Theoretical Studies on the Thermodynamic Properties and Detonation Performances of Bicyclic Nitramines:TNAD Isomers

Ab initio molecular orbital calculations have been performed at Hartree-Fock （HF）, second-order Mrller-Plesset （MP2）, and hybrid density functional theory （DFT） B3LYP levels with 6-31G^＊＊ basis set to investigate the low sensitive explosive trans-1,4,5,8-tetranitro-1,4,5,8- tetraazadecalin （TNAD） and its seven bicyclic isomers. Their molecular geometries, electronic structures, thermodynamic properties, and detonation performances were predicted and compared. The relationships between structures and various properties were discussed in detail. The calculated results agree well with the available experimental data, and suggest that some compounds may be novel potential candidates of high energy density materials （HEDMs） with performances better than TNT （2,4,6-trinitrotoluene） and similar to RDX （1,3,5-trinitro-1,3,5-triazacyclohexane）.

Intermolecular Interactions, Thermodynamic Properties, Detonation Performance, and Sensitivity of TNT/CL-20 Cocrystal Explosive

Intermolecular interactions and properties of TNT（2,4,6-trinitrotoluene）/CL-20（2,4,6,8,10,12-hexanitrohexaazaisowurtzitane） cocrystal were studied by density functional theory（DFT） methods. Binding energy, natural bond orbital（NBO）, and atom in molecules（AIM） analysis were performed to investigate the intermolecular interactions in the cocrystal. Results show that the unconventional CH···O type hydrogen bond plays a key role in forming the cocrystal. The variation tendency of entropy and enthalpy shows that the formation of the cocrystal is an exothermic process and low temperature will be benefit for the assembling of complexes. The calculated detonation velocity of the cocrystal agrees well with the experimental value which is higher than that of the physical mixture of TNT and CL-20. In addition, bond dissociation energies（BDEs） of the weakest trigger bond in TNT/CL-20 complex were calculated and the results show that the TNT/CL-20 complex is thermally stable. Finally, first-principles calculations were performed and analysis of the nitro group Mulliken charge indicates that the cocrystal is less sensitive than pure CL-20.

Calculating detonation performance of explosives by VLWR thermodynamics code introduced with universal VINET equation of state

Thermodynamic calculation is the theoretical basis for the study of initiation and detonation,as well as the prerequisite for forecasting the detonation performance of unknown explosives.Based on the VLWR(Virial-Wu)thermodynamic code,this paper introduced the universal solid equation of state(EOS)VINET.In order to truly reflect the compressibility of nanocarbon under the extremely high-temperature and high-pressure environment in detonation,an SVM(support vector machine)was utilized to optimize the input parameters of carbon.The detonation performance of several explosives with different densities was calculated by the optimized universal EOS,and the results show that the thermodynamic code coupled with the universal solid EOS VINET can predict the detonation performance parameters of explosives well.To investigate the application of the thermodynamic code with the improved VINET EOS in the working capacity of explosives,the interrelationship between pressure P-particle velocity u and pressure P-volume V were computed for the detonation products of TNT and HMX-based PBX(HMX:binder:insensitive agent=95:4.3:0.7)in the CJ isentropic state.A universal curve proposed by Cooper was used to compared the computed isentropic state,where the ratio of pressure to CJ state were plotted against the ratio of velocity to CJ state.The parameters of the JWL(Jones-Wilkins-Lee)EOS for detonation products were obtained by fitting the P-V curve.The cylinder tests of TNT and HMX-based PBX were numerically simulated using the LS-DYNA,it is verified that,within a certain range,the improved algorithm has superiority in describing the working capacity of explosives.

Analysis on damage characteristics and detonation performance of solid rocket engine charge subjected to jet

To further explore the damage characteristics and impact response of the shaped charge to the solid rocket engine(SRE) in storage or transportation, protective armor was designed and the shelled charges model(SCM)/SRE with protective armor impacting by shaped charge tests were conducted. Air overpressures at 5 locations and axial acceleration caused by the explosion were measured, and the experimental results were compared with two air overpressure curves of propellant detonation obtained by related scholars. Afterwards, the finite element software AUTODYN was used to simulate the SCM impacted process and SRE detonation results. The penetration process and the formation cause of damage were analyzed. The detonation performance of TNT, reference propellant, and the propellant used in this experiment was compared. The axial acceleration caused by the explosion was also analyzed.By comprehensive comparison, the energy released by the detonation of this propellant is larger, and the HMX or Al particles contained in this propellant are more than the reference propellant, with a TNT equivalent of 1.168-1.196. Finally, advanced protection armor suggestions were proposed based on the theory of woven fabric rubber composite armor(WFRCA).

Direct ink writing of 3D-Honeycombed CL-20 structures with low critical size

3D-Honeycombed CL-20 structures with low critical size of detonation have been fabricated successfully for intelligent weapon systems using a micro-flow direct ink writing(DIW) technology.The CL-20-based explosive ink for DIW technology was prepared by a two-component adhesive system with waterborne polyurethane(WPU) and ethyl cellulose(EC).Not only the preparation of the explosive ink but also the principle of DIW process have been investigated systematically.The explosive ink displayed stro ng shea rthinning behavior that permitted layer-by-laye r deposition from a fine nozzle onto a substrate to produce complex shapes.The EC content was varied to alter the pore structure distribution and rheological behavior of ink samples after curing.The deposited explosive composite materials are of a honeycombed structure with high porosity,and the pore size distribution increases with the increase of EC content.No phase change was observed during the preparation process.Both WPU and EC show good compatibility with CL-20 particles.Apparently high activation energy was realized in the CL-20-based composite ink compared with that of the refined CL-20 due to the presence of non-energetic but stable WPU.The detonation performance of the composite materials can be precisely controlled by an adjustment in the content of binders.The 3D honeyco mbed CL-20 structures,which are fabricated by DIW technology,have a very small critical detonation size of less than 69 μm,as demonstrated by wedge shaped charge test.The ink can be used to create 3D structures with complex geometries not possible with traditional manufacturing techniques,which presents a bright future for the development of intelligent weapon systems.

Energetic materials based on poly furazan and furoxan structures

Furazan and furoxan represent fascinating explosophoric units with intriguing structures and unique properties.Compared with other nitrogen-rich heterocycles,most poly furazan and furoxan-based heterocycles demonstrate superior energetic performances due to the higher enthalpy of formation and density levels.A large variety of advanced energetic materials have been achieved based on the combination of furazan and furoxan moieties with different kinds of linkers and this review provides an overview of the development of energetic poly furazan and furoxan structures during the past decades,with their physical properties and detonation characteristics summarized and compa red with traditional energetic materials.Various synthetic strategies towards these compact energetic structures are highlighted by covering the most important cyclization methods for construction of the hetercyclic scaffolds and the following modifications such as nitrations and oxidations.Given the synthetic availabilities and outstanding properties,energetic materials based on poly furazan and furoxan structures are undoubtedly listed as a promising candidate for the development of new-generation explosives,propellants and pyrotechnics.

Theoretical Study on the High Energy Density Compound Hexanitrohexaazatricyclotetradecanedifuroxan

Density functional theory （DFT） has been employed to study the molecular geometries, electronic structures, infrared （IR） spectra, and thermodynamic properties of the high energy density compound hexanitrohexaazatricyclotetradecanedifuroxan （HHTTD） at the B3LYP/6-31G^＊＊ level of theory. The calculated results show that there are four conformational isomers （α, β, γ and δ） for HHTTD, and the relative stabilities of four conformers were assessed based on the calculated total energies and the energy-gaps between the frontier molecular orbitals. The computed harmonic vibrational frequencies are in reasonable agreement with the available experimental data. Thermodynamic properties derived from the IR spectra on the basis of statistical thermodynamic principles are linearly correlated with the temperature. Detonation performances were evaluated by using the Kamlet-Jacobs equations based on the calculated densities and heats of formation. It was found that four HHTTD isomers with the predicted densities of ca. 2 g·cm^-3, detonation velocities near 10 km·s^-1, and detonation pressures over 45 GPa, may be novel potential candidates of high energy density materials （HEDM）. These results may provide basic information for the molecular design of HEDM.

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Density functional theory (DFT) method has been employed to study the effect of nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct the polycyclic or caged nitra-mines. Molecular structures were investigated at the B3LYP/6-31G** level, and isodesmic reactions were designed for calculating the group interactions. The results show that the group interactions ac-cord with the group additivity, increasing with the increasing number of nitroamino groups. The dis-tance between substituents influences the interactions. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the predicted densities and heats of formation, while thermal stability and pyrolysis mechanism were studied by the computations of bond dissociation energy (BDE). It is found that the contributions of nitroamino groups to the detonation heat, detonation velocity, detonation pressure, and stability all deviate from the group additivity. Only 3a, 3b, and 9a-9c may be novel potential candidates of high energy density materials (HEDMs) according to the quantitative cri-teria of HEDM (ρ ≈ 1.9 g/cm3, D ≈ 9.0 km/s, P ≈ 40.0 GPa). Stability decreases with the increasing number of N-NO2 groups, and homolysis of N-NO2 bond is the initial step in the thermolysis of the title com-pounds. Coupled with the demand of thermal stability (BDE > 20 kcal/mol), only 1,2,4-trinitrotriazacy-clohexane and 1,2,4,5-tetranitrotetraazacyclohexane are suggested as feasible energetic materials. These results may provide basic information for the molecular design of HEDMs.

Bridged Effects of Various Heterocyclic Linkages in Bis-1,2,4-triazoles

There are numerous studies on nitrogen-rich heterocycles explosive design and synthesis due to their good detonation activity.A series of bistriazoles with different heterocyclic linkages were designed and calculated by density functional theory(DFT)b3 lyp/6-311+G^(*)method.The structure,detonation properties and stability of the energetic compounds have been investigated.According to the results from heats of formation(HOFs),the HOF values of bistriazole with heterocycle linkage(M1~M4)are higher than those of the corresponding diamino-heterocycle bridged ones(M5~M8).By analyzing the bond dissociation energy(BDE),-NH-is not conducive to increase the stability of the derivatives.In terms of detonation performances and stability of bistriazole derivatives,the combination of furazan or tetrazole linkages with bis-triazoles may be considered as potential candidates for energetic materials.

Are the Nitro-and Amino-substituted Piperidine High-energy-density Compounds?

Nitro and amino groups were introduced into piperidine skeleton to design derivatives of piperidine(labeled asα,β1,β2,β3,γandδ).Heats of formation(HOFs)are calculated in detail at the B3PW91/6-311+G(d,p)level for these aminonitropiperidines.The results show that all derivatives have negative heats of formation,which were affected by the positions of substituted groups.The molecular stability is estimated and analyzed based on bond dissociation energies(BDE)and characteristic heights(H50).All derivatives designed in this paper are confirmed with lower impact sensitivity than 1,3,5-trinitro-1,3,5-triazinane(RDX)and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX).Furthermore,the detonation velocities(D)and the detonation pressures(P)are predicted via the Kamlet-Jacobs equation.In all these molecules,δhas comparable detonation character with that of RDX and HMX and can be the candidate of high-energy-density compounds(HEDCs).