In order to explore the polymorphic transition law for ε-CL-20 in composite systems, the polymorphic transition process of pure ε-CL-20 crystals stimulated by heat was investigated by the X-ray Diffraction (XRD) method, and the kinetic parameters of the polymorphic transition process were calculated (including the apparent activation energy Ea and the pre-exponential factor lnA). Meanwhile the effects of different additives on the polymorphic transition process and kinetics of ε-CL-20 were explored in detail. The experimental results showed that the ε-form tends to transform into the γ- form on heating and that the Ea and lnA for the transition process were 209.97 kJ/mol and 57.47, respectively. The first group of additives clearly promoted the polymorphic transition of ε-CL-20 and lowered the initial transition temperature and the activation energy. The second and third groups of additives inhibited the polymorphic transition of ε-CL-20 and raised the initial transition temperature and the activation energy.
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