High boron nitrides

Yoo C S, Akella J, Nicol M and Cynn H 1997 Direct elementary synthesis of hexagonal and cubic boron nitrides at high pressures and temperatures Phys. Rev. B 56 140... 

By subjecting boron nitride (a white powder) to high pressure and temperature small crystals of a substance harder than diamond, known as borazon, are obtained. This pressure-temperature treatment changes the structure from the original graphite-like layer structure (p. 163) to a diamond-like structure this hard form can withstand temperatures up to 2000 K. 

Sihcon nitride has good strength retention at high temperature and is the most oxidation resistant nitride. Boron nitride [10043-11 -5] has excellent thermal shock resistance and is in many ways similar to graphite, except that it is not an electrical conductor. 

HSS = high speed steel cBN = cubic boron nitride. DCL = depth of cut line. 

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... 

Uses. In spite of unique properties, there are few commercial appUcations for monolithic shapes of borides. They are used for resistance-heated boats (with boron nitride), for aluminum evaporation, and for sliding electrical contacts. There are a number of potential uses ia the control and handling of molten metals and slags where corrosion and erosion resistance are important. Titanium diboride and zirconium diboride are potential cathodes for the aluminum Hall cells (see Aluminum and aluminum alloys). Lanthanum hexaboride and cerium hexaboride are particularly useful as cathodes ia electronic devices because of their high thermal emissivities, low work functions, and resistance to poisoning. 

Properties. Under nitrogen pressure hexagonal boron nitride melts at about 3000°C but sublimes at about 2500°C at atmospheric pressure. Despite the high melting point, the substance is mechanically weak because of the relatively easy sliding of the sheets of rings past one another (3). The theoretical density is 2.27 g/mL and the resistivity is about 10 H-cm. 

Preparation. Hexagonal boron nitride can be prepared by heating boric oxide with ammonia, or by heating boric oxide, boric acid, or its salts with ammonium chloride, alkaU cyanides, or calcium cyanamide at atmospheric pressure. Elemental nitrogen does not react with boric oxide even in the presence of carbon, though it does react with elemental boron at high temperatures. Boron nitride obtained from the reaction of boron trichloride or boron trifluoride with ammonia is easily purified. 

The cubic 2inc blende form of boron nitride is usually prepared from the hexagonal or rhombohedral form at high (4—6 GPa (40—60 kbar)) pressures and temperatures (1400—1700°C). The reaction is accelerated by lithium or alkaline-earth nitrides or amides, which are the best catalysts, and form intermediate Hquid compounds with BN, which are molten under synthesis conditions (11,16). Many other substances can aid the transformation. At higher pressures (6—13 GPa) the cubic or wurt2itic forms are obtained without catalysts (17). 

Uses. Hot-pressed hBN is useful for high temperature electric or thermal insulation, vessels, etc, especially in inert or reducing atmospheres, and for special materials such as IITV semiconductors (qv). Its low thermal expansion makes it resistant to thermal shock. The powder can be used as a mold release agent or as thermal insulation. Boron nitride is also available in fiber form (19). BN deposited pyrolyticaHy on refractory substrates at 1200—1800°C has a turbostratic stmcture and low porosity it has greater chemical resistance and is impervious to helium. 

The greatest use of cubic boron nitride is as an abrasive under the name Bora2on, in the form of small crystals, 1—500 p.m in si2e. Usually these crystals are incorporated in abrasive wheels and used to grind hard ferrous and nickel-based alloys, ranging from high speed steel tools and chilled cast-iron to gas turbine parts. The extreme hardness of the crystals and their resistance to attack by air and hot metal make the wheels very durable, and close tolerances can be maintained on the workpieces. 

Materials made of siHcon nitride, siHcon oxynitride, or sialon-bonded siHcon carbide have high thermal shock and corrosion resistance and may be used for pump parts, acid spray nozzles, and in aluminum reduction ceUs (156—159). A very porous siHcon carbide foam has been considered for surface combustion burner plates and filter media. It can also be used as a substrate carrying materials such as boron nitride as planar diffusion source for semiconductor doping appHcations. 

Cubic boron nitride (c-BN) is a different material altogether from h-BN, with a structure similar to that of diamond, which is characterized by extremely high hardness (second to diamond) and high thermal conductivity.As such, it is a material of great interest and a potential competitor to diamond, particularly for cutting and grinding applications. Its characteristics and properties are shown in Table 10.3... 

Cubic boron nitride is obtained from hexagonal boron nitride at high pressure and temperature in the presence of lithium nitride as a catalyst. It is almost as hard as diamond and has superior chemical resistance and a much higher oxidation threshold.Efforts to... 

A pellet is pressed of an intimate mixture of finely divided reactants and reaction induced either by arc melting and high-T annealing or by solid-state sintering in an electrical or high-frequency furnace. Isolating the borides from reactive container components can be a problem. The use of boron nitride liners has proved effective. In some cases the protective liner is made of sintered boride containing the same elements as the boride in preparation. 

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