A comparative study of the thermal decomposition of naturally and artificially aged double-base propellants has been carried out at five different heating rates in a dynamic nitrogen atmosphere using differential scanning calorimetry (DSC) technique. The results show that there is only one decomposition peak on DSC curves, and this decomposition has been accelerated by ageing. The influence of the heating rate on the DSC behaviour of the propellants was verified. The kinetic parameters such as activation energy and frequency factor and the thermodynamic parameters such as the enthalpy of activation, free energy of activation and critical explosion temperature for the compounds were obtained from DSC data using non-isothermal methods proposed by Kissinger and Ozawa. On the other hand, a prediction of the in-service period by van't Hoff's equation was performed and compared with the experimental results in order to check the constancy and validity of this method. As a result, the prediction procedure used to obtain the time–temperature profile was achieved with good accordance. Copyright © 2012 John Wiley & Sons, Ltd.