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In the present work, a green synthesis of copper oxide nanoparticles (CuO NPs) has been performed through a precipitation method using three different copper precursors and sylvestrys leaf extract as a capping agent. Morphology and structure of the obtained CuO NPs were confirmed by X‐ray diffraction (XRD), ultraviolet‐visible (UV/Vis), Fourier transform infrared (FT‐IR) and Raman spectroscopy, as well as scanning electron microscopy (SEM). Moreover, their thermal behavior and catalytic performance were studied using thermogravimetry (TG) and differential scanning calorimetry (DSC). Four isoconversional kinetic methods have been applied to the DSC data obtained at different heating rates in order to determine the kinetic triplets. The results showed that the introduction of CuO NPs has noticeably lowered the thermal decomposition temperature by 91.7, 89.9, and 83.0 °C, and increased the exothermic enthalpy by 1053, 832, and 962 J·g–1 for AP‐CuO‐S, AP‐CuO‐N, and AP‐CuO‐Cl, respectively. Furthermore, CuO NPs were found to reduce the activation energy of AP decomposition. Besides that, ammonium perchlorate decomposes following different reaction models g(α), depending on the decomposition stage and the addition of CuO NPs. These results indicate further that the green synthesized CuO nanoparticles are promising ballistic modifiers for composite solid propellants.

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