Carbides boron

Boron carbide B C is very hard, 9.6 on the Mohs scale . There are only two substances that are harder, namely cubic boron nitride (9.8) and diamond (10). Boron carbide is manufactured through the reaction between boron trioxide and carbon at 2000°C in an electric arc furnace. 

Boron carbide is used as an abrasive material for grinding, lapping and pohshing. It is also used to some extent as an industrial ceramic in nozzles for sand-blasters, turbines for turbojet engines and mortars. 

High-resolution transmission electron microscopy (HRTEM), using lattice imaging techniques, allows polytype analysis within single grains in the microstmcture of dense SiC bodies [20]. 

Joly [21] reported the preparation of boron carbide in 1883, labeling the product as B3C, whilst in 1899 Moisson [22] labeled the compound as BeC. Yet, another 50 years passed until Ridgeway [23] suggested the stoichiometry to be 4 to 1. Today, it is well established that the composition of boron carbide has no exact stoichiometric composition but ranges from B4 3C to B10.4C. The composition of commercially produced boron carbide, using the carbothermal reduction of boron oxide in arc furnaces, is usually close to B4C, which corresponds to the stoichiometric limit on the high-carbon side. 

Non-oxide ceramics exhibit a veiy high intrinsic stability (see Tables 7.2 and 7.3) and veiy high melting points. 

Material Oxidation starting temperature °C Maximum usage temperature °C  

T able 7.4. Oxidation starting temperature or maximum usage temperature of non-oxide ceramics 

Thermodynamic computations and experimental results show that there are two oxidation regimes depending on the oxygen pressure and the temperature. 

For high pressures and moderate temperatines, the sihca formed gradually covers and protects the substrate (SiC, Si3N4) this is passive oxidation  

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The covalent carbides These include boron carbide B4C and silicon carbide SiC the latter is made by heating a mixture of silica and coke in an electric furnace to about 2000 K ... 

Except for siUca and natural abrasives containing free siUca, the abrasive materials used today are classified by NIOSH as nuisance dust materials and have relatively high permissable dust levels (55). The OSHA TWA allowable total dust level for aluminum oxide, siUcon carbide, boron carbide, ceria, and other nuisance dusts is 10 mg/m. SiUca, in contrast, is quite toxic as a respkable dust for cristobaUte [14464-46-1] and tridymite [15468-32-3] the allowable TWA level drops to 0.05 mg/m and the TWA for quartz [14808-60-7] is set at 0.1 mg/m. Any abrasive that contains free siUca in excess of 1% should be treated as a potential health hazard if it is in the form of respkable dust. Dust masks are requked for those exposed to such materials (see Industrial hygene). 

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). 

Another important function of metallic coatings is to provide wear resistance. Hard chromium, electroless nickel, composites of nickel and diamond, or diffusion or vapor-phase deposits of sUicon carbide [409-21-2], SiC , SiC tungsten carbide [56780-56-4], WC and boron carbide [12069-32-8], B4C, are examples. Chemical resistance at high temperatures is provided by aUoys of aluminum and platinum [7440-06-4] or other precious metals (10—14). 

The third control is by use of a fixed burnable poison. This consists of rods containing a mixture of aluminum oxide and boron carbide, included in the initial fuel loading using the vacant spaces in some of the fuel assembhes that do not have control clusters. The burnable poison is consumed during operation, causing a reactivity increase that helps counteract the drop owing to fuel consumption. It also reduces the need for excessive initial soluble boron. Other reactors use gadolinium as burnable poison, sometimes mixed with the fuel. 

These are made of boron carbide ia a matrix of aluminum oxide clad with Zircaloy. As the uranium is depleted, ie, burned up, the boron is also burned up to maintain the chain reaction. This is another intrinsic control feature. The chemical shim and burnable poison controls reduce the number of control rods needed and provide more uniform power distributions. 

Research-grade material may be prepared by reaction of pelleted mixtures of titanium dioxide and boron at 1700°C in a vacuum furnace. Under these conditions, the oxygen is eliminated as a volatile boron oxide (17). Technical grade (purity > 98%) material may be made by the carbothermal reduction of titanium dioxide in the presence of boron or boron carbide. The endothermic reaction is carried out by heating briquettes made from a mixture of the reactants in electric furnaces at 2000°C (11,18,19). 

Ceramics (qv) such as those in Table 12 find high temperature use to over 800°C (32). Advanced ceramics finding interest include alumina, partially stabilized zitconia, siUcon nitride, boron nitride, siUcon carbide, boron carbide, titanium diboride, titanium carbide, and sialon (Si—Al—O—N) (33) (see... 

Sdicon carbide, hot pressed Alumina, dense sintered Boron nitride, hot pressed Sdicon nitride, hot pressed Boron carbide, hot pressed... 

A number of boron chemicals are prepared directly from boric acid. These include synthetic inorganic borate salts, boron phosphate, fluoborates, boron ttihaHdes, borate esters, boron carbide, and metal aHoys such as ferroboron [11108-67-1]. 

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. 

In general, the purified boron carbide is ultimately obtained as a granular soHd that subsequendy may be molded or bonded into usehil shapes. To achieve high density and strength, it is hot pressed at 1800—2400°C in graphite molds. 

Uses. Apphcations for boron carbide relate either to its hardness or its high neutron absorptivity ( B isotope). Hot-pressed boron carbide finds use as wear parts, sandblast no22les, seals, and ceramic armor plates but in spite of its hardness, it finds Httie use as an abrasive. However, this property makes it particulady usehil for dressing grinding wheels. 

Boron carbide is used in the shielding and control of nuclear reactors (qv) because of its neutron absorptivity, chemical inertness, and radiation stabihty. For this appHcation it may be molded, bonded, or the granular material may be packed by vibration. 

Handbook on Boron Carbide, Elemental Boron, and Other Stable, Boron-BJch Materials, Norton Co., Worcester, Mass., 1955. 

Reactions of boron ttihalides that are of commercial importance are those of BCl, and to a lesser extent BBr, with gases in chemical vapor deposition (CVD). CVD of boron by reduction, of boron nitride using NH, and of boron carbide using CH on transition metals and alloys are all technically important processes (34—38). The CVD process is normally supported by heating or by plasma formed by an arc or discharge (39,40). 

Boron Triiodide. Boron ttiiodide is not manufactured on a large scale. Small-scale production of BI from boron and iodine is possible in the temperature range 700—900°C (70—72). Excess I2 can be removed as Snl by reaction with Sn, followed by distillation (71). The reaction of metal tetrahydroborates and I2 is convenient for laboratory preparation of BI (73,74). BI can also by synthesized from B2H and HI in a furnace at 250°C (75), or by the reaction of B with excess Agl or Cul between 450—700°C, under vacuum (76). High purity BI has been prepared by the reaction of I2 with mixtures of boron carbide and calcium carbide at elevated temperatures. 

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. 

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