Silicon boride

Last updated

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). [1] The silicon borides may be grown from boron-saturated silicon in either the solid or liquid state.

The SiB6 crystal structure contains interconnected icosahedra (polyhedra with 20 faces), icosihexahedra (polyhedra with 26 faces), as well as isolated silicon and boron atoms. Due to the size mismatch between the silicon and boron atoms, silicon can be substituted for boron in the B12 icosahedra up to a limiting stoichiometry corresponding to SiB2.89. [2] The structure of the tetraboride SiB4 is isomorphous to that of boron carbide (B4C), B6P, and B6O. It is metastable with respect to the hexaboride. Nevertheless, it can be prepared due to the relative ease of crystal nucleation and growth. [3]

Both SiB4 - x and SiB6 become superficially oxidized when heated in air or oxygen and each is attacked by boiling sulfuric acid and by fluorine, chlorine, and bromine at high temperatures. The silicon borides are electrically conducting. The hexaboride has a low coefficient of thermal expansion and a high nuclear cross section for thermal neutrons.

The tetraboride was used in the black coating of some of the space shuttle heat shield tiles. [4]

Related Research Articles

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

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 but slightly softer than the cubic form.

<span class="mw-page-title-main">Boron</span> Chemical element, symbol B and atomic number 5

Boron is a chemical element; it has symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral sodium borate, and the ultra-hard crystals of boron carbide and boron nitride.

<span class="mw-page-title-main">Carbide</span> Inorganic compound group

In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece.

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 is also sometimes considered a lanthanide, despite being a d-block element and a transition metal.

<span class="mw-page-title-main">Boron carbide</span> Extremely hard ceramic compound

Boron carbide (chemical formula approximately B4C) is an extremely hard boron–carbon ceramic, a 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.

<span class="mw-page-title-main">Superhard material</span> Material with Vickers hardness exceeding 40 gigapascals

A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are virtually 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, disc brakes, and wear-resistant and protective coatings.

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.

<span class="mw-page-title-main">Boron arsenide</span> Chemical compound

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.

<span class="mw-page-title-main">Lanthanum hexaboride</span> Chemical compound

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 is extremely hard, with a Mohs hardness of 9.5. 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. LaB6 is a superconductor with a relatively low transition temperature of 0.45 K.

<span class="mw-page-title-main">Boron compounds</span>

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

Silicon compounds are compounds containing the element silicon (Si). As a carbon group element, silicon often forms compounds in the +4 oxidation state, though many unusual compounds have been discovered that differ from expectations based on its valence electrons, including the silicides and some silanes. Metal silicides, silicon halides, and similar inorganic compounds can be prepared by directly reacting elemental silicon or silicon dioxide with stable metals or with halogens. Silanes, compounds of silicon and hydrogen, are often used as strong reducing agents, and can be prepared from aluminum–silicon alloys and hydrochloric acid.

<span class="mw-page-title-main">Calcium hexaboride</span> Chemical compound

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. 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.

<span class="mw-page-title-main">Plutonium borides</span>

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

Aluminium magnesium boride or Al3Mg3B56, colloquially known as 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 0.04 in unlubricated and 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.

<span class="mw-page-title-main">Yttrium borides</span> Chemical compound

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).

<span class="mw-page-title-main">Allotropes of boron</span> Materials made only out of boron

Boron can be prepared in several crystalline and amorphous forms. Well known crystalline forms are α-rhombohedral (α-R), β-rhombohedral (β-R), and β-tetragonal (β-T). In special circumstances, boron can also be synthesized in the form of its α-tetragonal (α-T) and γ-orthorhombic (γ) 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 β-rhombohedral 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.

This article contains crystal structure data used in the article crystal structure of boron-rich metal borides.

<span class="mw-page-title-main">Crystal structure of boron-rich metal borides</span> Boron chemical complexes

Metals, and specifically rare-earth elements, form numerous chemical complexes with boron. Their crystal structure and chemical bonding depend strongly on the metal element M and on its atomic ratio to boron. When B/M ratio exceeds 12, boron atoms form B12 icosahedra which are linked into a three-dimensional boron framework, and the metal atoms reside in the voids of this framework. Those icosahedra are basic structural units of most allotropes of boron and boron-rich rare-earth borides. In such borides, metal atoms donate electrons to the boron polyhedra, and thus these compounds are regarded as electron-deficient solids.

<span class="mw-page-title-main">Iron boride</span> Chemical compound

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.

Samarium compounds are compounds formed by the lanthanide metal samarium (Sm). In these compounds, samarium generally exhibits the +3 oxidation state, such as SmCl3, Sm(NO3)3 and Sm(C2O4)3. Compounds with samarium in the +2 oxidation state are also known, for example SmI2.

References

  1. J. W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry Vol. 5, Longmans & Co. (1924) p. 27.
  2. Holleman and Wiberg Inorganic Chemistry, Wiley & Sons, (2001) p. 93.
  3. T. L. Aselage J. Mater. Research, 13 (1998) pp. 1786–1794.
  4. Scheffler, Michael; Colombo, Paolo (2005). Cellular ceramics: Structure, manufacturing, properties and applications. Wiley. pp. 110–111. ISBN   978-3-527-31320-4.