Theoretical investigations into effects of adulteration crystal defect on properties of HMX by molecular dynamics method

  • Gui-Yun HangEmail author
  • Wen-Li Yu
  • Tao Wang
  • Jin-Tao Wang
Regular Article


To investigate the influences of adulteration crystal defect on properties of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), the primitive crystal model and defective crystal models of HMX with different adulteration ratios (crystal defect ratios) of hexahydro-1,3,5-trinitro-1,3,5-triazine molecules were established. The structures were optimized, and the sensitivity, detonation performance, and mechanical properties of crystal models were predicted through molecular dynamics method. The trigger bond length distribution, interaction energy of trigger bond, cohesive energy density, detonation parameters, and mechanical properties of each crystal model were calculated and compared. The results show that compared with the “perfect” model, the trigger bond length of defective models is increased by 0.33–5.94%, while the interaction energy of trigger bond is decreased by 0.94–13.01%, and cohesive energy density is decreased by 0.82–9.91%, indicating that sensitivity is increased and safety is worsened. The density, detonation velocity, detonation pressure, and detonation heat of defective models are decreased by 0.21–5.87%, 0.17–4.52%, 0.44–11.64%, and 0.15–1.84%, respectively, meaning that the power and energetic performance are weakened. Owing to the influence of adulteration crystal defect, tensile modulus, bulk modulus, and shear modulus are decreased by 0.421–4.930 GPa, 0.194–2.777 GPa, and 0.181–2.042 GPa, respectively, while Cauchy pressure is increased by 0.072–1.373 GPa, illustrating that the rigidity and stiffness of defective HMX crystals are lessened, while the ductility is improved.


Crystal defect Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) Sensitivity Detonation performance Mechanical properties Molecular dynamics 



  1. 1.
    Sewell TD, Menikoff R (2003) A molecular dynamics simulation study of elastic properties of HMX. J Chem Phys 119:7417–7426CrossRefGoogle Scholar
  2. 2.
    Stevens LL, Eckhardt CJ (2005) The elastic constants and related properties of β-HMX determined by Brillouin scattering. J Chem Phys 122:174701CrossRefGoogle Scholar
  3. 3.
    Bedrov D, Smith GD, Sewell TD (2000) Thermal conductivity of liquid octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from molecular dynamics simulations. Chem Phys Lett 324:64–68CrossRefGoogle Scholar
  4. 4.
    Zhu WH, Xiao JJ, Ji GF, Zhao F, Xiao HM (2007) First-principles study of the four polymorphs of crystalline octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. J Phys Chem B 111:12715–12722CrossRefGoogle Scholar
  5. 5.
    Long Y, Chen J (2014) A molecular dynamics study of the early-time mechanical heating in shock-loaded octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine-based explosives. J Appl Phys 116:033516CrossRefGoogle Scholar
  6. 6.
    Chang SC, Henry PB (1970) A study of the crystal structure of β-cyclotetramethylene tetranitramine by neutron diffraction. Acta Crystallogr B 26:1235–1240CrossRefGoogle Scholar
  7. 7.
    Cady HH, Larson AC, Cromer DT (1963) The crystal of α-HMX and a refinement of the structure of β-HMX. Acta Crystallogr 16:617–623CrossRefGoogle Scholar
  8. 8.
    Kuklja MM, Kunz AB (1999) Simulation of defects in energetic materials. 3. The structure and properties of RDX crystals with vacancy complexes. J Phys Chem B 103:8427–8431CrossRefGoogle Scholar
  9. 9.
    Zhou TT, Huang FL (2011) Effects of defects on thermal decomposition of HMX via ReaxFF molecular dynamics simulations. J Phys Chem B 115:278–287CrossRefGoogle Scholar
  10. 10.
    Mathew N, Picu CR, Chung PW (2013) Peierls stress of dislocations in molecular crystal cyclotrimethylene trinitramine. J Phys Chem A 117:5326–5334CrossRefGoogle Scholar
  11. 11.
    Xue XG, Wen YS, Long XP, Li JS, Zhang CY (2015) Influence of dislocations on the shock sensitivity of RDX: molecular dynamics simulations by reactive force field. J Phys Chem C 119:13735–13742CrossRefGoogle Scholar
  12. 12.
    Luscher DJ, Addessio FL, Cawkwell MJ, Ramos KJ (2017) A dislocation density-based continuum model of the anisotropic shock response of single crystal α-cyclotrimethylene trinitramine. J Mech Phys Solids 98:63–86CrossRefGoogle Scholar
  13. 13.
    Sun H, Ren PJ, Fried R (1998) The COMPASS force field: parameterization and validation for phosphazenes. Comput Theor Polym Sci 8:229–246CrossRefGoogle Scholar
  14. 14.
    Michael JM, Sun H, Rigby D (2004) Development and validation of COMPASS force field parameters for molecules with aliphatic azide chains. J Comput Chem 25:61–71CrossRefGoogle Scholar
  15. 15.
    Xiao JJ, Huang H, Li JS, Zhang H, Zhu W, Xiao HM (2008) A molecular dynamics study of interface interactions and mechanical properties of HMX-based PBXs with PEG and HTPB. J Mol Struct Theochem 851:242–248CrossRefGoogle Scholar
  16. 16.
    Xiao JJ, Zhu W, Ma XF, Xiao HM, Huang H, Li JS (2008) A novel model for the molecular dynamics simulation study on mechanical properties of HMX/F2311 polymer-bonded explosive. Mol Simul 34:775–779CrossRefGoogle Scholar
  17. 17.
    Qiu L, Xiao HM (2009) Molecular dynamics study of binding energies, mechanical properties, and detonation performances of bicyclo-HMX-based PBXs. J Hazard Mater 164:329–336CrossRefGoogle Scholar
  18. 18.
    Xu XJ, Xiao JJ, Huang H, Li JS, Xiao HM (2010) Molecular dynamic simulations on the structures and properties of ε-CL-20(0 0 1)/F2314 PBX. J Hazard Mater 175:423–428CrossRefGoogle Scholar
  19. 19.
    Nosé S (1984) A unified formulation of the constant temperature molecular dynamics methods. J Chem Phys 81:511–519CrossRefGoogle Scholar
  20. 20.
    Parrinello M, Rahman A (1981) Polymorphic transitions in single crystals: a new molecular dynamics method. J Appl Phys 52:7182–7190CrossRefGoogle Scholar
  21. 21.
    Allen MP, Tildesley DJ (1987) Computer simulation of liquids. Oxford University Press, OxfordGoogle Scholar
  22. 22.
    Ewald PP (1921) Evaluation of optical and electrostatic lattice potentials. Ann Phys 64:253–287CrossRefGoogle Scholar
  23. 23.
    Zhu W, Xiao JJ, Zhu WH, Xiao HM (2009) Molecular dynamics simulations of RDX and RDX-based plastic-bonded explosives. J Hazard Mater 164:1082–1088CrossRefGoogle Scholar
  24. 24.
    Xu XJ, Xiao HM, Xiao JJ, Zhu W, Huang H, Li JS (2006) Molecular dynamics simulations for pure ε-CL-20 and ε-CL-20-based PBXs. J Phys Chem B 110:7203–7207CrossRefGoogle Scholar
  25. 25.
    Qiu L, Zhu WH, Xiao JJ, Zhu W, Xiao HM, Huang H, Li JS (2007) Molecular dynamics simulations of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin-based polymer-bonded explosives. J Phys Chem B 111:1559–1566CrossRefGoogle Scholar
  26. 26.
    Xiao JJ, Wang WR, Chen J, Ji GF, Zhu W, Xiao HM (2012) Study on the relations of sensitivity with energy properties for HMX and HMX-based PBXs by molecular dynamics simulation. Phys B 407:3504–3509CrossRefGoogle Scholar
  27. 27.
    Hang GY, Yu WL, Wang T, Wang JT, Li Z (2017) Theoretical insights into the effects of molar ratios on stabilities, mechanical properties, and detonation performance of CL-20/HMX cocrystal explosives by molecular dynamics simulation. J Mol Model 23:30CrossRefGoogle Scholar
  28. 28.
    Murray JS, Lane P, Politzer P (1995) Relationships between impact sensitivities and molecular surface electrostatic potentials of nitroaromatic and nitroheterocyclic molecules. Mol Phys 85:1–8CrossRefGoogle Scholar
  29. 29.
    Murray JS, Concha MC, Politzer P (2009) Links between surface electrostatic potentials of energetic molecules, impact sensitivities and C-NO2/N-NO2 bond dissociation energies. Mol Phys 107:89–97CrossRefGoogle Scholar
  30. 30.
    Politzer P, Murray JS (2015) Impact sensitivity and maximum heat of detonation. J Mol Model 21:262CrossRefGoogle Scholar
  31. 31.
    Hu XH, Chen NN, Li WC (2016) A method for fast safety screening of explosives in terms of crystal packing and molecular stability. J Mol Model 22:170CrossRefGoogle Scholar
  32. 32.
    Zhu W, Wang XJ, Xiao JJ, Zhu WH, Sun H, Xiao HM (2009) Molecular dynamics simulations of AP/HMX composite with a modified force field. J Hazard Mater 167:810–816CrossRefGoogle Scholar
  33. 33.
    Xiao JJ, Zhao L, Zhu W, Chen J, Ji GF, Zhao F, Wu Q, Xiao HM (2012) Molecular dynamics study on the relationships of modeling, structural and energy properties with sensitivity for RDX-based PBXs. Sci China Chem 55:2587–2594CrossRefGoogle Scholar
  34. 34.
    Sun T, Xiao JJ, Liu Q, Zhao F, Xiao HM (2014) Comparative study on structure, energetic and mechanical properties of a ε-CL-20/HMX cocrystal and its composite with molecular dynamics simulation. J Mater Chem A 2:13898–13904CrossRefGoogle Scholar
  35. 35.
    Xiao JJ, Li SY, Chen J, Ji GF, Zhu W, Zhao F, Wu Q, Xiao HM (2013) Molecular dynamics study on the correlation between structure and sensitivity for defective RDX crystals and their PBXs. J Mol Model 19:803–809CrossRefGoogle Scholar
  36. 36.
    Liu DM, Xiao JJ, Chen J, Ji GF, Zhu W, Zhao F, Wu Q, Xiao HM (2013) MD simulation on the structure and properties of different models for HMX crystal. Chin J Energ Mater 21:765–770Google Scholar
  37. 37.
    Liu DM, Xiao JJ, Zhu W, Xiao HM (2013) Sensitivity criterion and mechanical properties prediction of PETN crystals at different temperatures by molecular dynamics simulation. Chin J Energ Mater 21:563–569Google Scholar
  38. 38.
    Liu Q, Xiao JJ, Chen J, Ji GF, Zhu W, Zhao F, Wu Q, Xiao HM (2014) Molecular dynamics simulation on sensitivity and mechanical properties of ε-CL-20 crystal at different temperatures. Chin J Explos Propellants 37:7–12Google Scholar
  39. 39.
    Liu Q, Xiao JJ, Zhang J, Zhao F, He ZH, Xiao HM (2016) Molecular dynamics simulation on CL-20/TNT cocrystal explosive. Chem J Chin Univ 37:559–566Google Scholar
  40. 40.
    Zhu W, Liu DM, Xiao JJ, Zhao XB, Zheng J, Zhao F, Xiao HM (2014) Molecular dynamics study on sensitivity criterion, thermal expansion and mechanical properties of multi-component high energy systems. Chin J Energ Mater 22:582–587Google Scholar
  41. 41.
    Kamlet MJ, Adoiph HG (1979) The relationship of impact sensitivity with structure of organic high explosives. Propellants Explos Pyrotech 4:30–34CrossRefGoogle Scholar
  42. 42.
    Mullay J (1987) Relationship between impact sensitivity and molecular electronic structure. Propellants Explos Pyrotech 12:121–124CrossRefGoogle Scholar
  43. 43.
    Brill BT, James JK (1993) Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives. Chem Rev 93:2667–2692CrossRefGoogle Scholar
  44. 44.
    Guo YX, Zhang HS (1983) Nitrogen equivalent (NE) and modified nitrogen equivalent (MNE) equations for predicting detonation parameters of explosives-prediction of detonation velocity of explosives. Explos Shock Waves 3:56–66Google Scholar
  45. 45.
    Hang GY, Yu WL, Wang T, Wang JT, Li Z (2017) Comparative studies on structures, mechanical properties, sensitivity, stabilities and detonation performance of CL-20/TNT cocrystal and composite explosives by molecular dynamics simulation. J Mol Model 23:281CrossRefGoogle Scholar
  46. 46.
    Pugh SF (1954) Relations between the elastic moduli and the plastic properties of polycrystalline pure metals. Philos Mag 45:823–843CrossRefGoogle Scholar
  47. 47.
    Pettifor DG (1992) Theoretical predictions of structure and related properties of intermetallics. Mater Sci Technol 8:345–349CrossRefGoogle Scholar
  48. 48.
    Wu JL (1993) Mechanics of elasticity. Tongji University Press, ShanghaiGoogle Scholar
  49. 49.
    Weiner JH (1983) Statistical mechanics of elasticity. Wiley, New YorkGoogle Scholar
  50. 50.
    Watt JP, Davies GF, O’Connell RJ (1976) The elastic properties of composite materials. Rev Geophys Space Phys 14:541–563CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Gui-Yun Hang
    • 1
    Email author
  • Wen-Li Yu
    • 1
  • Tao Wang
    • 1
  • Jin-Tao Wang
    • 1
  1. 1.Xi’an Research Institute of High-TechXi’anPeople’s Republic of China

Personalised recommendations