Synthesis 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... 

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). 

The emphasis in the approaches to boron nitride [10043-11 -5] BN, precursors has been concentrated on cycHc compounds. There have been recent reports of trimethylsilyl-substituted aminoboranes being evaluated as B—N precursors. These are linear borylamines containing up to four boron atoms. Compounds were also synthesized with free —NH2 groups amenable to condensation with either dihaloboranes or dihaloborazines (65) and offering suitable monomers for linear B—N polymer synthesis and borazine-ring-linking appHcations. 

Haubner R, Wilhelm M, Weissenbacher R, Lux B (2002) Boron Nitrides - Properties, Synthesis and Applications 102 1-46... 

Cubic Phase of Boron Nitride c-BN. The cubic phase of boron nitride (c-BN) is one of the hardest materials, second only to diamond and with similar crystal structure. It is the first example of a new material theoretically predicted and then synthesized in laboratory. From automated synthesis a microcrystalline phase of cubic boron nitride is recovered at ambient conditions in a metastable state, providing the basic material for a wide range of cutting and grinding applications. Synthetic polycrystalline diamonds and nitrides are principally used as abrasives but in spite of the greater hardness of diamond, its employment as a superabrasive is limited by a relatively low chemical and thermal stability. Cubic boron nitride, on the contrary, has only half the hardness of diamond but an extremely high thermal stability and inertness. 

The c-BN phase was first obtained in 1957 [525] by exposing hexagonal boron nitride phase (h-BN) to high pressures and low temperatures. A pressure of more than 11 GPa is necessary to induce the hexagonal to cubic transformation, and these experimental conditions prevent any practical application for industrial purposes. Subsequently, it has been found that the transition pressure can be reduced to approximately 5 GPa at very high temperature (1300-1800°C) by using catalysts such as alkali metals, alkali metal nitrides, and Fe-Al or Ag-Cd alloys [526-528]. In addition, water, urea, and boric acid have been successfully used for synthesis of cubic boron nitride from hexagonal phase at 5-6 GPa and temperature above 800-1000°C [529]. It has been... 

Cubic BC2N. Hetero-diamond B C—N compounds have recently received a great interest because of their possible applications as mechanical and optical devices. The similar properties and structures of carbon and boron nitrides (graphite and hexagonal BN, diamond, and cubic BN) suggested the possible synthesis of dense compounds with all the three elements. Such new materials are expected to combine the best properties of diamond (hardness) and of c-BN (thermal stability and chemical inertness). Several low-density hexagonal phases of B,C, and N have been synthesized [534] while with respect to the high-density phases, different authors report contradictory data [535-538], but the final products are probably solid mixtures of c-BN and dispersed diamonds [539]. 

Lithium nitride is used as a catalyst to prepare boron nitride. It also is used as a reducing and nucleophilic reagent in organic synthesis, and to convert metals into their nitrides. 

A complex nanostructured catalyst for ammonia synthesis consists of ruthenium nanoclusters dispersed on a boron nitride support (Ru/BN) with barium added as a promoter (33). It was observed that the introduction of barium promoters results in an increase of the catalytic activity by 2—3 orders of magnitude. The multi-phase catalyst was first investigated by means of conventional HRTEM, but this technique did not succeed in identifying a barium-rich phase (34). It was even difficult to determine how the catalyst could be active, because the ruthenium clusters were encapsulated by layers of the boron nitride support. By HRTEM imaging of the catalyst during exposure to ammonia synthesis conditions, it was found that the... 

In the following sections some examples are given of the ways in which these principles have been utilized. The first example is the use of these techniques for the low temperature preparation of oxide ceramics such as silica. This process can also be used to produce alumina, titanium oxide, or other metal oxides. The second example describes the conversion of organic polymers to carbon fiber, a process that was probably the inspiration for the later development of routes to a range of non-oxide ceramics. Following this are brief reviews of processes that lead to the formation of silicon carbide, silicon nitride, boron nitride, and aluminum nitride, plus an introduction to the synthesis of other ceramics such as phosphorus nitride, nitrogen-phosphorus-boron materials, and an example of a transition metal-containing ceramic material. 

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