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Title: Oxidation kinetics of aluminum diboride

The oxidation characteristics of aluminum diboride (AlB{sub 2}) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB{sub 2} in the onset of oxidation and final conversion fraction, with AlB{sub 2} beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB{sub 2} and Al+2B in both air and oxygen. AlB{sub 2} exhibited O{sub 2}-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O{sub 2} than in air. Differences in the composition and morphology between oxidized Al+2B and AlB{sub 2} suggested that Al{sub 2}O{sub 3}–B{sub 2}O{sub 3} interactions slowed Al+2B oxidation by converting Al{sub 2}O{sub 3} on aluminum particles into a Al{sub 4}B{sub 2}O{sub 9} shell, while the same Al{sub 4}B{sub 2}O{sub 9} developed a needle-like morphology in AlB{sub 2} thatmore » reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB{sub 2}, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB{sub 2} in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time–temperature plots, (b) conversion as a function of time, (c) Arrhenius plots used to calculate activation energies, and (d) activation energy as a function of conversion. Display Omitted - Highlights: • First reported kinetic parameters for AlB{sub 2} and Al+2B oxidation in air and O{sub 2}. • Possible mechanism of enhanced boron combustion presented. • Moisture sensitivity shown to be problematic for AlB{sub 2}, less for Al+2B.« less
Authors:
 [1] ;  [2] ;  [3]
  1. Department of Materials Science and Engineering, University of Utah, 122S. Central Campus Drive, Salt Lake City, UT 84112 (United States)
  2. Department of Metallurgical Engineering, University of Utah, 135S 1460 E, Rm 00412, Salt Lake City, UT 84112 (United States)
  3. Ceramatec, Inc., 2425S. 900W., Salt Lake City, UT 84119 (United States)
Publication Date:
OSTI Identifier:
22274160
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 207; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; ALUMINIUM; ALUMINIUM OXIDES; COMBUSTION; DIFFUSION; HEATING RATE; INTERACTIONS; KINETICS; OXYGEN; SENSITIVITY; THERMAL GRAVIMETRIC ANALYSIS; TIME DEPENDENCE