Sensitivity of Energetic Materials: Theoretical Relationships to Detonation Performance and Molecular Structure

It has been known for decades that high performances for explosives (as characterized by detonation velocity D, detonation pressure P, or Gurney energy EG) are connected with high impact sensitivities, i.e., low values of the drop weight impact height h50. This trade-off is theoretically substantiated for the first time. It stems from the primary role of the amount of chemical energy evolved per atom for both performance and sensitivity. Under realistic assumptions, log(h50) increases linearly with D–4 or equivalently with P–2 or EG–1. This prediction proves consistent with experimental data for nonaromatic nitro compounds. The occurrence of different explosophores on the same molecule is suggested as a factor influencing the performance-sensitivity trade-off. Finally, it is shown that a large body of data may be explained by the present approach, which naturally integrates thermodynamic (energy content) as well as kinetic (activation energies) aspects. This model should help in designing powerful high en...

[1]  Philip F. Pagoria,et al.  High Power Explosive with Good Sensitivity: A 2:1 Cocrystal of CL-20:HMX , 2012 .

[2]  P. Politzer,et al.  Computational analysis of some properties associated with the nitro groups in polynitroaromatic molecules , 1985 .

[3]  D. Mathieu.  Simple Alternative to Neural Networks for Predicting Sublimation Enthalpies from Fragment Contributions , 2012 .

[4]  J. Murray,et al.  High Performance, Low Sensitivity: Conflicting or Compatible? , 2016 .

[5]  Feng-sheng Li,et al.  Dependence of particle morphology and size on the mechanical sensitivity and thermal stability of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. , 2008, Journal of hazardous materials.

[6]  T. Klapötke,et al.  Covalent and Ionic Insensitive High‐Explosives , 2016 .

[7]  F. Huang,et al.  Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study. , 2016, Physical chemistry chemical physics : PCCP.

[8]  A. Nichols,et al.  Analyses on the effect of hot spot density on material consumption rate , 2013 .

[9]  M. Fayer,et al.  Shocked molecular solids: Vibrational up pumping, defect hot spot formation, and the onset of chemistry , 1990 .

[10]  J. Murray,et al.  Relationships between dissociation energies and electrostatic potentials of CNO2 bonds: applications to impact sensitivities , 1996 .

[11]  Q. Bao,et al.  Preparation and Characterization of a Novel Cocrystal Explosive , 2011 .

[12]  A. Matzger,et al.  Design and Synthesis of a Series of Nitrogen-Rich Energetic Cocrystals of 5,5′-Dinitro-2H,2H′-3,3′-bi-1,2,4-triazole (DNBT) , 2015 .

[13]  R. Peng,et al.  Two important factors influencing shock sensitivity of nitro compounds: Bond dissociation energy of X-NO2 (X = C, N, O) and Mulliken charges of nitro group. , 2010, Journal of hazardous materials.

[14]  Zesheng Li,et al.  Theoretical design of highly energetic poly-nitro cage compounds , 2016 .

[15]  S. Menon,et al.  A model for hot spot formation in shocked energetic materials , 2015 .

[16]  M. Koshi,et al.  Energy transfer rates and impact sensitivities of crystalline explosives , 2003 .

[17]  Xinlu Cheng,et al.  Relationship between the Bond Dissociation Energies and Impact Sensitivities of Some Nitro‐Explosives , 2006 .

[18]  Qi Zhang,et al.  Cocrystal explosive hydrate of a powerful explosive, HNIW, with enhanced safety , 2014 .

[19]  Heming Xiao,et al.  Quantum Chemistry Derived Criteria for Impact Sensitivity , 2014 .

[20]  A. Matzger,et al.  Energetic-Energetic Cocrystals of Diacetone Diperoxide (DADP): Dramatic and Divergent Sensitivity Modifications via Cocrystallization. , 2015, Journal of the American Chemical Society.

[21]  Xinlu Cheng,et al.  Investigation of correlation between impact sensitivities and bond dissociation energies in some triazole energetic compounds , 2010 .

[22]  E. Bernstein,et al.  Sensitivity and performance of azole-based energetic materials. , 2013, The journal of physical chemistry. A.

[23]  L. Pérez-Maqueda,et al.  The Mitigation Effect of Synthetic Polymers on Initiation Reactivity of CL-20: Physical Models and Chemical Pathways of Thermolysis , 2014 .

[24]  Monica C. Concha,et al.  A possible crystal volume factor in the impact sensitivities of some energetic compounds , 2010, Journal of molecular modeling.

[25]  Muhamed Sućeska,et al.  Evaluation of Detonation Energy from EXPLO5 Computer Code Results , 1999 .

[26]  J. Field.  HOT SPOT IGNITION MECHANISMS FOR EXPLOSIVES , 1992 .

[27]  O. Takahashi,et al.  Molecular dynamics and first-principles studies of structural change in 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) in crystalline state under high pressure: Comparison of hydrogen bond systems of TATB versus 1,3-diamino-2,4,6-trinitrobenzene (DATB) , 2016 .

[28]  B. Rice,et al.  Density functional calculations of bond dissociation energies for NO2 scission in some nitroaromatic molecules , 2002 .

[29]  D. Mathieu,et al.  Impact sensitivities of energetic materials: Exploring the limitations of a model based only on structural formulas. , 2015, Journal of molecular graphics & modelling.

[30]  D. Mathieu.  Physics-Based Modeling of Chemical Hazards in a Regulatory Framework: Comparison with Quantitative Structure–Property Relationship (QSPR) Methods for Impact Sensitivities , 2016 .

[31]  Anbang Zhang,et al.  Crystal Packing of Impact-Sensitive High-Energy Explosives , 2014 .

[32]  B. Rice,et al.  A quantum mechanical investigation of the relation between impact sensitivity and the charge distribution in energetic molecules , 2002 .

[33]  Sensitivity and the available free space per molecule in the unit cell , 2011, Journal of molecular modeling.

[34]  J. Agrawal,et al.  High Energy Materials , 2010 .

[35]  W. Goddard,et al.  Anisotropic Impact Sensitivity and Shock Induced Plasticity of TKX-50 (Dihydroxylammonium 5,5′-bis(tetrazole)-,1′-diolate) Single Crystals: From Large-Scale Molecular Dynamics Simulations , 2015 .

[36]  R. Belmas,et al.  Physical Origin of Hot Spots in Pressed Explosive Compositions , 1995 .

[37]  D. Mathieu.  Toward a physically based quantitative modeling of impact sensitivities. , 2013, The journal of physical chemistry. A.

[38]  Theoretical chemical characterization of energetic materials , 2006 .

[39]  Ming Lu,et al.  Molecular Design and Property Prediction for a Series of Novel Dicyclic Cyclotrimethylene Trinitramines (RDX) Derivatized as High Energy Density Materials. , 2015, The journal of physical chemistry. A.

[40]  An alternative method for calculating gurney velocities , 1979 .

[41]  C. Storm,et al.  Sensitivity relationships in energetic materials , 1990 .

[42]  Jinshan Li.  Relationships for the impact sensitivities of energetic C-nitro compounds based on bond dissociation energy. , 2010, The journal of physical chemistry. B.

[43]  L. Fried,et al.  Design and Synthesis of Energetic Materials1 , 2001 .

[44]  A. Matzger,et al.  Cocrystals of 1,3,5,7-Tetranitro-1,3,5,7-tetrazacyclooctane (HMX) , 2012 .

[45]  X. Ju,et al.  Easy methods to study the smart energetic TNT/CL-20 co-crystal , 2013, Journal of Molecular Modeling.

[46]  D. Mathieu.  Theoretical shock sensitivity index for explosives. , 2012, The journal of physical chemistry. A.

[47]  Optimal partitioning of molecular properties into additive contributions: the case of crystal volumes. , 2007, Acta crystallographica. Section B, Structural science.

[48]  I. Borges,et al.  Topological analysis of the molecular charge density and impact sensitivy models of energetic molecules. , 2011, The journal of physical chemistry. A.

[49]  A. Devi,et al.  Computer-Aided Design of Energetic Tris(tetrazolyl)amine Derivatives and Salts , 2016 .

[50]  J. Murray,et al.  Impact sensitivity and crystal lattice compressibility/free space , 2014, Journal of Molecular Modeling.

[51]  X. Long,et al.  Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study. , 2016, The journal of physical chemistry. A.

[52]  D. Mathieu.  Prediction of Gurney Parameters Based on an Analytic Description of the Expanding Products , 2015 .

[53]  Svatopluk Zeman,et al.  Sensitivities of High Energy Compounds , 2007 .

[54]  S. J. Jacobs,et al.  Chemistry of Detonations. I. A Simple Method for Calculating Detonation Properties of C–H–N–O Explosives , 1968 .

[55]  J. Murray,et al.  Some molecular/crystalline factors that affect the sensitivities of energetic materials: molecular surface electrostatic potentials, lattice free space and maximum heat of detonation per unit volume , 2015, Journal of Molecular Modeling.

[56]  Cheng Xin-lu,et al.  Correlation between normal mode vibrations and impact sensitivities of some secondary explosives , 2007 .

[57]  D. Mathieu.  Formation Enthalpies Derived from Pairwise Interactions: A Step toward More Transferable Reactive Potentials for Organic Compounds. , 2012, Journal of chemical theory and computation.

[58]  M. B. Talawar,et al.  Advances in science and technology of modern energetic materials: an overview. , 2008, Journal of hazardous materials.

[59]  J. Murray,et al.  A relationship between impact sensitivity and the electrostatic potentials at the midpoints of CNO2 bonds in nitroaromatics , 1990 .

[60]  Chenghua Zhang,et al.  Crystal Packing of Low-Sensitivity and High-Energy Explosives , 2014 .

[61]  Shikha Gupta,et al.  Three-Tier Strategy for Screening High-Energy Molecules Using Structure–Property Relationship Modeling Approaches , 2016 .

[62]  L. Kazandjian,et al.  A Discussion of the Kamlet‐Jacobs Formula for the Detonation Pressure , 2006 .

[63]  Didier Mathieu,et al.  MATEO: a software package for the molecular design of energetic materials. , 2010, Journal of hazardous materials.

[64]  D. Mathieu,et al.  Predicting impact sensitivities of nitro compounds on the basis of a semi-empirical rate constant. , 2014, The journal of physical chemistry. A.

[65]  J. Murray,et al.  Perspectives on the crystal densities and packing coefficients of explosive compounds , 2016, Structural Chemistry.

[66]  P. Pagoria.  A Comparison of the Structure, Synthesis, and Properties of Insensitive Energetic Compounds , 2016 .