Carbon boron carbides

Hafnium Boride. Hafnium diboride [12007-23-7] HfB2, is a gray crystalline soHd. It is usually prepared by the reaction of hafnium oxide with carbon and either boron oxide or boron carbide, but it can also be prepared from mixtures of hafnium tetrachloride, boron trichloride, and hydrogen above 2000°C, or by direct synthesis from the elements. Hafnium diboride is attacked by hydrofluoric acid but is resistant to nearly all other reagents at room temperature. Hafnium dodecaboride [32342-52-2] has been prepared by direct synthesis from the elements (56). 

Preparation. The simplest method of preparation is a combination of the elements at a suitable temperature, usually ia the range of 1100—2000°C. On a commercial scale, borides are prepared by the reduction of mixtures of metallic and boron oxides usiag aluminum, magnesium, carbon, boron, or boron carbide, followed by purification. Borides can also be synthesized by vapor-phase reaction or electrolysis. 

Boron and carbon form one compound, boron carbide [12069-32-8] B C, although excess boron may dissolve ia boron carbide, and a small amount of boron may dissolve ia graphite (5). Usually excess carbon appears as graphite, except for the special case of boron diffused iato diamonds at high pressures and temperatures, eg, 5 GPa (50 kbar) and 1500°C, where boron may occupy both iaterstitial and substitutional positions ia the diamond lattice, a property utilized ia synthetic diamonds (see Carbon, diamond, synthetic). 

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]. 

Boron carbide is resistant to most acids but is rapidly attacked by molten alkalies. It may be melted without decomposition in an atmosphere of carbon monoxide, but is slowly etched by hydrogen at 1200°C. It withstands metallic sodium fairly well at 500°C and steam at 300°C (8). 

Preparation. Boron carbide is most commonly produced by the reduction of boric oxide with carbon in an electric furnace between 1400 and 2300°C. In the presence of carbon, magnesium reduces boric oxide to boron carbide at 1400—1800°C. The reaction is best carried out in a hydrogen atmosphere in a carbon tube furnace. By-product magnesium compounds are removed by acid treatment. 

Diamondlike Carbides. SiUcon and boron carbides form diamondlike carbides beryllium carbide, having a high degree of hardness, can also be iacluded. These materials have electrical resistivity ia the range of semiconductors (qv), and the bonding is largely covalent. Diamond itself may be considered a carbide of carbon because of its chemical stmeture, although its conductivity is low. 

Boron carbide from boron oxide and carbon Calcium silicate from lime and silica Calcium carbide by reaction of lime and carbon Leblanc soda ash... 

Boron carbide from boron oxide and carbon... 

Other monomeric precursors similar to 6-hexynyl-decaborane such as 6-norbornenyl-decaborane (129) and 6-cyclooctenyl-decaborane (131) (Fig. 75) underwent ROMP in the presence of either first- or second-generation Grubbs catalysts to produce the corresponding poly(norbornenyl-decaborane) (130) (Fig. 75) and poly(cyclooctenyl-decaborane) (132) (Fig. 75) with Mn > 30 kDa and polydis-persities between 1.1 and 1.8.152 Electrostatic spinning and pyrolysis of poly (norbomenyl-decaborane) was discovered to produce nanoscale, free-standing porous boron-carbide/carbon, ceramic fiber matrices.153... 

On heating in air at 10°C per min, poly(m-carborane-siloxane) shows typically only 4% mass loss at 450°C and 7% mass loss at 600°C (see Fig. 4). In comparison, siloxanes without carborane units, show an approximate 50% mass loss at 450°C. As a consequence of the relatively high boron and carbon content of these materials, pyrolysis is expected to generate ceramic residues of boron carbide/silicon carbide. 

The hardness of boron carbide (carbon hexaboride) is not well defined because it is made as sintered compacts which have variable densities, compositions, and defect densities. It is very hard (up to 4400kg/mm2), and of relatively low density, so it has been used extensively as body-armor (McColm,... 

Boron carbide is prepared by reduction of boric oxide either with carbon or with magnesium in presence of carbon in an electric furnace at a temperature above 1,400°C. When magnesium is used, the reaction may be carried out in a graphite furnace and the magnesium byproducts are removed by treatment with acid. 

Niobium combines with carbon, boron, silicon and other elements at very high temperatures, forming interstitial binary compounds of varying compositions. With carbon, it forms niobium carbide having compositions varying from NbCo.7 to NbC [12069-94-2]. With boron, the products are orthorhombic niobium boride, NbB [12045-19-1], and the hexagonal diniobium diboride, Nb2B2[12007-29-3]. 

It is especially important to CTeate and develop terminology of nanochemistry as a part of a new area of science - nanology, or the science of the nanoworld (nanologists prefer this term to a more widely used word nanoscience). Figures 3.2-3.8, show the diversity of the morphology of nanostructures of carbon, sihcon and boron carbides, which were synthesised via hydrocarbon pyrolysis [2-5] or from elanental substances [6-10]. Morphologies of carbon nanotubes thus obtained are very unusual (Fig. 3.2). 

For the first time we have discovered transparent (painted in various colours) thread-like crystals of carbon among the products of hydrocarbon pyrolysis and during synthesis of silicon and boron carbides (Fig. 3.6) [12]. The X-ray spectral analysis has shown that the transparent threads consist of carbon (Fig. 3.7). 

Part of a mass spectrum for the determination of Fe and Cr contamination in boron nitride contaminated with carbon measured by LIMS is shown in Figure 6.9. The analyte ions 53Cr+ and 54Fe+ due to different masses of isobaric atomic and cluster ions are clearly separated from boron and boron carbide cluster ions as demonstrated in Figure 6.9. Cluster ion formation has been studied by laser ionization mass spectrometry (LIMS) on a boron nitride target.10... 

Boron Carbide, B4C coml prod called, tNor-bide, mp ca 2375°, d 2.52 is prepd by heating anhyd boric oxide B30, with carbon in graphite resistance furnace at ca 2500°. Its special interest is due to its remade able hardness jwhich lies on the Moh s scale betw thatjof silicon carbide and diamond. Used as an abrasive. Detailed description of this compd is given in Kirk Othmer 2(1948), 830-4(21 refs)... 

---