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Ultrasonic curing is an effective way to enhance the curing extent of composite material bonding in the aerospace industry. The non-thermal effect of ultrasonic has been revealed to improve curing efficiency. However, the mechanism of the ultrasonic non-thermal effect is still not clear. In this work, a variable activation energy model of ultrasonic curing was established by utilizing the iso-conversional method, including the activation energy of the thermal effect and activation energy of the non-thermal effect. The thermal effect caused by ultrasonic was accurately peeled off. An obvious decrease in activation energy was found from 54 kJ/mol in thermal curing to 38 kJ/mol in ultrasonic curing. The activation energy of the reaction system in ultrasonic curing was substituted into the modified Kamal autocatalytic equation, and the parameters of the ultrasonic curing kinetic model were estimated by means of an ALO algorithm. Further discussion based on in situ FTIR showed that the non-thermal effect of ultrasonic can affect the vibration strength, stability, and chemical bond energy of internal groups, but cannot cause the fracture of chemical bonds. Moreover, frontier molecular orbital analysis showed that the chemical reactivity of epoxy/amine molecules increased and the HOMO–LUMO energy gap decreased from 6.511 eV to 5.617 eV under the effect of ultrasonic. [ABSTRACT FROM AUTHOR]