Crystalline Hexagonal Boron Nitride Research Articles

Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp 2 bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400 nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp 3 hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.

Boron Nitride Fibers Prepared from Symmetric and Asymmetric Alkylaminoborazines

The thermolysis of 2,4,6-[(CH3)2N]3B3N3H3 (1), 2,4-[(CH3)2N]2-6-(CH3HN)B3N3H3 (2), and 2-[(CH3)2N]-4,6-(CH3HN)2B3-N3H3 (3) led to polyborazines 4, 5, and 6 respectively. The polymers display direct B–N bonds between borazinic B3N3 rings and, in addition, a proportion of –N(CH3)– bridges for 5 and 6, as clearly underlined by 13C NMR spectroscopy. Melt-spinning of these three polymeric precursors exemplified that their ease of processing increases in the order 4 < 5 < 6. Nevertheless, polyborazine filaments could be prepared from each of them and a subsequent thermal treatment up to 1800 °C resulted in the formation of crystalline hexagonal boron nitride fibers, which were characterized by X-ray diffraction analysis, Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy. Scanning electron microscopy (SEM) images showed that the ceramic fibers are circular and dense without major defects. The mechanical properties for 4-derived fibers could not be measured because of their brittleness, whereas measurements on 5- and 6-derived fibers gave tensile strength σR = 0.51 GPa, Young’s modulus E = 67 GPa, and σR = 0.69 GPa, E = 170 GPa, respectively. The improvement in mechanical properties for ceramic fibers prepared respectively from 4, 5, and 6 could be explained to a large extent by the improvement of the processing properties of the preceramic polymers. This evolution could be related to the increased ratio of bridging –N(CH3)– groups between the B3N3 rings within the polymers 4, 5, and 6 and therefore to the functionalities of the starting monomers 1, 2, and 3.