Boron nitride preparation

Yokoyama H., Okamoto M. et al.. Effects of a negative self-bias on the growth of cubic boron nitride prepared by plasma chemical vapor deposition, Jpn. J. Appl. P/2yj., 30 (1991) pp. 344-348. 

Aminoboranes as Versatile Precursors of Boron Nitride Preparation of BN Matrices, Coatings and Fibres... 

Boron nitride can be prepared by allowing ammonia to react with boron trichloride. The first product is boron amide which decomposes on heating to give the nitride ... 

Lithium Nitride. Lithium nitride [26134-62-3], Li N, is prepared from the strongly exothermic direct reaction of lithium and nitrogen. The reaction proceeds to completion even when the temperature is kept below the melting point of lithium metal. The lithium ion is extremely mobile in the hexagonal lattice resulting in one of the highest known soHd ionic conductivities. Lithium nitride in combination with other compounds is used as a catalyst for the conversion of hexagonal boron nitride to the cubic form. The properties of lithium nitride have been extensively reviewed (66). 

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. 

Rhombohedral boron nitride can be prepared by heating a mixture of NaBH and NH Cl rapidly to 750—1000°C (15). The presence of NaCl appears to favor the rhombohedral form. 

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). 

Nakamura, K., Preparation and Properties of Boron Nitride Films by Metal Organic Chemical Vapor Deposition, /. Electochem. Soc., 133-6 120-1123 (1986)... 

Elements dissolved in boron influence its crystal structure. Dissolved impurities also influenee the physical and chemical properties of boron, especially the electrical properties, because boron is a semiconductor. Preparation of solid solutions in jS-rh boron requires a careful choice of crucible material. To avoid contamination, boron nitride or a cold, coinage-metal crucible should be used or the levitation or floating-zone melting techniques applied. 

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. 

Typically, Be-containing alloys and intermetallic phases have been prepared in beryllia or alumina crucibles Mg-containing products have been synthesized in graphite, magnesia or alumina crucibles. Alloys and compounds containing Ca, Sr and Ba have been synthesized in alumina , boron nitride, zircon, molybdenum, iron , or steel crucibles. Both zircon and molybdenum are satisfactory only for alloys with low group-IIA metal content and are replaced by boron nitride and iron, respectively, for group-IIA metal-rich systems . Crucibles are sealed in silica, quartz, iron or steel vessels, usually under either vacuum or purified inert cover gas in a few cases, the samples were melted under a halide flux . 

Non-oxide ceramics such as silicon carbide (SiC), silicon nitride (SijN ), and boron nitride (BN) offer a wide variety of unique physical properties such as high hardness and high structural stability under environmental extremes, as well as varied electronic and optical properties. These advantageous properties provide the driving force for intense research efforts directed toward developing new practical applications for these materials. These efforts occur despite the considerable expense often associated with their initial preparation and subsequent transformation into finished products. 

Boron nitride may be obtained in three primary crystalline modifications (2) a, j3, and y. The most commonly encountered a form has a graphitic structure (hexagonal cell, a = 2.504 A, c = 6.661 A). For many years, this modification has been prepared from combinations of cheap boron and nitrogen containing reagents, e.g. B(0H)3 and (NH2)C0, B(0H)3, C and N2 or KBH4 and NH4C1 (3-5). More... 

Boron-containing nonoxide amorphous or crystalline advanced ceramics, including boron nitride (BN), boron carbide (B4C), boron carbonitride (B/C/N), and boron silicon carbonitride Si/B/C/N, can be prepared via the preceramic polymers route called the polymer-derived ceramics (PDCs) route, using convenient thermal and chemical processes. Because the preparation of BN has been the most in demand and widespread boron-based material during the past two decades, this chapter provides an overview of the conversion of boron- and nitrogen-containing polymers into advanced BN materials. 

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