Crystallization-Based Modification of Ammonium Perchlorate Heat Release

Composite propellants use the decomposition of crystalline oxidizers, such as ammonium perchlorate (AP), to produce oxidizing species that can combust with fuels. Controlled crystal microstructure must be leveraged to tailor reactivity to minimize the use of exotic energetic materials. This work uses meniscus-guided coating (MGC) to fabricate films of AP with a high degree of control over the AP crystal microstructure. Exploring a wide range of crystallization parameters resulted in film thickness ranging from 200 nm to 14 μm, particle size ranging from 18 to 110 μm, variable preferential orientation with respect to the substrate, and relative defect density ranging from 2.74 × 10⁵ to 6.78 × 10⁵ μm^-3. Increasing coating blade speed and substrate temperature within the MGC process shifts the preferential orientation of the AP crystals from predominantly exhibiting (002) and (210) crystal planes parallel to the substrate to (200)/(011) crystal planes parallel to the substrate. This shift in orientation is accompanied by an increase in defect density, which is shown to increase the heat release from the low-temperature decomposition regime and decrease the heat release from the high temperature regime. These results demonstrate the ability to use recrystallization, defect density control, and orientation control to tune the heat release profiles of energetic materials to augment propellant performance.