Aluminum micro and nanoparticles are key ingredients in the synthesis of nano energetic materials. Hence it is important to characterize the kinetics and the rate controlling process of their oxidation. The literature shows that the mass diffusion and phase transformation within the aluminum oxide shell are important. However, the description of physical processes regarding simultaneous oxidation and phase transformation is lacking. In this paper, the controlled thermogravimetric (TGA) oxidation of 40-60 nm and 1 µm Al powders is investigated at constant heating rates and under isothermal conditions, respectively, upon varying the partial pressure of oxygen. It is found that the core-shell model of homogenous oxidation is applicable to explain the TGA results when the shell does not undergo phase transformation, which predicts the apparent activation energy in good agreement with the literature data. On the other hand, the simultaneous oxidation and phase transformation is able to be addressed using the JMAK model which reveals key parameters of the rate controlling processes. Mass diffusion is indeed rate determining during the oxidation of Al micro and nanopowders while the kinetics of the reaction is fast. Unlike the micron powders, the particle size distribution has a significant effect on the shape of the oxidation curves of the nanopowders.
This paper reports on the ignition and flame propagation characteristics of aluminum/copper oxide (Al/CuO) nanothermite at different packing density, manufactured from 40 nm commercial Al and CuO nanopowders. A 3.5 W continuous wave laser was used to ignite the samples in argon at atmospheric pressure, and a high speed camera captured the flame propagation. The high speed images revealed that the fast laser heating creates significant material ablation, followed by heat transfer along the heated surface. The bulk ignition occurs near the edge of the top surface, followed by the self-sustained burning. Lightly pressed powders (90% porosity) ignited in ~0.1 ms and the burning front propagated at around 200 m/s, while the dense pellets (40–60% porosity) ignited in ~1 ms and the burning front propagated at around 10 m/s. These results indicate that the reaction mechanism changes from mass convection to heat diffusion with increasing the packing density. The ignition and burn speeds of these Al/CuO nanothermites at different equivalence ratios (ERs), along with SEM images of pre- and post-combustion, illustrate that the homogeneity of the mixture is a critical parameter for optimizing the performance. The Al rich mixtures show significantly lower ignition delays and higher burn speeds.
Summary This paper reports on the kinetics and reaction processes of 40‐nm and 1‐μm aluminum powders with water to produce hydrogen at atmospheric pressure. This reaction produces aluminum hydroxide with irregular morphologies as by‐products. It was found that the nucleation and growth of the aluminum hydroxides affect the kinetics of the reaction and thus the hydrogen production. The heat release in isothermal microcalorimetry and hydrogen production in a nonisothermal batch reactor were used to determine the rate‐determining steps of the reaction mechanism and the corresponding activation energies. Model and model‐free methods have been implemented to describe the reaction sequence between aluminum particle and water while the phase of newly produced aluminum hydroxide in the system plays an important role. The reaction of nanoaluminum particles and water, being more sensitive to temperature, goes to completion to produce bayerite, Al (OH)3 at 30°C, and boehmite, AlOOH at 50°C, whereas the microaluminum particles do not react completely and produce only bayerite at 30°C and also low‐amount boehmite at 50°C. Nevertheless, these processes exhibit two distinct and sequential stages: a kinetically controlled stage with the apparent activation energy (Ea) of 100 to 110 kJ/mol, where nucleation and growth are limited by the chemical reactions on the surface of aluminum, and a diffusion controlled stage with Ea of 44 kJ/mol for the 40‐nm Al/water reaction and 86 kJ/mol for the 1‐μm Al/water reaction, where growth is limited by the mass diffusion through the aluminum hydroxide by‐products. The separation of these two stages is more obvious under isothermal conditions. For nonisothermal conditions, two stages are overlapped, and the one with a lower Ea dominates.
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