Boron nitride (BN) is a III-V compound which is the focus of important research since its discovery in the early 19th century. BN is electronic to carbon and thus, in the same way that carbon exists as graphite, BN exists in the hexagonal phase. The latter offers an unusual combination of properties that cannot be found in any other ceramics. However, these properties closely depend on the synthesis processes. This review states the recent developments in the preparation of BN through the chemistry, shaping and ceramic conversion of borazine derivatives. This concept denoted as Polymer-Derived Ceramics (PDCs) route allows tailoring the chemistry of precursors to elaborate complex BN shapes which cannot be obtained by conventional process. The effect of the chemistry of the molecular precursors, i.e., borazine and trichloroborazine, and their polymeric derivatives i.e., polyborazylene and poly[tri(methylamino)borazine], in which the specific functional groups and structural motifs determine the shaping potential by conventional liquid-phase process and plastic-forming techniques is discussed. Nanotubes, nano-fibers, coatings, monoliths and fiber-reinforced matrix composites are especially described. This leads to materials which are of significant engineering interest.
Keywords: B-tri(methylamino)borazine; borazine; boron nitride; composites; poly[B-tri(methylamino)borazine]; polyborazylene; pyrolysis; shaping.