1,3,5,7-Tetranittro-1,3,5,7-tetrazocaneMitrocellulose (HMX/NC) nanocomposites were successfully synthesized by an improved sol-gel-supercritical method. NC nanoparticles with a size of 30 nm were cross-linked to form a network structure, and HMX nanoparticles were imbedded in the nano-NC matrix. The key factors, i.e., the selection of catalyst and solvent, were probed. No phase transformation of the HMX occurred before or after fabrication, and the molecular structures of the HMX and NC did not change. Thermal analyses were performed, and the kinetic and thermodynamic parameters, such as activation energy (EK), per-exponent factor (InA(kappa)), rate constant (k), activation heat (Delta H-not equal), activation free energy (Delta G(not equal)), activation entropy (Delta S-not equal), critical temperature of thermal explosion (T-b), and critical heating rate of thermal explosion (dT/dt)(Tb), were calculated. The results indicate that HMX/NC presented a much lower activation energy (165.03 kJ/mol) than raw HMX (282.5 kJ/mol) or raw NC (175.51 kJ/mol). The chemical potential (Delta G(not equal)) for the thermal decomposition of HMX/NC has a positive value, which means that the activation of the molecules would not proceed spontaneously. The significantly lower Delta H-not equal value of HMX/NC, which represents the heat needed to be absorbed by an explosive molecule to change it from its initial state to an activated state, implies that the molecules of HMX/NC are much easier to be activated than those of raw HMX. Similarly, the HMX/NC presented a much lower T-b (168.2 degrees C) than raw HMX (283.2 degrees C). From the results of the sensitivity tests, the impact and friction sensitivities of HMX/NC were significantly decreased compared with those of raw HMX, but the thermal sensitivity was distinctly higher. The activation of the particles under external stimulation was simulated, and the mechanism was found to be crucial. Combining the thermodynamic parameters, the mechanism as determined from the results of the sensitivity tests was discussed in detail. (C) 2016 Elsevier B.V. All rights reserved.