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  • 1 Semenov Institute of Chemical Physics, Russian Academy of Science, Moscow, Russia
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Abstract

This study deals with a well-known monocyclic nitramine HMX and a relatively new polycyclic strained-cage nitramine CL-20. Experimental data on the powder morphology, simultaneous thermal analysis (STA) and burning rate of binary formulations Al/HMX and Al/CL-20 are presented. Kinetic modelling for HMX and CL-20 are considered based on analysis of STA data obtained for low heating rates. The processing of STA data by the Kissinger method was shown to need to be supplemented with the construction of a thermokinetic model. The thermal decomposition of HMX is reliably described by the reaction of the first order with the autocatalysis. Obtained kinetic parameters of the HMX thermal decomposition correlate with literature-known data on kinetics of the lead stage of HMX combustion. Two types of aluminium powder, i.e. micron-sized and ultrafine, are used to investigate the interaction with both nitramines. Thermal analysis revealed the higher Al oxidation ability of the solid compounds produced at CL-20 thermolysis, than that one of HMX. Burning rate experiments show the differences in the combustion parameters between CL-20- and HMX-based formulations, specifically along with the burn rate level increase for CL-20 monopropellant as compared to HMX one, the pressure exponent and effect of the aluminium particle size variation are also distinct. Results are analyzed and compared to available literature data.

  • 1. Nielsen AT . Synthesis of polynitropolyaza caged nitramines chemical propulsion information agency; 1987, Publication no. 473.

  • 2. Lobbecke S , Bohn MA, Pfeil A, et al. Thermal behavior and stability of HNIW (CL 20). In: Proceedings of the 29th International Annual Conferrence on ICT, Karlsruhe; 1998. p. 145/1145/15.

    • Search Google Scholar
    • Export Citation
  • 3. Kimura, J, Kubota, N. Thermal decomposition process of HMX. Propell Expl Pyrotech. 1980;5: 1 18. .

  • 4. Brill, TB, Gongwer, PE, Williams, GK. Thermal decomposition of energetic materials 66. Kinetic compensation effects in HMX, RDX and NTO. J Phys Chem. 1994;98: 47 1224212247. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Constable, FH. The mechanism of catalytic decomposition. Proc R Soc Lond. 1925;108:355378. .

  • 6. Gallagher, PK, Johnson, DW. Kinetics of the thermal decomposition of CaCo3 in Co2 and some observations on the kinetic compensation effect. Thermochim Acta. 1976;14:255261. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Dollimore, D, Rodgers, PF. The appearance of a compensation effect in the thermal decomposition of manganese(II) carbonates, prepared in the presence of other metal ions. Thermochim Acta. 1979;30: 1 273280. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Leffler, JE, Grunwald, E. Rates and equilibria of organic reactions. New York: Wiley; 1963.

  • 9. Vyazovkin, S, Wight, CA. Kinetics in solids. Annu Rev Phys Chem. 1997;48:125149. .

  • 10. Muravyev N , Frolov Yu, Ordzhonikidze O, et al. Particle size and mixing technology influence on combustion of HMX/Al compositions. In: Proceedings of the 36th International Pyrotechnic Seminar, Rotterdam; 2009. p. 43.

    • Search Google Scholar
    • Export Citation
  • 11. Bulusu, S, Behrens, RA. Review of the thermal decomposition pathways in RDX, HMX and other closely related cyclic nitramines. Def Sci J. 1996;46: 5 347360.

    • Search Google Scholar
    • Export Citation
  • 12. Geetha, M, Nair, UR, Sarwade, DB, et al. Studies on CL-20: the most powerful high energy material. J Therm Anal Calorim. 2003;73:913922. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Melius, SF. Thermochemical modeling: II. Application to ignition and combustion of energetic materials Bulusu, S, eds. Chemistry and physics of energetic materials. Boston: Kluwer; 1990 5178.

    • Search Google Scholar
    • Export Citation
  • 14. Shaw, R, Walker, FE. Estimated kinetics and thermochemistry of some initial unimolecular reactions in the thermal decomposition of l,3,5,7-Tetranitro-l,3,5,7-tetraazacyclooctane in the gas phase. J Phys Chem. 1977;81:25722576. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Kissinger, HE. Reaction kinetics in differential thermal analysis. J Anal Chem. 1957;29: 11 17021706. .

  • 16. Pinheiro, GFM, Lourenco, VL, Iha, K. Influence of the heating rate in the thermal decomposition of HMX. J Therm Anal Calorim. 2002;67:445452. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Brill, TB, Karpowicz, RJ. Solid phase transition kinetics: the role of intermolecular forces in the condensed-phase decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. J Phys Chem. 1982;86: 21 42604265. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Tarver, CM, Tran, TD. Thermal decomposition models for HMX-based plastic bonded explosives. Combust Flame. 2004;137: 1–2 5062. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Korsounskii, BL, Nedelko, VV, Chukanov, NV, et al. Kinetics of thermal decomposition of hexanitrohexazaisowurtzitane. Russ Chem Bull. 2000;49: 5 812818. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Sinditskii, VP, Egorshev, VY, Serushkin, VV, et al. Evaluation of decomposition kinetics of energetic materials in the combustion wave. Thermochim Acta. 2009;496: 1–2 112. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Zeldovich, YB. Theory of combustion of propellants and explosives. Zh Eksp Teor Fiz. 1942;12: 11–12 498524.

  • 22. Sinditskii, VP, Egorshev, VY, Berezin, MV, et al. Study on combustion of energetic cyclic nitramines. Zh Khim Fiz. 2003;22: 7 6469.

    • Search Google Scholar
    • Export Citation

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