection of magnetic field lines from the interior of the superconductor during its transitions into the superconducting state. The occurrence of the Meissner effect indicates that superconductivity cannot be understood simply as the idealization of perfect conductivity in classical physics.

In physics, the Kondo effect describes the scattering of conduction electrons in a metal due to magnetic impurities, resulting in a characteristic change in electrical resistivity with temperature. The effect was first described by Jun Kondo, who applied third-order perturbation theory to the problem to account for s-d electron scattering. Kondo's model predicted that the scattering rate of conduction electrons of the magnetic impurity should diverge as the temperature approaches 0 K. Extended to a lattice of magnetic impurities, the Kondo effect likely explains the formation of heavy fermions and Kondo insulators in intermetallic compounds, especially those involving rare earth elements like cerium, praseodymium, and ytterbium, and actinide elements like uranium. The Kondo effect has also been observed in quantum dot systems.

In atomic physics, the Bohr magneton is a physical constant and the natural unit for expressing the magnetic moment of an electron caused by either its orbital or spin angular momentum.

CaB6 is insoluble in H2O, MeOH (methanol), and EtOH (ethanol) and dissolves slowly in acids. [5] Its microhardness is 27 GPa, Knoop hardness is 2600 kg/mm2), Young modulus is 379 GPa, and electrical resistivity is greater than 2·1010 Ω·m for pure crystals. [6] [7] CaB6 is a semiconductor with an energy gap estimated as 1.0 eV. The low, semi-metallic conductivity of many CaB6 samples can be explained by unintentional doping due to impurities and possible non-stoichiometry. [8]

## Structural Information

The crystal structure of calcium hexaboride is a cubic lattice with calcium at the cell centre and compact, regular octahedra of boron atoms linked at the vertices by B-B bonds to give a three-dimensional boron network. [5] Each calcium has 24 nearest-neighbor boron atoms [1] The calcium atoms are arranged in simple cubic packing so that there are holes between groups of eight calcium atoms situated at the vertices of a cube. [9] The simple cubic structure is expanded by the introduction of the octahedral B6 groups and the structure is a CsCl-like packing of the calcium and hexaboride groups. [9] Another way of describing calcium hexaboride is as having a metal and a B62− octahedral polymeric anions in a CsCl-type structure were the Calcium atoms occupy the Cs sites and the B6 octahedra in the Cl sites. [10] The Ca-B bond length is 3.05 Å and the B-B bond length is 1.7 Å. [9]

43Ca NMR data contains δpeak at -56.0 ppm and δiso at -41.3 ppm where δiso is taken as peak max +0.85 width, the negative shift is due to the high coordination number. [10]

Raman Data: Calcium hexaboride has three Raman peaks at 754.3, 1121.8, and 1246.9 cm−1 due to the active modes A1g, Eg, and T2g respectively. [1]

Observed Vibrational Frequencies cm−1 : 1270(strong) from A1g stretch, 1154 (med.) and 1125(shoulder) from Eg stretch, 526, 520, 485, and 470 from F1g rotation, 775 (strong) and 762 (shoulder) from F2g bend, 1125 (strong) and 1095 (weak)from F1u bend, 330 and 250 from F1u translation, and 880 (med.) and 779 from F2u bend. [1]

## Preparation

• One of the main reactions for industrial production is: [6]
CaO + 3 B2O3 + 10 Mg → CaB6 + 10 MgO

Other methods of producing CaB6 powder include:

• Direct reaction of calcium or calcium oxide and boron at 1000 °C;
Ca + 6B → CaB6
Ca(OH)2 +7B → CaB6 + BO(g) + H2O(g)
• Reacting calcium carbonate with boron carbide in vacuum at above 1400 °C (carbothermal reduction)
• Reacting of CaO and H3BO3 and Mg to 1100 °C. [5]
• Low-temperature (500 °C) synthesis
CaCl2 + 6NaBH4 → CaB6 + 2NaCl + 12H2 + 4Na

results in relatively poor quality material. [12]

• To produce pure CaB6 single crystals, e.g., for use as cathode material, the thus obtained CaB6 powder is further recrystallized and purified with the zone melting technique. The typical growth rate is 30 cm/h and crystal size ~1x10 cm. [11]
• Single-crystal CaB6 Nanowires (diameter 15–40 nm, length 1–10 micrometres) can be obtained by pyrolysis of diborane (B2H6) over calcium oxide (CaO) powders at 860–900 °C, in presence of Ni catalyst. [7]

## Uses

Calcium hexaboride is used in the manufacturing of boron-alloyed steel [5] and as a deoxidation agent in production of oxygen-free copper. The latter results in higher conductivity than conventionally phosphorus-deoxidized copper owing to the low solubility of boron in copper. [6] CaB6 can also serve as a high temperature material, surface protection, abrasives, tools, and wear resistant material.

CaB6 is highly conductive, has low work function, and thus can be used as a hot cathode material. When used at elevated temperature, calcium hexaboride will oxidize degrading its properties and shortening its usable lifespan. [13]

CaB6 is also a promising candidate for n-type thermoelectric materials, because its power factor is larger than or comparable to that of common thermoelectric materials Bi2Te3 and PbTe. [7]

CaB also can be used as an antioxidant in carbon bonded refractories.

## Precautions

Calcium hexaboride is irritating to the eyes, skin, and respiratory system. This product should be handled with proper protective eyeware and clothing. Never put calcium hexaboride down the drain or add water to it.

## Related Research Articles

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite and may even be harder than the cubic form.

In chemistry, a carbide is a compound composed of carbon and a less electronegative element. Carbides can be generally classified by the chemical bonds type as follows: (i) salt-like, (ii) covalent compounds, (iii) interstitial compounds, and (iv) "intermediate" transition metal carbides. Examples include calcium carbide (CaC2), silicon carbide (SiC), tungsten carbide (WC; often called, simply, carbide when referring to machine tooling), and cementite (Fe3C), each used in key industrial applications. The naming of ionic carbides is not systematic.

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 that repeat along the principal directions of three-dimensional space in matter.

Boron carbide (chemical formula approximately B4C) is an extremely hard boron–carbon ceramic, and covalent material used in tank armor, bulletproof vests, engine sabotage powders, as well as numerous industrial applications. With a Vickers Hardness of >30 GPa, it is one of the hardest known materials, behind cubic boron nitride and diamond.

A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are highly incompressible solids with high electron density and high bond covalency. As a result of their unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools and wear-resistant and protective coatings.

Diamond is the allotrope of carbon in which the carbon atoms are arranged in the specific type of cubic lattice called diamond cubic. Diamond is an optically isotropic crystal that is transparent to opaque. Diamond is the hardest naturally occurring material known. Yet, due to important structural weaknesses, diamond's toughness is only fair to good. The precise tensile strength of bulk diamond is unknown, however strength up to 60 GPa has been observed, and it could be as high as 90–100 GPa in the form of nanometer-sized wires or needles ,with a corresponding local maximum tensile elastic strain in excess of 9%. The anisotropy of diamond hardness is carefully considered during diamond cutting. Diamond has a high refractive index (2.417) and moderate dispersion (0.044) properties which give cut diamonds their brilliance. Scientists classify diamonds into four main types according to the nature of crystallographic defects present. Trace impurities substitutionally replacing carbon atoms in a diamond's crystal structure, and in some cases structural defects, are responsible for the wide range of colors seen in diamond. Most diamonds are electrical insulators but extremely efficient thermal conductors. Unlike many other minerals, the specific gravity of diamond crystals (3.52) has rather small variation from diamond to diamond.

Magnetic semiconductors are semiconductor materials that exhibit both ferromagnetism and useful semiconductor properties. If implemented in devices, these materials could provide a new type of control of conduction. Whereas traditional electronics are based on control of charge carriers, practical magnetic semiconductors would also allow control of quantum spin state. This would theoretically provide near-total spin polarization, which is an important property for spintronics applications, e.g. spin transistors.

A boride is a compound between boron and a less electronegative element, for example silicon boride (SiB3 and SiB6). The borides are a very large group of compounds that are generally high melting and are covalent more than ionic in nature. Some borides exhibit very useful physical properties. The term boride is also loosely applied to compounds such as B12As2 (N.B. Arsenic has an electronegativity higher than boron) that is often referred to as icosahedral boride.

Boron arsenide is a chemical compound involving boron and arsenic, usually with a chemical formula BAs. Other boron arsenide compounds are known, such as the subarsenide B12As2. Chemical synthesis of cubic BAs is very challenging and its single crystal forms usually have defects.

Lanthanum hexaboride (LaB6, also called lanthanum boride and LaB) is an inorganic chemical, a boride of lanthanum. It is a refractory ceramic material that has a melting point of 2210 °C, and is insoluble in water and hydrochloric acid. It has a low work function and one of the highest electron emissivities known, and is stable in vacuum. Stoichiometric samples are colored intense purple-violet, while boron-rich ones (above LaB6.07) are blue. Ion bombardment changes its color from purple to emerald green.

Strontium boride (SrB6) is an inorganic compound. At room temperature, it appears as a crystalline black powder. Closer examination reveals slightly translucent dark red crystals capable of scratching quartz. It is very stable and has a high melting point and density. Although not thought to be toxic, it is an irritant to the skin, eyes, and respiratory tract.

Boron suboxide (chemical formula B6O) is a solid compound with a structure built of eight icosahedra at the apexes of the rhombohedral unit cell. Each icosahedron is composed of twelve boron atoms. Two oxygen atoms are located in the interstices along the [111] rhombohedral direction. Due to its short interatomic bond lengths and strongly covalent character, B6O displays a range of outstanding physical and chemical properties such as great hardness (close to that of rhenium diboride and boron nitride), low mass density, high thermal conductivity, high chemical inertness, and excellent wear resistance.

Several plutonium borides can be formed by direct combination of plutonium and boron powders in an inert atmosphere at reduced pressure.

Aluminum magnesium boride or BAM is a chemical compound of aluminium, magnesium and boron. Whereas its nominal formula is AlMgB14, the chemical composition is closer to Al0.75Mg0.75B14. It is a ceramic alloy that is highly resistive to wear and has an extremely low coefficient of sliding friction, reaching a record value of 0.02 in lubricated AlMgB14−TiB2 composites. First reported in 1970, BAM has an orthorhombic structure with four icosahedral B12 units per unit cell. This ultrahard material has a coefficient of thermal expansion comparable to that of other widely used materials such as steel and concrete.

Yttrium boride refers to a crystalline material composed of different proportions of yttrium and boron, such as YB2, YB4, YB6, YB12, YB25, YB50 and YB66. They are all gray-colored, hard solids having high melting temperatures. The most common form is the yttrium hexaboride YB6. It exhibits superconductivity at relatively high temperature of 8.4 K and, similar to LaB6, is an electron cathode. Another remarkable yttrium boride is YB66. It has a large lattice constant (2.344 nm), high thermal and mechanical stability, and therefore is used as a diffraction grating for low-energy synchrotron radiation (1–2 keV).

Boron can be prepared in several crystalline and amorphous forms. Well known crystalline forms are α-rhombohedral, β-rhombohedral, and β-tetragonal. In special circumstances, boron can also be synthesized in the form of its α-tetragonal and γ-orthorhombic allotropes. Two amorphous forms, one a finely divided powder and the other a glassy solid, are also known. Although at least 14 more allotropes have been reported, these other forms are based on tenuous evidence or have not been experimentally confirmed, or are thought to represent mixed allotropes, or boron frameworks stabilized by impurities. Whereas the β-rhombohedral phase is the most stable and the others are metastable, the transformation rate is negligible at room temperature, and thus all five phases can exist at ambient conditions. Amorphous powder boron and polycrystalline rhombohedral β-boron are the most common forms. The latter allotrope is a very hard grey material, about ten percent lighter than aluminium and with a melting point (2080 °C) several hundred degrees higher than that of steel.

Silicon borides (also known as boron silicides) are lightweight ceramic compounds formed between silicon and boron. Several stoichiometric silicon boride compounds, SiBn, have been reported: silicon triboride, SiB3, silicon tetraboride, SiB4, silicon hexaboride, SiB6, as well as SiBn (n = 14, 15, 40, etc.). The n = 3 and n = 6 phases were reported as being co-produced together as a mixture for the first time by Henri Moissan and Alfred Stock in 1900 by briefly heating silicon and boron in a clay vessel. The tetraboride was first reported as being synthesized directly from the elements in 1960 by three independent groups: Carl Cline and Donald Sands; Ervin Colton; and Cyrill Brosset and Bengt Magnusson. It has been proposed that the triboride is a silicon-rich version of the tetraboride. Hence, the stoichiometry of either compound could be expressed as SiB4 - x where x = 0 or 1. All the silicon borides are black, crystalline materials of similar density: 2.52 and 2.47 g cm−3, respectively, for the n = 3(4) and 6 compounds. On the Mohs scale of mineral hardness, SiB4 - x and SiB6 are intermediate between diamond (10) and ruby (9). The silicon borides may be grown from boron-saturated silicon in either the solid or liquid state.

Erbium hexaboride (ErB6) is a rare-earth hexaboride compound, which has a calcium hexaboride crystal structure.

Iron boride refers to various inorganic compounds with the formula FexBy. Two main iron borides are FeB and Fe2B. Some iron borides possess useful properties such as magnetism, electrical conductivity, corrosion resistance and extreme hardness. Some iron borides have found use as hardening coatings for iron. Iron borides have properties of ceramics such as high hardness, and properties of metal properties, such as thermal conductivity and electrical conductivity. Boride coatings on iron are superior mechanical, frictional, and anti-corrosive. Iron monoboride (FeB) is a grey powder that is insoluble in water. FeB is harder than Fe2B, but is more brittle and more easily fractured upon impact.

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