Yingxin Tan

1,1-diamino-2,2-dinitroethene (FOX-7) is a novel explosive with low sensitivity and high performance. The compatibility of FOX-7 with nine common energetic materials including hexanitrohexazaisowurtzitane (CL-20), cyclotetramethylenetetranitramine (HMX), cyclotrimethylenetrinitramine (RDX), 3,4-dinitrofurazanfuroxan (DNTF), 3-nitro-1,2,4-triazol-5-one (NTO), hexanitrostilbene (HNS-II), 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), 2,4,6-triamino-1,3,5-trinitrobenzene (TATB), and 2,4,6-trinitrotoluene (TNT) were tested by differential scanning calorimetry (DSC) and the vacuum stability test (VST) as the thermal technique and X-ray diffractometry (XRD) as a nonthermal technique. DSC measurements showed that the binary systems of FOX-7/CL-20, FOX-7/HMX, FOX-7/NTO, and FOX-7/TNT were compatible in grade of A, the systems of FOX-7 with heat-resistant explosives including HNS-II, LLM-105, and TATB were compatible as well in grade of A-B, and the binary systems of FOX-7/DNTF and FOX-7/RDX had poor compatibility. VST results indicated that FOX-7 was compatible with nine energetic materials. Besides, the compatibility results of the thermal analysis were confirmed by the XRD technique.

In order to reveal the nature of DNA cleavage by inorganic intercalator GO (graphene oxide) with cation, the cooperativity effects among the π⋯π, cation⋯π/σ and H-bonding interactions were evaluated in the cytosine⋯GO⋯Mⁿ⁺ (Mⁿ⁺ = Na⁺, Mg²⁺, Al³⁺) model systems using the M06-2X, MP2 and ω B97X-D methods with the 6-311++G(2d,p) and 6-311++G(3df,3pd) basis sets. The Mⁿ⁺⋯O (ether) and N–H⋯O interactions induce the formation of the π⋯π stacking between cytosine and GO, and the anti-cooperativity effect are dominant in controling of the aggregation process of cytosine, GO and Mⁿ⁺, which was confirmed by the AIM (atoms-in-molecules) and RDG (reduced density gradient) analyses. Furthermore, the solvent effects of H₂O weaken greatly the anti-cooperativity effects. Thus, a deduction on the DNA cleavage by GO⋯cation with the intercalation mode is put forward: due to the anti-cooperativity effect and solvent effect, the π⋯π stacking is weakened in the complexes with Na⁺ or broken in those with Mg²⁺ or Al³⁺. Then the GO⋯Mg²⁺ moiety is squeezed out from the intercalating sites, leading to an invalid cleavage of DNA, while Na⁺ or Al³⁺ is bound tightly to cytosine, with a notable DNA cleavage. This deduction was used to explain reasonably the previous experimental phenomena.

Nanoparticle-stacked 1,1-diamino-2,2-dinitroethylene (FOX-7) microspheres were successfully prepared by spray-drying, and rod-shaped FOX-7 was obtained by the solvent/nonsolvent method for comparison. The microstructure features of samples were characterized using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD), and the thermal properties were also investigated by differential scanning calorimetry (DSC). From the SEM analysis, the particle size of the rod-shaped FOX-7 is about 10 μm, whereas FOX-7 microspheres having a particle size ranging from 1 to 5 μm are formed by stacking nanoparticles with size of 100-250 nm. The crystal form of the samples prepared by the two methods did not change. The thermal performance test results showed that the rd-shaped FOX-7 had no significant change compared with the raw FOX-7, while the nanoparticle-stacked FOX-7 microspheres had higher thermal stability.

To improve the safety of ammonium nitrate explosives, the melamine urea-formaldehyde resin (MUF resin) was selected for the preparation of three typical nitramine explosives (cyclotetramethylenetetranitramine, HMX; cryclo-trimethylenetrinitramine, RDX; and hexanitrohexaazaisowurtzitane, CL-20) based green polymer-bonded explosives (GPBXs) via interfacial polymerization. Meanwhile, the corresponding composite particles prepared by physical mixing and drying bath methods were studied and compared. The particle morphology, crystal structure, thermal stability, and safety performance of the resultant composite particles were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, differential scanning calorimeter (DSC), and impact sensitivity test, respectively. SEM results showed that MUF was successfully coated on the surface of the three explosives, and different composite particles prepared by the same method have their own unique characteristics. Such effect is attributed to the resin’s ability to isolate and buffer external stimuli. It is obvious that the interfacial polymerization is an effective desensitization technique to prepare core-shell composite particles for explosives.

Herein, a green process for preparing nano-HMX, mechanical demulsification shearing (MDS) technology, was developed. Nano-HMX was successfully fabricated via MDS technology without using any chemical reagents, and the fabrication mechanism was proposed. Based on the “fractal theory,” the optimal shearing time for mechanical emulsification was deduced by calculating the fractal dimension of the particle size distribution. The as-prepared nano-HMX was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). And the impact sensitivities of HMX particles were contrastively investigated. The raw HMX had a lower fractal dimension of 1.9273. The ideal shearing time was 7 h. The resultant nano-HMX possessed a particle size distribution ranging from 203.3 nm to 509.1 nm as compared to raw HMX. Nano-HMX particles were dense spherical, maintaining β-HMX crystal form. In addition, they had much lower impact sensitivity. However, the apparent activation energy as well as thermal decomposition temperature of nano-HMX particles was decreased, attributing to the reduced probability for hotspot generation. Especially when the shearing time was 7 h, the activation energy was markedly decreased.