Boron atoms carbide

Properties. Boron carbide has a rhombohedral stmcture consisting of an array of nearly regular icosahedra, each having twelve boron atoms at the vertices and three carbon atoms ia a linear chain outside the icosahedra (3,4,6,7). Thus a descriptive chemical formula would be [12075-36-4]. 

MP2, MAs2 and MSb2 all have a compressed form of the marcasite structure, while the carbides MC have trigonal prismatic coordination in the WC structure. Several borides are known MB2 has nets of boron atoms. RunBg has branched chains while RU7B3 has isolated borons. 

The prototype hard metals are the compounds of six of the transition metals Ti, Zr, and Hf, as well as V, Nb, and Ta. Their carbides all have the NaCl crystal structure, as do their nitrides except for Ta. The NaCi structure consists of close-packed planes of metal atoms stacked in the fee pattern with the metalloids (C, N) located in the octahedral holes. The borides have the A1B2 structure in which close-packed planes of metal atoms are stacked in the simple hexagonal pattern with all of the trigonal prismatic holes occupied by boron atoms. Thus the structures are based on the highest possible atomic packing densities consistent with the atomic sizes. 

Properties. Boron carbide has a rhombohedral structure consisting of an array of nearly regular icosahedra, each having twelve boron atoms at the vertices and three carbon atoms in a linear chain outside the icosahedra (3,4,6,7). Thus a descriptive chemical formula would be B12C3 [12075-36 4], Each boron atom is bonded to five others in the icosahedron as well as either to a carbon atom or to a boron atom in an adjacent icosahedron. The structure is similar to that of rhombohedral boron (see Boron, elemental). The theoretical density for B12C3 is 2.52 g/mL. The rigid framework of... 

Boron forms a binary carbide, often written B4C but actually non-stoichiometry, and compounds with most metals. The stoichiometries and structures of these solids mostly defy simple interpretation. Many types of chains, layers and polyhedra of boron atoms are found. Simple examples are CaB6 and UB12, containing linked octahedra and icosahedra, respectively. 

Boron carbide (B4C) is also an extremely hard, infusible, and inert substance, made by reduction of B203 with carbon in an electric furnace at 2500°C, and has a very unusual structure. The C atoms occur in linear chains of 3, and the boron atoms in icosahedral groups of 12 (as in crystalline boron itself). These two units are then packed together in a sodium chloride-like array. There are, of course, covalent bonds between C and B atoms as well as between B atoms in different icosahedra. A graphite-like boron carbide (BQ) has been made by interaction of benzene and BC13 at 800°C. 

H. C. Longuet-Higgins and M. de V. Roberts, who predicted thereby that the icosahedron of 12 boron atoms familiar from elemental boron, boron carbide, and some borides should be stabilized in molecular hydride form, not as the neutral entity B Hu (which if icosahedral would be a diradical) but as the dianion [B12H12] , which contained the 25 valence shell electron pairs needed for the 12 exo B-H bonds and 13 skeletal bonding MOs. Subsequent MO treatments of the closo deltahedral anions B I 1 and carboranes (AB, 2H, in Figure 3.1 have shown that these are the shapes that make best bonding use of their (n + 1) pairs of electrons available for skeletal bonding. ... 

Boron compounds with nonmetals, i.e., boron hydrides, carbides, nitrides, oxides, silicides, and arsenides, show simple atomic structures. For example, boron nitride (BN) can be found in layered hexagonal, rhombohedral, and turbostratic or denser cubic and wurtzite-like structures, as well as in the form of nanotubes and fullerenes. Boron compounds with metalloids also differ from borides by electronic properties being semiconductors or wide-gap insulators. 

The homogeneity range of this boron carbide results from a substitution of some boron atoms of the chains and/or of the icosahedra by carbon. Also, some related... 

The boron-rich compounds N Bj2 of nonmetals (N = C, Si, P, As, O n = 1-3, but usually 2) are structurally related to both a-rhombohedral and a-tetragonal boron, which are built up of boron icosahedra and intericosahedral boron atoms (Figure 4.13). In the boron carbides B12Q (n = 1-3) the boron atoms in and between the icosahedra are replaced by carbon atoms. In the other compounds in this category the atoms (called N above) are between the polyhedra and not in them. 

The atomic and crystalline structures of covalent carbides are less complex and generally better understood and characterized than those of interstitial carbides. Bonding is essentially covalent where the carbon atoms bond to the silicon or boron atoms by sharing a pair of electrons and, like all covalent bonds, these atoms form definite bond angles. The bonding is achieved by the hybridization of the valence electrons of the respective atoms. 

The bonds between the carbon atoms and boron atoms as well as between the boron atoms themselves in the icosahedra are essentially covalent. But like silicon carbide (Sec. 3.3), the bonding of boron carbide is also partially ionic. 1 1 The difference between the atomic spacing of SiC and the sum of the covalent radii of carbon and silicon on one hand and the sum of the ionic radii (m the other hand show that the bonding, although mainly covalent, includes a certain d rce of ionicity. The calculated covalent bond energy E is 9.42 eV and die ionic bond energy Ep is 1.41 eV. 

Boron is an important material for nuclear applications due to its high neutron absorption cross section (760 bam at neutron velocity of 2200 m/ sec). The cross section of the isotope is considerably higher (3840 bam).l l In addition, boron does not have decay products with long half-life and high-energy secondary radioactive materials. However, pure boron is extremely brittle and difficult to produce in shapes such as control rods. Boron carbide is usually the material of choice since it provides a high concentration of boron atoms in a strong and refractory form and is relatively easy to mold (see Ch. 16). 

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