Nano-boron, as a potential high-energy additive due to its high calorific value, is widely studied in propellants, explosives, and thermites. However, the unexpected agglomeration of surface oxidation hinders its further application, especially in the casting of energetic materials. The fluorine-modified nano-boron nB@F2603 and nB@F2603@CL-20 preagglomerated microspheres were prepared by electrospray to improve the ignition and combustion reactions and the rheological properties of boron-containing casting systems. Sphericity microspheres could be obtained by controlling the voltage and propulsion rate. The morphology and elemental distribution of the microspheres were characterized by the scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffractometer (XRD). Results showed that the particle size of the microspheres ranged from 4 to 14 µm. Boron, fluorine and nitrogen were uniformly distributed on the surface of the microspheres. XRD results showed that CL-20 in nB@F2603@CL-20 microspheres was β-crystal. The thermal reaction properties were studied by differential scanning calorimetry, thermogravimetry and mass spectrometry (TG-DSC-MS), oxygen bomb calorimeter, laser ignition, and volume combustion cell test. Results showed that F2603 could significantly promote the ignition and combustion of nano-boron, causing higher energy release and pressurization rates, and lower ignition temperature. Adding CL-20 to the microspheres could also greatly promote the reaction rates and energy release. The hydrophobicity and corrosion resistance of the structures were also studied, and results showed that the preagglomerated microspheres had good stabilities. Therefore, fluorine-containing nB@F2603 and nB@F2603@CL-20 microspheres might be used in composite energetic materials, replacing nano-boron.

To enhance both the mechanical properties of hydroxyl-terminated polybutadiene (HTPB) binder and the combustion efficiency of aluminized propellants, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (OFHD) was employed as a chain extender to impart mechanical regulation to the HTPB binder. Mechanical testing showed that the mechanical properties of fluoride-modified HTPB polyurethane (FPU) were significantly improved: the peak tensile strength of the optimized samples reached 1.99 MPa, and the elongation at break attained 486%. The structural characterization of the FPUs was conducted using Fourier transform infrared (FTIR) spectroscopy. Thermogravimetry-mass spectrometer (TG-MS) analysis revealed that the initial thermal decomposition temperature of the FPU shifted from 170 °C to 162 °C, accompanied by the release of fluorine-containing fragments during decomposition. Analysis of the combustion residue indicated that the addition of OFHD can reduce the agglomeration of aluminum (Al) powder in aluminized propellants. Dynamic pressure characteristics results showed an augmented pressurization rate under argon and oxygen atmospheres, increased by 18.67% and 37.29%, respectively. Heat release tests indicated that the aluminized propellants with the addition of OFHD had a higher combustion heat, being increased by 6.57%. The binder system is expected to be applied in aluminized propellants to improve the mechanical properties and combustion efficiency of Al powder.