Boron Nitride Fibers Prepared from Symmetric and Asymmetric Alkylaminoborazines

• Published in: Advanced functional materials Vol. 12; no. 3; pp. 228 - 234
• Main Authors: Toury, B., Miele, P., Cornu, D., Vincent, H., Bouix, J.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-03-2002; WILEY‐VCH Verlag
• Subjects: Borazines; Boron nitride; Fibers; Polymers preceramic
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/1616-3028(200203)12:3<228::AID-ADFM228>3.0.CO;2-U

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.
Hexagonal boron nitride (h‐BN) fibers should be useful for the preparation of composites similar to “carbon/carbon” materials but suitable for higher‐temperature applications. The thermolysis of symmetric and asymmetric alkylaminoborazines (see Figure for an example) to polyborazines is reported, along with their subsequent processing to polyborazine filaments and h‐BN fibers. The performance of some of the fibers arouses interest in this preparative route.