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Mechanistic studies of the conversion of borazine polymers to boron nitride

Journal Article · · Chemistry of Materials; (USA)
DOI:https://doi.org/10.1021/cm00014a016· OSTI ID:5492322
;  [1]; ; ;  [2]
  1. Sandia National Laboratories, Albuquerque, NM (USA)
  2. Univ of New Mexico, Albuquerque (USA)

The thermal chemistry of thin films of a borazinylamine polymer deposited on KOH-etched aluminum and sapphire has been examined by thermal decomposition mass spectroscopy, thermogravimetric analysis, and Raman spectroscopy. The majority of the gas evolution chemistry is found to occur below 400{degree}C. All products desorb with the same temperature profile, and the major desorbing species are NH{sub 3} and N{sub 2} (polymer decomposition products) and HCl (side reaction products). The hydrogen remaining in the solid at 400{degree}C ({approx}50%) is continuously lost from 400 to 1,200{degree}C. Facile ring-opening steps are evidenced by the complete isotope mixing that occurs for samples in which the ring nitrogens are labeled with {sup 15}N. With increasing pyrolysis temperature, the Raman spectra change from that characteristic of the polymer (25{degree}C) to an intense featureless fluorescence spectrum (up to 400{degree}C) to an intense three-peak resonance Raman spectrum ({approx}400 to 1,200{degree}C), and finally to a less intense Raman spectrum characteristic of h-BN superimposed on a fluorescence background at 1,600{degree}C. The implications of these observations to the pyrolysis mechanism are discussed.

OSTI ID:
5492322
Journal Information:
Chemistry of Materials; (USA), Journal Name: Chemistry of Materials; (USA) Vol. 3:2; ISSN CMATE; ISSN 0897-4756
Country of Publication:
United States
Language:
English