CL-20 Molecules Research Articles

Quantitative analysis of CL-20 explosive by smartphone-based chemiluminescence method.

A new smartphone-based chemiluminescence method has been introduced for the quantitative analysis of CL-20 (Hexanitroazaisowuertzitan) explosive. The solvent mixture, oxidizer agent, and concentration of the reactants were optimized using statistical procedures. CL-20 explosive showed a quenching effect on the chemiluminescence intensity of the luminol-NaClO reaction in the solvent mixture of DMSO/H2O. A smartphone was used as a detector to record the light intensity of chemiluminescence reaction as a video file. The recorded video file was converted to an analytical signal as intensity luminescence-time curve by a written code in MATLAB software. Dynamic range and limit of detection of the proposed method were obtained 2.0-240.0 and 1.1mg⋅L-1, respectively, in optimized concentrations 1.5 × 10-3mol⋅L-1 luminol and 1.0 × 10-2mol⋅L-1 NaClO. Precursors TADB, HBIW, and TADNIW in CL-20 explosive synthesis did not show interference in measurement the CL-20 purity. The analysis of CL-20 spiked samples of soil and water indicated the satisfactory ability of the method in the analysis of real samples. The interaction of CL-20 molecules and OCl- ions is due to quench of chemiluminescence reaction of the luminol-NaClO.

Research on vibrational features of CL-20/MTNP cocrystal by terahertz spectroscopy

Cocrystals represent an effective method to manipulate the physicochemical properties of materials at a molecular level. However, understanding the relationship between their complex crystal structures and macroscopic properties is a challenge. In this paper, by using terahertz (THz) spectroscopy to characterize non-covalent interactions within crystals, the THz vibrational spectra of the CL-20/MTNP cocrystal are studied. Firstly, the THz spectra of CL-20, MTNP, and the CL-20/MTNP cocrystal are measured at room temperature. Both absorption positions and intensities of the cocrystals differ from those of their original components, confirming the unique advantage of terahertz spectroscopy in cocrystal identification. Secondly, the THz vibrational features of the three materials are calculated based on density functional theory (DFT). Then, the experimental absorptions are matched with the calculated vibrations. Furthermore, a vibrational decomposition method is employed to decompose the molecular vibrations into intermolecular and intramolecular vibrations. The vibrational variations of the cocrystal compared with its original components are analyzed. The results reveal that in the cocrystal, the intermolecular vibrational modes of both CL-20 and MTNP molecules have changed compared with their raw materials. This indicates that the non-covalent interactions in the cocrystal have changed the original intermolecular interactions of these molecules. Consequently, this enhancement promotes the heat transfer between MTNP and CL-20 molecules, thereby improving the thermal stability of the cocrystal. These findings in this study demonstrate that the THz vibrational spectroscopy technology helps establish a relationship between the molecular structure of cocrystal and its macroscopic properties. This research contributes to deepening our understanding of cocrystal systems and opens up a new way for designing and optimizing materials.

Theoretical investigations on CL‑20/TNBA co-crystal explosive via density functional method and molecular dynamics method

The study of CL-20 co-crystal has always been a focal point within the field of energetic material modification. In this study, we employed the density functional method and molecular dynamics method to investigate the properties of hexanitrohexaazaisowurtzitane (CL-20)/ 2,4,6-trinitro-3-bromoanisole (TNBA) with different molar ratios ranging from 9:1–1:9. This investigation encompassed surface electrostatic potential, atomic interaction line, binding energy, trigger bond length, radial distribution function, cohesive energy density, and mechanical properties. Additionally, EXPLO-5 software was utilized to predict the detonation properties and products of pure CL-20, TNBA, and CL-20/TNBA systems. The results revealed significant differences in the surface electrostatic potential between CL-20 and TNBA molecules, indicating stronger interactions between different molecules than between identical molecules and suggesting the potential for co-crystal formation. At the molar ratio of 5:5, the binding energy was found to be the highest, signifying the most likely formation of a co-crystal. The main driving forces for co-crystal formation were electrostatic force and van der Waals force. The co-crystal explosive exhibited moderate sensitivity and excellent mechanical properties. Furthermore, the co-crystal detonation performance at a molar ratio of 5:5 was between that of CL-20 and TNBA, representing a new type of insensitive high-energy material.

Theoretical investigations on CL-20/ANTA co-crystal explosive via molecular dynamics method.

The study of CL-20 co-crystal has always been a focal point within the field of energetic material modification. In this study, we employed a combination of density functional theory and molecular dynamics simulations to investigate the properties of hexanitrohexaazaisowurtzitane (CL-20)/3-amino-5-nitro-1,2,4-triazole (ANTA) with different molar ratios ranging from 4:1 to 1:4. Additionally, EXPLO-5 software utilized to predict the detonation properties and products of pure CL-20, ANTA, and CL-20/ANTA systems. The results revealed that there was an interaction between CL-20 and ANTA molecules, which had the potential to form a co-crystal. The most likely molar ratio for co-crystal formation was 1:1, and the main driving forces for co-crystal formation were electrostatic force, dispersion force, and van der Waals force. The co-crystal explosive exhibited moderate sensitivity and excellent mechanical properties. Furthermore, the co-crystal detonation performance at a molar ratio of 1:1 was between that of CL-20 and ANTA, representing a new type of insensitive high-energy material. The properties of CL-20/ANTA co-crystal were predicted by molecular dynamics (MD) method under Materials Studio software. For the whole MD simulations, set the temperature at 298 K, and the pressure was 0.0001 GPa. Conducted MD simulation under the NPT ensemble for a total simulation duration of 1 ns. The first 0.5 ns was used for thermodynamic equilibrium, and the last 0.5 ns was used for statistical calculation and analysis. Sampling was recorded every 10 fs during the calculation.

Enhanced Thermal Decomposition and Safety of Spherical CL-20@MOF-199 Composites via Micro-Nanostructured Self-Assembly Regulation.

The characteristics of high burning rate, high energy output, and low pressure exponent have always been the focus of development in the field of composite solid rocket propellants. In this paper, a metal-organic framework (MOF-199) compound is introduced to prepare micro-nanospherical CL-20@MOF-199 composites via the spray-drying self-assembly technique to reach the above goals. MOF-199, which acts as an attractive combustion catalyst and a safety regulator, is uniformly coated on the surface of CL-20 with close interface contact between particles, effectively accelerating the thermal decomposition of CL-20 and ensuring safety performance. The average noncovalent interaction (aNCI) analysis illustrates that there are strong C-H···O hydrogen bonds and van der Waals interaction between CL-20 and MOF-199 molecules, greatly enhancing the effect of interparticle assembly. The effects of different contents of MOF-199 on the thermal, safety, and energy properties of CL-20 were discussed. The thermal analysis demonstrates that MOF-199 has a significant thermal catalytic effect on CL-20, with an advanced peak temperature of thermal decomposition of 14.2 °C and a reduced activation energy barrier of 34.2 kJ·mol-1, mainly benefitting from more exposed catalytic active sites and close interface contact. In addition, CL-20@MOF-199 composites exhibit decreased mechanical sensitivity (IS: 21-40 cm, FS: 80-240 N) and excellent energy performance. This work clearly demonstrates that MOF-199 is both a superior combustion catalyst and a good safety buffer for CL-20, and it opens new potential for further applications of CL-20 in composite solid propellants.

Molecule Dynamics Simulation of the Effects of Temperature and Vacancy Defects on the Eutectic Sensitivity of CL-20_TNT

For contemporary applications, CL-20’s energy density is the highest of any explosive, but it has a very high susceptibility and very low stability. Eutectic techniques can successfully lower CL-20’s susceptibility. However, the eutectic susceptibility can be significantly impacted by the high temperature and many flaws found in its manufacture. By removing CL-20 molecules in Materials Studio (MS) using a molecular dynamics approach, a CL-20/TNT eutectic model with various vacancy concentrations was created in this study. Equilibrium state simulations of the model were run at various temperatures to determine the corresponding kinetic parameters. The susceptibility of CL-20/TNT eutectic-containing vacancy defects is found to increase with the increase in defect concentration and with the increase in temperature, which guides the study of CL-20’s stability and the reduction of susceptibility methods in engineering preparation. Cohesive energy density and binding energy are used at the molecular level as the evaluation criteria of the susceptibility at the macroscopic level.

Self-assembly Hybridization of CL-20 and Hydrazone-based Polymeric Carbon Nitrides for High Performance Explosive

A strategy for desensitization of the highly sensitive explosive CL-20 with polymeric carbon nitrides is described. The hybrid energetic material (MHGP-CL-20) was synthesized via a self-assembly approach, where CL-20 molecules are immobilized on the hydrazone-based polymeric carbon nitrides. The good detonation performances (detonation velocity 9608 m·s−1, detonation pressure 42.8 GPa) show that MHGP-CL-20 retains the excellent performance of CL-20 to the greatest extent. More importantly, its sensitivities were effectively reduced with the impact sensitivity (IS) 10 J and the friction sensitivity (FS) 160 N, which is much lower compared with raw ε-CL-20 (IS: 4 J; FS: 94 N). In addition, its specific impulse was improved to 276.6 s, higher than that of ε-CL-20 (272.4 s). By preparing solid composite propellants, the burning rate of the propellant grain PMC20 based on MHGP-CL-20 is higher than PC20 based on ε-CL-20. The addition of hybrid energetic complex could keep the stability of combustion and improve the burning rate of solid propellant. The combination of PCNs material and CL-20 sustains the excellent performance of CL-20 and reduces the sensitivity effectively. The preparation of hybrid energetic material MHGP-CL-20 finds a new balance in the contradictory system of high energy and low sensitivity.

Molecular dynamics simulation of polymorphic transformation between ε-CL-20 and β-CL-20 by short range order and orientational order parameter

Phase transition simulation of molecular crystals is a challenge. In order to clarify the polymorphic transformation mechanism of molecular crystal, a molecular dynamics (MD) simulation of the transformation between ε-CL-20 and β-CL-20 was carried out by the short range order g(r) and local orientational order parameter (OPs) P2(cosθ) as well as the spatial orientation correlation function. The effects of the temperature on them were performed. The results indicate that the g(r), orientational OPs and spatial orientation correlation function, composed of the structural parameters from three CL-20 molecules in three different single crystal, could be used to simulate the process of the polymorphic transformation between ε-CL-20 and β-CL-20. Only at a high temperature, could two kinds of the CL-20 supercells realize the transformation of crystal form. Furthermore, there were local and global minimum energy points, indicating that there could be the metastable or stable crystal forms in the process of the transformation from β-CL-20 to ε-CL-20. The values of P2(cosθ) were well related to results of the surface electrostatic potentials (ESPs), suggesting that the ESPs have an influence on polymorphic transformation.

Isothermal structural evolution of CL-20/HMX cocrystals under slow roasting at 190 °C.

As a new type of energetic material, cocrystal explosives demonstrate many excellent properties, such as high energy density and low sensitivity, due to the interaction between the molecules of the two components. The known decomposition temperature is 235 °C for CL-20/HMX cocrystals at a faster heating rate. CL-20 molecules could separate from the cocrystal matrix and decompose at a higher temperature, much lower than the decomposition temperature. The current work provided deep insight into the isothermal structural evolution of CL-20/HMX cocrystals with slow roasting at 190 °C. We found that the initial decomposition originates from separating CL-20 molecules from the surface along the (010) plane of the cocrystals. The gas products, such as NO2 and NO, escape from the largest exposed surface of the (010) plane and generates microbubbles and microholes. At the same time, the residual HMX molecules form δ-phase HMX crystals and shrink the volume by 72%. By increasing the time held at 190 °C, the decomposition of CL-20 molecules and recrystallization of the residual HMX molecules form a gully-like structure on the (010) plane of the CL-20/HMX cocrystal. After a long time at 190 °C, the CL-20 component completely decomposes, and all HMX molecules recrystallize in the δ-HMX form. The interaction between HMX and CL-20 molecules makes the decomposition rate of the CL-20/HMX cocrystal much slower than that of the CL-20 pure crystal with a similar decomposition activation energy during isothermal heating. This work can help to deeply understand the safety of CL-20/HMX cocrystal explosives at a temperature lower than the recognized decomposition temperature.

Reaction mechanism and electronic properties of host-guest energetic material CL-20/HA under high pressure by quantum-based molecular dynamics simulations.

The novel host-guest material 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)/hydroxylamine (HA) improves the detonation energy of CL-20 explosives without compromising its safety. However, the reaction mechanism of CL-20/HA under high pressure is not yet fully understood for the complex host-guest structure. A multiscale shock simulation technique by quantum-based molecular dynamics was performed to investigate the reaction mechanism of CL-20/HA under shock with different velocities along different directions, focusing on charge transfer, electronic properties, reaction path and product evolution. The structural changes caused by both insertion of HA and charge overlap between CL-20 and HA are responsible for the electronic changes and gap decrease. Directional charge transfer was observed between CL-20 and HA molecular fragments during shock in all shock loading directions, causing the CL-20 molecular group to become electrically non-neutral. The C-N bond in the CL-20 cage then broke, leading to the release of nitro and nitrous oxide at high temperatures and pressures. The HA molecules or free H atoms from HA could bond with the O atom in the nitro group, leading to the N-O bond cleavage. Some free H atoms could act as an intermediary, connecting two CL-20 molecules and forming dimeric molecules briefly. Compared with the pure CL-20 system, HA can inhibit the reaction of CL-20 in the CL-20/HA system to some extent during the initial shock stage. A further understanding of the chemical reaction mechanism and energy release in dense host-guest materials can be advanced by focusing on the microscopic internal effects of the guest molecule on the host molecule reactions.

Energy and Electronic Properties of Nanostructures Based on the CL-20 Framework with the Replacement of the Carbon Atoms by Silicon and Germanium: A Density Functional Theory Study.

We consider SinCL-20 and GenCL-20 systems with carbon atoms replaced by silicon/germanium atoms and their dimers. The physicochemical properties of the silicon/germanium analogs of the high-energy molecule CL-20 and its dimers were determined and studied using density functional theory with the B3LYP/6-311G(d,p) level of theory. It was found that the structure and geometry of SinCL-20/GenCL-20 molecules change dramatically with the appearance of Si-/Ge-atoms. The main difference between silicon- or germanium-substituted SinCL-20/GenCL-20 molecules and the pure CL-20 molecule is that the NO2 functional groups make a significant rotation relative to the starting position in the classical molecule, and the effective diameter of the frame of the systems increases with the addition of Si-/Ge-atoms. Thus, the effective framework diameter of a pure CL-20 molecule is 3.208 Å, while the effective diameter of a fully silicon-substituted Si6CL-20 molecule is 4.125 Å, and this parameter for a fully germanium-substituted Ge6CL-20 molecule is 4.357 Å. The addition of silicon/germanium atoms to the system leads to a decrease in the binding energy. In detail, the binding energies for CL-20/Si6CL-20/Ge6CL-20 molecules are 4.026, 3.699, 3.426 eV/atom, respectively. However, it has been established that the framework maintains stability, with an increase in the number of substituting silicon or germanium atoms. In addition, we designed homodesmotic reactions for the CL-20 molecule and its substituted derivatives Si6CL-20/Ge6CL-20, and then determined the strain energy to find out in which case more energy would be released when the framework breaks. Further, we also studied the electronic properties of systems based on CL-20 molecules. It was found that the addition of germanium or silicon atoms instead of carbon leads to a decrease in the size of the HOMO–LUMO gap. Thus, the HOMO–LUMO gaps of the CL-20/Si6CL-20/Ge6CL-20 molecules are 5.693, 5.339, and 5.427 eV, respectively. A similar dependence is also observed for CL-20 dimers. So, in this work, we have described in detail the dependence of the physicochemical parameters of CL-20 molecules and their dimers on the types of atoms upon substitution.

Theoretical Studies on the Role of Guest in α-CL-20/Guest Crystals

The contradiction between energy and safety of explosives is better balanced by the host–guest inclusion strategy. To deeply analyze the role of small guest molecules in the host–guest system, we first investigated the intermolecular contacts of host and guest molecules through Hirshfeld surfaces, 2-D fingerprint plots and electrostatic interaction energy. We then examined the strength and nature of the intermolecular interactions between CL-20 and various small molecules in detail, using state-of-the-art quantum chemistry calculations and elaborate wavefunction analyses. Finally, we studied the effect of the small molecules on the properties of CL-20, using density functional theory (DFT). The results showed that the spatial arrangement of host and guest molecules and the interaction between host and guest molecules, such as repulsion or attraction, may depend on the properties of the guest molecules, such as polarity, oxidation, hydrogen content, etc. The insertion of H2O2, H2O, N2O, and CO2 had significant influence on the electrostatic potential (ESP), van der Waals (vdW) potential and chemical bonding of CL-20. The intermolecular interactions, electric density and crystal orbital Hamilton population (COHP) clarified and quantified the stabilization effect of different small molecules on CL-20. The insertion of the guest molecules improved the stability of CL-20 to different extents, of which H2O2 worked best.

Roles of Small Molecules in the Stability and Sensitivity of CL-20-Based Host-Guest Explosives under Electric Fields: A Reactive Molecular Dynamics Study.

Host-guest inclusion, constructed by inserting small molecules into voids of energetic crystals, is a novel strategy for creating new energetic materials (EMs) with desired energy and safety. To provide an atomistic-level insight into the fact that small guest molecules can effectively regulate the stability and sensitivity of CL-20, we conducted ReaxFF-lg reactive molecular dynamics simulations on electric-field (EF)-induced decomposition of two typical host-guest EMs, CL-20/H2O2 and CL-20/N2O, and compared it to that of α-CL-20 and ε-CL-20. Our findings show that the sensitivity order of the CL-20-based EMs under EFs, α-CL-20/H2O2 > ε-CL-20 > α-CL-20 > α-CL-20/N2O, agrees well with the sensitivity obtained from the experiment (ε-CL-20 > α-CL-20 > α-CL-20/N2O). Different effects of H2O2 and N2O molecules were found responsible for the distinct stability and sensitivity of these materials toward EFs. On the one hand, H2O2 accelerate(s) the structural transformation of CL-20 and thus increases the sensitivity, because the wobbling NO2 group reduces the stability of CL-20 by weakening its adjacent C-N bonds, whereas N2O makes this transition less likely, resulting in low sensitivity of α-CL-20/N2O. On the other hand, H2O2 and its decomposition intermediate OH radical can promote destruction of CL-20's cage structure and produce a large amount of water molecules to release heat, making CL-20/H2O2 to decompose faster than ε-CL-20. N2O molecules rarely react with CL-20 molecules but absorb heat from the surrounding decomposed CL-20 and thus slow down CL-20's decomposition, resulting in low sensitivity of α-CL-20/N2O, as confirmed by transition-state calculations. The results provide a comprehensive understanding of the stability and sensitivity of CL-20-based host-guest explosives under EFs.

The role of electric field on decomposition of CL-20/HMX cocrystal: A reactive molecular dynamics study.

Electric field can initiate decomposition or detonation of explosives, but underlying mechanism is unclear. Here, we performed ReaxFF molecular dynamics simulation for decomposition of a cocrystal, formed by 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX), solely induced by electric field. A new analytical method was proposed to obtain detailed decomposition mechanism. Results show that electric fields play important roles in decomposition of CL-20/HMX cocrystal, such as heating the system and causing the explosive to decompose. Strong constant field makes CL-20 molecules in the cocrystal decompose at significantly lower temperature, which greatly increases sensitivity. This is ascribed to the distinct decomposition mechanism that CN bond rupture dominates the initial step of CL-20's decomposition. Contrarily, oscillating field has a stronger heating effect but weaker influence on sensitivity. Moreover, HMX exhibits desensitizing effect in CL-20/HMX cocrystal under electric field. These results enhance our understanding of sensitivity mechanism beyond mechanical stimuli in explosives.

External electric field induced structural transformation and decreased sensitivity of CL-20/EPDM composites

We reported molecular dynamics studies of the effect of external electric field on CL-20/EPDM composites. The results show that CL-20 molecules transformed from ε phase into α phase at 0.6 V/Å. The results indicate that external electric field could reduce N-NO2 trigger bond length, enhance hydrogen bonding interactions, increase cohesive energy density, decrease potential energies and improve the mechanical properties, thereby improving the thermodynamics stability of energetic systems. The results suggest external electric field can effectively reduce sensitivity and improve thermodynamics stability of CL-20/EPDM systems. Our results shed light on improving performances of energetic systems by external electric field.

Investigation on Adsorption and Decomposition Properties of CL-20/FOX-7 Molecules on MgH2(110) Surface by First-Principles.

Metal hydrides are regarded as promising hydrogen-supplying fuel for energetic materials while CL-20 (Hexanitrohexaazaisowurtzitane) and FOX-7 (1,1-Diamino-2,2-dinitroethylene) are typical principal components commonly used in energetic materials. Hence, it is interesting to explore the interactions between them for development of new energetic systems. In this paper, the adsorption and decomposition of CL-20 or FOX-7 molecules on the MgH2 (110) crystal surface were investigated by employing the First-Principles. In total, 18 adsorption configurations for CL-20/MgH2 (110) and 12 adsorption configurations for FOX-7/MgH2 (110) were considered. The geometric parameters for the configurations, adsorption energies, charge transfer, density of states, and decomposition mechanism were obtained and analyzed. In most of the configurations, chemical adsorption will occur. Moreover, the orientation of the nitro-group in CL-20 or FOX-7 with regard to the MgH2 (110) surface plays an important role on whether and how the energetic molecule decomposes. The adsorption and decomposition of CL-20 or FOX-7 on MgH2 could be attributed to the strong charge transfer between Mg atoms in the first layer of MgH2 (110) surface and oxygen as well as nitrogen atoms in the nitro-group of CL-20 or FOX-7 molecules.

Study on phonon spectra and heat capacities of CL-20/MTNP cocrystal and co-formers by density functional theory method.

The phonon spectra and heat capacities of 2, 4, 6, 8, 10, 12-hexanitrohexaazaisowurtzitane/1-methyl-3, 4, 5-trinitropyrazole (CL-20/MTNP) cocrystal and co-formers were calculated in the framework of DFT. By analyzing the phonon density of states (DOS), the energy flow directions and trigger bonds of cocrystal and co-formers have been obtained and the microscopic physical nature was revealed for thermal decomposition mechanism, detonation performance, and sensitivity. For CL-20/MTNP cocrystal, the phonon number of "doorway" modes and the characteristic vibrational frequencies Δωd are between those of its co-formers, which can provide the microscopic understanding for the ordering of impact sensitivity at experiment, ε-CL-20 > CL-20/MTNP > MTNP. In CL-20/MTNP cocrystal, more phonons and stronger phonon DOS peaks of CL-20 molecules than those of MTNP molecules mean cocrystal's detonation performance is mainly dominated by CL-20 molecules. The heat capacities obtained by the Debye model rise with elevated temperatures at 0-600K and the order is ε-CL-20 > CL-20/MTNP > MTNP. Graphical abstract The phonon spectra and heat capacities of CL-20/MTNP cocrystal and co-formers were calculated by density functional theory (DFT). In CL-20/MTNP cocrystal, the detonation performance and impact sensitivity are mainly dominated by CL-20 molecules. The broken bonds caused by energy transfer may undergo a multi-phonon pumping process.

Effect of solvent mixture on the formation of CL-20/HMX cocrystal explosives.

2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)/1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) cocrystal is widely concerned due to its high safety and low sensitivity. A CL-20/HMX-solution interface model was constructed to investigate the effect of solvent mixture on cocrystal morphology. The interface models of different solvent mixtures were simulated by molecular dynamics (MD) and quantum chemistry (QC) methods at room temperature. The analyses of binding energy show that CL-20 and HMX molecules are easier to be adsorbed on the cocrystal surface in the presence of solvent mixture dimethyl sulfoxide (DMSO)/acetonitrile (ACN). Mass density distribution and diffusion coefficient analyses demonstrated that the growth of CL-20/HMX cocrystal will be freer in DMSO/ACN. Cooperativity effect analysis shows that the CL-20 binding to HMX is tighter in the presence of DMSO/ACN and the system is more stable. Our findings may provide some guidelines for preparing cocrystal in solvent mixture. Graphical abstract.

Theoretical calculation into the structures, stability, sensitivity, and mechanical properties of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12 hexaazai-sowurtzitane (CL-20)/1-amino-3-methyl-1,2,3-triazoliumnitrate (1-AMTN) cocrystal and its mixture

Molecular dynamics (MD) simulation was conducted to research the effect of temperature (200–350 K) on the thermal stability, sensitivity, and mechanical properties of 1-AMTN (1-amino-3-methyl-1,2,3-triazoliumnitrate), CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazai-sowurtzitane), cocrystal, and composite explosive. The binding energy, the maximum trigger bond length ($$ {L}_{N-{NO}_2} $$), and cohesive energy density (CED), as well mechanical properties of the pure CL-20, 1-AMTN, cocrystal, and composite, were got and contrasted. The results demonstrate that temperature has a great influence on the binding capacity between CL-20 and 1-AMTN molecules in the cocrystal. The binding energies decrease with the rising temperature and the cocrystal has larger values than those of mixture. The $$ {L}_{N-{NO}_2} $$of all models increases and the CEDs decrease with the rising temperature, demonstrating that their sensitivities increase. While the $$ {L}_{N-{NO}_2} $$ values of cocrystals are all smaller than those of CL-20 and the CED values are all between those of CL-20 and 1-AMTN, indicating that the sensitivity has been reduced through co-crystallization. The mechanical properties of all models have an evident downtrend. Simultaneously, the tensile modulus (E), bulk modulus (K), and shear modulus (G) values of the cocrystal model are between those of CL-20 and 1-AMTN at the same temperature, thus co-crystallization can weaken the brittleness and enhance the ductility of CL-20. Compared with the mixture, the cocrystal has better ductility and stability.

Molecular Dynamics Simulations of an Initial Chemical Reaction Mechanism of Shocked CL-20 Crystals Containing Nanovoids

To understand the initial chemical reaction mechanism of the heterogeneous explosive hexanitrohexaazaisowurtzitane (CL-20), it is necessary to study the shock initiation mechanism of this nanovoid-containing crystal. In this paper, supercells of CL-20 with different void sizes were constructed. The chemical reactions induced by different impact velocities were calculated using molecular dynamics based on the ReaxFF-lg reactive force field. The effects of impact velocities and void sizes on the chemical reactions of the CL-20 crystal were discussed. The initial reaction of CL-20 molecules around the voids was analyzed, and the evolution of the formation and breakage of chemical bonds as well as the elementary reactions were also obtained. It is found that under an impact, the CL-20 molecules around the voids first undergo polymerization of the N–O bonds and then breakage of the C–N, N–N, and C–H bonds occurs. Increased void size and impact velocity lead to higher temperature “hot spots” and more intense chemical reactions, but have little effect on the breaking sequence of chemical bonds in the CL-20 molecules.