This work provides a lab-scale investigation of the ballistics of solid fuel formulations based on hydroxyl-terminated polybutadiene and loaded with Al-based energetic additives. Tested metal-based fillers span from micron- to nano-sized powders and include oxidizer-containing fuel-rich composites. The latter are obtained by chemical and mechanical processes providing reduced diffusion distance between Al and the oxidizing species source. A thorough pre-burning characterization of the additives is performed. The combustion behaviors of the tested formulations are analyzed considering the solid fuel regression rate and the mass burning rate as the main parameters of interest. A non-metallized formulation is taken as baseline for the relative grading of the tested fuels. Instantaneous and time-average regression rate data are determined by an optical time-resolved technique. The ballistic responses of the fuels are analyzed together with high-speed visualizations of the regressing surface. The fuel formulation loaded with 10 wt.% nano-sized aluminum (ALEX-100) shows a mass burning rate enhancement over the baseline of 55% ± 11% for an oxygen mass flux of 325 ± 20 kg/(m2
∙s), but this performance increase nearly disappears as combustion proceeds. Captured high-speed images of the regressing surface show the critical issue of aggregation affecting the ALEX-100-loaded formulation and hindering the metal combustion. The oxidizer-containing composite additives promote metal ignition and (partial) burning in the oxidizer-lean region of the reacting boundary layer. Fuels loaded with 10 wt.% fluoropolymer-coated nano-Al show mass burning rate enhancement over the baseline >40% for oxygen mass flux in the range 325 to 155 kg/(m2
∙s). The regression rate data of the fuel composition loaded with nano-sized Al-ammonium perchlorate composite show similar results. In these formulations, the oxidizer content in the fuel grain is <2 wt.%, but it plays a key role in performance enhancement thanks to the reduced metal–oxidizer diffusion distance. Formulations loaded with mechanically activated ALEX-100–polytetrafluoroethylene composites show mass burning rate increases up to 140% ± 20% with metal mass fractions of 30%. This performance is achieved with the fluoropolymer mass fraction in the additive of 45%.
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