Graphite-like boron nitride

CP = bT1 layer lattice crystals, like graphite and boron nitride, and surface heat capacity Cp = yr + aT3 metals... 

Craphite-Like Boron Nitride (h-BN) As in graphite, h-BN forms a structure of hexagonal sheets stacked along the c-axis with ABA... sequence (Figure 11.11a). 

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. 

All three have similar cubic structures (although boron nitride also has a graphite-like structure). 

PI5.9 Boron nitride (BN) is isoelectronic with carbon and the B, C, and N atoms are about the same size. The result is that BN forms crystal structures similar to those of carbon, in that it crystallizes in a hexagonal (graphite-like hBN) and a cubic (diamond like cBN) structure. The data summarized at the end of the problem are available for the two forms of BN.17... 

The traditional method for the preparation of boron nitride is by the fusion of urea with boric acid in an atmosphere of ammonia at 750 °C.54 The product from these reactions is hexagonal boron nitride with a layer structure like that of graphite. Unlike graphite, it is colorless and is not an electronic conductor. Conversion of the hexagonal form to a cubic modification requires heating at 1,800 °C at 85,000 atmospheres pressure. 

Boron nitride (BN) can normally be prepared from the reaction of boric acid and urea or melamine. For example, the pyrolysis of MB can yield hexagonal BN. It is commonly referred to as white graphite because of its platy hexagonal structure similar to graphite. Under high pressure and at 1600°C, the hexagonal BN is converted to cubic BN, which has a diamond-like structure. 

As for hydrides, borides, and carbides, different types of nitrides are possible depending on the type of metallic element. The classifications of nitrides are similarly referred to as ionic (salt-like), covalent, and interstitial. However, it should be noted that there is a transition of bond types. Within the covalent classification, nitrides are known that have a diamond or graphite structure. Principally, these are the boron nitrides that were discussed in Chapter 8. 

In retrospect, it is ironic to it that when I met Ernst Schumacher in 1969 (he was then Professor at the University of Bern in Switzerland) we did not talk about the experiments he did at Zurich in the same building where I was at that time. Instead, his interest focussed on our work on borazine transition metal compounds and we discussed in some detail whether it would be possible to incorporate metal atoms like chromium or molybdenum between the layers of hexagonal boron nitride (BN) in a similar way as it can be done with graphite. In the course of these discussions I did not mention that, after I had moved to Zurich, we had begun to investigate the reactivity of nickelocene towards both nucleophilic and electrophilic substrates. The reason was that we were still at the beginning, and while we had been able to prepare a series of monocyclopentadienyl nickel complexes from Ni(C5H5)2 and Lewis bases, our attempts to obtain alkyl- or acyl-substituted nickelocenes by the Friedel-Crafts reaction failed. 

In graphite, which can be considered as a giant two-dimensional molecule from the series of condensed rings, the bonding between the separate layers is very weak, being due, as in molecular lattices, to Van der Waals-London interaction. The now infinite system of n electrons results in metallic conduction, only, however, in the plane of the rings Boron nitride has perhaps also a diamond-like form as well as the common graphite-like modification (p. 235). 

Boron nitride (BN) exists in a hexagonal modification with a graphite-like crystal structure and a cubic high temperature/high pressure modification with a diamondlike structure. 

BN-powder is, due to its graphite-like properties, predestined for utilization as a high temperature lubricant or as a mold lubricant in metal casting. Formed articles of boron(III) nitride are used as melting crucibles for high purity metals or semiconductor alloys and as refractory linings for plasma burners, rocket jets and combustion chambers. 200 t/a of hexagonal BN were produced in 1995. 

Boron nitride BN can form two solid structures, one containing hexagonal BN layers similar to graphite, and the other with tetrahedral sp bonding like diamond (see Topic D21. Borazine B- n3h6... 

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