CL-20/FOX-7共晶的分子动力学模拟

依据共晶形成的氢键规则,搭建了7种CL-20/1,1-二氨基-2,2-二硝基乙烯(FOX-7)共晶模型;采用分子动力学(MD)模拟研究了CL-20/FOX-7共晶形成的可能性;通过径向分布函数(RDF)考察了共晶模型内分子的相互作用力;采用X-射线粉末衍射(XRD)模拟分析了共晶模型与纯组分间衍射峰的区别。结果表明,FOX-7和CL-20分子间存在较强的氢键和范德华力,7种共晶模型的结合能大小顺序为:Eb(1 0 1)Eb(1 1-1)E_b(随机晶面)E_b(0 1 1)E_b(0 0 2)E_b(1 1 0)E_b(1 0-1);7种共晶模型的分子间作用力以FOX-7取代CL-20(1 0 1)、(11-1)晶面较强;7种共晶模型的XRD衍射峰相较纯组分CL-20或FOX-7区别较大。据此推测在制备CL-20/FOX-7共晶过程中,FOX-7取代CL-20(1 0 1)晶面的共晶模型易于形成。     

Facile Preparation of Self‐Sensitized FOX‐7 with Uniform Pores by Heat Treatment

Self‐sensitized FOX‐7 (1,1‐diamino‐2,2‐dinitroethylene) was prepared by a facile heat treatment process near the decomposition temperature. Field emission scanning electron microscopy (FE‐SEM) shows the self‐sensitized FOX‐7 becomes multiple layers and porous after heat treatment. N₂ adsorbance measurements revealed that its specific surface area (6.754 m² g⁻¹) is 20 times of the area of expanded ammonium nitrate. The SAXS tests further indicate the existence of a large amount of voids in self‐sensitized FOX‐7 and the pore size is about 30 nm, belonging to mesopore (2.0–50 nm). Based on the analysis of X‐ray powder diffraction (XRD), the self‐sensitized porous FOX‐7 consists of α‐phase and a spot of γ‐phase. The TG‐DSC results show that the self‐sensitized FOX‐7 exhibits excellent thermal stability. The impact, frication and electrostatic spark sensitivities of self‐sensitized FOX‐7 also have considerable enhancement. This new method provides a promising route for exploring new green primary explosive replacements.     

Review on the Reactivity of 1,1‐Diamino‐2,2‐dinitroethylene (FOX‐7)

1,1‐Diamino‐2,2‐dinitroethylene (FOX‐7) is a novel high‐energy insensitive material with good thermal stability and low sensitivity, and exhibits excellent application performance in the field of insensitive ammunitions and solid propellant. Although FOX‐7 is simple in molecular composition and structure, its chemical reactivity is abundant and surprising, including salification reaction, coordination reaction, nucleophilic substitution reaction, acetylate reaction, oxidizing reaction, reduction reaction, electrophilic addition reaction, among other reactions. These reactions are systemically summarized and some reaction mechanisms are analyzed in this review.     

High‐Temperature Structural Transformations of 1,1‐Diamino‐2,2‐dinitroethene (FOX‐7)

Stuctural transformations of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7) were investigated in the temperature range 298–513 K by means of DSC, TG, isothermal calorimetry, PXRD, IR spectroscopy, and electron microscopy. The data obtained confirm the existence of the high‐temperature δ‐FOX‐7 polymorph stable above 480 K. The heat effect of the γ→δ transformation is − 4.6 J g⁻¹ (−680 J mol⁻¹). Metastable γ‐phase formed in the reverse process δ→γ has a perfect crystal structure and is stable towards thermal decomposition. Possible mechanisms of sharp deceleration of thermal decomposition of FOX‐7 at the 40 % conversion are discussed.     

γ‐FOX‐7: Structure of a High Energy Density Material Immediately Prior to Decomposition

1,1‐Diamino‐2,2‐dinitroethene, C₂H₄N₄O₄ (FOX‐7), is a novel high energy density material with low friction and impact sensitivity and a high activation barrier to detonation. In this study, the previously unknown crystal structure of the γ‐polymorph of trimorphic FOX‐7 is reported. γ‐FOX‐7 is stable from ∼435 K until the compound decomposes just above 504 K. A single crystal of α‐FOX‐7 (P2₁/n, Z=4, a=694.67(7) pm, b=668.87(9) pm, c=1135.1(1) pm, β=90.14(1)°, T=373 K) was first transformed into a single crystal of β‐FOX‐7 (P2₁2₁2₁, Z=4, a=698.6(1) pm, b=668.6(2) pm, c=1168.7(3) pm, T=423 K) and then into a single crystal of γ‐FOX‐7 at 450 K. The γ‐FOX‐7 crystal was then subsequently quenched to 200 K. The structure of γ‐FOX‐7 (P2₁/n, Z=8, a=1335.4(3) pm, b=689.5(1) pm, c=1205.0(2) pm, β=111.102(8)°, T=200 K) consists of four planar layers, each containing two crystallographically independent FOX‐7 molecules found in the asymmetric unit.     

溶剂对FOX-7晶体相变和热性能的影响

采用重结晶法在二甲基甲酰胺(DMF)/H2O、二甲基亚砜(DMS)O/H2O和N-甲基吡咯烷酮(NMP)/H2O等不同溶剂体系中得到FOX-7晶体,用扫描电子显微镜(SEM)测试晶体的形貌、变温X-射线粉末衍射(XRD)分析晶型和相变、差示扫描量热仪(DSC)测试其热性能。结果表明,不同溶剂重结晶得到的FOX-7晶体形貌有较大差别,在DMSO/H2O溶剂中得到的晶体质量要优于其他两种;3种溶剂中得到FOX-7晶体的晶型和相变过程相同,即常温下FOX-7的晶型为α晶型,在120℃时,FOX-7完成α→β相变,至185℃时,完成β→γ相变;重结晶的FOX-7晶体5s爆发点温度提高了4~9℃,说明热稳定性增强。     

Directional Interactions of α‐Particles with FOX‐7. A DFT Study

FOX‐7 is exposed to the effects of α‐particles from selected directions of approach. Various energies and properties of these composite FOX‐7 systems (FOX‐7+α‐particle) are obtained. The effect of α‐particles on FOX‐7 is drastic. The CC double bond turns into a single bond and one of the C NO₂ bonds highly elongates. The approach from the side of amino groups results more stable composite system compared to the approach from the side of nitro groups.     

Application of Thin Layer Chromatography for Monitoring of FOX‐7 Synthesis

In this paper, results of the research on the application of thin layer chromatography (TLC) for the determination of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7, DADNE) and its precursors produced in the synthetic path starting from 2‐methylpyrimidine‐4,6(1H,5H)‐dione are presented. Analytical parameters of the substances and methodology of their quantitative analysis were determined, and the results obtained were used for monitoring the FOX‐7 synthesis process.     

Thermal and crystallization behavior of hydrogen‐bonded miscible blend of poly(3‐hydroxybutyrate) and enzymatically polymerized polyphenol

Enzymatically prepared novel polyphenol poly(4,4′‐dihydroxydiphenyl ether) (PDHDPE) is blended to modify the properties of biodegradable polyester poly[(R)‐3‐hydroxybutyrate] (PHB). Because the differential scanning calorimetry data show a single composition‐dependent glass transition for each blend, PHB and PDHDPE are found to be miscible in the amorphous phase. The crystallization of PHB is depressed by PDHDPE because PDHDPE reduces the molecular mobility and the flexibility of molecular chains of PHB. The Fourier transform IR spectra clearly indicate that PHB and PDHDPE interact through strong intermolecular hydrogen bonds between the carbonyl groups of PHB and the hydroxyl groups of PDHDPE. However, when PHB is blended with DHDPE monomer, no obvious hydrogen bonds are observed because of the phase separation and strong self‐intermolecular hydrogen bonds between DHDPE molecules. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2439–2449, 2005     

FOX-7和RDX基含铝炸药的冲击起爆特性

为研究FOX-7和RDX基含铝炸药的冲击起爆特性,对其进行了冲击波感度试验和冲击起爆试验,结合冲击波在铝隔板中的衰减特性,确定了FOX-7和RDX基含铝炸药的临界隔板值和临界起爆压力,并通过锰铜压阻传感器记录了起爆至稳定爆轰过程压力历程的变化。结果表明,以Φ40mm×50mm的JH-14为主发装药时,FOX-7和RDX基含铝炸药临界隔板值分别为37.51和34.51mm,对应的临界起爆压力为10.91和11.94GPa;起爆压力为11.58GPa时,FOX-7炸药的到爆轰距离为25.49~30.46mm,稳定爆轰后的爆轰压力为27.68GPa,爆轰速度为8 063m/s;起爆压力为14.18GPa时,RDX基含铝炸药的到爆轰距离为17.27~23.53mm,稳定爆轰后的爆轰压力为17.16GPa,爆轰速度为6 261m/s。     

Hydrogen‐bonding interaction between poly(ε‐caprolactone) and low‐molecular‐weight amino compounds

The specific interactions between several low‐molecular‐weight diamino compounds and poly(ε‐caprolactone) (PCL) have been investigated by FT‐IR. It was found that PCL and 3,3′‐diaminodiphenylmethane (3,3′‐DADPM) interact through strong intermolecular hydrogen bonds in the blend. Thermal and mechanical properties of PCL/3,3′‐DADPM blends were investigated by DSC and tensile measurements, respectively. The glass transition temperature of the blend increases while both the melting point and the elongation‐at‐break of the blend decrease with the increase of 3,3′‐DADPM content. Besides 3,3′‐DADPM, several other low‐molecular‐weight compounds containing two amino groups, such as o‐phenylenediamine or 1,6‐diaminohexane, were also added into PCL and the corresponding blend systems were investigated by FT‐IR and DSC. The effect of the chemical structure of the additives on the properties of PCL is discussed. © 2001 Society of Chemical Industry     

Preparation of Magnesium‐based Hydrogen Storage Materials and Their Effect on the Thermal Decomposition of Ammonium Perchlorate

Magnesium‐based hydrogen storage materials (MgH₂, Mg₂NiH₄, and Mg₂Cu‐H) were prepared and their structures were determined by XRD and ICP investigations. Mg₂NiH₄ has a monoclinic crystal structure and Mg₂Cu‐H is a mixture of MgCu₂ and MgH₂. The effects of magnesium‐based hydrogen storage materials on the thermal decomposition of ammonium perchlorate (AP) were studied by thermal analysis (DSC). It was found that magnesium‐based hydrogen storage materials show obvious boosting effects on the thermal decomposition of AP. The thermal decomposition peak temperature of AP was decreased, while the heat release of the decomposition of AP was increased. It was revealed that the effects of magnesium‐based hydrogen storage materials on the decomposition of AP become stronger with increasing content. The influence mechanism on the thermal decomposition of AP is suggested as follows: hydrogen released from magnesium‐based hydrogen storage materials and Mg, Ni, or Cu react with the decomposed products of AP.     

Investigation of the thin film crystallization of a DNA copolymer hybrid composed of chitosan

We describe for the first time the crystallization in thin films of a DNA copolymer composed of a low molecular weight chitosan backbone to which a sequence of nucleic acids is grafted (chitosan‐g‐ssDNA). As assessed by atomic force microscopy, optical microscopy and spectroscopy, crystallization occurs due to intermolecular hydrogen bonding in which the nucleic acid strands engage. The morphology of the crystals depends on the affinity for the surface of the polymer segments that compose the DNA copolymer hybrid. The nucleic acids adsorb on mica and silica on which side‐branched structures are observed whereas chitosan interacts preferentially with gold, and dendritic crystals are assembled. Attenuated total reflectance infrared spectroscopy supports the high ordering of the structure and the establishment of strong intermolecular interactions by hydrogen bonding. © 2016 Society of Chemical Industry     

Nucleation mechanism of polyhydroxybutyrate and poly(hydroxybutyrate‐co‐hydroxyhexanoate) crystallized by orotic acid as a nucleating agent

The mechanism involved in the crystallization of bacterial polyhydroxybutyrate (PHB) and poly(hydroxybutyrate‐co‐hydroxyhexanoate) P(HB‐co‐HH) induced by orotic acid as a nucleant was investigated by using differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and proton nuclear magnetic resonance spectroscopy (¹H‐NMR). GPC measurements both carried on solvent cast and hot pressed samples did not show any significant drop of the molecular weight caused by the addition of the nucleant, indicating that no chemical reaction happened during the nucleation process. This result was confirmed by ¹H‐NMR analysis of oligohydroxybutyrate (OHB) treated with an excess amount of orotic acid. The possibility of epitaxial growth of the polymer crystal on the surface of the nucleant crystal was then investigated. It was found that there is an outstanding crystalline lattice matching between the plane (100) of the PHB crystal and the plane (001) of the orotic acid crystal. In comparison, the matching obtained with conventional nucleating agents, such as boron nitride and talc, was worse. Moreover, some regular hydrogen bonds between the polyester and orotic acid could stabilize the physical process. According to these results, the physical mechanism involving the epitaxial matching between orotic acid and PHB appears to be the most probable nucleation mechanism. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Smokeless GAP‐RDX Composite Rocket Propellants Containing Diaminodinitroethylene (FOX‐7)

Composite rocket propellants prepared from nitramine fillers (RDX or HMX), glycidyl azide polymer (GAP) binder and energetic plasticizers are potential substitutes for smokeless double‐base propellants in some rocket motors. In this work, we report GAP‐RDX propellants, wherein the nitramine filler has been partly or wholly replaced by 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7). These smokeless propellants, containing 60% energetic solids and 15% N‐butyl‐2‐nitratoethylnitramine (BuNENA) energetic plasticizer, exhibited markedly reduced shock sensitivity with increasing content of FOX‐7. Conversely, addition of FOX‐7 reduced the thermochemical performance of the propellants, and samples without nitramine underwent unsteady combustion at lower pressures (no burn rate catalyst was added). The mechanical characteristics were quite modest for all propellant samples, and binder‐filler interactions improved slightly with increasing content of FOX‐7. Overall, FOX‐7 remains an attractive, but less than ideal, substitute for nitramines in smokeless GAP propellants.     

A Quantum Mechanical Molecular Dynamics Study of Binary Collisions of Pentaerythritol Tetranitrate (PETN): Its Correlation to Shock Sensitivity

We have carried out semi‐empirical quantum mechanical molecular dynamics (MD) simulations involving collisions of two pentaerythritol tetranitrate (PETN) molecules at different molecular orientations and at several intermolecular separations. The common features of reactive scattering among all molecular orientations are (1) the dissociation mechanism of PETN remains unimolecular and (2) the dominant reaction channel is the breaking of an O NO₂ bond. However, the probability of collision‐induced decomposition of PETN depends strongly on initial conditions, in agreement with the experimentally observed sensitivity of shock‐initiated detonation in bulk PETN along different crystalline orientations. In addition, the next most frequent reaction path shows a dependence on initial orientations.     

Relative strength of H‐bonding groups on biodegradable polymer‐based blends in solution

The intermolecular hydrogen bonding interactions between poly(3‐hydroxybutyrate) and poly(styrene‐co‐vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady‐state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly‐(3‐hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3‐hydroxybutyrate) and poly(styrene‐co‐4‐vinylphenol) chains are well separated and remain so independently of the mixed polymer ratio and overall polymer concentration as well. Conversely, when the OH content reaches 5.8 mol % or more, a significant decrease of the intrinsic fluorescence intensity emitted by the copolymer is detected upon addition of aliquots of poly(3‐hydroxybutyrate). In these cases, an average value for the interassociation equilibrium constant, K_A = 8.7, was obtained using a binding model formalism. A good agreement of these results with those obtained from complementary viscosity measurements, through the interaction parameter, Δb, was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 900–910, 2006     

The Method of Choice for Ring Cleavage of 2‐(Dinitroethylene)‐ 4,5‐Imidazolidinedione

2‐(dinitroethylene)‐4,5‐imidazolidinedione, which is the intermediate in preparing FOX‐7, was synthesized by acetamidine hydrochloride and diethyl oxalate. Ring cleavage reaction could be carried out more quickly, when methanol, water, and formic acid were used as ring cleavage reagents; the disadvantages from using ammonia as ring cleavage reagent could be overcome with yields of up to 65.5%. When water is used as ring cleavage reagent, the reaction rate will be high and the reaction conditions will be milder. So this method is more suitable for further up‐scaling research.     

Laboratory‐Scale Method for Estimating Explosive Performance from Laser‐Induced Shock Waves

A new laboratory‐scale method for predicting explosive performance (e.g., detonation velocity and pressure) based on milligram quantities of material is demonstrated. This technique is based on schlieren imaging of the shock wave generated in air by the formation of a laser‐induced plasma on the surface of an energetic material residue. The shock wave from each laser ablation event is tracked for more than 100 μs using a high‐speed camera. A suite of conventional energetic materials including DNAN, TNT, HNS, TATB, NTO, PETN, RDX, HMX, and CL‐20 was used to develop calibration curves relating the characteristic shock velocity for each energetic material to several detonation parameters. A strong linear correlation between the laser‐induced shock velocity and the measured performance from full‐scale detonation testing has been observed. The Laser‐induced Air Shock from Energetic Materials (LASEM) method was validated using nitrocellulose, FOX‐7, nano‐RDX, three military formulations, and three novel high‐nitrogen explosives currently under development. This method is a potential screening tool for the development of new energetic materials and formulations prior to larger‐scale detonative testing. The main advantages are the small quantity of material required (a few milligrams or less per laser shot), the ease with which hundreds of measurements per day can be obtained, and the ability to estimate explosive performance without detonating the material (reducing cost and safety requirements).