Microstructural Behavior of the Alumina Shell and Aluminum Core Before and After Melting of Aluminum Nanoparticles

The oxidation mechanism of nanoaluminum particles, nominally employed as fuel component, is still an unsettled problem, because of the complex nature of thermomechanical properties of the oxide shell surrounding the elemental core. Although mechanical breakage of the alumina shell upon or after melting of aluminum core has been thought to play a key role in the combustion of aluminum nanoparticles, there has been little direct evidence. In this study, the microstructural behaviors of Al core and alumina shell lattices were investigated with increasing temperatures. Three in situ techniques, high-temperature X-ray diffraction analysis, hot-stage transmission electron microscopy, and high-resolution transmission electron microscopy for heat-treated samples, were employed to probe the thermal behaviors of aluminum and alumina lattices before and after melting of the aluminum core. High-temperature X-ray diffraction analysis revealed that nano aluminum lattice was initially expanded under tension at room temperature, and then when heated passed through a zero-strain state at ∼300 °C. Upon further heating above the bulk melting temperature of aluminum, the aluminum lattice expanded under almost no constraint. This interesting observation, which is contrary to almost all of the previous results and models, was ascribed to the inhomogeneous (localized) crystalline phase transformation of amorphous alumina. High-resolution transmission electron microscopy and in situ hot-stage transmission electron microscopy evidenced localized phase transformation accompanied by a significant shell thickening, presumably resulting from diffusion processes of Al cations and O anions, which is to absorb the pressure built in aluminum core, by creating a more ductile shell.