The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H2O, O2, Cl2, N2O and HCl, and is shown to occur in the solid phase within the AP particles. 200(micro) diameter AP particles undergo 25% decomposition in the solid phase, whereas 20(micro) diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH3 + HClO4 followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.