The performance of Al as nanoenergetic material in solid fuel propulsion or additive in liquid fuels is limited by the presence of the native oxide layer at the surface, which represents a significant weight fraction, does not contribute to heat release during oxidation, and acts as a diffusion barrier to Al oxidation. We develop an efficient technique in which the oxide layer is effectively turned into an energetic component via a reaction with fluorine that is coated in the form of a fluorocarbon nanofilm on the Al surface by plasma-enhanced chemical vapor deposition. Perfluorodecalin vapors are introduced in a low-pressure plasma reactor to produce nanofilms on the surface of Al nanoparticles, whose thickness is controlled with nanolevel precision as demonstrated by high-resolution transmission electron microscopy images. Coated particles show superior heat release, with a maximum enhancement of 50% at a thickness of 10 nm. This significant improvement is attributed to the chemical interaction between Al2O3 and F to form AlF3, which removes the oxide barrier via an exothermic reaction and contributes to the amount of heat released during thermal oxidation. The chemistry and mechanism of the enhancement effect of the plasma nanofilms are explained with the help of X-ray photoelectron spectroscopy, X-ray diffraction, high-angle annular dark-field scanning transmission electron microscopy-energy dispersive spectroscopy, thermogravimetric analysis, and differential scanning calorimetry.
Keywords: PECVD; aluminum; combustion; core−shell; fluorocarbon; heat release; interfacial chemistry; nanoenergetic materials; native oxide; oxidation.