Massive Preparation of Reduced-Sensitivity Nano CL-20 and Its Characterization

Nano 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) was produced massively by ball milling. One thousand grams of the raw CL-20 were used per batch. The product was characterized using laser granularity measurement, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The results show that the pulverized particles were pseudo-spheres with an average particle size (d₅₀) of 200 nm, and the thermal decomposition peak temperature of the nano CL-20 was 239.61°C lower than that of the micrometer-sized CL-20 at a heating rate of 15°C · min^?1. Furthermore, compared with the raw CL-20, the impact and friction sensitivities of the nano CL-20 were considerably reduced by 116.2 and 22%, respectively, indicating the great improvement in safety of CL-20.     

Computational Study of Picric Acid and Potassium Picrate

ABSTRACT

The density functional theory (DFT) method at the B3LYP/6-311 + g** level was used for predicting the structures, natural bond orbital (NBO) atomic charges, thermodynamic properties, and IR spectroscopy of picric acid (PA) and potassium picrate (PP). The IR spectroscopies were assigned. The C–NO₂ bond is generally lengthier than all the other covalent bonds in both PA and PP, indicating that this bond is the weakest and prone to rupture in the decomposition process. The carbon atom that connects with oxygen atom in PP carries larger positive charges, and nitro oxygen atoms carry larger negative charges than the corresponding atoms in PA. The C–C populations of PP are more unevenly distributed than those of PA, indicating that the benzene ring of the former is less conjugated. Some C–C bonds in PP are much weaker. This weak C–C bond could be ruptured at the same time as the C–N bond in the initial decomposition process.     

Synthesis and Thermal Decomposition Mechanism of the Energetic Compound 3,5-Dinitro-4-nitroxypyrazole

A novel energetic material, 3,5-dinitro-4-nitroxypyrazole (DNNP), was synthesized via nitration and nucleophilic substitution reaction using 4-chloropyrazole as raw material. The structure of DNNP was characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and elemental analysis. Its detonation properties were calculated and compared with those of other commonly used energetic compounds. The thermal decomposition mechanism of DNNP was studied by means of thermogravimetry and differential scanning calorimetry coupled with a mass spectrometry (DSC-MS). The results show that the detonation properties of DNNP were better than those of TNT and comparable to those of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). In addition, the thermal decomposition mechanism of DNNP was supposed. Initially, the O–NO₂ bond was broken, thereby producing a nitropyrazole oxygen radical. Subsequently, the nitropyrazole oxygen radical was decomposed by free radical cleavage of nitro or isomerized to nitritepyrazole and subsequently decomposed by free radical cleavage of the nitroso group. Finally, pyrazole ring fission occurred and produced N₂, NO, N₂O, and CO₂.     

Kinetics and mechanism of the thermal decomposition of dimethylnitramine at low temperatures

Abstract

Dimethylnitramine (DMNA) was pyrolyzed between 466 and 524 K at about 475 Torr pure DMNA pressure in static cells. A radical mechanism was proposed and computer-modeled to account for the disappearance of DMNA and the production of (CH₃)₂NNO and CH₃NO₂. The rate constant for DMNA decomposition into (CH₃)₂N and NO₂, based on these low-temperature results and other high-temperature shock tube data, covering 460–960 K, can be given by k₁ = 10^15.9±0.2 exp(?22,000±200/T) sec^?1. This result leads to values for the N-N bond energy of 43.3±0.5 kcal/mole and the heat of formation of the (CH₃)₂N radical, 35±2 kcal/mole at 298 K. Kinetic modeling of the CH₃NO₂ and (CH₃)₂NNO production profiles has been carried out.     

GAP/CL-20-Based Compound Explosive: A New Booster Formulation Used in a Small-Sized Initiation Network

With ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and glycidyl azide polymer (GAP) as the solid filler and binder, respectively, GAP/CL-20-based compound explosives were designed and prepared. Using micro injection charge technology, the compound explosives were packed into small grooves to explore their application in a small-sized initiation network. The detonation reliability, detonation velocity, mechanical sensitivity, shock sensitivity, and brisance of the explosive were measured and analyzed. The results show that when the solid content of CL-20 is 82 wt%, the explosive charged in the groove has a smooth surface from a macroscopic view. From a microscopic view, a coarse surface is bonded with many CL-20 particles by GAP binder. The GAP/CL-20-based explosive charge successfully generates detonation waves in a groove larger than 0.6 mm × 0.6 mm. When the charge density in the groove is 1.68 g·cm^?3 (90% theoretical maximum density), the detonation velocity reaches 7,290 m·s^?1. Moreover, this kind of explosive is characterized by low impact and shock sensitivity.     

Heteropolyacids: An Efficient Catalyst for Synthesis of CL-20

CL-20, a high-energy material with a cage-like structure, is considered the most powerful explosive today. It is usually prepared via nitration with concentrated nitric and sulfuric acid, but this technique pollutes the environment. In this article, CL-20 was synthesized by nitration of 2,6,8,12-tetraacetyl 2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0^3,11,0^5,9]dodecane (TAIW) using a clean nitrating agent, heteropolyacids. Using the new nitrating agent caused the elimination of concentrated sulfuric acid during the reaction. This is an environmentally friendly technique.     

Theoretical Studies on 4-amino-3,5-dinitropyrazole and Its Analogues

Seven analogues of a new high-energetic material, 4-amino-3,5-dinitropyrazole (LLM-116), were designed through changing NH₂ or NO₂ groups on the pyrazole ring of LLM-116. Density functional theory studies on LLM-116 and its analogues were performed at the B3LYP/6-31G(d) level. The geometric and electronic structures, natural bond orbital, charge on the nitro group (-Q_NO2 ), density, detonation properties, and bond dissociation energies (BDEs) of these molecules were investigated and compared with LLM-116. The results showed that molecules E , F , and G had comparable performance with better insensitivity characteristics and might be potential candidates of powerful energetic materials.     

Synthesis and Characterization of a New Co-Crystal Explosive with High Energy and Good Sensitivity

A new energetic co-crystal consisting of one of the most powerful explosive molecules 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and the military explosive cyclotrimethylenetrinitramine (RDX) was prepared with a simple solvent evaporation method. Scanning electron microscopy (SEM) revealed the morphology of the bar-shaped product, which differed greatly from the morphology of the individual components. Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction spectrum (XRD), and differential scanning calorimetry (DSC) proved the formation of the co-crystal at the molecular level. The result of mechanical sensitivity test indicated the sensitivity was effectively reduced compared to raw CL-20. Finally, a possible crystallization mechanism was discussed.     

Theoretical Insight into the Influences of Molecular Ratios on Stabilities and Mechanical Properties,Solvent Effect of HMX/FOX-7 Cocrystal Explosive

A molecular dynamics method was employed to study the binding energies of the selected crystal planes of the 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane/1,1-diamino-2,2-dinitroethylene (HMX/FOX-7) cocrystal in different molecular molar ratios. Mechanical properties, densities, and detonation velocities of the cocrystals in different ratios were estimated. The intermolecular interactions and bond dissociation energies (BDEs) of the N–NO₂ bond in the HMX:FOX-7 (1:1) complex were calculated using the B3LYP and MP2(full) methods at the 6–311++G (d,p) and 6–311++G(2df,2p) basis sets. Solvent effects on stability are discussed. The results indicate that HMX/FOX-7 cocrystals prefer cocrystalizing in a 1:1 molar ratio, which has good mechanical properties. The N–NO₂ bond becomes strong upon the formation of a complex and the sensitivity of HMX might decrease in cocrystals. The sensitivity change of HMX/FOX-7 originates from not only the formation of intermolecular interaction but also the increment in the N–NO₂ BDE. HMX/FOX-7 cocrystals exhibit good detonation performance and meet the requirements of high-density energetic materials. Solvents with low dielectric constants may be chosen to obtain stable HMX/FOX-7 cocrystals.     

Compatibility of 2, 4, 6, 8, 10,12-Hexanitrohexaazaisowurtzitane with a Selection of Insensitive Explosives

Thermal techniques (differential scanning calorimetry (DSC) and the vacuum stability test (VST)), according to STANAG 4147, and non-thermal techniques (Fourier transform infrared (FTIR) spectrometry and X-ray diffractometry (XRD)) were used to examine compatibility issues for 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) with a selection of insensitive explosives, including nitroguanidine (NQ), 2,4,6-trinitrotoluene (TNT), 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO), 2,4,6-triamino-1,3,5-trinitrobenzene (TATB), 3-nitro-1,2,4-triazol-5-one (NTO) and 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105). DSC measurements showed that ANPyO, TATB, NTO and LLM-105 were compatible with CL-20. The compatibility of CL-20/NQ, CL-20/TNT, CL-20/ANPyO, CL-20/TATB, CL-20/NTO and CL-20/LLM-105 mixtures was further explored using the VST, which revealed that all the selected insensitive explosives were compatible with CL-20. Possible chemical interactions were suspected for CL-20/TATB from the FTIR results and for CL-20/NTO from XRD analysis. In summary, ANPyO and LLM-105 demonstrated the optimal compatibility with CL-20.     

INTERMOLECULAR FORCES IN AGGREGATES OF ASPHALTENES AND RESINS

ABSTRACT

In order to determine the forces acting in the asphaltene and resin molecular aggregates, an analysis of the origin of the intermolecular interactions in organic molecules was made. The results showed that the forces present in the aggregates of asphaltenes and resins were only those originated in the van der Waals, Coulombic (electrostatic), charge transfer and induction plus the exchange–repulsion interaction. No other forces were found to be significant in these aggregates that are formed by molecules containing well-known atomic groups. Molecular orbital calculations in resins and model asphaltene suggested that charge transfer is small or negligible in their aggregates. Although the H bonds present could be quite strong, other intermolecular interactions should not be disregarded in the analysis of the energy of their aggregates.     

Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

The method of thermogravimetry/differential scanning calorimetry–mass spectrometry–Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N₂O and NO₂ were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N₂O and that of NO₂ during the process with an iso-concentration point of N₂O and NO₂. The dependence of the activation energy calculated by Friedman's iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.     

Theoretical Investigation of the Relationship between Impact Sensitivity and the Charges of the Nitro Group in Nitro Compounds

ABSTRACT

By means of density functional theory (DFT), the general gradient approximation method (GGA), and the Beck LYP hybrid functional and DNP basis set, nitro group Mulliken charges (Q _{NO 2} ) are calculated and defined to assess and correlate with the impact sensitivities (H ₅₀ ) of nitro compounds: very negative Q _{NO 2} and high H ₅₀ . By calculating, analyzing, and comparing, we find that Q _{NO 2} can be regarded as a structural parameter to estimate impact sensitivity and has more availability in almost all nitro compounds in contrast to the length of the C?NO ₂, N?NO ₂ , or O?NO ₂ bond R _{R ? NO 2} , molecular electrostatic potential (V _mid ), and oxygen balance (OB). At the same time, it has good reliability and accuracy even though there are some exceptions. According to the data in this paper, the compound may be sensitive (H ₅₀  ≤ 0.4 m) when its nitro group has fewer negative charges than about 0.23.     

Magnetically Recyclable Cufe2o4 Nanoparticles as an Efficient and Reusable Catalyst for the Green Synthesis of 2,4,6,8,10,12-Hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane as CL-20 Explosive Precursor

Magnetic nanoparticles of copper ferrite (CuFe₂O₄ MNPs) have been simply prepared and applied as an efficient recyclable and reusable catalyst for the green synthesis of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^5,9.0^3,11]dodecane (HBIW). The structure of the synthesized pure HBIW (recrystallization from ethanol) was confirmed by using various spectral techniques like infrared (IR), ¹H-NMR, ¹³C-NMR and some of its physical properties. The prepared catalyst was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR). In addition, CuFe₂O₄ MNPs could be reused up to seven runs without any significant loss of activity. Finally, the remarkable advantages of this method are the simple experimental procedure, shorter reaction times, simple workup, and green aspects by avoiding toxic catalysts and high yield of product.     

1-methyl-2,4,5-trinitroimidazole (MTNI), a melt-cast explosive: synthesis and studies on thermal behavior in presence of explosive ingredients

ABSTRACT

Traditionally, TNT based melt-castable explosives have been used till date. Recently, energetics communities are looking for an alternate to TNT in melt-cast formulation because of its toxicity and environmental concerns. 1-Methyl-2,4,5-trinitroimidazole (MTNI) is an insensitive high energy material and potential for use as a melt-cast high explosive formulations in place of TNT. MTNI has superior explosive performance as compared to that of TNT. Typically MTNI is synthesized starting from imidazole by step-wise nitration using strong nitric acid mixture followed by N-methylation offers poor yield. The key step involves during synthesis of MTNI is substitution of third nitro group at fifth position of 2,4-dinitroimidaziole which is limiting for its large-scale preparation. We report herein, an improved method for synthesis of MTNI from 1-methyl-2,4-Dinitroimidazole (MDNI) under different nitration conditions in good yield. Heteropoly acid (HPA) is an efficient, mild and green catalysts used as nitric acid activator. The synthesized MTNI by this method was characterized by FT-IR, NMR & elemental analysis. Thermal behavior of MTNI was determined by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ignition temperature tester. Further, the effects of thermal energy on decomposition of formulations containing MTNI with solid high explosives such as RDX & CL-20 or polymeric binders like HTPB & GAP were investigated. Thermal decomposition mechanisms of MTNI and its precursor, MDNI based on Pyrolysis-GC/MS analysis were also described.     

Application of Liquid Paraffin in Castable CL-20-Based PBX

Hydroxy-terminated polybutadiene (HTPB)/CL-20 castable explosives plasticized with liquid paraffin were processed successfully by a cast-curing method. The compatibility of liquid paraffin with CL-20, influence of liquid paraffin on CL-20 phase transition, and viscosity of the cast mixture were tested and analyzed. The thermal decomposition characteristics, thermal stability, mechanical sensitivity, and velocity of detonation (VOD) of the HTPB/CL-20 plastic-bonded explosives (PBXs) were also measured. The experimental results showed that liquid paraffin was well compatible with CL-20, and it did not have a distinct effect on the ?- to γ-phase transition of CL-20. In addition, the casting mixture was free-flowing with sufficiently low viscosity. When the content of CL-20 is 90% by weight, the measured VOD reached 8,775 m/s (density of 1.78 g/cm³), and the PBXs exhibited moderate mechanical sensitivity and good thermal stability.     

Catalyst Effects of Nanometer CuCr2O4 on the Thermal Decomposition of TEGDN Propellant

The catalyst effects of nanometer CuCr₂O₄ on the thermal decomposition of triethyleneglycol dinitrate (TEGDN) propellant were investigated using thermogravimetric analysis, differential scanning calorimetry, mass spectrometry, and Fourier transform infrared spectroscopy. The Ozawa equation and step integral equation were used to calculate the activation energy. The results showed that the thermal decomposition reaction of TEGDN propellant can be seen as two reactions. Nanometer CuCr₂O₄ added in TEGDN propellant reduced the activation energy of the second reaction step; therefore, the second reaction step was sped up. Mass spectrometry, Fourier transform infrared spectrometry and the combustion residue analysis results also supported this conclusion.     

MS/MS of energetic compounds. A collisional induced dissociation study of some polynttrobishcmocubanes

A collisional induced dissociation (CID) study was done on 3,5,5-trinitropentacyclodecane and 5,5-dinitropentacyclodecane-3-carboxylic acid using tandem high-resolution MS/MS. Fragmentation pathways were determined in the El ionization mode. It was found that fragmentation of the C-N bonds–resulting in losses of the NO₂groups–takes place before the fragmentation of the C-C bonds.