Investigation on the Thermal Expansion of Four Polymorphs of Crystalline CL-20

Abstract

The thermal expansion behaviors of α-CL-20 · 1/2H2O, anhydrous α-, β-, ε-, and γ-CL-20 crystals have been investigated by means of variable-temperature X-ray powder diffraction (XRD) together with Rietveld refinement. The results show that hexanitrohexaazaisowurtane (CL-20) with four polymorphs exhibits linear thermal expansion. The ε phase performs approximately isotropic expansion in the temperature range of 30 to 130°C, but α, β, and γ phases exhibit anisotropic expansion in the temperature ranges of 30 to 130°C, 30 to 120°C, and 30 to 180°C, respectively. The different expansion behaviors are due to the different structures of the four polymorphs. The different thermal expansion behaviors of α-CL-20 · 1/2H2O and anhydrous α are revealed in this work. The a-axis expansion of α-CL-20 · 1/2H2O exhibits a switch from positive thermal expansion (PTE) to negative thermal expansion (NTE) at 90°C, whereas the a-axis of anhydrous α is resilient to PTE. The cause is the loss of the structural water. Moreover, it is easily found that the b-axis of the γ phase shows a constriction that may be attributed to the distortion of the six-membered ring.