The ignition and combustion property of solid propellant is the main content in internal ballistic research, which has a great significance for propulsion application and combustion mechanism. In this study, the detailed gas‐phase reaction mechanism of Nitrate Ester Plasticized Polyether Propellant (NEPE) was developed. It is helpful to understand the intricate processes of solid‐propellant combustion. The factors which may have influences on ignition delay time and temperature distribution of propellant surface was analyzed by laser ignition experiment. Using high‐speed camera and an infrared thermometer, the ignition and combustion process and the surface temperature distribution of NEPE propellant under laser irradiation were measured. Laser heat flux, ambient pressure and initial temperature of NEPE propellant have an influence on the ignition delay time and the surface temperature. Results show that the ignition delay time decreases with the increase of laser heat flux, ambient pressure and initial temperature of NEPE propellant. At the same time, with the increase of laser heat flux, the influences of ambient pressure and initial temperature on the ignition delay time decrease. Besides, laser irradiation, ambient pressure and initial temperature have significant influences on the surface temperature distribution of the propellant.

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