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High-Energy Nitramine Explosives: A Design Strategy from Linear to Cyclic to Caged Molecules.

Junqing Yang1, Guixiang Wang2, Xuedong Gong2

  • 1State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China.

ACS Omega
|August 29, 2019
PubMed
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New nitramine explosives were designed and studied. Caged compound IIIA2 shows comparable energetic properties to CL-20 but with improved sensitivity and thermal stability, suggesting limitations in linear chain elongation for explosives.

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Area of Science:

  • Computational Chemistry
  • Materials Science
  • Energetic Materials

Background:

  • Established explosives like RDX, HMX, and CL-20 serve as benchmarks.
  • The Kamlet-Jacobs (K-J) equations provide a theoretical framework for predicting explosive performance.
  • Understanding structure-property relationships is crucial for designing advanced energetic materials.

Purpose of the Study:

  • To design and computationally investigate novel nitramine explosives with varying molecular architectures.
  • To evaluate the impact of structural modifications, including linear, cyclic, and caged motifs, on energetic properties.
  • To identify promising candidates with enhanced performance and safety characteristics compared to existing explosives.

Main Methods:

  • Density Functional Theory (DFT) calculations using B3LYP/6-31G* and B3PW91/6-31G** methods.
  • Design of diverse nitramine molecular models (IA, IB, IC, II, IIIA, IIIB) incorporating -CH2NNO2 units.
  • Analysis of energetic parameters including density, detonation velocity, and detonation pressure.

Main Results:

  • Energetic parameters followed the order: IIIBn > IIIA > II > IAn > IBn > ICn.
  • Increasing chain length (n) in linear nitramines led to stable or diminishing detonation properties.
  • Oxygen balance and K-J parameter ϕ significantly influenced detonation performance.
  • Caged compound IIIA2 exhibited comparable energetic properties to CL-20, with superior sensitivity and thermal stability.

Conclusions:

  • Elongating linear nitramine chains offers limited benefits for explosive performance.
  • Caged nitramine structures, like IIIA2, present a promising avenue for developing next-generation energetic materials.
  • IIIA2 demonstrates a favorable balance of energetic output, sensitivity, and thermal stability, outperforming CL-20 in key safety aspects.