Abstract:In order to investigate the effect of aggregation structure on the properties of hexanitrohexaazaisowurtzitane/octogen （CL?20/HMX） co?crystal， the droplet confined crystallization was used to prepare spherical CL?20/HMX co?crystal. The morphology and structure of the samples were characterized by field emission scanning electron microscopy （FE?SEM）， X?ray powder diffraction （XRD） and fourier transform infrared spectroscopy （FT?IR）. The properties of the samples were analyzed by thermal analysis， sensitivity and combustion tests. The results show that the spherical CL?20/HMX co?crystal was successfully prepared by this method. The diameter of the spherical CL?20/HMX co?crystal is 1.3-1.85 mm， the hollow ratio is about 40%， and the specific surface area is 6.890 m2·g-1. The exothermic peak temperature of spherical CL?20/HMX co?crystal is located at 245.8 ℃ ， the thermal decomposition activation energy （463.02 kJ?mol-1） and the critical temperature of thermal explosion （241.28 ℃） are higher than those of flake CL?20/HMX co?crystal， exhibiting the excellent thermal stability of spherical CL?20/HMX. The impact sensitivity is better than that of raw material and flake CL?20/HMX co?crystal， and the friction sensitivity falls between raw CL?20 and HMX， but lower than that of flake CL?20/HMX co?crystal. The ignition delay time is less than 8 ms and the combustion is efficient and stable， while the flake CL?20/HMX co?crystal， raw materials and their physical mixture exhibit flameless combustion.The construction of millimeter?sized hollow spheres for CL?20/HMX co?crystal has significantly improved the thermal stability，sensibility and combustion performances.

Abstract:In order to understand the flow state of supercritical carbon dioxide （SC-CO₂）-assisted double-base propellant within the metering section during extrusion， and to analyze the distribution and variations of parameters such as pressure， fluid velocity， shear rate， and shear viscosity in the flow field， the CFD simulation software Polyflow was employed for simulating the flow state of the material in the metering section during SC-CO₂-assisted double-base propellant extrusion. The results show that both fluid pressure and shear viscosity decrease with increasing process temperature， gas injection rate， and solvent ratio. An increase in screw speed leads to a decrease in shear viscosity but a sharp increase in fluid pressure. The pressure on the outer wall of the fluid gradually increases in steps， with pressure at the cross-section exhibiting an approximately annular distribution， decreasing gradually from the inner wall of the barrel towards the screw surface. The shear viscosity at the cross-section forms a ring-shaped high-viscosity zone on the center of the screw. The closer the zone is to the inner wall of the barrel and the screw surface， the smaller the shear viscosity. Furthermore， changes in process parameters do not affect the distribution pattern of shear viscosity. The shear rate on the outer wall of the fluid increases with higher screw speed and concentrates at the thread. The maximum fluid velocity at the cross-section occurs near the thread， while the fluid velocity close to the inner wall of the barrel is minimal. As one moves away from the inner wall of the barrel and the screw surface， fluid velocity rapidly increases， with a greater gradient observed in zones closer to the screw surface and the inner wall of the barrel.

Abstract:In order to explore novel nitrogen-rich heterocyclic energetic compounds， an amide bridged energetic compound 1-hydroxy-N-（1H-1，2，4-triazol-3-yl）-1H-tetrazole-5-carboxamide was synthesized from 5-cyano-1-（1H-1，2，4-triazol-5-yl）-1H-tetrazole through several steps involving amidoximation， diazotization， substitution and electrophilic addition. Its structure was fully characterized by nuclear magnetic resonance （NMR）， Fourier transform infrared spectroscopy （FT-IR） and elemental analysis （EA）. X-ray diffraction analysis （SC-XRD） was adopted to further confirm its structure； its thermal decomposition process was studied by differential scanning calorimetry （DSC） and thermogravimetry （TG）. The compound has a high onset decomposition temperature of 265 ℃ and shows good properties with detonation velocity of 8017 m·s^-1， and detonation pressure of 23.1 GPa， impact sensitivity of 20 J， and friction sensitivity of 288 N.

Abstract:Solubility is an important parameter for the crystallization of molecular perovskite energetic materials （H₆N₂H₁₄）［NH₄（ClO₄）₃］（DAP-4）. In this work， the dissolution behaviors of DAP-4 at different temperatures （288-323 K） and in different solvents （ethanol， ethyl acetate， formic acid， deionized water， acetone， cyclohexane， methanol， acetonitrile， n-propanol） were studied by the gravimetric method. The dissolution models were established by the Apelblat equation and the λh equation， respectively. Meanwhile， the dissolution thermodynamic parameters （ΔH_d， ΔS_d， ΔG_d） were obtained by Van’t Hoff equation based on the thermodynamic principle of solid-liquid equilibrium. Results show that the solubility of DAP-4 is the largest in water and the smallest in ethyl acetate， which are increased with the increasing of temperature in different solvents. The fitting result of dissolution model from the Apleblat equation is better than that of the λh equation. Positive values of ΔH_d， ΔS_d， and ΔG_d indicate that the dissolving process of DAP-4 are non-spontaneous endothermic.

Abstract:Using droplet microfluidics technology， an aqueous solution of the active agent at a concentration of 0.5% was used as the continuous phase， and an ethyl acetate solution of DAAF was employed as the dispersed phase. DAAF/F2602 composite microspheres were prepared by fluid-focused microchanneling. The effects of two-phase flow rate ratio， concentration of dispersed phase， and type of active agent on particle morphology， particle size， and roundness of DAAF/F2602 composite microspheres were investigated. The optimal process conditions， including a suspension concentration of 4%， a two-phase flow rate ratio of 16∶1 and an active agent of CTAB， were obtained and compared with the aqueous suspension method. The results show that the DAAF crystalline shape of the samples obtained from two preparation methods are unchanged， the impact sensitivity is higher than 100 J， and the friction sensitivity is 0% and the friction sensibility are more than 360 N， indicating that the two samples have good safety performance. Among them， the particle sizes of DAAF/F2602 composite microspheres which obtained by the droplet microfluidization method were in the range of 20.22 to 53.85 μm， which were smaller than that obtained by the aqueous suspension method （121-356 μm）.Furthermore， the particle sizes distribution was observed to be more uniform. Thethermal decomposition exhibited a delayed peak temperature by 6.45 ℃， and the activation energy was increased by 6.12 kJ·mol^-1， which lead to improved thermal stability. The cone angle generated by the stacking of DAAF/F2602 composite microspheres which obtained by the droplet microfluidization method， is 34°. This angle is smaller than that of composite particles obtained by the water suspension method （40°）， which indicate better dispersion property.

Abstract:In order to rapidly analyze the product quality of 2，6-diamino-3，5-dinitropyrazine-1-oxide （ANPZO） and optimize the synthesis process， high-performance liquid chromatography （HPLC） method was developed to quantitatively analyze the purity of ANPZO. The effects of mobile phase composition， elution mode and detector wavelength on the resolution have been studied. The separation of ANPZO and its intermediate 2，6-diamino-3，5-dinitropyrazine （ANPZ） was accomplished by using C18 analytical column with size of 250×4.6 mm and 5 µm. The initial mobile phase composition was 0.1% trifluoroacetic acid and methanol （95∶5， v/v）. The methanol ratio was increased to 100% from 2 min to 7 min after the sample injection. Gradient elution was performed at a flow rate of 1.0 mL·min^-1， the column oven temperature was set at 30 ℃， and detection wavelength was 425 nm. The validation of the developed methods showed good linearity （R²=0.9996）， repeatability （%Area RSD%=0.30%） over the concentration range of 0.1 mg·mL^-1 to 0.6 mg·mL^-1. The limit of detection（signal/noise=3） and quantitation（signal/noise=10） of ANPZO were found to be 20 ng·g^-1 and 67 ng·g^-1， respectively. Therefore， the reported method is accurate， precise and sensitive， which can be used for the quality control of ANPZO.

Abstract:Fused-ring energetic compounds， composed of two or more rings sharing two atoms and one chemical bond， have sizeable π-π conjugate structures and are a kind of popular new energetic materials. The polycyclic coplanar structure of energetic fused rings shows good molecular stability. Furthermore， the coplanar structure is featured with high heat of formation， significant ring tension， and high energetic performance. It can achieve a balance between high performance and molecular stability. With a C—N bond as the common building block， these nitrogen heterocycles have good density， stability， and numerous modifiable sites， which have become a new class of backbones in the field of energetic fused heterocycles. In this paper， the authors review the recent advance of synthesis， detonation properties， stability， and outlook of C—N type fused-ring energetic materials， which will be useful for the energetic community in future studies.

Abstract:The reaction mechanism of intermediate 3，3′-Bis（1，2，4-oxadiazole）］-5，5′-diyldimethanol acetate （BODM） hydrolyzed to 3，3"-Bi（1，2，4-oxadiazole）-5，5"-diyldimethanol （BOD） was investigated by theoretical calculation. The synthesis process was optimized by single factor experiment and orthogonal experiment. The structure and properties of BOD were analyzed by XRD， FTIR， NMR and DSC. It was found that the reaction mechanism was the lone pair electrons in BODM —［O］— formed an OH…O hydrogen bond with H in H₂O， then the O—C bond in —［O］—［C═O］—broke， and the H and OH bonds in H2O formed —OH and —COOH group in —［O］— and —［C═O］—， respectively. and found that the crystal of BOD belong to the monoclinic system， the space group is C2/c， the cell angle α=90°， β=105.361（7）°， γ=90°， the cell volume v=774.9（2） A³， the density ρ=1.698 g·cm^-3. The melting point and decomposition peak temperature were 197.18 ℃ and 278.37 ℃， respectively. The results of single factor experiment showed that with the increase of reaction time and solvent， the yield of BOD increased at first and then became stable. With the increase of reaction temperature， the yield of BOD increased slowly and then decreased rapidly. With the increase of material ratio， the yield of BOD increased first and then decreased. In addition， the optimal process conditions were obtained by orthogonal experiment： BODM hydrolyzed in potassium carbonate methanol solution at 45 ℃ for 8 h， in which the molar ratio of BODM to potassium carbonate was 15∶1， and the yield was 94%. This study provides theoretical basis and experimental reference for scaling up and large-scale production of BOD.

Abstract:In order to improve the safety performance of hexanitrohexaazaisowurtzitane （CL-20）， the CL-20 with self-assembled stacking structures were prepared by the solvent-nonsolvent method using nitrified graphene （NG） as a crystallization inducer. The morphologies， structures， and thermal properties of the stacking structure CL-20 were characterized by field emission scanning electron microscopy （FE-SEM）， X-ray diffraction （XRD）， fourier transform infrared spectroscopy （FT-IR）， and synchronous thermal analyzer （DSC-TG） respectively， and their mechanical sensitivities were tested and analyzed. The results show that under the induction of different content of NG， CL-20 recrystallizes into square flake crystals， and self-assembles and stacks into petal-shaped， spiral-shaped， tower-shaped， and other structures. During the formation of the self-assembled stacking CL-20， the induction effects of NG are reflected in the adsorption effect of its sheet layer on CL-20 and the formation of hydrogen bonds between NG′s active functional groups with CL-20. Compared with the raw CL-20， the thermal decomposition temperature of the self-assembled stacking CL-20 is reduced by about 5 ℃， the maximum thermal decomposition enthalpy is increased by about 33%， and the mass loss is increased from 81% to 99%. The prepared self-assembled stacking CL-20 has a significantly lower mechanical sensitivity than that of the raw CL-20. When the NG content is 0.5%， the self-assembled petal CL-20 prepared by NG induction has the lowest impact sensitivity of 6 J.

Abstract:Data derived from high-accuracy quantum-chemistry calculations plays a significant role in designing， synthesizing， and characterizing energetic compounds. Therefore， constructing a quantum-chemistry database of energetic compounds， which collects high-accuracy quantum-chemistry calculation data， can circumvent massive duplicated calculation research and resource consumption. In addition， such an approach guarantees the quality of data， facilitates in-depth analysis and data mining， and obtains reliable analytical and predictive models for the structures and properties of energetic compounds. This review summarized data related to critical structures and properties of energetic compounds from quantum-chemistry calculations and the development of molecular design using a database and high-throughput virtual screening technique. The design and application of the quantum-chemistry database of energetic compounds were envisioned， including （1） the establishment of calculation standards and prediction models to generate customized data in the field of energetic materials； （2） the construction of an open and shared database to join high-throughput virtual screening； and （3） the development of database management systems to realize data inquiry， acquisition， and data mining. It is hopeful to provide insights for the design and practical application of the quantum-chemistry database of energetic compounds.

Abstract:The spheroidization of energetic materials can significantly improve the processing and application properties of explosive crystals. Based on the current research on spheroidization technology of typical energetic materials both in China and abroad， the research progress of spherical single crystals， spherical agglomerates and spherical branched crystals are reviewed from the perspective of crystallization strategy. The crystallization process， spheroidization mechanism and desensitization effect of spherical products are emphatically introduced. It is showed that spherical products have the virtues of good flowability， high bulk density and low sensitivity， and have great potential in explosive applications. Combining crystal engineering thinking， it is suggested to construct the crystallization database of typical energetic materials， strengthen online process monitoring， improve model calculations and multidisciplinary cross study， thus providing guidance for precise regulation and industrial production of spherical crystallization process of energetic materials.

Abstract:To improve the stability of aluminum hydride （AlH₃）， three kinds of embedded-coated AlH₃@Al@xAP（AHAPs） energetic composite particles were prepared by the combination of using acoustic resonance and spray drying technology. The mass ratios of AlH₃@Al and AP were 9∶1（AHAPs-10%）， 7∶3（AHAPs-30%）， and 1∶1（AHAPs-50%）， respectively. The morphologies and structures of the AHAPs and their condensed combustion products were characterized by SEM， EDS， and XRD. The thermal reactivity and stability of the prepared samples were comparatively studied by TG-DSC analysis and vacuum stability tester （VST）. Results show that AHAPs energetic composite particles could not only improve the stability of AlH₃ but also promote the decomposition of AP. With the increase of AP content， the initial decomposition temperatures of AlH₃ are increased by 8.5-11 ℃， and the peak temperature at high-temperature decomposition stage of AP is decreased by about 80 ℃. Compared with the total decomposition time of pure AlH₃（1006 min）， the decomposition time of AHAPs-50% composite particles extend to 1518 min， which corresponds to a 50.9% increment. In addition， the reaction heat of embedded-coated composite particles AlH₃@Al/63.5% AP reaches 9125.6 J·g^-1， which is 1054.1 J·g^-1 higher than that of mechanically mixed samples， and the particle sizes of the condensed combustion products appear to be finer， indicating that their combustion become more complete and the combustion efficiency is greatly enhanced.

Abstract:A series of ionic liquids based on N，N-（dimethylcyclopropyl）cyclopropylamines as cations and dicyandiamide/cyanoborohydride as anions were synthesized by using the three-member carbocyclic ring as the tension energy structural unit. The structures of ionic liquids were confirmed with the characterizations such as nuclear magnetic （NMR）， infrared spectroscopy （IR） and high-resolution mass spectrometry （HRMS）. Their physicochemical properties （e.g.， melting point， thermal decomposition temperature， density， viscosity， heat of formation， specific impulse， and ignition delay time） were measured and/or calculated in detail. The results demonstrate that all ten synthesized ionic liquids show hypergolicity with white fuming nitric acid （WFNA）， and the cyanoborohydride based ionic liquids have the shorter ignition delay times than the corresponding dicyandiamide ionic liquids. More strained ring groups lead to the higher heats of formation （0.87-1.96 kJ·g^-1）， and the compact stacking of small ring structures makes an increase in the densities （1.01-1.18 g·cm^-3） of the ionic liquids. Therefore， the strained ring-based hypergolic ionic liquids exhibit the higher density-specific impulse （436.7-454.4 s·g·cm^-3）. The introduction of high-energy strained ring groups in the molecular structures provides a way to improve the energy densities of hypergolic ionic liquids.

Abstract:In order to solve the problems of high energy consumption， difficulty in particle size control and serious pollution in the preparation of nano-aluminum powder. green and safe preparation of nano-aluminum powder is fulfilled by liquid chemical method through adding diisobutyl aluminum hydride （DIBAL） to aluminum chloride-1-ethyl-3-methylimidazole chloride（AlCl₃-EMIC） ionic liquid with the molar ratio of 2∶1. By means of X-ray diffraction （XRD）， nano-particle size detection， transmission electron microscopy （TEM）， scanning electron microscopy （SEM）， energy dispersive spectrum of X-ray （EDS） and linear scanning voltammetry （LSV）， the nano-aluminum powder was characterized and its growth process and reaction mechanism were explored The results show that when DIBAL concentration is 0.25 mol·L^-1 and reaction time is 0.5 min， the non-agglomerated aluminum powder with uniform particle size of 40-100 nm is obtained， which is more uniform than the one obtained by other liquid chemical methods. The abnormal growth of aluminum powder is observed at different DIBAL concentrations， which is related to the Ostwald ripening. In addition， the AlCl₃-EMIC ionic liquid is not only the reaction medium， but also the Al source of the nano-aluminum powder.

Abstract:Refined 3-nitro-1，2，4-triazol-5-one （NTO） product were prepared by spray drying technology to improve the morphology and reduce the particle size. Acetone was used as the experimental solvent. The effects to inlet temperature， inlet flow rate， feed rate and precursor mass concentration on the morphology and particle size of the refined NTO were investigated， and the optimal spray drying process parameters was selected. The surface morphology， molecular structure and thermal stability of refined NTO products were characterized by scanning electron microscopy （SEM）， X-ray diffraction （XRD） and fourier transform infrared spectroscopy （FT-IR）， and synchronous thermal analyzer （TG-DSC）. The results show that the sphere-like NTO with good morphological， stable crystal structure， narrow particle size distribution range and an average particle size of 1.2 μm can be obtained when the inlet temperature is 60 ℃， the inlet gas flow rate is 357 L·h^-1， the feed rate is 3 mL·min^-1， the NTO precursor concentration is 16.57 mg·mL^-1. Compared with the feedstock， the thermal decomposition activation energy of the refined NTO was enhanced by 41.7 kJ·mol^-1， and the thermal explosion critical temperature was increased by 10.4 ℃， which has better thermal stability.

Abstract:Triazole-based energetic compound is a new class of energetic materials with the features of high heat of formation， high nitrogen content and good thermal stability. In this paper， the latest research achievements on synthesis of more than 40 series of energetic compounds based on mono-triazole， bis-triazole， pyrazole-triazole， oxadiazole-triazole and tetrazole-triazole were reviewed， and the performances of some compounds were introduced in detail. It is showed that designing new triazole-based energetic compounds based on structure-performance relationship and balancing energy and safety are the effective strategy to develop high energy and insensitive energetic compounds. On this basis， design and synthesis of cage triazole-based energetic compounds are the promising developing direction. The application study of existing triazole-based energetic compounds with outstanding overall performance is proposed.

Abstract:The introduction of fluorodinitromethyl group into energetic molecules can not only improve oxygen balance， density and explosive performance， but also increase thermal decomposition temperature and reduce sensitivity. The construction of energetic compounds containing fluorodinitromethyl groups has become a hot research topic in the field of high energy dense and insensitive materials. By reviewing the energetic compounds containing fluorodinitromethyl groups in the past two decades， we analyzed and compared the molecular structures， summarized the synthesis methods of fluorodinitromethyl-containing compounds， physicochemical and explosive properties of these compounds， providing some references for the molecular design and synthesis of novel fluorodinitromethyl substituted compounds.

Abstract:To explore low sensitivity and environmental-friendly energetic combustion catalysts， three new energetic copper complexes， ［Cu（NH₃）₄（DN）₂］， ［Cu（IMI）₄（DN）₂］， ［Cu（ATO）₄］（DN）₂ were synthesized. Ammonium dinitramide （ADN） was used as a precursor to prepare dinitramide acid （HDN） by ion exchange reaction， and the resultant solution reacted with basic copper（Ⅱ） carbonate continually to produce copper（Ⅱ） dinitramide， which reacted further with nitrogen-rich ligands （ammonia， imidazole， 4-amino-1，2，4-triazole-5-one）. The structures of the three complexes were characterized accurately by X-ray single crystal diffraction， infrared spectroscopy and elemental analysis. Their thermal stability， hygroscopicity， sensitivities toward impact （IS）， friction （FS） and electrostatic discharge （ESD） were investigated. Furthermore， the effect of ［Cu（IMI）₄（DN）₂］ towards the burning rate of propellants were performed. Results show that the thermal stability of three complexes can meet the application requirement of solid propellants， and the initial decomposition temperatures are all higher than 140 ℃. The hygroscopicity of the complexes were improved obviously， which could be as low as 2%-5% of the precursor ADN. ［Cu（IMI）₄（DN）₂］ has the lowest sensitivity （IS 28.6 J， FS 0%， ESD 185 mJ） of the three complexes. With 4% of ［Cu（IMI）₄（DN）₂］， the burning rate of the basic formula propellants was increased by 27.7%， which was expected to be used as low sensitivity burning rate catalyst in high burning rate solid propellants.

Abstract:Polycyclic structures with high nitrogen content exhibit great potential in balancing the contradiction between energy and safety of energetic compounds. As an important structural unit for the design of high nitrogen content polycyclic energetic molecules， furazan has the characteristics of good stability， high nitrogen content， high positive enthalpy of formation and good oxygen balance tendency. The design and synthesis of polycyclic energetic compounds containing furazan unit have become a focus that has been studied extensively and deeply in the research field of energetic materials. This review article summarized and evaluated the molecular structures， synthetic methods， physicochemical properties of furazan based polycyclic energetic compounds. Meanwhile， the potential applications of these compounds in high energy and low sensitivity explosives， heat-resistant explosives and primary explosives were also prospected， providing a reference for the design and synthesis of new polycyclic energetic compounds.

Abstract:A novel cage-like energetic compound， 6-nitro-2-oxa-6-azaadamantane-4，8-diol dinitrate， was synthesized from 1，5-cyclooctadiene via oxidative cyclization， O-acylation， elimination， epoxidation， aminolysis and nitration with an overall yield of 20.7%. The single crystal structure of 6-nitro-2-oxa-6-azadamantane-4，8-diol dinitrate was obtained by X-ray single crystal diffraction. Its structure was characterized using NMR， IR， and elemental analysis. Thermogravimetric analysis （TG） and differential scanning calorimetry （DSC） were used to study the thermal stability of the target compound. Density functional theory method was used to study the detonation properties of the target compound. Result show that it has a density of 1.75 g·cm^-3， a thermal decomposition temperature of 184 ℃， a detonation velocity of 7730 m·s^-1， and a detonation pressure of 26.07 GPa.

Abstract:For the problems of low nitrification yield and the use of highly toxic substances in the synthesis of high-energy oxidant 1，4-bis（trinitromethyl）-3，6-dinitropyrazole［4，3-c］pyrazole （ONPP）， a new synthetic process of ONPP was developed. The single crystal of ONPP was cultivated by slow evaporation from an ethyl acetate solution. The energy levels of different formulations based on ONPP were estimated. In the presence of base and phase transfer catalyst Bu₄NBr（TBAB）， 3，6-dinitropyrazole［4，3-c］pyrazole （DNPP） reacted with bromoacetone to introduce two acetone groups on pyrazole ring. Followed by nitrating with HNO₃/H₂SO₄/P₂O₅， ONPP was obtained in the total yield of 31%. Compared with the literature （10.4% total yield from two steps）， the yield of new synthetic route from DNPP increase by nearly three times. Meanwhile the use of highly toxic butenone is avoided， which is more suitable for large-scale production. The crystal structure of ONPP belongs to the monoclinic crystal system， P2₁/c space group. Its crystal density is 1.983 g cm^-3 at 293 K. Through the energy estimation of HTPB （10%）， Al （20%） and oxidizer （70%） formulations， the energy level is optimal when ONPP （40%） and AP （30%） are used together as oxidizers， which is significantly higher than the formulation energy levels when they used as single oxidant.

Abstract:Energetic molecules with cage-like backbones， owning additional strain energy and stability， are potential candidates for optimizing the long-known contradiction between high energy density and low sensitivity of energetic materials. However， the reaction mechanism of caged energetic materials under shock compression is still unclear. Here， a series of ab initio molecular dynamics calculations were conducted to simulate the early decay of typical caged energetic compounds when compressed by shock waves of 8 to 11 km·s^-1，and the studied compounds included octanitrocubane （ONC）， hexanitrohexaazaisowoodethane （CL-20）， 4，10-dinitro-2，6，8，12-tetraoxa-4，10-diazatetracyclododecane （TEX）， and the reference plane system triaminotrinitrobenzene （TATB）. The shock sensitivity of the four studied systems was calculated as ONC > CL-20 > TEX > TATB， which is in good agreement with reference experimental shock/impact sensitivity tests. The reaction initiation mechanism was revealed （i） the presence of electron-rich oxygen/nitrogen elements increases electron delocalization over the cage and the proper degree of freedom of the covalent bonds confers them additional elastic deformation capacity upon shock stimulus， both enhance the structural stability of hetero-cage， （ii） the dissociation of the nitro groups takes precedence over the collapse of the hetero-cage， which can delay the reaction process and reduce the shock sensitivity， and （iii） intermolecular hydrogen bonds （HB） is highly plastic deformable and enriched HB can delay the onset of reactions by buffering shocks. The current study proposed that the hetero-cage backbone with enhanced electron delocalization effect and proper degree of freedom， and the enriched intermolecular hydrogen bonding interactions could reduce the shock wave sensitivity， thereby providing theoretical guidance for the rational design of novel insensitive energetic materials.

Abstract:In order to explore new energetic material with both good thermal stability and high safety performance， 4，8-di（2，4，6-trinitro-3，5-diaminophenyl）difurazanopyrazine （NADFP） was synthesized by substitution reaction using 1-chloro-2，4，6-trinitro-3，5-diaminobenzene and 4H，8H-difurazanopyrazine as raw materials. Its structure was characterized by nuclear magnetic resonance （¹H and ¹³C spectrum）， infrared spectroscopy and element analysis. The single crystal of NADFP·DMF was obtained by solvent evaporation method， and the crystal structure was determined by single crystal X-ray diffraction. Results show that NADFP·DMF belongs to monoclinic system， space group P2₁/c， a=7.854（3） Å， b=18.466（6） Å， c=11.093（3） Å， ρ=1.640 g·cm^-3. The inter-/intramolecular interactions were calculated by Hirshfeld surfaces analysis with hydrogen bond interactions accounting for 53.5%. The thermal behavior of NADFP was studied by DSC and TG/DTG methods， which show that its decomposition peaks are 337.2 ℃ and 368.8 ℃. The theoretical detonation performances and mechanical sensitivities of NADFP were investigated. The measured density is 1.81 g·cm^-3， the solid formation enthalpy is 827.1 kJ·mol^-1， the calculated detonation velocity and pressure are 7968 m·s^-1 and 36.0 GPa， respectively. The impact sensitivity is above 40 J， and the friction sensitivity is above 360 N. The overall performance of NADFP is obviously better than that of traditional heat-resistant explosive 2，2′，4，4′，6，6′-hexanitrostilbene.

Abstract:The eutectic mixtures of 2，4，6-trinitro-3-bromoanisole （TNBA） and 1，3，3-trinitroazetidine （TNAZ） with different mass ratios were prepared by the electrostatic spray method. T-X and H-X phase diagrams were drawn according to the differential scanning calorimetry （DSC） curves of the eutectic mixtures to obtain the mass ratio of the lowest eutectic. Scanning Electron Microscopy （SEM）， Energy Dispersive Spectroscopy （EDS）， High Performance Liquid Chromatography （HPLC）， X-ray Powder Diffraction （XRD）， Infrared （IR）， X-ray Photoelectron Spectroscopy （XPS）， DSC， and thermogravimetry-mass （TG-MS） spectrometry were used to determine the morphology， component content， element distribution， crystal structure and thermal decomposition properties of the lowest eutectic. And the mechanical sensitivity， thermal sensitivity and detonation performances of the lowest eutectic were tested and theoretically calculated. The results showed that 60.95∶39.05 is the optimal mass ratio of TNBA/TNAZ lowest eutectic mixture； the microscopic morphology has no sharp edges and corners； the component proportion is the same as before electrostatic spraying； the surface elements are evenly distributed； and the crystal structure is basically the same as that of the raw materials. The eutectic temperature is 350.18 K， which is 22.72 K and 24.82 K lower than that of raw materials TNBA and TNAZ. The thermal decomposition reaction rate constant （k）， activation enthalpy （ΔH^≠）， activation energy （E_K）， activated Gibbs free energy （ΔG^≠）， and activation entropy （ΔS^≠） of the lowest eutectic are 0.33 s^-1， 60.10 kJ·mol^-1， 64.44 kJ·mol^-1， 135.21 kJ·mol^-1， and -143.78 J·（mol∙K）^-1， respectively. The impact sensitivity （H₅₀）， friction sensitivity （FS）， and 5s explosion temperature of the lowest eutectic mixture are 42 cm， 20%， and 558 K， respectively. Its detonation performance （OB=-34.83%，Q=5101.78 kJ·kg^-1，V_D=7598.37 m·s^-1） is between TNBA and TNAZ. The main detonation products are N₂、C（d）、CO、CO₂ and H₂O.

Abstract:As a kind of clean energy， microwave is widely used in energetic materials due to its unique penetrability and high safety， which can interact with energetic materials in volume. The application of microwave in the testing of energetic materials， microwave assisted synthesis of energetic materials， excitation of energetic materials and enhancement of propellant combustion were summarized. The mechanism of microwave-assisted synthesis of energetic materials is not clear， the absorption materials introduced in microwave sensitized explosives is relatively single， and the microwave enhanced combustion is only suitable for some propellants were pointed out. The future development directions were put forward： expanding the types of absorbing materials， activating non-metallic energetic materials by microwave ignition of nano-thermites， and realizing the dexterity and convenience of microwave devices.

Abstract:Glycidyl azide polymer （GAP） has been considered as excellent energetic binder or plasticizer in high energetic solid propellants because of its high heat of combustion， low burning temperature， good thermal stability， clear exhaust and good compatibility with oxidizers. However， the presence of bulky， polar azide side group and reduced backbone flexibility， causing poor mechanical properties， especially the inferior low-temperature mechanical properties. Owing to chemical modification could better regulate the performance of GAP， it has attracted extensive attention. This paper illustrates the synthetic methods and processes of GAP， such as direct and indirect methods； summarizes various chemical modification methods of GAP and clarifies the relationship between the structures and properties of the GAP-based copolymers. At last， the future development of controllable， facile and green synthesis strategies for high molecular weight GAP， performance research methods and application prospects in high energy thermoplastic elastomers are described and discussed.

Abstract:The mixture and composite of dihydroxylammonium-5，5"-bistetrazole-1，1"-diolate （HATO） and ammonium perchlorate （AP） were prepared by dry-mixing and solvent-nonsolvent recrystallization， respectively. The microstructure and mechanical sensitivity of HATO， AP， HATO+AP mixture and HATO-AP composite were analyzed by scanning electron microscope （SEM） and military standard methods， and the ignition and combustion pressure characteristics of four materials mentioned above were also compared experimentally. In addition， the reaction characteristics of HATO-AP composite was discussed based on the thermogravimetry-mass spectrometry （TG-MS） results. Results show that HATO and AP may be cocrystal， crystal mixed or coated with each other in HATO-AP composite， which makes the mechanical sensitivity of HATO-AP composite significantly lower than that of HATO+AP mixture. The peak of combustion pressure and pressurization rate of HATO are much higher than that of AP. The HATO-AP composite can eliminate the adverse effects of AP in combustion property， and increase the peak of combustion pressure by 17.3% compared with raw. Because of the intimate contact between HATO and AP on a smaller microscopic scale in the composite， this allows these two molecules to react directly. The N element may directly react to form NH₃， HCN， NO or other NO_x instead of N₂ in the reaction process. The changes in reaction mechanism may make a difference on combustion pressure characteristics of HATO-AP composite.

Abstract:Furoxan is a nitrogen-rich aromatic ring with a potential "nitro" fragment. The compactness of the skeleton and outstanding enthalpy of formation make it an important molecular skeleton for the research of energetic materials. The unique arrangement of nitrogen and oxygen atoms significantly increases the tendency of furoxan to tautomerism， and the presence of tautomers reduces the stability of the furoxan skeleton and increases the difficulty of its synthesis. This account reviews the research on the synthetic methodologies of furoxan based on different strategies. Focusing on the synthetic mechanism of furoxan framework itself， the advantages and disadvantages of different synthetic methodologies are analyzed and compared. Moreover， the progress of energetic materials based on the strategy developed for the synthesis of furoxan is also summarized. Considering the high density， high oxygen balance and high enthalpy of formation of furoxan ring， energetic structures based on the furoxans will still be a key direction of research and development of high energy density materials.

Abstract:In order to easily synthesize sodium pentazolate， the synthesis method and conditions of sodium pentazolate were studied. Diazoniums 4a-b and sodium pentazolate were characterized by infrared （IR）， nuclear magnetic resonance （NMR）， mass spectrometry （ESI-MS）， or ion chromatography （IC）. Results show that sodium pentazolate can be easily synthesized via the cyclization/C—N cleavage one-pot method； the appropriate reaction conditions for the synthesis of sodium pentazolates from diazonium chloride 4a are as follows： the molar ratio of NaHCO₃ to 2，6-dimethyl-4-aminophenol is 0.6， the cyclization temperature is -45 ℃， the cyclization time is 2 h， the C—N cleavage temperature is -35 ℃， the C—N cleavage reaction time is 24 h， and the molar ratio of m-CPBA to 2，6-dimethyl-4-aminophenol is 3∶1； the suitable reaction conditions for synthesizing sodium pentazolate from diazonium tetrafluoroborate 4b are as follows： the molar ratio of NaHCO₃ to diazonium tetrafluoroborate is 0.3， the cyclization temperature is -45 ℃， the cyclization time is 7 h， the C—N cleavage temperature is -35 ℃， the C—N cleavage reaction time is 24 h， and the molar ratio of m-CPBA to diazonium tetrafluoroborate is 4∶1； sodium pentazolate can be easily isolated by ethanol extraction， of which the purity is up to 98.87 % （area normalization）.

Abstract:In order to obtain spherical granulations with regular shape， good dispersibility and uniform particle size， the effects of different binders on 2，2"，4，4"，6，6"-hexanitrodiphenylethylene （HNS） composite microspheres were studied by using droplet microfluidic technology. Fluoroelastomer （F₂₆₀₄）， nitrocellulose （NC） and glycidyl azide polymer （GAP） were selected to prepare spherical granulation of submicron HNS， and submicron-level HNS/F₂₆₀₄ （95/5）， HNS/NC （95/5） and HNS/GAP （95/5） composite microspheres were successfully prepared. Resultant microspheres were characterized by scanning electron microscope， X-ray diffractometer， specific surface area， thermal analyzer， true density tester and mechanical sensitivity tester. Results indicated that such methods could obtain the HNS composite microspheres with high sphericity， monodisperse， narrow size distribution， good roundness and improved safety performances. The average circularities were 0.934， 0.915 and 0.925 with D₅₀ of 45.39， 58.68 μm and 45.43 μm （the span was less than 0.55）， respectively. Thermal decomposition peak temperatures were 354.44， 349.53 ℃ and 339.37 ℃ for HNS/F₂₆₀₄， HNS/NC and HNS/GAP， respectively. The spheroidization process increases the true density of the microspheres to 1.9408， 1.9383 g·cm^-3 and 1.9204 g·cm^-3， respectively， which can effectively improve the HNS charge performance. The cone angles of 27°， 24.3°， and 24° indicated that microspheres have good dispersion performances. Compared with submicron HNS， the impact sensitivity of the three microspheres was increased by 5.5， 4， 3.5 J， and the friction sensitivity was increased by 52， 36 N and 4 N， respectively， indicating a better safety performance.

Abstract:Aluminum based hydrogen storage composite fuel namely Q3 with a content of boron 15% and MgH₂ 15% was prepared by means of chimeric assembly. The powder had a spheroidic morphology. Its theoretical combustion heat was as high as 34.8 MJ·kg^-1. Thermogravimetric Analysis （TGA） was employed to test the oxidation performance of spherical aluminum and Q3. The results indicated that the initial oxidation temperature of Q3 was 430 ℃， which was around 100 ℃ lower than that of spherical aluminum. When the temperature was up to 1000 ℃， the weight of Q3 increased by 60% due to the oxidation， which was higher than that of spherical aluminum （23%）. This result indicated that the aluminum based hydrogen storage composite fuel had a better ignition performance and higher oxidability. The tests of underwater explosion with two RDX based explosive formulas containing 35% metal powder or equivalent Q3 were carried out respectively. The test results showed that for the formula with equivalent Q3， the explosion specific shock wave energy was reduced by 3.0%， the specific bubble energy was increased by 9.5%， and the total explosion energy was increased by 7.6% in contrast to the counterpart formula containing aluminum. The metal hydride and aluminum in aluminum based hydrogen storage composite fuel could effectively improve the energy release efficiency and rate of boron， resulting in increasing the total energy of the explosive in underwater explosion.

Abstract:Diatomite particles with size distribution of 200-300 μm were used as emulsifying matrix carrier to prepare low detonation velocity emulsified explosive. The microscopic properties of diatomite were characterized. The effects of diatomite mass fraction on the particle size and detonation mechanism of explosive were analyzed. The density， detonation velocity and air explosion shock wave pressure of explosive were measured. The compatibility of diatomite and emulsified matrix was tested. The results show that when the mass fraction of diatomite increases from 15% to 35%， the particle size of explosive is negatively correlated with the content of diatomite， the density of explosive decreases from 0.79 g·cm^-3 to 0.51 g·cm^-3， and the detonation velocity decreases from 2561 m·s^-1 to 1655 m·s^-1. The peak pressure of air explosion shock wave decreases from 0.061 MPa to 0.023 MPa. The addition of diatomite has no effect on the thermal stability of emulsified matrix， and the diatomite and emulsified matrix do not react with each other under room temperature or heating conditions. The detonation velocity and the peak pressure of air explosion shock wave of the explosive stored for 2 days and 120 days drop less than 5%， indicating that diatomite has good compatibility with emulsified matrix.

Abstract:This review focused on the four major construction methods of 1，2，3-triazole energetic materials and corresponding research progress since the 1960s， including： Ⅰ） energetic compounds constructed based on 1-amino-1，2，3-triazole； Ⅱ） energetic compounds constructed based on dicyano substituted 1，2，3-triazole； Ⅲ） 1，2，3-triazole based energetic compounds prepared through azide involved cyclization reaction； Ⅳ） fused polycyclic energetic compounds built from 1，2，3-triazole. By analyzing the relationship between the molecular structure and energetic properties of several representative 1，2，3-triazole based energetic compounds， the influence of molecular structures on their energetic performances and stabilities could be profoundly clarified. Meanwhile， the potential application values of the mentioned high-performance 1，2，3-triazole based energetic compounds， such as their application prospects of main explosives， heat-resistant explosives and lead-free primary explosive， were discussed， providing a reference for the design and development of next-generation high energy density materials （HEDMs）.

Abstract:To investigate the effect of mesoporous carbon nanospheres （MCS） on the thermal decomposition properties of cyclotrimethylenetrinitramine（RDX）， MCS was prepared by double template method with the particle size of about 350 nm. RDX crystals were introduced into the pore and surface of MCS by host-guest chemistry technology. The morphology and structure of MCS and MCS/RDX composite were characterized by scanning electron microscopy （SEM） and X-ray powder diffraction （XRD）. The interface interaction between MCS and RDX was studied by Fourier transform infrared spectroscopy （FTIR） and differential scanning calorimetry-thermogravimetry （DSC-TG）. Compared with pure RDX， the decomposition temperature of MCS/RDX composite decreased by 13 ℃ and the heat release increased. The apparent activation energy decreased from 234.87 kJ·mol^-1 to 126.48 kJ·mol^-1. The sensitivity tests were carried out by the drop hammer impact sensitivity instrument and the electrostatic spark device. Compared with the pure RDX， the impact sensitivity and electrostatic spark sensitivity of the obtained MCS/RDX composite are apparently reduced. Therefore， the obtained MCS has good catalytic performance for the thermal decomposition of RDX and can reduce the sensitivity of RDX.

Abstract:A series of energetic salts （5-11） were synthesized by reacting polyamino-fused heterocyclic 4，7-diaminopyridazino［4，5-c］furoxan （4） with nitrogen-rich energetic acids including NTO or some other high-nitrogen nitroamino derivatives. The structures of 5-11 were characterized by nuclear magnetic resonance （NMR） spectroscopy， elemental analysis and infrared spectroscopy. In addition， the ¹⁵N NMR spectrum of 6 was measured and assignedbased on the quantum calculations. The crystal structure of 9 was also confirmed by single crystal X-ray diffraction. The detonation properties of these compounds （5-11） were calculated by Explo5 （version 6.05.02） software， and the impact and friction sensitivities were also measured. Among them， compound 5 exhibits good detonation performances （D_v： 8816 m·s^-1， P： 32.1 GPa） and low sensitivities（IS： 15 J， FS： 200 N）.

Abstract:Aiming at the problems that the crystallization methods （evaporation， antisolvent and cooling， etc.） of the conventional explosive are difficult to accurately control the uniformity of supersaturation and the low solvent recovery rate， an organic solvent nanofiltration（OSN） membrane crystallization apparatus based on pressure-driven and cross-flow filtration was designed and used to study the membrane crystallization process of 1，3，5，7-tetranitro-1，3，5，7-tetrazacyclooctane（HMX）. The effects of key process parameters （temperature and pressure） on the crystal morphology and particle size were discussed， and the crystal morphology and structure were compared with those of evaporative crystallization. The HMX crystals after recrystallization by both methods were characterized by scanning electron microscopy（SEM），X-ray powder diffractometer（XRD） and thermogravimetric-differential scanning calorimeter（TG-DSC）. The long-term operational stability of the nanofiltration membrane was further investigated， and the solvent recovered by permeation was used to re-crystallize. Results show that by the optimal control of temperature and pressure， the membrane crystallization process can obtain β-phase HMX with narrow particle size distribution （coefficient of variation < 46%）， high crystal density （ρ_avg=1.8997-1.9004 g·cm^-3） and excellent thermal stability. Compared with evaporation crystallization， the supersaturation control in the membrane crystallization process is easier to operate， and the prepared crystal morphology is more uniform. After repeated use， the rejection of HMX molecules in the solvent still remained above 92%， showing a good permeation selectivity stability. The β-phase HMX crystals with an median particle size of 34.92 μm and a coefficient of variation of 37.22% can still be prepared by membrane crystallization using permeation-recovered solvent， indicating that this technology can realize the efficient recovery and reuse of the crystallization solvent.

Abstract:In order to investigate the infrared extinction performance of nickel-plated graphene and explore the best formulation， nickel-plated graphene was prepared by the redox and chemical plating methods. The influence of various factors on the extinction performance of nickel-plated graphene was analyzed by designed orthogonal experiments with the infrared decay rate as the evaluation index， and the optimal formulation was determined. The infrared transmittance of nickel-plated graphene was measured in a smoke-screen chamber test. The average mass extinction coefficient of nickel-plated graphene was calculated by linear fitting according to the “Lambert-Beer” law. The results showed that the optimal process parameters for the preparation of nickel-plated graphene were： c（NiSO₄·6H₂O）=20 g·L^-1， c（NaH₂PO₂·H₂O）=24 g·L^-1， c（C₆H₅Na₃O₇·2H₂O）=10 g·L^-1， c（NH₄Cl）=30 g·L^-1， pH=8-9， and plating temperature of 65 ℃. The nickel-plated graphene prepared under the optimal conditions exhibited good infrared extinction in both mid- and far-infrared wavelengths. The average mass extinction coefficients of the nickel-plated graphene in the infrared bands of 3-5 μm and 8-14 μm were 2.38 m²·g^-1 and 2.19 m²·g^-1， respectively. Compared with the modified graphene， the average mass extinction coefficients of nickel-plated graphene in the mid-infrared bands were improved by 30% and 35%， respectively， which have broader application prospects.

Abstract:The preparations of high-energy pentazolate salts is a research hotspot in the field of energetic materials. The preparation of pentazolate anion is a key step in the preparations of high-energy pentazolate salts. However， as the important precursors for pentazolate anion， the stability of existing arylpentazoles is generally not high. In order to develop new precursors of pentazolate anion with better properties， 18 substituted derivatives of PyN₅ with the electron-withdrawing and electron-donating groups， i.e.， R-PyN₅ （R=－NO₂， －CN， －NF₂， －OH， －OMe， －N（Me）₂）， were designed and studied by using the density functional theory method. The bond dissociation energy（E_BD）， and the activation energy（E_a1） of the bridged C—N bond and the activation energy（E_a2） of the cracking of the N₅ ring were calculated， and the stability of the bridged C—N bond and pentazolate ring were discussed. E_a1 of all molecules is smaller than E_BD， indicating that the breakage of the bridged C—N bond is more likely to follow the path 2 rather than path 1. E_a2 of all molecules is smaller than E_a1， indicating that the stability of the N₅ ring is the key factor to determine the stability of the arylpentazoles. Compared with PhN₅， —N（Me）₂ meta-substituted and bis-substituted compounds have lower E_a1， higher E_a2 and lower ΔE （E_a2－E_a1）. Therefore，—N（Me）₂ meta-substituted and bis-substituted compounds are the most potential precursors of N₅ˉ ion for replacing PhN₅.

Abstract:The design efficiency of energetic compounds depends on many factors， such as the proportion of potential high performance samples in the screening space and the accurate prediction method of key properties. In this study， we proposed a scheme to improve the overall performance of virtual screening space by pre-screening molecular skeletons， and a method combining high-throughput computing and deep learning is applied to the design of energetic compounds. It was found that there is a moderate positive correlation between crystal density molecular skeleton density of energetic molecules， and the overall density of virtual screening space can be effectively improved by pre-screening high-density molecular skeletons. Based on the density data-set of energetic crystals collected from the crystallography database CCDC， a new density prediction model of energetic crystals was obtained via deep learning， with reliable accuracy and generalization. We took fused-ring energetic molecules as the research object， obtained high-density fused-ring skeletons through skeleton pre-screening， and then the virtual screening space composed of potential high-density molecules was constructed through fragment docking. The formation enthalpy， detonation performance and chemical stability were predicted by quantum chemical calculation and the equation of state of detonation products. Finally， 6 novel energetic molecules with energy level better than RDX and stability better than TNT were selected by performance ranking. This study shows that the overall performance of virtual screening space can be effectively improved by pre-screening molecular skeletons， and on this basis， high-throughput computing and deep learning can be used to achieve efficient design of energetic molecules.

Abstract:For achieving engineering application of pentazolium anionic energetic materials， it is necessary to realize large-scale production of 3，5-dimethyl-4-hydroxyphenylpentazole （HPP） as the precursor of pentazole. The pilot synthesis techniques of HPP were performed based on accessibly lab-leveled method using 10 L and 100 L reactors for scale-up experiments. The dropping time of aqueous solutions of sodium nitrite and sodium azide， the purity and the feeding mass of 3，5-dimethyl-4-hydroxyaniline hydrochloride （DAC）， on the production of HPP were investigated. Results indicate that HPP production increases with the increasing of the total dropping time of sodium nitrite aqueous solution and sodium azide aqueous solution. After a certain value， the production of HPP remains. The purity of DAC affects the HPP production significantly that the production increases with the increasing of purity. With the scale up， HPP production increases along with the reducing of production ratio. With the feeding mass of DAC reached to 6 kg， a batch of product increased to 11.5 kg as well as the production rate decreased to 1.91.

Abstract:To improve the compatibility of dihydroxylammonium 5，5′-bitetrazole-1，1′-diolate（TKX-50） with nitrocellulose（NC）， silane coupling agent （KH550） was used as the coating agent and three TKX-50/KH550 composites （TK1， TK2， TK3） were obtained.The morphology， structure and thermal stability of the composites were studied by using scanning electron microscopy （SEM）， Fourier infrared spectroscopy （FTIR）， and differential scanning calorimetry （DSC）. Accelerating rate calorimeter （ARC） and DSC were used to examine the compatibility of TKX-50/KH550 composites with NC. The results show that the apparent activation energy of thermal decomposition of the prepared TKX-50/KH550 composites are 190.03， 195.82 and 194.42 kJ·mol^-1 respectively higher than that of TKX-50 （138.86 kJ·mol^-1）， indicating the thermal stability of TKX-50 is improved by KH550 coating. In adiabatic conditions， the initial thermal decomposition temperature of the mixtures of TKX-50/KH550 composites and NC are 14.93， 18.18 and 17.90 ℃ respectively higher than that of TKX-50 and NC. After coated with KH550， the compatibility of TKX-50 and NC is improved， and the compatibility level of TKX-50/KH550 composites and NC is raised from Level 3 to Level 2.

Abstract:In order to synthesize high-purity 3，5-diamino-2，4，6-trinitrochlorobenzene （DATNCB）， the synthesis route screening and process optimization of DATNCB were studied with 1，3，5-trichloro-2，4，6-trinitrobenzene （TCTNB） or picric acid （2） as raw materials， respectively. The structure of the product was characterized by IR， NMR and MS； the thermal behavior of DATNCB was studied by DSC-TG； the purity of DATNCB was analyzed by HPLC. The results show that： the best synthetic route of DATNCB is starting from picric acid， then by via VNS amination followed by chlorination. The total yield is 39.2%. The highest yield of 3，5-diamino-2，4，6-trinitrophenol （3） was 74.8% when VNS amination temperature was 90 ℃ and post-treatment pH value was 3； the highest yield of DATNCB was 52.4% when phosphorus oxychloride/N，N-dimethylaniline was used as the chlorination reagent， the reaction temperature was 80 ℃ and the reaction time was 10 h. The melting point of DATNCB is 224.0 ℃. There is only one weight loss stage in the range of 179.7-270.9 ℃ and the weight loss rate is 91.6%； the peak decomposition temperature is 256.1 ℃. The purity of DATNCB reach 97.09% without further purification， and up to 99.8% after recrystallization with ethyl acetate/petroleum.

Abstract:The fluorescence properties and fluorescence stability of 2，4，8，10-tetrabroitro-benzopyrido-1，3a，6，6a-tetraazapentylene （BPTAP） were comprehensively investigated. The spectral properties of BPTAP in different solvents （acetonitrile， methanol， tetrahydrofuran， acetone， trichloromethane， ethyl acetate， N"-N"-dimethylformamide， dimethyl sulfone）， content of water （0-100%）， pH （2.0-12.0） were studied in detail. The effects of light， temperature and pH value on the fluorescence stability of BPTAP solution were investigated， and the mechanism of fluorescence decay of BPTAP solution was analyzed by ultra performance liquid chromatography-high resolution mass spectrometry （UPLC-HRMS）. The results show that although BPTAP has four nitro groups， it exhibits strong green fluorescence in some organic solvents. The fluorescence intensity of BPTAP in acetonitrile is the highest， and its maximum absorption/emission wavelength is 460 nm/508 nm. Low content of water （≤10%） can increase fluorescence intensity of BPTAP， while high content of water （>10%） decrease the fluorescence of BPTAP sharply. BPTAP has higher fluorescence in acidic， neutral and weak alkaline conditions. When the pH value is above 9.0， the fluorescence of BPTAP decreases rapidly with the increase of pH value. BPTAP shows good stability in room temperature and natural light. The closer the light wavelength is to the maximum absorption wavelength of BPTAP and the higher the temperature， the worse the fluorescence stability of BPTAP. The increase of pH value not only reduces the fluorescence intensity of BPTAP， but also accelerates the decline of BPTAP fluorescence. The mechanism of fluorescence decay of BPTAP under alkaline condition is based on nucleophilic substitution. The nitro group at para site of pyridine ring is replaced by the hydroxyl group in alkaline solution to form a new compound 1 （the elemental composition ［M-H］^- is C₁₁H₃N₈O₇）.

Abstract:In order to explore the infrared extinction properties of three-dimensional graphene， three-dimensional （3D） graphene powders were prepared by thermochemical deposition method. The morphological and structural characteristics of the three-dimensional graphene powder were confirmed by electron microscopy and X-ray diffractometer， and the dispersion properties were tested by using a comprehensive powder characteristic tester. Then the infrared extinction properties of three-dimensional graphene were tested by using smoke chamber test， and compared with the extinction properties of composite graphite and carbon fiber under the same test conditions. The results show that the infrared extinction performance of three-dimensional graphene is excellent. The average mass extinction coefficients are about 1.32 m²·g^-1 and 1.09 m²·g^-1 in the infrared wavelength range of 3-5 μm and 8-14 μm， respectively. Compared with composite graphite and carbon fiber， the average mass extinction coefficients of 3-5 μm are improved by 57% and 132%， respectively. And the average mass extinction coefficients of 8-14 μm are improved by 35 % and 102 %， respectively. It can be seen that 3D graphene shows better infrared extinction ability.

Abstract:Bridged nitrogen-rich heterocyclic energetic compounds are of the rich diversity， good thermal stability and excellent energy density. They are potential materials with high energy density and have been widely studied and reported by scholars all over the world. Among them， the imino group （—NH—）， which acts as bridged unit， can not only improve the enthalpy of formation and energy density， but also reduce the sensitivity by the formation of hydrogen bonds through the bridged imino group， thereby constructing high-energy and low-sensitivity energetic materials. This paper introduces the research progress of imino-bridged nitrogen-rich heterocyclic energetic molecules and their salts， and reviews the preparation methods， physicochemical properties and detonation properties of these energetic compounds， the future development potential and research trend of imino-bridged nitrogen-rich heterocyclic compounds are prospected， so as to provide a reference for the design and synthesis of imino-bridged energetic compounds.

Abstract:High purity 2，4，6-trinitro-5-ethoxy-1，3-phenylenediamine （DATNEB） can be used as an internal standard in high performance liquid chromatography （HPLC） to accurately analyze the purity of TATB synthesized by the chlorine-containing method. To study the synthesis and energetic properties of DATNEB， high purity DATNEB was prepared from picric acid by aminating with 4-amino-1，2，4-triazole （ATA） and then ethylating with triethyl orthoformate. The overall yield was 32.5% and the purity was over 99.8%. The structure of the product was characterized by IR， ¹H NMR， ¹³C NMR， MS and X-ray single crystal diffraction. The mechanisms of amination and ethylation were discussed， the thermal and detonation properties of DATNEB were also studied. The results show that DATNEB crystallizes in a monoclinic system， space group P2₁/c with a=1.21261（7） nm， b=0.89654（4） nm， c=1.12310（6） nm， V=1.17675（11） nm³， Z=4， ρ=1.62 g·cm^-3. DATNEB exhibits an endothermic peak at 193.9 ℃ and exothermic peak at 236.0 ℃， indicating a good thermal stability. It has a detonation velocity of 7.05 km·s^-1 and detonation pressure of 21.14 GPa，which is comparable to TNT， while the sensitivityis much lower than that of TNT and RDX. Therefore， the synthesized high-purity DATNEB can not only be used as an internal standard， but also an auxiliary component of molten-cast explosives.

Abstract:Nitrobenzene compounds widely exist in the explosives， petrochemical， dye and other industries， and a large amount of nitrobenzene wastewater are produced in the production process， which is of great concern to scientists because of its stable structure， high toxicity and poor biodegradability. Traditional wastewater treatment methods have limited mass transfer and low treatment efficiency， and the enhanced treatment of nitrobenzene wastewater using high gravity technology has become a new and promising method. In this paper， the research progress in the treatment of nitrobenzene wastewater by high gravity enhanced physical method， reduction method and advanced ozone oxidation method is reviewed， including enhancing mass transfer process， material preparation， catalytic degradation and so on， and the key issues of scale-up process and future development for improving structure and extending the liquid residence time for high gravity enhanced treatment of nitrobenzene wastewater that should be concerned are discussed and prospected.

Abstract:Explosive TNT is the most important weapon energy source in military activities. It not only has a powerful damaging effect， but also has chemical toxicity. Even a trace amount of TNT will pose a serious threat to the natural environment and human health. Therefore， the development of trace explosive detection technology with high sensitivity， high accuracy and fast response has far-reaching research significance for protecting the ecological environment and maintaining human health. Among many trace detection technologies， biosensing technology has the advantages of good selectivity， simple synthesis， fast response and high sensitivity， and has good application prospects. This paper reviews the research progress of biosensor technology in the detection of trace explosives in recent years， focusing on the advantages and limitations of five types of biosensors： antibody immunity， peptides， aptamers， enzymes and multi-parameter loading. Among them， the sensor prepared based on aptamer has good affinity and specificity for explosive molecules， the detection limit is 1000 times lower than other types of sensors， and has good stability， easy modification and modification， and strong structural expansion ability. Future research will focus on the construction of high-throughput trace explosives sensing systems based on bioreceptor components such as aptamers， combined with neural network algorithms and machine learning to construct biosensors with multiple detection and bionic remote sensing properties.

Abstract:This review summarized progress of 2，4，6-trinitrotoluene （TNT） multifarious reutilization in the aspects of chemical transformation and microorganism degradation. Chemical transformation pathways are classified into TNT methyl oxidation， nitro reduction， and substitution reaction. The diverse chemical transformation pathways were systematically summarized according to the green environmental protection， reaction mechanism， reaction efficiency and product properties combined with resource reuse. The microorganism transformation pathways are classified into aerobic bacteria， anaerobic bacteria and fungus. A more comprehensive overview of the aerobic and anaerobic metabolic pathways of TNT microorganisms is presented， summarizing the relevant microorganisms. Finally， the development direction of waste TNT resourceful reuse based on chemical and biological transformation is prospected. Chemical transformation of TNT will go beyond the laboratory research stage， and green process research and safety will be the focus of this stage of research. Microbial transformation of TNT remains the focus of research， and combined with genetic engineering and modern molecular biology technology， it is expected to provide new solutions for deep reuse of waste TNT.

Abstract:Nitrobenzene， nitrotoluene and dinitrophenol in aromatic nitro compounds are the main components of explosives. In addition to their own explosiveness and danger， they also have high stability and high toxicity， which can cause great harm to human health， soil， water source and ecological environment. In this paper， the current status of aromatic nitro compound wastewater treatment technology is summarized. Based on three treatment methods of physical treatment， chemical treatment and biodegradation， the advantages and disadvantages of various technologies are summarized， and the development trend is prospected. Among the three treatment methods， the physical treatment method has potential secondary pollution risks， and the biodegradation method has higher time cost， therefore， it is considered that the chemical treatment method is considered to be the most promising method. Among them， the photocatalytic method can efficiently degrade aromatic nitro compounds wastewater only with the help of sunlight， which has the advantages of green environmental protection and energy saving. Although this method has not been applied to practical applications， other treatment technologies can be combined with photocatalytic methods to achieve the effect of complementing each other.

Abstract:In order to investigate the application effect of fluorocarbon resin （FEVE） in explosive ink， a new type of oil-in-water emulsion bonded system was designed by employing polyvinyl alcohol （PVA） aqueous solution as water phase and FEVE/ethyl acetate solution as oil phase. By adding sub-micron CL-20 particles into bonded system， CL-20-based explosive ink was prepared for direct writing. Scanning electron microscope， rheometer， X-ray diffractometer， and impact and friction sensitivity tester were used to characterize morphology and detonation performance of printed samples. The results show that PVA/FEVE oil-in-water emulsion binder system can stably exist for 174 h. The CL-20 explosive ink with 90% solid content exhibits optimal rheological properties and good printability. The obtained direct writing sample with microporous internal structure displays a smooth surface， and the crystal form of CL-20 explosive is still ε type. The impact energy and friction force of printed samples are 216 N and 4.5 J， respectively. Compared with raw ε-CL-20， impact sensitivity and friction sensitivity of printed samples are reduced by 125% and 200%， respectively. The detonation velocity， critical detonation corner turning， critical detonation thickness of 1-mm line width， and critical detonation size of square section of printed samples are 6772 m·s^-1， 160°， 0.039 mm， and 0.4 mm×0.4 mm， respectively， which show excellent micro-scale detonation capability.

Abstract:Aiming at the difficulty in purification of metal pentazolates， the separation and purification of metal pentazolates were studied by precipitation method based on the aqueous solution of sodium pentazolate， which was obtained via C—N cleavage reaction of arylpentazole. Results show that the aqueous solution of sodium pentazolate contains a lot of organic acid salts， as well as inorganic salt impurities such as sodium nitrate and sodium chloride. Compared with N₅ anions， the organic acid salts prefer to precipitate with metal ions in aqueous solution， thus affecting the precipitation of metal pentazolates. Cobalt pentazolate was precipitated from the aqueous solution of sodium pentazolate via acidification， removal of organic acid salts by extraction， and then addition of cobalt chloride. The lower the pH value is， the higher the removal efficiency of organic acid salts is and the higher the purity of cobalt pentazolate is. The optimized separation conditions of cobalt pentazolate are as follows： the pH value is 3， and the molar ratio of cobalt chloride to 4-amino-2，6-dimethylphenol （1） is 0.26∶1. The purity of cobalt pentazolate is up to 97.9% after simple recrystallization as shown by ion chromatography. The applicability of this precipitation method to other metal pentazolates was also studied. Results show that it is also suitable for the separation and purification of iron， ferrous and copper pentazolates.

Abstract:4H-［1，2，3］Triazolo［4，5-c］［1，2，5］oxadiazole 5-oxide （TODO）hydroxylamine salts and TODO amine salts were synthesized via nitration， cyclization and salt-forming reaction using 3，4-diaminofuran. At the same time， an energetic eutectic（HATODO/ATODO cocrystal） was synthesized by TODO hydroxylamine salts（NH₃OH⁺C₂H₅O^-）and TODO amine salts（NH₄⁺C₂H₅O^-）as raw materials. Its structure was characterized by SXRD，FT-IR and NMR， and the thermal decomposition was studied by TG-DSC. The mechanical sensitivities were tested according to the GJB772A-97 method and the detonation performance was calculated. Results show that the structure of the HATODO/ATODO cocrystal belongs to the monoclinic crystal system， the P2₁/c space group， a=8.5202（3） Å， b=10.3870（4） Å，c=13.4481（4）Å， α=90°， β=102.0510（10）， γ=90°， V=1163.92（7） ų， Z=4.TODO hydroxylamine salts initial decomposition temperature is about 147.9 ℃， TODO amine salts initial decomposition temperature was about 181.3 ℃， whereas the initial decomposition temperature of energetic HATODO/ATODO cocrystal is about 151.2 ℃. The sensitivities of HATODO/ATODO cocrystal is comparable to ADN. The calculated detonation velocity and pressure of HATODO/ATODO cocrystal is 8462 m·s^-1 and 32.07 GPa.

Abstract:The particle size and morphology of energetic material crystal have a great influence on its performance. In order to study the relationship between crystal morphology， particle size and thermal decomposition performance of 1，1-diamino-2，2-dinitroethylene （FOX-7） explosive， FOX-7 explosive particles with different morphologies and particle sizes were prepared according to solvent/non-solvent method. Scanning electron microscope （SEM）， X-ray diffractometer （XRD）， differential scanning calorimeter （DSC） and impact sensitivity tester were used to investigate the crystal morphology and particle size， crystal form， thermal decomposition property and safety property of FOX-7 explosives， respectively. The results show that by changing the cooling rate， stirring rate and other process conditions， FOX-7 explosive particles with different morphologies such as sea urchin shape， spherical shape， flower shape and block shape can be obtained. The crystal form of prepared FOX-7 explosive is consistent with that of raw material as α-form. The crystal morphology and particle size of FOX-7 have a great influence on the breaking of intramolecular hydrogen bonds and the destruction of the conjugated system， and the spherical shape is beneficial to increase the thermal decomposition temperature. For the FOX-7 sample with a same shape， the larger the particle size， the better the thermal stability. Among the FOX-7 samples with diameters of tens of microns， the sample with spherical morphology has the best safety performance.

Abstract:The performance prediction methods for high-throughput energetic molecule design and screening are required to balance accuracy and efficiency. In the present work， the suitability of three common theoretical methods on different levels， including semi-empirical PM6 method， density functional theory method B3LYP/6-31G（d，p）， and high-precision complete basis set CBS-4 method， for heat of formation （HOF） prediction under the atomization scheme for high-throughput energetic molecule design and screening were evaluated. The solid HOF of twenty energetic molecules were compared， and the results of different theoretical levels are found to differ greatly. Based on the predicted HOF， experimental density， and three models （K-J， BKW and VLW）， the detonation performance of ten common energetic molecules were predicted. The results show that B3LYP method possesses the best suitability and efficiency， and the predicted detonation performance is closed to that obtained by CBS method. For example， the average relative deviation of the detonation velocity and detonation pressure predicted by BKW are only 0.4% and 1.2%， respectively. However， both the low-precision PM6 method and the time-consuming CBS method are difficult to balance the requirements of precision and efficiency in high-throughput energetic molecule design and screening. It suggests that， for the high-throughput design of energetic molecules， a medium-precision method is adequate for rapid HOF prediction.

Abstract:In order to study the aluminum-water reaction characteristics of PVA-nAl/HTPB， the PVA-nAl/HTPB composites were prepared by dispersing nAl/HTPB in the polyvinyl alcohol （PVA）， which was obtained by physical cross-linking method. In order to explore the aluminum-water reaction mechanism， the aluminum-water reaction characteristics of the polyvinyl alcohol-nAl/HTPB with 0.1 mol·L^-1 NaOH solution at different temperatures （25， 40， 55， 70， 85 ℃ and 100 ℃））were investigated and the residue after the aluminum-water reaction were characterized. The results show that the maximum hydrogen production and rate of PVA-nAl/HTPB is 76 mL·g^-1 and 80 mL·g^-1·min^-1， respectively， which is higher than that of PVA-nAl. The product of the aluminum-water reaction is aluminium oxyhydroxide （AlO（OH））.

Abstract:In order to improve the safety performance of potassium perchlorate （KClO₄）， KClO₄/ Silver （KClO₄/Ag） composite particles were prepared by chemical reaction of glucose and silver ammonia on the surface of KClO₄ particles. The particle morphology， phase composition， thermal decomposition temperature and mechanical sensitivity of the modified particles were analyzed by means of scanning electron microscope （SEM）， X-ray diffraction （XRD）， differential scanning calorimeter （DSC）， et al. The results show that KClO₄/Ag composite particles have obvious spherification effect， smooth surface and no obvious edges and corners. On the basis of retaining the original good stability and high decomposition temperature of KClO₄， it also has the characteristics of silver metal. Compared with the initial raw KClO₄， the mechanical sensitivity of KClO₄/Ag composite particles decreased significantly， the friction sensitivity explosion probability decreased from 90% to 50%， and the impact sensitivity explosion probability decreased from 70% to 40%. At the same time， the thermal decomposition performance of KClO₄/Ag composite particles is obviously different from that of raw KClO₄. The exothermic peak of KClO₄/Ag composite particles is 12 ℃ earlier and the decomposition efficiency is higher than that of raw KClO₄.

Abstract:In order to meet the requirements of explosives， thermoplastic elastomers with different number-average molecular weight （M_n） were prepared. Controllable polymerization and application of glycidyl azide polymer （GAP）-based energetic thermoplastic elastomers （GETPE） were conducted. The influence of polymerization medium and solid content on controllable polymerization of GETPE was investigated， and on-line viscosity monitoring on M_n was explored. The results show that M_n of GETPE can be accurately controlled by on-line viscosity monitoring. The error of M_n in the range of 20000-50000 can be tuned within ±2000， and the error rate can be controlled within 5%. GETPE has excellent compatibility with commonly used explosives and good application potential in high solid content propellant and high energy polymer bonded explosives （PBXs）.

Abstract:The crystallization process of 1，3，5-triamino-2，4，6-trinitrobenzene （TATB） will be affected by dioctyl sulfosuccinate sodium salt （AOT） and the molecular dynamics （MD） method was used to study this crystallization process in this work. The crystal morphologies of TATB crystal in vacuum were predicted by Bravis-Friedel-Donnary-Harker （BFDH） and attachment energy （AE） models. Seven important crystal planes of TATB were determined， which are （0 0 1）， （1 0 -1）， （1 -1 0）， （1 0 0）， （1 -1 1）， （0 1 -1） and （0 1 0）. The interface model for TATB with AOT was established and performed the molecular dynamics simulation. The modified AE model was used to analysis simulation data. After calculation， we found that the crystallization rate of TATB was improved under the influence of AOT solution. After analyzing the molecular structure and the intermolecular interaction of TATB， it is considered that because of the special plane structure， the intermolecular interaction between （0 0 1） plane and AOT is weak and the attachment energy （119.832 kJ·mol^-1） of （0 0 1） plane is low. So， the growth rate of （0 0 1） plane is relatively slow. The attachment energies of （1 0 -1）， （1 -1 0）， （1 0 0）， （1 -1 1）， （0 1 -1） and （0 1 0） planes are all higher than （0 0 1） and they all grow faster than （0 0 1）. Therefore， in the experimental process， a leaf-like TATB structure formed first. With the reaction time was further， the （0 0 1） plane gradually grows， the leaves become longer.

Abstract:The phase transition behavior of HMX-based polymer-bonded explosives （PBX） and pure HMX pellet， prepared by compression molding， was studied by variable temperature wide-angle X-ray scattering （WAXS） and differential scanning calorimetry （DSC）. The HMX-based PBX contained polyester polyurethane （HMX-Estane）， fluororubber （HMX-F₂₃₁₄）， as well as nitrocellulose （HMX-F₂₃₁₄-NC）. The initial β→δ phase transition temperatures （T_i）， as determined by WAXS， were found to be 186 ℃ for HMX-Estane（95∶5）， 188 ℃ for HMX pellet， 192 ℃ for HMX-F₂₃₁₄（95∶5）， and 198 ℃ for HMX-F₂₃₁₄-NC（95∶3∶2）. The addition of the small amount of nitrocellulose （2%） to the binder increased the T_i by about 10 ℃， compared with HMX pellet. All samples retained the δ-phase when cooled from the high temperature phase to 100 ℃ and kept in vacuum for 12 h， except HMX-Estane which went through a reversible phase transition and changed β phase completely after kept at 100 ℃ for 3.5 h. Among the three types of binders only Estane promoted the β→δ phase transition and the reversed δ→β transition of HMX. This result was attributed to the dissolution （on heating） and the precipitation （on cooling） of β-HMX at the HMX-Estane interface.

Abstract:To determine the purity of 1，3-dichloro-2，4，6-trinitrobenzene （DCTNB） product accurately， a high-performance liquid chromatography （HPLC） real-time （or in-situ）method for the determination of DCTNB and its impurities， 1，5-dichloro-2，4-dinitrobenzene （DCDNB） and 2，3，4-trichloro-1，5-dinitrobenzene （TCDNB） was established.. The effect of different mobile phase system， mobile phase ratio， flow rate and injection volume etc. conditions on the separation of high performance liquid chromatography for DCTNB was discussed. The quantitative analysis method was carried out by an external standard method. Results show that The optimal chromatographic conditions obtained are as follows： hypersil ODS2 chromatographic column （250 mm×4.6 mm， 5 μm）， UV detection wavelength 240 nm， acetonitrile /water with a volume ratio of 55∶45 as mobile phase， flow rate 1.2 mL·min^-1， column temperature 25 ℃， injection volume 10 μL. Under the above chromatographic conditions， the retention times of DCDNB， DCTNB and TCDNB are 9.20， 10.50， and 14.17 min in sequence with good resolution of all peaks（greater than 3.70）. DCDNB， DCTNB and TCDNB show a good linear relationships in the concentration ranges of 5-250， 5-500 and 5-250 mg·L^-1， respectively， and the linear correlation coefficient R² is greater than 0.999. The detection limits of DCDNB， DCTNB and TCDNB are 0.47， 0.68， 0.85 mg·L^-1， the quantification limits are 1.58， 2.28， 2.82 mg·L^-1， respectively， the relative standard deviation of 1.01%-1.27%， and the standard recovery rates are 98.82%-102.13%．

Abstract:Nano 2，6-diamino-3，5-dinitropyrazine-1-oxide （LLM-105） was prepared by ultrasound-assisted microfluidic technology based on the solvent and non-solvent method to improve the morphology and reduce the particle size. The microscopic morphology and crystal structures of the samples were characterized by field emission scanning electron microscopy （FE-SEM） and X-ray diffraction （XRD）. In addition， The promotion of fluid mixing by ultrasonic method was demonstrated by fluid visualization. The results showed that the spherical particles prepared by ultrasound were smaller and homogeneous， with an average particle size of 137.65 nm. Meanwhile， the crystal structures remained unchanged from the raw material. Differential scanning calorimetry （DSC） showed that the thermal decomposition temperature of nano-LLM-105 was reduced compared to the raw material， demonstrating that ultrasonic assistance can not only improve the efficiency of preparing nano-LLM-105， but also significantly reduce the particle size.

Abstract:1²，1⁴，1⁶，3⁴，3⁶，5²，5⁴，5⁶，7⁴，7⁶-decanitro-2，4，6，8-tetraoxa-1，3，5，7（1，3）-tetrabenzenacyclooctaphane-1⁵，5⁵-diol （ZXC-51） was obtained from phloroglucinol and 1，3-difluorobenzene through nitration and cyclization. A series of calixarene energetic salts were received by the reaction between ZXC-51 and different organic base. The single crystal structures of compound ZXC-51 and its four salts were proved by X-ray single crystal diffraction analysis. And the structures of these compounds were also characterized by NMR and elemental analysis. Meanwhile their thermal properties were also analyzed by differential scanning calorimetry. The detonation and safety performance of ZXC-51 were studied. The results show that its theoretical detonation velocity and detonation pressure are 8193 m·s^-1 and 31.18 GPa respectively. And its impact sensitivity is 36 J and the friction sensitivity is more than 360 N.

Abstract:The comprehensive performance of explosives depends not only on their chemical components， but also on their structures and morphologies to a greater extent. Microfluidics has become a new research focus owing to its superb mass transfer and heat transfer efficiency， precise parameter control and intrinsic safety. This paper analyzed and summarized the research status of droplet flow and continuous flow in the aspects of particle size， particle size distribution， crystal morphology and aggregate structure of primary and high explosives. The stable reaction environment and flexible residence time of the droplet flow are applicable to the structural control of the primary explosives， and the superior size uniformity and monodispersity of the droplet flow are appropriate for the preparation of spherical explosive particles. The high mixing efficiency of the continuous flow is in line with the crystalline properties of the high explosive. Combined with the deficiencies of current related research in post-processing methods， theoretical applicability， microfluidic manipulation methods and the degree of intelligence， suggestions and ideas for the further development of microfluidic technology in the field of explosives were put forward.

Abstract:To improve the yield and purity of 2，6-dimethyl-4-hydroxyphenylpentazole， the preparation method of 2，6-dimethyl-4-hydroxyphenylpentazole （DMAPH） crystal， the raw material of arylpentazole， was investigated through three steps including nitrification， reduction and salification from 2，6-dimethylphenol （DMP）. The structure， crystal morphology and stability were characterized with infrared spectroscopy （IR）， single crystal X-ray diffraction （SCXRD）， scanning electron microscopy （SEM）， powder X-ray diffraction （PXRD）， differential scanning calorimetry （DSC） and theoretical calculation. The results reveal that the yield of 2，6-dimethyl-4-nitrosophenol is up to 90% in the presence of glacial acetic acid and sodium nitrite. The different shapes of DMAPH crystal including sheet， needle， block and plate morphology can be obtained by changing the solvent， while the temperature only affect the particle size of precipitated crystals. The （400） face is the main crystal face of DMAPH crystal from methanol， while in other solvents it is the （214） face. The DMAPH crystals exhibit good thermal stability with decomposition peak temperature ranging from 220-240 ℃. In contrast to amorphous DMAPH powders， the crystalline DMAPH solids have better stability in air， and are more suitable for long-term storage.

Abstract:A measurement method of explosive crystallization thermodynamic parameters based on optofluidics was proposed to obtain the crystallization thermodynamic parameters such as solubility and metastable zone width of explosive crystal， and the applicability of this method was verified by taking HNS explosive as a sample. The solubility of HNS in DMSO/DMF solvent system with volume ratio of 10∶0， 7∶3， 5∶5， 3∶7 and 0∶10 from 318.15 to 353.15 K and the metastable zone width of HNS in the above DMSO/DMF solvent system from 318.15 to 333.15 K were measured with a step of 5 K. Apelblat model and λh model were employed to fit the collected solubility data. The effect of solvent system on the metastable zone width was studied， and the crystallization parameters were screened. According to the classical nucleation theory， the apparent nucleation order m of HNS was calculated， and the nucleation mechanism of HNS by cooling crystallization was analyzed. The results indicate that the measurement method of crystallization thermodynamic parameters based on optofluidics exhibit exceptional applicability to HNS crystals. With the increase of temperature and the volume ratio of DMSO in the system， the solubility of HNS increases. With the increase of DMSO volume ratio in the system， the width of metastable zone becomes narrower. The optimum crystallization conditions are as follows： pure DMSO is utilized as solvent， the solution temperature is set at 333.15 K， and the solute concentration is 0.029 g·mL^-1. The value of m is approximately 4， which is not affected by the initial temperature. It can be inferred that the nucleation mechanism of HNS belongs to continuous nucleation.

Abstract:In order to explore a continuous， safe and controllable microfluidic synthesis strategy of emulsion explosive， silicon-based microporous array chips with four apertures（10 μm，20 μm，30 μm，40 μm） were designed and prepared by MEMS technology， and the microfluidic reaction device of emulsion explosive was constructed. It is found that the main factors affecting the droplet size of dispersed phase in latex matrix are micropore diameter and continuous phase velocity. The effects of pore size and oil-water two-phase flow rate on the particle size distribution and exothermic properties of emulsion droplets were studied. The results show that the particle size distribution of dispersed droplets in the matrix is the narrowest when the pore size is 30 μm and the continuous phase flow rate is 0.5 mL·min^-1 and D₅₀=8.169 μm. Microporous array chip can generate highly homogeneous droplets in batch， which provides a new choice for emulsification in the preparation of emulsion explosive.

Abstract:To control the morphology， particle size distribution and coating covering effect of high polymer binder explosives （PBXs）， TATB/F2602 microspheres could be prepared via high sensitivity droplet microfluidic technology， and investigated the effects of binder content and flow rate on the morphology and particle size of TATB-based microspheres. Moreover， it studied the morphology， structure， composition and thermal behavior of microsphere samples systematically using scanning electron microscopy， X-ray diffraction， specific surface area， DSC and TG， respectively. Results show that， when the binder content is 5%， the microspheres have smooth surfaces， regular spherical shapes and high spherical monodispersity， and the average roundness is 0.921 （span=0.04）. With the increase of flow ratio， the D₅₀ of microsphere sample decreased from 51.73 to 44.31 μm， and the particle size distribution is narrow （span<0.4）. Fluororubber （F2602） is uniformly distributed in the interior and surface of TATB microspheres， and uniform coating of TATB particles delay the thermal decomposition of microspheres by 4.08 ℃. Compared with raw TATB， the true density of TATB/F2602 increases to 1.9780 g∙cm^-3 during spheroidization. The droplet microfluidic technology can effectively control the morphology and particle size of explosive microspheres， and provide experimental reference for the spherical preparation of polymer bonded explosives.

Abstract:In order to achieve the safety of the preparation process of ultrafine zirconium （Zr） powder， a method for preparing core-shell Zr powder by continuous flow at microscale was studied. A continuous microfluidic system consisting of microfluidic unit and spray-drying unit was established to verify the feasibility. The system can realize the microscale mixing of components， the formation of core-shell structure and the post-processing of samples continuously. Using Zr powder and nitrocellulose （NC） as composite components， the structure regulation of Zr@NC was studied by controlling content of NC and adjusting dry gas pressure at the microscale. In addition， the activity and safety of Zr@NC were analyzed by thermal analysis and electrostatic spark sensitivity test. The results show that the Zr powder with uniform morphology and core-shell structure can be prepared by the continuous microfluidic system. Thermal analysis results show that the oxidation weight gain of Zr@NC is only 1.04% lower than that of the raw Zr， and the energy release is faster. According to the electrostatic spark sensitivity test， it was found that the 50% ignition energy of Zr@NC is increased from 1.42 mJ to 197.82 mJ compared with the raw Zr， which means the electrostatic spark sensitivity is greatly reduced.

Abstract:In order to improve the economic benefit of producing 2，2，4-trimethyl-1，3-pentanediol（TMDP）， a more efficient and safe microchannel continuous flow process was selected to replace the traditional kettle-type batch production method with using isobutyl aldehyde as raw material and sodium hydroxide solution as catalyst. The effects of catalyst sodium hydroxide concentration， dosage， temperature and residence time on the reaction were investigated. The optimum conditions were determined as follows： sodium hydroxide concentration 50%， v（isobutyral）∶v（NaOH）=1， residence time 10 min， reaction temperature 40 ℃. Under these conditions， the conversion of isobutyraldehyde was 99.02%， the selectivity of TMDP was 93.57%， and the yield was 92.65%. The process made full use of the excellent mass and heat transfer characteristics of the microchannel reactor， greatly shortened the reaction time， increased the reaction rate， extended the selection range of process conditions， and realized the effective control of the reaction process of hydroxylaldehyde condensation. At the same time， the kinetic studies were carried out at different temperatures and concentrations of sodium hydroxide， and the kinetic equations and corresponding parameters were obtained with the concentration of sodium hydroxide being 50% and 45% respectively. The macroscopic kinetics obtained by fitting is second-order， and the activation energy and pre-exponential factors are： 26.34 kJ·mol^-1， 2888.26 L·K^-1·mol^-1·min^-1.

Abstract:The mixing uniformity and processing safety of widely used zirconium/lead tetroxide （Zr/Pb₃O₄） composites are indispensable. In the current paper， a Zr/Pb₃O₄ microcapsule bonded with the adhesive alginate was prepared by crosslinking the liquid phase with sodium alginate（SA） and Ca²⁺ in aqueous phase to form calcium alginate （CA） gel. The morphology， particle size， sphericity， fluidity and apparent density of CA/Zr/Pb₃O₄ microcapsules and the traditional-made NC/Zr/Pb₃O₄ controlled sample were evaluated. The average particle size， variance， sphericity and repose angle of CA/Zr/Pb₃O₄ microcapsules is measured to 517.10 μm， 44.21 μm， 0.90， and 27.44°， respectively. The flame sensitivity， burning rate， flame length and sensitivity of CA/Zr/Pb₃O₄ microcapsules were tested to 65.38 mm， which was lower than that of Zr/Pb₃O₄ powder （81.83 mm）. Besides， the combustion rate deviation of CA/Zr/Pb₃O₄ microcapsules and Zr/Pb₃O₄ powder is 6.86 and 12.04， respectively， implying an excellent combustion consistency. Furthermore， much more flame length of 17.1 mm and burning particles than Zr/Pb₃O₄ were obtained in of CA/Zr/Pb₃O₄ microcapsules. In addition， a reduced the electrostatic sensitivity of CA/Zr/Pb₃O₄ microcapsules （156.25 mJ） and Zr/Pb₃O₄ powder （0.71 mJ） were realized. More importantly， the water-phase preparation carried out in the current paper may pave a high-safety and universal way for a variety of pyrotechnic agents.

Abstract:To explore organic amine oxyanions with simple synthesis procedure and high energy， ethylenediamine diiodic acid and ethylenediamine hexamiodic acid were synthesized with iodic acid and ethylenediamine. The structures were characterized by single crystal X-ray diffraction， powder X-ray diffraction （PXRD） and Fourier transform infrared spectroscopy （FT-IR）. Differential scanning calorimetry（DSC）and thermogravimetric analyzer（TG）were used to study the thermal decomposition process. The power test of lead plate as main charge in 8^# industrial detonator and the burning test were carried out. The results show that two ethylenediamineIodate salts are successfully prepared. The ethylenediamine diiodic acid belongs to orthorhombic system， Pbca space group， cell parameters： a=7.4427 Å， b=6.7418 Å， c=18.2884 Å， Z=8， F（000）=760， D_c=2.982 g·cm^-3， and the peak temperature of thermal decomposition is 185.18 ℃. The ethylenediamine hexamiodate is a cocrystallization of ethylenediamine diiodate and iodate acid. It belongs to monoclinic system， P2₁/c space group， cell parameters： a=7.2350 Å， b=18.498 Å， c=7.5494Å， β=107.947°，Z=4， F（000）=996， D_c=3.840 g·cm^-3， and the peak temperature of thermal decomposition is 179.48 ℃ and 356.87 ℃. The 5 mm lead plate can not be made through when the ethylenediamine hexamiodic acid is used as main charge， while the opposite result occurs when mixed with 10% aluminum powder. The ethylenediamine diiodate can be used as a simple purple smoke agent.

Abstract:Three energetic coordination compounds with strong reducibility were prepared with cyanoborohydride （CBH） as anion， 1-vinyl imidazole （VIM） as ligand and transition metals Co， Mn and Ni as central ions. The crystal structures were determined by single crystal X-ray diffraction and their molecular formulas are Co（VIM）₄（CBH）₂， Mn（VIM）₄（CBH）₂ and Ni（VIM）₄（CBH）₂， respectively. The thermal decomposition performance， oxygen bomb calorimetry and mechanical sensitivities of the complexes were tested. The results show that the complexes have high burning calorific capacity （26.5-29.1 kJ·g^-1）， low friction sensitivity （>360 N） and impact sensitivity （>40 J）. Hypergolic testing with white fuming nitric acid shows that the complexes can combust spontaneously， and the ignition delay time is short （4-13 ms）， which confirm the high reduction activity of the complexes. To explore the application of active coordination compounds in initiating explosive devices， three new composite igniting powders were obtained by mixing three complexes with sodium bromate in the mass ratio of 1∶7， respectively. The composite powders were ignited and tested with electric heating wire. After being ignited by electric heating wire， the three composite agents can burn continuously and produce large flame. Results show that the composite agents have potential applications as new ignition agents.

Abstract:The lack of plenty of gas products during the combustion reaction of thermite is an important constraint on the development of high energy. To make up for the lack of gas production and improve the reactivity of nano-thermite， Al@KIO₄ and Al@NaIO₄ nano-thermites with core-shell structure were prepared by spray drying method. Scanning electron microscope， X-ray diffractometer， thermal analyzer， constant volume combustion chamber， hygroscopicity test and initiation power test were used to characterize the morphologies and structures， and also thermal properties， combustion performances， moisture-resistance performances and detonation performances. Results show that Al@KIO₄ and Al@NaIO₄ nano-thermites are seperatelly in high purities and with regular morphologies； the heat release are 1262.12 J∙g^-1 and 1414.7 J∙g^-1， respectively； the starting temperatures of the decomposition reactions are lower than the raw materials and accompanied with a large number of oxidizing gas products. The mass balances were reached on the 6th and 10th day， and the mass gains were about 0.64% and 0.65% in high humidity for the Al@KIO₄ and Al@NaIO₄ nano-thermites. Initiation power test showed that 96 mg samples charged into No.8 industrial detonator as primary explosive could completely detonate RDX， the perforation diameter of 5 mm thick lead plate showed that the initiation capacity of Al@KIO₄ and Al@NaIO₄ nano-thermites were comparable to LA. According to the perforation diameters， the order of initiating power is LA＞Al@NaIO₄＞Al@KIO₄＞LTNR.

Abstract:In order to improve the synthesis performance of 3，3′-diamino-4，4′-azoxyfurazan （DAAF） by conventional methods， broaden the synthetic pathway of DAAF. A microfluidic reaction system was designed to synthesize DAAF using 3，4-diaminofurazan （DAF） as the main raw material by microfluidic technology. Orthogonal experiment was designed to optimize the synthesis conditions. DAAF with a purity of 99.33% and a yield of 89.96% was synthesized at 25 ℃， a flow rate of 4 mL·min^-1 and a length of 5 m in the outlet crystallizer. The structure of the synthesized product was characterized by infrared， nuclear magnetic and elemental analysis， and was characterized by scanning electron microscope （SEM）， X-ray diffraction （XRD）， thermal analyzer （DSC/TG） and mechanical sensitivity. The results show that DAAF was clustered flower ball with an average particle size of 5.36 µm； Microfluidic synthesis has no effect on the crystal structure of DAAF. At the heating rate of 10 ℃·min^-1， the thermal decomposition peak temperature is 262.36 ℃， and the mass loss rate during thermal decomposition is 82.79%. The mechanical sensitivity test shows that the impact sensitivity is 90 J， and the friction sensitivity is 0%. Compared with the DAAF synthesized by the conventional method， the average particle size decreased by 7.36 µm， the particle size distribution is uniform and the particle size distribution range is narrowed， the crystal structure does not change， the thermal decomposition peak temperature was advanced by 9.57 ℃， the mass loss rate was reduced by 6.99%， the impact sensitivity is increased by 5 J， and the safety performance is improved.

Abstract:［1，2，5］ oxadiazole ［3，4-b］ pyrazine-5，6-（1H，3H）-dione（1） was synthesized directly from 3，4-diaminofurazan and oxalic acid by one-step amide condensation reaction， and the corresponding ionic salts 2-5 were further synthesized by reaction with base. The structures of compounds 1-5 were characterized by infrared spectrum （IR）， 1H and 13C nuclear magnetic resonance（NMR）. The structures of compounds 1 and 5 were further characterized by X-ray single crystal diffraction. The thermal behaviors of compounds 1-5 were investigated based on differential scanning calorimetry （DSC） measurement. The thermal decomposition temperatures of compounds 1-5 ranged from 210.5 ℃ to 313.5 ℃. The physicochemical properties and detonation performances of compounds 1-5 were estimated by Gaussian 09 program and Explo 5（v. 6.01）. The calculated detonation velocities of compounds 1-5 ranged from 7327 m·s^-1 to 8555 m·s^-1， and the detonation pressures ranged from 20.5 GPa to 30.6 GPa. The impact and friction sensitivities were determined by using BAM technology. The impact sensitivity of compound 1 is 27 J and the friction sensitivity is 280 N. The impact sensitivities of compounds 2-4 are all greater than 40 J and the friction sensitivities of 2-4 are 360 N. The impact sensitivity of sodium salt is 7 J and the friction sensitivity is 120 N. Among them， energetic salts 3 and 4 are expected to be new energetic materials with high energy and low sensitivity.

Abstract:In order to explore the thermal decomposition behavior of 3，5-dimethyl-4-hydroxyphenylpentazole， UV-visible light absorption spectrum combined with quantum chemical calculation was adopted. The thermal decomposition of 3，5-dimethyl-4-hydroxyphenylpentazole （HMPP） with increasing temperature was tracked. The thermal stability of HMPP was tested by differential scanning calorimeter. The results show that the initial decomposition temperature of HMPP is -14 ℃， and the characteristic absorption peak produced by the pentazole ring is at 284 nm in the UV-visible region. The characteristic absorption peak of 3，5-dimethyl-4-hydroxyphenyl azide （HMPA） is 258 nm. With the increase of temperature， the absorption peak of the whole system decreases gradually at 284 nm. In order to explore the specific reasons for the change of HMPP ultraviolet-visible light absorption spectrum， the decomposition products of HMPP were separated by column chromatography. The main decomposition products of HMPP were 2，6-dimethyl-p-benzoquinone and 4-（4-hydroxy-3，5-dimethylphenyl） amino）-2，6-dimethylcyclohexa-2，5-diene-1-one. After the thermal decomposition of HMPP， the uV-visible absorption of the whole system was determined to be caused by the superposition of uV-visible absorption of compounds 4 and 5.

Abstract:In order to improve the low-temperature resistance of emulsion explosives （EE）， dimethyl sulfoxide （DMSO） was added into the aqueous phase of emulsion explosive matrix （EEM）. The crystallization rate， and microscopic structure and detonation performance of brisance of the prepared EEM were studied. And the thermal decomposition characteristics of EEM were also tested thermogravimetry-derivative thermogravimetry （TG-DTG） technology. The results show that adding 1.5% （mass fraction） of DMSO can delay the time for the EEM to reach the maximum crystallization rate from 24 days to 51 days under the condition of freezing at -20 ℃， compared to the EEM without DMSO. After being frozen for 12 days， the EEM containing DMSO has a more uniform distribution of emulsion particles. DMSO （1.5%） can increase the brisance of EE by 29.9%. The addition of DMSO has no obvious effect on the thermal decomposition process of EEM， but the apparent activation energy of EEM decreased with the increase of the DMSO content. When the DMSO content reached 1.5%， the apparent activation energy of EEM decreased by about 18.5%

Abstract:2，4-MDNI/DNTF eutectic system was prepared by using 1-methyl-2，4-dinitroimidazole （2，4-MDNI）， a high energy insensitive explosive， to improve the high sensitivity and high melting point of the dynamite carrier 3，4-dinitrofuroxan （DNTF）. The melting and liquefaction processes of 2，4-MDNI/DNTF with different ratios were studied by differential scanning calorimetry （DSC）， and the T-x phase diagram was established. The melting and decomposition processes of 2，4-MDNI， DNTF and 2，4-MDNI/DNTF eutectic at different heating rates were studied. The kinetic parameters of 2，4-MDNi， DNTF and their eutectic were calculated by flynn-wall-Ozawa method， Doyle method and Kissinger method respectively. XRD and SEM analysis were carried out for the three substances. The hyposensitivity of 2，4-MDNI to DNTF was studied by sensitivity test.The detonation properties of 2，4-MDNI/DNTF eutectic were calculated by using EXPLO5. The results show that the molar composition of 2，4-MDNI/DNTF eutectic is 51∶49， and the average melting point is 92.7 ℃. As the heating rate increases， both melting and decomposition reactions are delayed. The activation energy E_a and pre-exponential factor A of thermal decomposition of eutectic are 146.0 kJ·mol^-1 and 4.09×10¹³， respectively. In XRD test， the low eutectic of 2，4-MDNI/PETN generates a new diffraction peak at 2θ=18.60°. The microstructure of the solidified surface is obviously better than that of DNTF. The impact and friction sensitivities of 2，4-MDNI are both 0%.The impact sensitivity and friction sensitivity of eutectic are 64% and 52%， respectively. The theoretical density of 2，4-MDNI/DNTF eutectic is 1.844 g·cm^-3， and the calculated detonation velocity is 8705 m·s^-1. The eutectic of 2，4-MDNI and DNTF was prepared with ideal melting point and good thermal stability. At the same time， the sensitivity of DNTF can be significantly reduced while maintaining its high energy level.

Abstract:A cyclo-pentazolate anion-based energetic cocrystal （NH₃OH⁺N₅^-）₂·NH₃OH⁺Cl^-·H₂O was designed and synthesized by AgN₅ （or NH₃OH⁺N₅^-） and hydroxylamine hydrochloride（NH₃OH⁺Cl^-） as raw materials. The structure of the compound was characterized by X-ray single crystal diffraction， infrared spectroscopy and elemental analysis. The structure belongs to the monoclinic crystal system，the P2₁/n space group， a=3.8390（6）Å， b=14.665（2）Å， c=21.975（3）Å， V=1236.4（3）ų， α=γ=90°， β=92.034（3）°， Z=1， D_c=1.589 g·cm^-3. In addition， the thermal stability of （NH₃OH⁺N₅^-）₂·NH₃OH⁺Cl^-·H₂O was studied using DSC and TG， and the results showed that its initial decomposition temperature was about 95.6 ℃. Its detonation velocity and detonation pressure were calculated by EXPLO5 to be 8260 m·s^-1 and 23.79 GPa. （NH₃OH⁺N₅^-）₂·NH₃OH⁺Cl^-·H₂O has low impact and friction sensitivities （IS>40 J； FS>360 N）， as the cocrystal of hydroxylamine hydrochloride can greatly reduce the mechanical sensitivity of NH₃OH⁺N₅^-.

Abstract:This study probed the influence of compounds containing NH_n （n=0-4） groups such as ammonium perchlorate （AP）， guanidine nitrate （GN）， nitroguanidine （NQ）， N-methyl-4-nitroaniline （MNA） and cyclotetramethylene-tetranitramine （HMX） on the solidification process and solidification temperature of 2，4-dinitroanisole （DNAN）. The effects of the type of additives and AP content on the solidification temperature of DNAN were disclosed by a DSC and an optical microscope technique. Furthermore， as-calculated solidification linear velocity and the characteristics of dynamic crystallization process were analyzed based on the solidification process of addictive-containing DNAN in thin layer observed by microscope. The influence of the additives on the formability of the DNAN was studied by cross-section images of a Φ20 mm test pieces. In addition， relationships between solidification enthalpy and corresponding temperature of DNAN was studied based on crystallization thermodynamics. Besides， the mechanisms towards the influences of NH_n compounds on DNAN solidification was analyzed and verified. The results showed that an remarkable-increased solidification temperature of DNAN was achieved by the AP， while being slightly influenced by the AP content and other compounds like GN， NQ， MNA and HMX. The lowest solidification line rate of AP containing object with dendrite-like crystallization could be attributed to the elevated solidification temperature. Influenced by crystallization latent heat during the bulk-growth of DNAN， the microstructure of pure DNAN could be demonstrated as columnar blocks while additive-containing counterparts were disclosed as tiny crystallization. Solidified thermodynamic analysis showed that the DNAN solidification enthalpy was positively correlated with the solidification temperature， which is also affected by heterogeneous additive particles on heterogeneous nucleation. The mechanism and verification of the solidification temperature of DNAN in the present paper demonstrated that the additives with NH₄⁺ can significantly improve the solidification temperature of DNAN.

Abstract:Herein， two energetic salts， 3，4-diamino-5-（3，4-diamino-1，2，4-triazol-5-yl）-1，2，4-triazolium perchlorate （2） and 3，4-diamino-5-（3，4-diamino-1，2，4-triazole-5-yl）-1，2，4-triazolium nitrate （3）， were prepared by neutralization reaction of 3，4-diamino-5-（3，4-diamino-1，2，4-triazol-5-yl）-1，2，4-triazole （1） with perchloric acid and nitric acid， respectively. The suitable single crystals of 2 and 3 were obtained and the crystal structures were measured by single crystal X-ray diffraction analysis. In the crystal structure of 2， each cation interacted with 12 adjacent perchlorates anions through hydrogen bonding. Layer structures were formed by the cations of protonated 1. Perchlorate anions were embedded into two nearby layers. In the crystal structure of 3， each cation interacted with 10 nearby nitrates through hydrogen bonding. Layer structures were built by the cations and nitrates. The thermal stabilities of 2 and 3 were measured by differential scanning calorimeter （DSC） and thermogravimetric analyzer （TG）. Compounds 2 and 3 had ultra-high thermal stabilities， and their thermal decomposition temperatures were 338.3 ℃ and 289.8 ℃， respectively. In addition， the calculated detonation velocity and specific impulse of 2 were 8308 m·s^-1 and 250.3 s， respectively， indicating 3 shows excellent energetic properties. Compound 3 had excellent mechanical sensitivity. The values of impact sensitivity and friction sensitivity were higher than 20 J and 360 N， respectively.

Abstract:In order to decrease the acidity of insensitive explosive 3-nitro-1，2，4-triazol-5-one （NTO）， NTO·（3，5-DATr） energetic ionic salt （Ⅰ） and NTO/IMZ energetic co-crystal （Ⅱ） were prepared by the reactions of NTO with 3，5-diamino-1，2，4-triazole （3，5-DATr） and imidazole（IMZ）. The single crystals were obtained by solvent volatilization， and the crystal structures were measured by single crystal X-ray diffraction. Crystal Ⅰ belongs to monoclinic crystal system， space group P2₁/c， with M_r=229.19，a=3.5687（7） Å，b=17.245（3） Å，c=14.655（3） Å，β=93.79（3）°，V=899.9（3） ų，Z=4，D_c=1.692 g·cm^-3；Crystal Ⅱ belongs to orthorhombic crystal system，space group Pbcn，with M_r=207.17，a=16.9398（16） Å，b=5.6802（5） Å，c=17.9111（19） Å， V=1723.4（3） ų， Z=8， D_c=1.597 g·cm^-3. Differential scanning calorimetry （DSC） and thermal weight loss method （TG） were used to test their thermal decomposition properties， and the results show that both Ⅰ and Ⅱ have good thermal stability. The Gaussian 09 program was used to optimize the molecular structures and calculate their enthalpy of formation. Software EXPLO 5 was used to calculate the detonation velocity and pressure of Ⅰ（D=7662.3 m·s^-1，p=21.0 GPa） and Ⅱ（D=6490.2 m·s^-1，p=14.6 GPa）. The mechanical sensitivity was tested by the BAM method. Results show that both of them are insensitive towards impact and friction （IS > 40 J， FS > 360 N）. The pH value of standard samples were measured by pH meter. The pH values of NTO， Ⅰ， and Ⅱ in 0.01 mol·L^-1 standard solution are 2.92 （22.8 ℃）， 4.10 （22.7 ℃）， and 4.98 （22.8 ℃）， respectively， indicating that the formation of salt and co-crystal significantly decrease the acidity of NTO.

Abstract:Iodine-rich compounds are a new type of bactericidal materials developed in recent years. Gaseous products comprised of large amounts of iodine or iodine-containing components are released can be used as strong biocides during the progress of decomposition or explosion of iodine-rich compounds. It has the advantages of short response time， good flexibility， high sterilization efficiency， and can adapt to the needs of complex environment. In this review， we summarized the iodination methods of preparing five-member or six-member nitrogen heterocycles by using I₂/KI， I₂/oxidants， NIS or ICl， and the range of application， advantages and disadvantages of different iodide methods were compared and analyzed， It is pointed out that the preparation of iodine-rich energetic compounds in the future should focus on improving the atom economy of iodine and the green and friendly synthesis process. It is hoped that this review will provide guidance for the design， synthesis and large-scale preparation of new iodine-rich energetic compounds in the future.

Abstract:In order to investigate the thermal decomposition mechanism of the energetic cocrystal TKX-55 and the effect of solvent component dioxane （1，4-dioxane， DIO） on the decay of the energetic component 5，5´-bis（2，4，6-trinitrophenyl）-2，2´-bis（1，3，4-oxadiazole） （BTNPBO）， the molecular dynamics simulations on TKX-55 and pure solvent component DIO were carried out with the ReaxFF-lg （Reactive Force Field-Low Gradients） force field. The results show that the initial decomposition reaction of TKX-55 includes the dimerization of energetic molecules， the hydrogen transfer between energetic and solvent components， the ring-opening reaction of 1，3，4-oxadiazole in energetic components， and the dissociation of nitro group. The dimerization reaction facilitates the rapid growth of the subsequent clusters， and the release of the heat and the stable small molecule products are restricted by the formation of a large number of clusters. It is one essential reason for the high heat resistance of TKX-55. For the pure solvent， the heat release and clustering are constrained at low temperatures； while enhanced at elevated temperatures. The main role of DIO molecules in TKX-55 is thought-to adsorb small reactive intermediates （such as OH， NO， NO₂， etc.） and thereby inhibit the decomposition of BTNPBO.

Abstract:Pentazoles are currently a research hotspot in the field of energetic materials， however， the stability of existing pentazoles is generally not high. In order to develop new pentazoles with better properties， based on the analyses of the available structures， 20 substituted derivatives of HN₅ with the electron-withdrawing groups， i.e.，N₅（CH₂）_x-1R（R=—NO₂，—CF₃，—CN， —CHO， —COOH； x=1， 2， 3， 4）， were designed and studied by using the density functional theory method. The bond dissociation energy （E_BD） of the bonds linked with the N₅ ring and the activation energy （E_a） of the cracking of the N₅ ring were calculated and compared with that of some pentazoles substituted by the electron-donating groups， and the effects of substituents on E_BD and E_a were discussed. Results show that the E_a of all molecules is much smaller than E_BD， indicating that the stability of the N₅ ring is the key factor to determine the stability of the pentazoles. When R is directly connected to the N₅ ring （N₅R）， the E_a of N₅R with R being an electron-withdrawing group is smaller than that of N₅R with R being an H or an electron-donating group. The N₅ ring is a strong electron-withdrawing group， and bearing too much or too little negative charges is not conducive to the stability of the N₅ ring.

Abstract:In order to clarify the influence mechanism of H₂O and H₂O₂ molecules on the thermal stability of energetic cocrystals， molecular dynamics （MD） simulation method was employed to analyze the diffusion behavior and thermal decomposition mechanism of solvent molecules in α-CL-20 and CL-20/H₂O₂ （orthogonal/monoclinic）. The results show that both H₂O and H₂O₂ will diffuse out of the cell as the temperature rises， among which H₂O molecules diffuse faster； when the temperature is lower than 500 K， the monoclinic CL-20/H₂O₂ lattice framework has the ability to hinder the diffusion of H₂O₂ molecules. When the temperature rises above 500 K， this hindering effect no longer exists. In the process of thermal decomposition， α-CL-20 releases energy the slowest， and the decomposition of CL-20 also proceeds the slowest； when the temperature is lower than 1500 K， the solvent exhibits a certain stabilizing effect on the thermal decomposition of energetic components， but this effect disappears as the temperature rises. In addition， the presence of solvents can increase the lattice energy significantly.

Abstract:A 1，3，5-trinitrobenzene /1，4-dinitroimidazole （TNB/1，4-DNI） cocrystal explosive was prepared by solvent evaporation. The crystal structure was characterized by single crystal X-ray diffraction analysis. Results shows that the cocrystal crystallizes in the orthorhombic space group P2₁2₁2₁ with crystal parameters of a = 6.4068（5） Å，b = 10.4569（8） Å， c = 20.7164（17） Å， α = β = γ = 90°， ρ = 1.776 g·cm^-3， Z = 4. The differential scanning calorimetry （DSC） was used to analyze the thermal properties of the TNB/1，4-DNI cocrystal explosive. The melting point is 84.4 ℃， which is significantly lower than that of both TNB （123.5 ℃） and 1，4-DNI （91 ℃）. The TNB/1，4-DNI cocrystal explosive can be re-formed into pure cocrystal explosive after melting and cooling. The detonation velocity and pressure of TNB/1，4-DNI cocrystal explosive were also calculated to be 7704 m·s^-1 and 26.08 GPa by the empirical nitrogen equivalent equations， which are significantly higher than those of the commonly used melt-cast explosive TNT. Therefore， TNB/1，4-DNI cocrystal explosive could be used as a new type of melt-cast explosive.

Abstract:High tension bonds or high-energy bonds are important elements in the formation of disruptive energetic materials， but it"s hard to form and easy to break，. Their construction has always been a difficult problemin the field of chemistry and energetic materials. By using the unique internal space of molecular cages to “assist” the construction of such chemical bonds provides a feasible route for related research， and has been put into practice. This review summarized “confinement effect”， weak interaction， electron transport and other characteristics of molecular cages. It is discussed that it can prevent oxygen oxidation of P₄ and other high-tension materials， stabilize aryl pentazoles and other high active substances， reactants such as NaN₃ to accelerate the reaction， change the reaction path. The roles of molecular cages in these processes， such as “firewall”， “stabilizer”， “accelerator”， “channel remover” and others， were reviewed， which provided references for the preparation of novel energetic compounds such as TdN₄ and the study of controllable energy release . At the same time， it also points out the key direction of future research： design and synthesis of new and efficient molecular cages. developing good characterization methods and means of molecular cage complex. Enhance the composite and release of multi-environment responsive molecular cages and energetic materials.

Abstract:The crystal habit of explosives significantly affects their physicochemical properties， application mode and effect. A novel strategy to fabricate the flower spherical 2，6-diamino-3，5-dinitropyrazine-1-oxide （LLM-105） crystals based on solvent-antisolvent method was developed by introducing 1-ethyl-3-methylimidazole acetate （EmimOAc） ionic liquid as the additives， DMSO as the solvent and ethyl acetate as the antisolvent. The results show that the EmimOAc ionic liquid is a crucial factor to modify the crystal morphology of LLM-105. Long needle-like LLM-105 crystals were produced in the absence of EmimOAc. In contrast， flower spherical LLM-105 crystals were obtained in the presence of EmimOAc. In addition， the EmimOAc significantly enhanced the solubility of LLM-105 in DMSO. Meanwhile， ¹H NMR experiments were conducted to understand the intermolecular hydrogen bonds between LLM-105 and the ionic liquid molecules. Furthermore， the flower spherical LLM-105 crystals exhibit excellent thermal stability and safety properties. The DSC/TG results show that the thermal stability of the flower spherical crystals is comparable to that of the long needle crystals. The impact sensitivity was tested according to GJB-772A-1997 method， while the impulse initiation voltage was tested by slapper detonator. Results indicate that for the flower spherical crystal， the characteristic drop height is 22 cm higher than that of the needle crystal， and the impact sensitivity is significantly lower than that of the needle crystal but equivalent to that of the submicron crystal. The impulse initiation voltage of the flower spherical crystals is lower than that of submicron crystals， suggesting that the flower spherical crystals have better initiation performance and high potential for application in primary explosives. This ionic liquid induced crystallization provides a new idea for tuning the crystal habit of LLM-105， as well as a new method for modifying the crystal habits of other organic explosive crystals.

Abstract:The attachment energy （AE） model and molecular dynamics （MD） methods were used to predict the crystal morphology of 1，1-diamino-2，2-dinitroethylene （FOX-7） under vacuum condition and in eight solvent systems including dimethylsulfoxide （DMSO）， acetone， methanol， N-methylpyrrolidone （NMP）， N，N-Dimethylacetamide （DMAC）， ethylacetate （EA）， water （H₂O）， and DMSO/H₂O （V/V=2/1）. By calculating the interaction energies between the solvent and crystal plane， and the attachment energies under the influence of the solvent， the simulated crystal habit and its aspect ratio were obtained. The results show that FOX-7 crystal has six important growth planes under vacuum： （1 0 ）， （1 0 1）， （0 1 1）， （0 0 2）， （1 1 0）， （1 1 ）. Among them， the area of （0 1 1） plane accounts for the largest proportion， which is the most important crystal plane affecting the crystal morphology of FOX-7. The influence degree of solvent on the aspect ratio of crystal is in the following order： DMSO2O2O. By recrystallization experiments， FOX-7 crystals have a bulk-like shape in DMSO， methanol， and DMSO/H₂O； a rod-like shape in acetone and NMP； a needle-like shape in DMAC and H₂O； a flake-like shape in EA. The theoretical prediction results are in good agreement with the experimental results， which proves that the simulation of the crystal habit of FOX-7 based on the AE model can provide better guidance for the crystallization experiment. Results in thermal properties show that the crystal surface morphology and internal defects affect the phase transition temperature and thermal decomposition temperature of FOX-7. The fewer the crystal defects， the higher the α→β transformation temperature. The larger the crystal aspect ratio， the smaller the particle size， and the lower the first decomposition temperature.

Abstract:In order to improve the adaptability of bonding agent to various energy-containing fillers and modify the interfacial bonds of solid propellants， a kind of multifunction telechelic bonding agent was designed and prepared. The bonding effectiveness was studied by molecular dynamics simulations and experimental evaluations. The results show that this bonding agent can show decent interactions with various energy-containing fillers. By altering the molecule backbone of this bonding agent， it can adapt to different adhesive systems. As compared to the three-claw bonding agent， the two-claw one has fewer branches， better diffusivity in adhesive， higher transferability toward interface， and better bonding effectiveness.

Abstract:A mixture of 3，3-bis（chloromethyl）oxetane （BCMO） and 3-ethyl-3-oxetane methanol （EHO） were used to synthesis the azide hyperbranched copolymers （r-POB-m） via cationic ring-opening polymerization and azidation reaction with different monomer molar ratio （BCMO/EHO=m）. The chemical structures were characterized with Infrared spectroscopy （FT-IR）， nuclear magnetic resonance （NMR）， gel permeation chromatography （GPC） and elemental analysis. The results showed that the copolymer has high molecular weight （>4400 g·mol^-1）， high nitrogen content （up to 43%） and controllable branching structure. X-ray diffractometer （XRD）， Hacker rheometer and differential scanning calorimeter （DSC） were utilized to characterize crystallinity， viscosity and chemical compatibility respectively. When m=4， r-POB-4 is amorphous， possesses the lowest process viscosity and has good compatibility with the main components of the propellant， indicating that it is a potential candidate for plasticizer. In addition， compared with the GAPA plasticizer， the energetic thermoplastic elastomer （ETPE）-based propellant with r-POB-4 plasticizer exhibits higher elongation at break， lower consistency coefficient and lower viscous flow activation energy， suggesting that the azide hyperbranched copolymer could be applied as the plasticizer to effectively improve the mechanical properties and processing properties of the propellant.

Abstract:In order to investigate the effects of graphene oxide （GO） on the thermal expansion coefficient of GAP modified spherical propellant composites， GAP modified spherical propellant composites containing GO with 0%， 0.5%， 1%， 1.5% were prepared， respectively. Fourier transform infrared spectroscopy （FTIR）， scanning electron microscopy （SEM） and differential scanning calorimetry （DSC） were used to investigate the structure， morphology and thermal properties of the composites， respectively. The effect of GO content on thermal expansion coefficient and glass transition temperature was investigated using a static thermomechanical tester （TMA）. The results showed that the addition of GO had little significant effect on the structure and thermal properties of the cured system and no chemical reaction occurred. The addition of GO resulted in a reduction to the expansion coefficient of the composites. When the content of GO is 1%， the expansion coefficient presents the greatest reduction， decreasing from 3.236×10^-4 K^-1 to 2.692×10^-4 K^-1. The glass transition temperature increased from 20.8 ℃ to 25.1 ℃ with the addition of GO content relative to the pure GAP modified spherical propellant composite.

Abstract:In order to improve the combustion efficiency of Al powder， Al/modified-fluororubber composite fuel（FKM-GW@Al） was prepared with the silane modified-fluororubber（FKM-GW） by sol-gel method. The stability of FKM-GW@Al in solvent was studied， and the results show that with functional groups， the FKM-GW@Al is stabile in ethyl acetate. The application of FKM-GW@Al in NEPE high-energy and low burning-rate solid propellant was studied. Results show that compared with Al powder， FKM-GW@Al with fluorine mass fraction 2.58%， make the explosion heat of the propellant increase from 6348.8 J·g^-1 to 6831.6 J·g^-1， the content of activated aluminum in residues decreased from 1.02% to 0.06%， and both the static and dynamic burning rates of the propellant containing FKM-GW@Al decrease. The thermal decomposition properties of FKM-GW@Al and the propellant containing FKM-GW@Al were studied by DSC-TG， and the influence mechanism of FKM-GW@Al on combustion characteristics of the propellant was analyzed.

Abstract:Starting from the multi-amine， hydroxy polybutadienes （AEHTPB）， multi-cyano， amine polybutadiene （AEHTPB-CN） was synthesized through appropriate synthesis strategies. The structure of the product was characterized via FT-IR and ¹H NMR， and its physicochemical properties such as viscosity， glass-transition temperature， hydroxyl value， and amine value were also determined. The effect of AEHTPB-CN on the mechanical properties of binder system was investigated via tensile tests， and the performance of the resultant propellant with AEHTPB-CN/HTPB mixture as a binder was explored. The results showed that the cyano groups in the AEHTPB-CN molecule could form hydrogen bonds with the urethane groups， which increased the physical crosslinking density of the elastomer and effectively improved the tensile strength. The propellant level study indicated that the AEHTPB-CN had a good bonding and burning rate inhibition effect on HTPB propellant. At room temperature， compared to HTPB-based propellant， the propellant containing AEHTPB-CN （5-8wt.%） were 35.4%-43.3% larger in tensile strength， 62.0%-91.3% higher in elongation， and the burning rate was reduced by 10.5%-11.4%.

Abstract:In order to enhance the comprehensive properties of glycidyl azide polymer （GAP）， the fluorine-containing GAP copolymer-based thermoplastic elastomers were developed using fluorine-containing GAP copolymer as prepolymer， butylene glycol （BDO） as chain extender and the toluene diisocyanate （TDI） as the curing agent. The molecular structure， relative molecular mass， glass transition temperature， thermally stability and mechanical properties of thermoplastic elastomers were explored via FT-IR， NMR， GPC， DSC， TG/DTG， tensile test and SEM characterizations， respectively. The number-average molecular weight of the thermoplastic elastomers was determined to be 33520 g·mol^-1. The glass transition temperature （T_g） and decomposition temperature （T_d） were found to be -33.3 ℃ and 220 ℃， respectively. The tensile strength at break was 5.94 MPa， and the corresponding elongation was 886%. Therefore， the thermoplastic elastomers exhibited good thermal stability and mechanical properties. Cook-off test was employed to investigate the thermal decomposition characteristics of the fluorine-containing GAP copolymer-based elastomers/Al composite， the response temperature peak of the composite was 301 ℃，suggesting an enhanced exothermal process.

Abstract:In order to obtain the metal alloy composite fuel with pressurization effect， Al/Mo/PMF composite powder was prepared by a combination of vacuum suspension smelting， ultra-high temperature gas atomization and mechanical alloying. The phase， morphology and thermal properties of the composite powder were analyzed by XRD， SEM， TG/DTA. The combustion enthalpy and pressurization properties of the composite powder was measured by oxygen bomb calorimeter and constant volume isothermic combustion experiments. Results show that PMF distributes homogeneously in the composite particles after mechanical ball milling， which is helpful to improve the thermal reactivity of the powder and advance the initial reaction temperature. The extra pressurization effect was obvious due to the production of AlF₃ and MoO₃ with low boiling point. The extra pressurization generated by the combustion of Al/Mo/PMF 64/16/20 composite powder was 4.49% higher than that of pure Al powder. With the increase of PMF in the composite， the combustion enthalpy and combustion completeness of the composite powder decreased. The measured combustion enthalpy of Al/Mo/PMF 76/19/5 composite powder was 22541.8 J∙g^-1， while the measured combustion enthalpy of Al/Mo/PMF 64/16/20 composite powder was 16788.5 J∙g^-1. When the PMF content was 5%， the composite can burn completely， meanwhile the extra pressurization can be presented effectively. The corresponding maximum pressure was 3.430 MPa. In addition， the oxidation process and the mechanism of Al/Mo/PMF 76/19/5 composite powder were also studied.

Abstract:To investigate the effect of Mg content on the properties of centrifugal atomized aluminum-magnesium （Al-Mg） alloy powders， Al-Mg alloy powders with different mass ratios （70∶30， 50∶50， 30∶70） were prepared by centrifugal atomization. The particle size， morphology， physical phase， and kinetics parameters of the samples were characterized via the particle size distribution meter， scanning electron microscope （SEM）， X-ray powder diffractometer （XRD） and TG-DSC. The effect of different Mg content on the activity of the alloy was also studied by thermal oxidation at 71 ℃. Results showed that all Al-Mg alloy powders had a good size distribution， regular morphology and high sphericity. The metallographic structure demonstrated that Al-Mg30 and Al-Mg50 had a dendritic structure， and Al-Mg70 was composed of α-solid solution and dendritic precipitates. The main phase of the alloy was α-Al， β-Al₃Mg₂ and γ-Al₁₂Mg₁₇. The β-Al₃Mg₂ phase gradually decreased and the γ-Al₁₂Mg₁₇ phase increased with the increasement of Mg content. Moreover， the deactivation rate of Al-Mg alloy powders was found to increase with the increasement of Mg content. The activity of alloy powders remained basically constant after 48 h. The TG-DSC results indicated that both the initial exothermic temperature and the activation energy of the alloys were gradually reduced as the Mg content increased， but the reactive speed was accelerated. The increasement ratio of weight of all Al-Mg alloys was greater than that of micron Mg （53.06%） and Al （8.63%）. The results of Laser ignition showed that the ignition delay of Al-Mg alloy was much shorter than monolithic aluminum， as well as the combustion duration. The microburst phenomenon was observed in the test.

Abstract:The dispersion characteristics of metal additives in binders might tremendously affect the processing properties of propellants and explosives. Rheological properties of the two metastable intermolecular composites （QAlPV and PAlPV） mixed with hydroxyl-terminated polybutadiene （HTPB）， glycidyl azide polymer （GAP） or poly （ethyleneoxide-co-teterafuran） （PET） separately were investigated by RS-300 rheometer respectively. Results show that all the six sorts of suspensions exhibited pseudoplastic fluid characteristics， and their apparent viscosity decreases with the increase of temperature between 20 ℃ and 60 ℃. In the systems containing GAP and PET， the flow activation energy of the suspensions with PALPV is greater than those containing QALPV. The results present that the suspensions filled with the lamellar aluminum-based composite exhibites more rigidity， meanwhile their apparent viscosity are more sensitive to temperature. Therefore， the dispersion of PALPV in binders could be improved by increasing the temperature. The dispersion and homogeneity of the suspensionsformed by QALPV， GAP or PET separately could be improved by accelerating the shear rate.

Abstract:In order to study the interface structure of aluminum core/oxide layer intuitively， the slicing method of aluminum powders （2-8 µm） were successfully established based on FIB micro and nano processing technology. The slices were obtained by combining FIB direct cutting with profile thinning. The interface structure of the prepared slice samples was clear and intact， and the oxide layers were not damaged. The microstructure， crystallinity and element distribution of “Al core/oxide layer” under different ageing conditions were obtained were characterized by SEM， HRTEM and EDS. The stoichiometric ratio of Al and O elements in the oxide layer of aluminum particles deviated from the standard Al₂O₃， showing a gradient distribution. The positive correlation between the oxide layer thickness of aluminum particles and the aging temperature has been quantitatively obtained. The oxide layer thickness of the samples without thermal aging was ~5.4 nm， and the oxide layer thickness of the samples aged at 75 ℃ and 95 ℃ increased to （34.1±2.1） nm and （51.3±2.2） nm， respectively.

Abstract:Aluminum powder was widely used to improve the energy characteristics of explosives and solid propellants due to its excellent properties， such as high activity， high density， high combustion enthalpy and low oxygen consumption. The transition metal Cu had a good catalytic effect on the combustion of aluminum powder and could make the aluminum powder burn more completely. As a binder component of solid propellant， hydroxy-terminated polybutadiene （HTPB） was beneficial to prevent the oxidation and agglomeration of aluminum particles， accordingly in favor of the press-packing and curing while uniformly coating on the surface of aluminum particles. Using the copper acetylacetonate as copper source， formaldehyde and hydrazine as reducing agent， HTPB/Cu/μAl composite particles were prepared by one-pot liquid phase reduction. The structure and morphology of the samples were characterized by IR， XRD， SEM and EDS. Meanwhile， the catalytic performance of HTPB/Cu/μAl on the decomposition of AP was studied. The results showed that the reduced Cu particles were scattered on the surface of aluminum particles， and HTPB was evenly coating on the surface of Cu/μAl. In the DSC curve of HTPB/Cu/μAl， the oxidation exothermic peak of transition metal Cu and the decomposition exothermic peak of HTPB appeared simultaneously between 150-350 ℃. However， the coating had almost no effect on the oxidation exothermic peak of micron aluminum powder at 550 ℃. The average activation energy of HTPB/Cu/μAl was 287.2 kJ·mol^-1， which was 36.35 kJ·mol^-1 lower than that of μAl （323.55 kJ·mol^-1）. Both of the decomposition peaks of AP at high temperature and low temperature had changes when HTPB/Cu/μAl composites were added. Compared with pure AP， the exothermic decomposition peak at high temperature of HTPB/Cu/μAl/AP was reduced by 127 ℃， indicating that the HTPB/Cu/μAl composites could promote the thermal decomposition behavior of AP.

Abstract:As a new generation of rapid prototyping technology， direct writing technology has the advantages of fast molding speed， good molding consistency， and high preparation accuracy. It has certain advantages in the preparation of MEMS energetic devices. In this paper， the common direct writing technologies of MEMS energetic devices were described. On this basis， according to the research status of direct writing technology in micro-nano energetic devices， the direct writing technologies used in micro-scale charges of MEMS energetic devices， ignition circuit and transducer element， and packaging materials were summarized. The future research directions were proposed： preparing energetic ink with high solid content and stable performance， increasing the charge density of energetic ink， preparing silver ink circuit with low sintering temperature， and at the same time developing direct writing technology for MEMS energetic device transducers and packaging materials， exploring the influencing factors and laws of direct writing accuracy， breaking through the application bottleneck of direct writing technology， and promoting the progress of engineering application of this technology.

Abstract:Cocrystal is composed of different neutral components through intermolecular non-bond interactions at molecular level and it has fixed ratio and particular structure. Cocrystallization technology is a novel method for ameliorating properties of energetic materials and it has wide development prospect and application value. It can decrease the sensitivity， improve the mechanical properties， thermal performance， and energy density of energetic materials. The research progress of preparation and application of energetic cocrystals was summarized， including the current research status， preparation method， characterization methods， and formation mechanism. The existing problems of energetic cocrystals were introduced： first， the properties of some cocrystal explosives need to be further improved； second， the preparation of cocrystal requires harsh conditions with low product yield； third， the characterization and test methods lack variety. The further development direction of cocrystal explosives were pointed out： strengthen the research of multiple components energetic cocrystals， improve the technologies to increase the yield， investigate the crystallization dynamics behavior to seek for the best cocrystallization conditions， and look for effective means to characterize the cocrystal structure.

Abstract:A novel melt-cast energetic compound bis（dinitromethyl-ONN-azoxyfurazanyl）furazan （BDNAF） was synthesized using 3，4-bis （3′-aminofurazal-4′-yl）furazan （BATF） and 2，2-dimethyl-5-nitro-5-nitroso-1，3-dioxane （DMNNDO） as starting materials via oxidation coupling， hydrolysis， bromization， reduction and nitration five-step reactions. The structures of the intermediates and the target material were fully characterized by infrared spectrum（IR）， nuclear magnetic resonance（NMR） and elemental analysis（EA）. The thermal behaviors of intermediate compound 3，3'-bis（nitromethyl-ONN-azoxyfurazanyl）furazan （BNAAF） and target compound BDNAF were investigated based on differential scanning calorimetry（DSC） measurement， and the physicochemical properties and detonation performances of BNAAF and BDNAF were estimated by Gaussian 09 program and Explo 5（v. 6.04）. Results show that the intermediate compound BNAAF directly decomposed at 106.4 ℃ without melting process， and the calculated density of BNAAF is 1.82 g·cm^-3， the detonation velocity is 8298 m·s^-1， and the detonation pressure is 29.0 GPa. The melting point of the target compound BDNAF is 95.4 ℃， the first decomposition point is 170.5 ℃ at the heating rate of 10 ℃·min^-1， and the theoretical density of BDNAF is 1.91 g·cm^-3， the detonation velocity is 9005 m·s^-1 and the detonation pressure 35.9 GPa， which revealed that BDNAF is a promising melt-cast explosive.

Abstract:In order to study the problem of impact strength and rheological properties of propellant substitutes （Cellulose Acetate， CA） assisted with supercritical carbon dioxide （SC-CO₂）， the in-line slit rheometer， drop hammer impact test machine， SEM were used， and the rheological properties， impact strength and cell morphology of product were characterized in varied experiment conditions. Research results prove that， when process temperature is 50 ℃， solvent ration is 1.2 mL·g^-1， flowability of CA is optimized evidently as injection speed of CO₂ increasing. However， impact strength of extrusion product only account for nearly 53.11% of those products prepared without SC-CO₂（when injected mass fraction of SC-CO₂/CA is 0.173%， screw speed is 10 r·min^-1）； SEM results prove that， quantities of irregular foam structure exist in product prepared with SC-CO₂， foam size are both over 2 μm， some of them even reach at 15-25 μm. Impact strength and product appearance could be modified as screw speed increase， product prepared in 14 r·min^-1 attain higher impact strength （nearly 170.33%） than 6 r·min^-1. During the process of propellant substitutes assisted with supercritical carbon dioxide， rheological properties of CA in barrel could be optimized as injection speed， solvent ratio， process temperature and screw speed increase， however， impact strength of CA could be positively modified as screw speed increase.

Abstract:The co-crystal of hexanitrohexaazaisowurtzitane （CL-20） and 2，4-dinitro-2，4-diazapentane （DMMD） was prepared by co-crystallization in solution. It was characterized by single crystal X-ray diffraction（SCXRD）， scanning electron microscopy（SEM）， powder X-ray diffraction（PXRD）， and fourier transform infrared （FT-IR）， and differential scanning calorimetry （DSC）. The results show that CL-20/DMMD co-crystal belongs to monoclinic system with space P2₁/c. Analysis of interactions in co-crystal shows that the main forces between two kinds of molecule in co-crystal are hydrogen bonds and features a layered motif. There is new crystal phase in the XRD pattern. The shift of peaks for CL-20/DMMD attributes to the formation of C─H…O hydrogen bonding in FT-IR pattern. Results of DSC show that the melting point of co-crystal is 180.8 ℃， which is 21.5 ℃ and 120.9 ℃ higher than that of CL-20 and DMMD. The main thermal decomposition peak temperature of CL-20/DMMD co-crystal is 240.1 ℃， which increases by 3.5 ℃ compared with CL-20. The predicted detonation velocity and detonation pressure of CL-20/DMMD co-crystal are 9386 m·s^-1 and 45.09 GPa according to the theories of Rothstein and Petersen， respectively. They are slightly lower than that of CL-20 and higher that of DMMD（D=7287 m·s^-1，P=21.79 GPa），HMX（D=9048 m·s^-1，P=40.55 GPa）， RDX（D=8945 m·s^-1， P=37.28 GPa）， and TNT（7042 m·s^-1， P=21.44 GPa）.

Abstract:To improve the thermal decomposition performance of ammonium perchlorate （AP）， Cu₁/Al₂O₃ single-atom catalyst was prepared through the evaporation induced self-assembly （EISA） method. The morphology and structure of prepared Cu₁/Al₂O₃ single-atom catalyst were characterized by X-ray diffractometer （XRD）， inductively coupled plasma （ICP-OES）， transmission electron microscopy （TEM）， X-ray absorption spectroscopy （XAS） and X-ray photoelectron spectrometer （XPS）. The effect on the thermal decomposition of ammonium perchlorate（AP）was also investigated by differential scanning calorimetry （DSC） and thermal gravimetry （TG）. Results show that Cu atoms were dispersed and stabilized through oxygen bridge bonds on the Al₂O₃ supporter. The Cu loading was determined to be 8.7%. When the content of Cu₁/Al₂O₃ single-atom catalyst is 5%， the high-temperature exothermic decomposition peak temperature of AP decreases to 319 ℃， which was 85 ℃ lower than that of pure AP. This Cu₁/Al₂O₃ single-atom catalyst exhibits superior catalytic performance on the thermal decomposition of AP， which was more effective than Cu（NO₃）₂·3H₂O and nano-CuO catalyst.

Abstract:In order to study the performance of 3，3''-bi（1，2，4-oxadiazole）-5，5''-diylbis（methylene）dinitrate （BOM）， the sample was prepared by using the melting casting process and its the detonation velocity was measured. The thermal safety of the BOM casting process was studied by the thermal decomposition and constant temperature test. The solidification properties of BOM were studied by macroscopic solidification molding and microscopic solidification crystallization test. The mechanical properties of the BOM casting were studied by compressive and tensile tests. The detonation velocity and detonation heat properties of BOM/HMX/Al melt-cast explosive system were analyzed by detonation performance calculation. The results show that the natural solidification density of BOM is 1.726 g·cm^-3 and the detonation velocity is 7679 m·s^-1. The peak temperature of BOM decomposition is 213.8 ℃， and the calculated critical temperature of thermal explosion is 190.7 ℃. There is no discoloration and smoke during the constant temperature heating， which shows satisfactory thermal safety of the melt-casting process. The solidification defects of BOM were concentrated in the feeding area at the top of the casting， The volume shrinkage rate of natural solidification was 15.7%， and the forming density was 94.7% of the theoretical density， indicating good solidification and forming performance. The compressive strength of the casting is 6.21 MPa and the tensile strength is 1.89 MPa. In the BOM/HMX/Al melt-cast explosive system， the detonation velocity decreases linearly with the increase of Al content. When the Al content is less than 24%， the detonation heat increases gradually with the increase of Al content. When the Al content is more than 24%， the detonation heat is related to the ratio of BOM and HMX in the formula， and the ratio of BOM and HMX system needs to be adjusted to meet the optimal Al/O ratio of the formula.

Abstract:Dichloroglyoxime is an efficient industrial bactericide and an important starting material for construction of nitrogen heterocyclic framework， which can be utilized as a pivotal precursor for a variety of high nitrogen energetic materials with excellent performances. Three synthetic methods of dichloroglyoxime， such as chlorine method， NCS/DMF method and NCS/DMF improved method， were introduced， and their advantages and disadvantages were also discussed. Based on the reaction characteristics of dichloroglyoxime， the methods of constructing N-heterocyclic frameworks， such as isoxazole，furoxan， furoxan， bistetrazole and oxadiazolone， were systematically described. Additionally， the physicochemical properties and detonation performances of typical energetic materials were also discussed. Using dichloroglyoxime as starting materials， it is expected to design and synthesize some new energetic materials with excellent performances，and comprehensively promote the innovation ability of energetic materials.

Abstract:2，4，8，10-Tetranitro-benzopyrido-1，3a，6，6a-tetraazapentalene （NBTTP） was synthesized from 1H-benzotriazole and 2-chloro-3-nitropyridine via displacement， cyclization and nitration.The structure of NBTTP was characterized by FTIR and NMR. In addition， the reaction condition of cyclization was optimized. Its thermalbehavior was analyzed by TG-DTG， while its thermal decomposition behavior， kinetic parameters and thermodynamic parameters were obtained by DSC. The results shows that the highest yield was up to 83.44%， when the molar ratio of triethylphosphite and the BTP was 3∶1. NBTTP presents a main single exothermal event with initial at around 388.79 ℃ and maximum at around 406.23 ℃. Its non-isothermal kinetics equations of thermal decomposition may be described as dα/dt=（6.36×10¹⁴/β）（1-α）exp［-2.34×10⁵/（RT）］. The entropy （ΔS^≠）， enthalpy （ΔH^≠）， free energy （ΔG^≠） and self-accelerating decomposition temperature （T_SADT） were 23.60 J·mol^-1·K^-1， 228.97 kJ·mol^-1， 213.46 kJ·mol^-1 and 655.11 K， respectively.

Abstract:Gem-dinitro group is an attracting moiety in designing novel high energy density compounds due to their high density and oxygen content comparing to the nitro group. The planar structure of gem-dinitro group is beneficial to improve the density， oxygen balance and detonation properties when cooperating with nitrogen-rich heterocycles. In this review， the method of preparing gem-dinitro salts from different precursors was listed， the advantages of using N₂O₄ or N₂O₅ or mixed acid as the nitration agent to prepare gem-dinitro compounds and their scopes of application were summarized， their energetic characteristics were discussed. It is hoped that this review could provide reference for the design and synthesis of new high-energy insensitive energetic materials.

Abstract:In order to obtain energetic materials with excellent performance， a new type of energetic ionic salt 4-hydroxy-3，5-dinitropyrazole guanidine salt （DNPOG） was synthesized by nitration， hydrolysis， acidification and salt formation reaction with 4-chloropyrazole as raw material. The structure was characterized by FTIR， NMR and EA analysis. The crystal structure of DNPOG was triclinic with space group P-1， relative molecular mass M_r=233.17 g·cm^-1， a=4.8958（5） Å， b=8.1933（8） Å， c=11.9669（11） Å， Z=2， and crystal density D_c=1.750 g·cm^-3. The contribution of hydrogen bond and π-π conjugation in DNPOG to the intermolecular interaction force was calculated and studied， and the hydrogen bond accounted for 47%. The thermal decomposition characteristics were investigated by differential scanning calorimetry （DSC） and thermogravimetry （TG）. The peak temperature of the first decomposition was 212.5 ℃. The detonation and safety properties of DNPOG were studied. The detonation velocity is 7871 m·s^-1， the detonation pressure is 23.8 GPa， the formation enthalpy is -160.2 kJ·mol^-1， the impact sensitivity is 20 J， and the friction sensitivity is 240 N. The results show that DNPOG is layered accumulation， with good thermal stability and low sensitivity， which is a kind of low sensitivity explosive with excellent performance.

Abstract:The azo functionality is not only a bridging block， but also can generally increase the density and heat of formation of energetic nitrogen-rich heterocycles. Therefore， building new energetic materials through the bridging method has gradually become a research hotspot in this field. This article reviewed synthesis method， physical and chemical properties and detonation properties of azo-bridged nitrogen-rich heterocycles focusing on azoles and azines from C—NH₂ and N—NH₂ oxidative couplings. This review will provide some references for the research and development of new azo-bridged nitrogen-rich heterocycles.

Abstract:Using 1，4-dihydrazide succinate as raw material， 1，2-bis（3，3"-dinitroamine-1H-1，2，4-triazol-5-yl）ethane monohydrate （1） was synthesized by the one-pot “MNNG ring method”. And the synthetic conditions of this reaction were carefully optimized. The corresponding 1，3-propanediamine salt （2） was obtained through the reaction of compound 1 and 1，3-propanediamine. The detailed single crystal structure of compound 2 was determined by X-ray single crystal diffraction. FT-IR， NMR and elementary analysis were used to characterize the structures of compounds 1 and 2. Moreover， the thermal properties of compounds 1 and 2 have been studied by TG-DSC. The results showed that the initial decomposition temperature of compounds 1 and 2 are 184 ℃ and 214 ℃， respectively. The main detonation parameters of compounds 1 and 2 were calculated by using EXPLO5 （v6.02） software. The calculated detonation velocity of compound 1 is 8602 m·s^-1 and its calculated detonation pressure is 28.10 GPa. For compound 2， the calculated detonation velocity and detonation pressure are 7740 m·s^-1 and 19.10 GPa， respectively. Furthermore， their mechanical sensitivities were tested by BAM sensitivity test. The impact sensitivity of compound 1 is 35 J and its friction sensitivity is 108 N. The impact sensitivity of compound 2 is greater than 40 J， and its friction sensitivity is more than 360 N.

Abstract:Using 4，5-dicyano-2-aminoimidazole as raw material， 4，5-Bis-（chloro-dinitro-methyl）-2-diazoimidazole was prepared through three-step reactions of oximation， chlorination， diazotization. The structure was characterized by X-ray single crystal diffraction analysis， Fourier transform infrared spectroscopy（FT-IR）， nuclear magnetic resonance spectroscopy （1H NMR， 13C NMR） and high resolution mass spectrometry（HRMS）. The thermal properties were studied by differential scanning calorimeter and thermogravimetric analyzer. Its structure was optimized using Gaussian09 and its performance was estimated using Explo5 v6.01.. The results show that the crystal of 4，5-Bis-（chloro-dinitro-methyl）-2-diazoimidazole belongs to the triclinic P1 space group. The unit cell parameters are a=6.6196 （10） Å， b=8.1685（13） Å， c=13.0272（19） Å， V=666.96（18） Å， α=100.166（4）°，β=102.560（4）°， γ=97.153（5）°， Z=2， F（000）=368； D_c=1.848 g·cm^-3. Its thermal decomposition temperature is 122.14 ℃.The theoretical detonation velocity is 8574 m·s^-1 and the theoretical detonation pressure is 32.8 GPa. According to the BAM standard method， the impact sensitivity is 4 J and the friction sensitivity is 100 N.

Abstract:3， 4-bis（3-cyanofurazan） furazan oxide（BCTFO） was synthesized from 3， 4-dicyanofurazan as raw material by multistep functional group transformation of cyanide. The structure of BCTFO was characterized by IR， ¹³C and ¹⁵N NMR and elemental analysis. Combined with the theoretical simulation of GIAO method， the attribution of ¹³C NMR and ¹⁵N NMR spectra was completed. The single crystal of BCTFO was cultivated for the first time， which belongs to monoclinic， C2/c space group. The unit cell parameters are a=19.742（4） Å， b=8.851（2） Å， c=29.275（7） Å，V=4951.3（19） ų，Z=8， ρ=1.75 g·cm^-3， F（000）=2600， S=1.043， R₁=0.0491， wR₂=0.1375. Based on the determined density （ρ=1.76 g·cm^-3） and calculated enthalpy of formation （Δ_fH（s）=806.7 kJ∙mol^-3）， the detonation velocity （D） and detonation pressure （P） of the BCTFO are estimated to be 8086 m·s^-1 and 27.3 GPa by using Explo5（V6.04）. Differential scanning calorimetry （DSC） and thermogravimetric analyzer （TG） were used to study the thermal decomposition process of BCTFO. The peak temperature of thermal decomposition was T_dec=235.4 ℃. The sensitivity of BCTFO was measured according to BAM standard method， the impact sensitivity is 16 J and the friction sensitivity is 330 N.

Abstract:Planar heteroaromatic compounds containing amino and nitro functional groups usually have excellent detonation performances. Hereby， the ─NH─ bond bridging two high-nitrogen fused rings was adopted aiming at constructing a nitrogen-rich energetic compound with a planar structure. The resulting compound is expected to have a regular packing in crystal and favorable detonation performance and stabilities. Reaction of 2，6-diamino-3，5-dinitropyrazine （2） with K₂CO₃ gives rise to 6-（2，6-diamino-3，5-dinitropyrazine）-1，2，4-triazole［4，3-b］［1，2，4，5］tetrazine （3） in a high yield of 81.3%. Compound 3 was characterized by NMR， IR， single crystal X-ray diffraction. The thermal decomposition process of 3 was studied by differential scanning calorimetry （DSC）， and its decomposition temperature （onset） is as high as 254.6 ℃. The detonation performances of 3 （D=7568 m·s^-1， P=23.5 GPa） were calculated by Gaussian 09 and Explo5 software.

Abstract:4-hydroxy-3，5-dinitropyrazole（H-DNOP， 2） was synthesized from 3，5-dinitro4-bromopyrazole（1） by hydrolysis and neutralization reaction. Three kinds of ionic energetic compounds （3-5） of DNOP were designed and synthesized by using its acidity. The structures of compounds 3-5 were characterized by FT-IR， NMR spectrum， elemental analysis as well as single-crystal X-ray diffraction， and their thermal stabilities were investigated by differential scanning calorimetry and thermogravimetry （DSC-TG）. The maximum decomposition temperature of hydrazine salt （3） was T_d=210.3 ℃. The impact sensitivity and friction sensitivity were measured by BAM method， while the detonation parameters were predicted based on the isodesmic reactions and the Kamlet-Jacobs equation. The results show that the measured impact sensitivity and friction sensitivity of the threecompounds 3-5 are all 36 J and 360 N， which are less sensitive than those of TNT（IS=15 J，FS=353 N） and RDX（IS=7.4 J，FS=120 N）. The theoretical detonation velocities of the three compounds are 7758-8288 m·s^-1， and the detonation pressures are 26.06-29.96 GPa， respectively.

Abstract:To improve the energy property and low vulnerability of cast HMX-Al based explosives， high solid -content aluminized PBX were designed by analyzing the influences of Al and HMX contents on detonation properties. A casted PBX GOL-42 of 90% solid content with HTPB/IPDI binder was manufactured by introducing desensitizers and process agents and was optimized by three-grade grain-size distribution. The GOL-42 explosive showed good processing and safety properties. The detonation property， low vulnerability， mechanical property， thermal property and accelerated storage property were measured by their corresponding standard test methods. The results showed that its measured density， detonation velocity， detonation pressure， Gurney coefficient of Φ25 mm cylinder test was 1.782 g·cm^-3， 8251 m·s^-1， 26.9 GPa， 2.76 mm·μs^-1， respectively. And in the low vulnerability examinations， including bullet impact test， slow cook-off test and fast cook-off test， all the reaction grades were combustion. Its estimated storage life was over 20 years. GOL-42 showed perfect overall properties and was predicted as a long-life low vulnerability cast explosive.

Abstract:High performance liquid chromatography （HPLC） has several advantages， such as high sensitivity， good reproducibility， high efficiency， and high automation. HPLC is widely used for purity analysis and quality monitoring of chemical materials. 2，4，8，10-Tetranitrobenzopyrido-1，3a，6，6a-tetraazapentalene （BPTAP） as a new heat-resistant explosive has received wide attentions in recent years. However， there is a lack of HPLC method for BPTAP at present. Thus， we investigated and optimized the chromatographic conditions of separating BPTAP， and established a HPLC method for the analysis of BPTAP purity. The method is based on a Plus C18 column （4.6×150 mm， 5.0 µm） by using the mixture of acetonitrile and water （containing 0.1 mg·mL^-1 ammonium acetate） as the mobile phase. Gradient elution mode was used with the detection wavelength at 230 nm. The retention time of BPTAP is 9.13 min with good resolution of all peaks （greater than 1.90）. The method was further verified， and it is found that BPTAP has a good linear relationship between 0.5 µg·mL^-1 and 200 µg·mL^-1 with correlation coefficient （R²） of 0.9997. The detection limit and quantification limit are 0.02 µg·mL^-1 and 0.07 µg·mL^-1， respectively. In addition， the method was used for the purity analysis of BPTAP after the recrystallization， and it is proved that this method has good performance for the analysis of BPTAP.

Abstract:In order to obtain the damage characteristics of polytetrafluoroethylene/aluminum （PTFE/Al）， five PTFE/Al reactive liners with different Al particle sizes， by mold pressing and sintering， were prepared acting on double spacered plates . The results show that with the increase of Al particle size from 10 μm to 200 μm， the broken hole area， equivalent broken hole diameter ，broken hole uplift height and the volume of damaged area of steel and aluminum targets both decrease. When Al particle size is 10 μm， the damaged parameters of steel target are S_steel=0.4 CD （charge diameter）， h_steel=0.48 CD， V_steel=420 cm³， and the damaged parameters of aluminum target are S_aluminum=3.82 CD， h_aluminum=1.72 CD， V_aluminum=2280 cm³. PTFE/Al reactive jet with Al particle size 50 nm/70 μm can significantly improve the perforation effect of steel target， and d_steel=0.59 CD. Based on the experimental data， the analysis model of rupturing damage effect of reactive jet on behind-tagert is obtained by fitting.

Abstract:ResoDyn Acoustic Mixers Incorporation developed a mixing technique known as Resonant Acoustic® Mixing （RAM） in the early 21st century. This technology uses acoustic waves to create multiple micro-mixing zones within a material rather than the bulk mixing generated by traditional impeller or rotor agitation or planetary mixer. RAM technology can be used for the large-scale production of pharmaceuticals， cosmetics， and bulk powder mixing. For energetic materials， RAM is considered to have potential advantages over traditional high-shear processing methods （e.g. planetary mixing）， including shorter time scales， improved mix homogeneity， reduced waste output， absence of moving parts （an ignition source）， and the potential to mix higher viscosity， ‘unmixable’ compositions （compared to planetary mixers）. RAM has become the processing technology of choice in the development and production of propellants， explosives， and pyrotechnics. A summary of applications of RAM in the field of energetic materials， including the formation of co-crystal explosives and nano thermites and the processing of propellants and PBXs， is detailly overviewed in this text.

Abstract:To study the synthetic mechanism and properties of 3，7-dinitro-［1，2，4］triazolo［5，1-c］［1，2，4］triazine-4-amine （TTX），the synthetic mechanism of TTX was studied by density functional theory （DFT）， and the influence of pH value on the cyclization reaction was investigated. Thermal properties and impact sensitivity were studied by differential scanning calorimetry （DSC） and BAM drophammer apparatus， respectively. TTX was synthesized by the coupling reaction of sodium cyanonitromethanide and azo salt of 5-amino-3-nitro-1，2，4-triazole （ANTA）， following by intramolecular cyclization reaction. TTX showed a decomposition temperature of 281.8 ℃ and a apparent activation energy of 356.7 kJ·mol^-1. The impact sensitivity of TTX was measured to be 60 J. Moreover， the compatibility of TTX with HMX， RDX， Al powder and NC was studied. TTX had a good compatibility with Al powder， but a fair compatibility with HMX and a poor compatibility with RDX and NC. Therefore， adding RDX or NC into TTK would apparently increase its sensitity.

Abstract:To select an optimum treatment technology to solve the TNT red water contaminated soil problem in explosive industry， the high temperature sintering resourcing technology was developed. Contaminated soil and clay soil were mixed in a volume ratio of 4∶6， dried for 26 h in the drying section of a tunnel kiln by residual heat from the roasting section， and then roasted for 24 h in the roasting section at 1100 ℃. Sintering tail gas of the tunnel kiln was emitted into ambient air from its 43 m high funnel after treatment of desulfurization and denitrification facilities. Finished bricks were cooled down naturally out of the kiln. The featured pollutant-dinitrotoluene sulfonate in contaminated soil is completely decomposed， sintering tail gas reaches the emission standards， resource-based products meet the quality standard of building material bricks without any featured pollutant residue， and soil restoration target （the content of dinitrotoluene sulfonate in soil less than 100 mg·kg^-1） is met. The effectiveness and practicability of the high temperature sintering resourcing technology in TNT red water contaminated soil restoration was verified through engineering application.

Abstract:The study of polynitrogen pentazolate salts， which are usually achieved from the precursors of N₅ covalent compounds， is the hotspot of research in the field of new energetic materials. In most cases， the stability of N₅ covalent compounds will significantly affect the possibility of successful preparations of pentazolate salts. Herein， the calculations of dissociation energy （E_BD） of the bonds in the straight side chain and activation energy （E_a） of the N₅ ring were carried out for the selected eighteen non-aryl substituted N₅ compounds （R—N₅ or N₅—R—N₅） by using the B3LYP/6-31G** method of density functional theory， and meanwhile the influence of the side chain on their stabilities and pyrolysis mechanism were investigated. When R is the hydroxyl or amino group， the side chain and the N₅ ring are more prone to break， making it difficult to obtain the N₅^- ring. When R is alkyl， the E_a of the N₅ ring cleavage is relatively larger， making it more likely to produce the N₅^- ring， and the stability of the side chain′s C—N bond as well as the N₅ ring will be little affected by the length of the alkyl chain. The sequential cleavage of two N₅ rings occurs in the bicyclic molecular structures and the energy barrier of the second ring is higher than that of the first one， resulting in the formation of N₂ and azide. The C—C bond on the side chain of the molecule will be broken before the break of C—N bond， which may significantly reduce the E_BD of the C—N bond but have little effect on the E_a of the N₅ ring. Therefore， for the preparations of pentazolate salts from covalent pentazoles， cutting off the C—C bond first may be more conducive to obtaining N₅^- ring.

Abstract:In order to further improve the compactness of energetic powder materials， an ultrasonic-assisted isostatic pressing method is proposed， and an experimental prototype is designed and produced. The simulation software COMSOL is used to analyze the sound field of a single ultrasonic vibrator and the whole isostatic ultrasonic assisted molding system， and the influence of the cover thickness， 10 MPa pre-pressure and ultrasonic power voltage amplitude on the sound field distribution is studied. The simulation results show the rationality and feasibility of the ultrasonic-assisted isostatic pressing. The press molding experiments of polymer-bonded explosive（PBX） simulants are carried out whether to consider ultrasonic-assisted and 10 MPa pre-pressure conditions. The computed tomography（CT） and scanning electron microscope（SEM） are used to test and analyze the samples. The results show that the internal uniformity and compactness of the materials with ultrasonic-assisted and 10 MPa pre-pressure are better than those materials without， and their internal grains are finer and the grain distribution is more uniform.

Abstract:Due to conjugated planar molecular structure and additional N-oxide bonds， nitrogen-rich fused-ring N-oxides usually exhibit the advantages of high density， good detonation performances and good sensitivity and they have gradually become a research hotspot of energy materials. This article reviewed molecular structure， synthesis method and physical and chemical properties of twenty nitrogen-rich fused-ring N-oxides that were synthesized in the last decade. At the same time， this article compared some main physical and chemical properties between nitrogen-rich fused-ring N-oxides and their precursors. This review will provide some references for the synthesis and property investigation of new nitrogen-rich fused-ring N-oxides.

Abstract:In order to study the influences of ZrH₂ onto mechanical properties and damage performances of Al/PTFE， both cylinder and liner specimens of Al/ZrH₂/PTFE， Al/PTFE and pure PTFE were prepared by cold-pressing sintering process. The mechanical properties， impact sensitivity and damage efficiency of the three materials were contrastively studied by the tests of quasi-static compression， drop-weight impact and high-speed target impact. The experimental results showed that all three kinds of PTFE-based materials exhibited elastic-plastic mechanical behaviors and strain hardening effects. Adding a mass fraction of 10% of ZrH₂ into Al/PTFE reactive material improved its yield strength and failure stress to 22.2 MPa and 93.3 MPa， respectively， increased its ignition excitation energy by 1.93 J， and participated in the reaction through activation and decomposition to ensure that its energy release level was not weakened. The two kinds of energetic liners can produce collision energy release reaction and perforation/pore enlargement sympathetic effects during its impacting process， and formed the perforation pattern of petal valgus. Compared with inert damage element， the reactive material greatly improved its hole-enlargement ability by the impact-reaction double damage effect. The introduction of ZrH₂ into Al/PTFE reactive material can further enhance the damage efficiency of the material.

Abstract:Metal oxide is a type of ionic compound in which metal cations and oxygen anions are arranged into different crystal structures through ionic bond. The d-shells of some metal oxides are not completely filled wtih various unique properties， such as wide band gap， high dielectric constant， active electron transfer ability and excellent conductivity， etc. So they are widely used in the catalytic field. The current research status of thermal decomposition of ammonium perchlorate catalyzed by four different types of metal oxide semiconductor materials， such as single metal oxide， composite metal oxide， doped metal oxide， and supported metal oxide were introduced， the catalytic mechanism and factors affecting the catalytic effect were discussed. For the P-type metal oxide semiconductor materials， the narrower the band gap ， the lower the Fermi energy level， the higher the escape energy， and the greater the catalytic effect. For the N-type metal oxide semiconductor materials， the wider the band gap， the higher the Fermi energy level， the lower the escape energy， and the better the catalytic effect. In order to make full use of the advantages and overcome the defects of metal oxides， impurity elements are often introduced into metal oxides to form ionic lattice defects and create new local impurity energy levels to change the electronic transition， so as to improve the catalytic performance of metal oxides. Whether composite metal oxide or supported metal oxide， there is a positive synergistic catalytic effect on AP. The development of porous nanotube P-type metal oxides， doped metal oxides， and supported metal oxide materials with small band gap is still a major concern. Exploring the core-shell composite materials based on ammonium perchlorate， P-N junction metal oxide semiconductor catalytic materials， and revealing the migration law of carriers between the two kinds of semiconductors P-N interface are expected to be a new way to improve the catalytic efficiency.

Abstract:To research the influence of the additives such as RDX， Al， AP and polymer PBNMO on the moulding and mechanical characteristics of DNAN， the crystallization process of different intermixtures and the initial solidification temperature were observed mainly by photic microscope. The solidification rate was calculated by measuring the solidification time and the distance change. The effects of additives on the molding process were studied by testing the relative density of the Φ20 mm samples. The effects of additives on the mechanical properties were studied by testing the tensile strength and the compressive strength. Results show that those additives could improve the crystallization process， increase the relative density and decrease the solidification rate of DNAN. The mechanical properties such as the tensile strength，compressive strength and the anisotropy of the DNAN were improved by adding polymer PBNMO. The tensile strength was over 6 MPa. The results showed that， DNAN based explosives with fine crystals， less defects and better mechanical properties could be got by the synergistic effects of RDX， Al， AP and PBNMO.

Abstract:It was proved that the sensitivity， safety and density of explosive compound were extremely affected by its morphology and particle size. The influence factor of hexanitrohexaazaisowurtzitane （CL-20） particle size was studied in the recrystallization process with the ultrasonic-assisted recrystallization method， the anti-solvent method and the optimization of agitator type， respectively . The effects of continuous and intermittent ultrasonic with different ultrasonic frequencies （20-40 kHz） were also investigated in order to obtain the small particle size product. In the recrystallization process with anti-solvent method， ethyl acetate and chloroform were applied as solvent and anti-solvent respectively. The dropping acceleration of chloroform （20， 50， 100 mL·h^-1）， the ratio chloroform and ethyl acetate （1∶1， 1∶2， 1∶3）， the recrystallization time （24， 48， 72 h） and temperature （30， 40， 50 ℃） were optimized by orthogonal experiments. In addition， three types of agitator including four straight-blade open turbine， six straight-blade turbine and double-layer dispersing discs were performed in the CL-20 product morphology study together with their stirring speed effect. It was concluded that the assistance of intermittent ultrasonic could considerably reduce CL-20 crystal size. Particle size of 14 μm CL-20 could be obtained by ultrasonic assistant method while the frequency was controlled at 40 kHz with every 30 minutes vibration after 5 minutes stop. Moreover， L9（3⁴）orthogonal experiments were designed and particle size of 140 μm CL-20 could be achieved when the crystallization time， temperature， the chloroform dropping rate， and the dropping amount was 72 h， 30 ℃， 20 mL·h^-1 and 150 mL， respectively. Furthermore， three kinds of agitators were employed in the recrystallization process which obviously effected CL-20 morphology and particle size. A controllable particle size between 40-100 μm CL-20 crystals with spherical shape， a smooth and uniform surface were prepared with the double-layer dispersion disc. Comparing with the four straight blades open turbine type and the six straight blades turbine type agitator， it is proved that the product with desired impact sensitivity and friction sensitivity could be prepared by the double-layer dispersion disc method， which characteristic drop height and the explosion probability were 23.5 cm and 44%， respectively.

Abstract:As a typical representative of the third generation energetic materials， 2，4，6，8，10，12-hexanitro-2，4，6，8，10，12-hexaazaisowurtzitane （CL-20） is currently the most powerful energetic compound that has already been commercially available. The important research directions are， at present， the optimum synthesis of CL-20 and the preparation of CL-20-based high energy and low sensitivity energetic compounds in the development of energetic materials. The development status of the intermediates in the preparation of CL-20 was analyzed and summarized. The solutions and prospects of the intermediates were also proposed. In addition， the research progress， structural characteristics and main properties of CL-20 crystal products were also discussed. Through sorting out the synthesis and crystals of CL-20， it is concluded that low-cost， high yield， high purity and environmental friendliness are the future development direction of the synthesis process of CL-20.

Abstract:Fluororubber/glycidyl azide polymer/hexanitrohexaazaisowurtzitane （F₂₆₀₂/GAP/CL-20） composite fibers were prepared through electrospinning process， and the effects of solution concentration， binder ratio， spinning voltage and injection rate on the morphology were explored. Scanning electron microscope （SEM） was used to observe the morphology of composite fibers prepared under different conditions. It is found that when the solution concentration is 20%， the binder F₂₆₀₂/GAP content is 10%， the spinning voltage is 14 kV， and the injection rate is 5×10^-3 L·h^-1， the F₂₆₀₂/GAP/CL-20 composite fiber exhibits a three-dimensional network structure and its surface is uniform and smooth. X-ray diffraction （XRD）， infrared spectroscopy （IR）， differential scanning calorimeter （DSC） and mechanical sensitivity tests were performed on the F₂₆₀₂/GAP/CL-20 composite fiber and raw CL-20. The results show that the crystal form of CL-20 in the composite fiber changes from ε to β after electrospinning. There is no chemical reaction between CL-20 and F₂₆₀₂/GAP during the electrospinning process. After electrospinning， the apparent activation energy of F₂₆₀₂/GAP/CL-20 increases from 178 kJ·mol^-1 of the raw CL-20 to 374.3 kJ·mol^-1， indicating that the composite possesses better thermal stability. The impact sensitivity H₅₀ increases from 21.2 cm to 62.6 cm， and the friction sensitivity decreases from 84% to 52%. Therefore， the effect of sensitivity reduction is significant.

Abstract:In order to get the phase diagrams of 3，4-dinitropyrazole （DNP）/3，4-bis（3-nitrofurazan-4-yl） furoxan （DNTF） binary mixture system and understand the eutectic melting process， DSC was used to investigate the liquefaction and melting process of DNP/DNTF mixed system with different proportions. The T-x phase diagram and H-x phase diagram were established， and the effects of different heating rates and additives on melting process of eutectic were studied. Finally， the kinetic parameters E_a and A of eutectic melting process were calculated by Kissinger equation and Šatava-Šestak equation. Results show that the mass percentage of DNP/ DNTF eutectic is 70.38/29.62 and the eutectic temperature is 76.38 ℃ based on T-x phase diagram， which is good consistent with that from H-x phase diagram as 70.57/29.43. With the increase of heating rate， the initial temperature and peak temperature of melting process are delayed correspondingly. After the addition of Octogen （HMX） and nitroguanidine （NQ）， the melting point of the low eutectic is significantly delayed， while ammonium perchlorate （AP） has little effect on the melting point. The melting kinetic parameters E_a and A of DNP/DNTF eutectic are 19.13 kJ·mol^-1 and 10^9.74 s^-1 respectively， and the integral form of the most probable mechanism function is： G（α）=（1-α）^-1-1.

Abstract:In order to improve the efficiency of charging and molding of the explosive network， as well as the energy performance， high-energy azide binder 3，3-diazide methyl oxetane-tetrahydrofuran copolymer （PBT）， ultraviolet （UV） curing acrylate and hexanitrohexaazaisowurtzitane （CL-20） were selected as bonding system and main explosive respectively， an ultraviolet assisted curing CL-20-based energetic ink was designed， and using a 3D printing device to write. Rheometer， scanning electron microscope （SEM）， X-ray diffractometer （XRD）， and shore durometer were employed to characterize and test the rheological properties， microstructure， crystal form and hardness of the molded composite. Results show that the ink system is stable when the content of CL-20 is 82%. The curing efficiency of ink is fast with UV assisting， and the surface of molded sample is smooth. The hardness is 70 HA. The special height of impact sensitivity of the composite is 20 cm higher than the raw material； the test of detonation performance shows that the detonation wave can transfer 90° corner， and the critical detonation size reaches 0.387 mm when the line width of charge is 1.2 mm.

Abstract:Using nitromethane， tert-butylamine and formaldehyde as raw materials， a novel melt-casting explosive 5-methylnitrate-1，5-dinitrooxazine （TNOP） was synthesized via condensation and nitration reactions with the total yield of 46.2%. FT-IR， ¹H NMR， ¹³C NMR， elemental analysis and single-crystal testing approaches were conducted to obtain the structure of TNOP， disclosing an orthorhombic crystal structure with a space group of Pbca and the density of 1.722 g·cm^-3. The melting point and thermal decomposition temperature were examined to 110.8 ℃ and 203.5 ℃ using DSC technique， respectively. Furthermore， the detonation velocity and the detonation pressure are predicted to be 8112 m·s^-1 and 29.23 GPa based on calculated enthalpy of solid phase formation （-346.6 kJ·mol^-1）. In addition， an impact sensitivity of 50 J could be obtained for TNOP. By coordinating the energetic groups N—NO₂， C—NO₂ and —ONO₂ and facile synthesis process， TNOP was revealed with high energy， low melting point and low sensitivity， implying that it can be used as potential melt-casting explosive in weapons.

Abstract:A new high-energy compound 3，4-bis（（4-chloro-3，5-dinitro-1H-pyrazol-1-yl）methyl）-furoxan was synthesized by using 4-chloropyrazole as raw material， and its single crystal was obtained by solvent evaporation. The structures of this compound and its intermediates were characterized by ¹H and ¹³C NMR， FT-IR， DSC and TG， and the crystal structure of the product was characterized by X-ray single crystal diffraction. Results show that the compound belongs to the orthorhombic space group Pbca， a=10.1817（7） Å， b=16.1917（11） Å， c=21.7300（16） Å， V=3582.4（4） ų， α=90°， β=90°， γ=90°， Z=8， D_c=1.836 g·cm^-1. The Kamlet-Jacobs semi-empirical equation was used to predict the explosion velocity of 8304 m·s^-1 and the explosion pressure of 30.5 GPa. The sensitivities of this compound were measured by the BAM standard method， and the measured impact sensitivity is 9 J and the friction sensitivity is 180 N.

Abstract:The oxidation reaction of micro and nano aluminum powder is an important way of energy release and aging inactivation. Molecular dynamics and reaction kinetics provide necessary means for elucidating the microscopic mechanism of oxidation reaction of aluminum powder and quantitatively describing the oxidation process. According to the type of reaction system， the oxidation of aluminum powder can be divided into aluminum-oxygen （Al-O₂）， aluminum-water （Al-H₂O） and aluminum-other oxides （Al-other oxides） reaction systems. The recent progress of molecular dynamics and reaction kinetics in the above reaction systems is reviewed. The mechanism of oxidation kinetics of aluminum powder and its key influencing factors， including the oxide layer， particle size， atomic diffusion rate， temperature and oxygen concentration， were discussed， which proved the flexibility and effectiveness of molecular dynamics and reaction kinetics. On this basis， the important problems in different oxidation reaction systems were analyzed and prospected. It is pointed out that the oxidation kinetics of aluminum powder under multiple factors， the kinetics of Al-water vapor reaction， and the intrinsic mechanism of Al-other oxides reaction are the key problems to be solved in the future.

Abstract:Hollow charges usually adopt compression molding process. Using the method of continuum mechanics， a finite element simulation of the compression process model was established. First， the relative density， displacement and equivalent stress change laws of the pressing process of the JO-9159 explosive were simulated and analyzed. Then， the influences of pressing rate， initial relative density and friction coefficient on the pressing quality of JO-9159 explosive are simulated and analyzed. Results show that the JO-9159 explosive powder flows mainly in the axial direction during the pressing process， and the explosive powder flows slowly near the female mold area； when the pressing rate is 0.5 mm·s^-1 and the friction coefficient is 0.25， the relative density of the charge after molding is more uniform and the amount of rebound is smaller.

Abstract:3，4‐Bis（3'‐aminofurazan‐4'‐yl）furazan（BATF）was synthesized by reduction with stannous chloride in glycerol using 3，4‐bis（3'‐aminofurazan‐4'‐yl）furoxan（BAFF） as raw material. 3，4‐Bis（3'‐nitrofurazan‐4'‐yl）furazan（BNTF） was prepared from BAFF by using hydrogen peroxide as oxidantwith total yield of 59.0%. The structures of BATF and BNTF were characterized by 1H NMR，13C NMR，IR，MS spectra and elemental analysis，and the single crystal structure data of BNTF was obtained successfully. The crystal belongs to orthorhombic system，space group P212121 with crystal parameters a=0.71437（10） nm， b=0.96839（11）nm，c=51555（17）nm，V=1.0484（2）nm3，Z=4，Dc=1.876 g·cm-3，F（000）=592. The influence of molar ratio，reaction time，and reaction temperature on the yield of BNTF was investigated. Results show that the optimum conditions are as follows：n（BATF）∶n（35% H2O2）∶n（98% H2SO4 ）∶n（Na2WO4?2H2O）=1∶60∶40∶0.86，the reaction time is 3 h，the reaction temperature is 30 ℃ and the yield of BNTF is 93.3%. The thermal stability of BNTF was determined by DSC and TG‐DTG methods. Apparent activation energy Ea（147.83 kJ·mol-1），pre‐exponential factor A（9.33×1015 min-1）and decomposition rate constant k （2.18×10-44）of thermal decomposition reaction for BNTF were calculated by Kissinger method，Rogers method and Arrenhis method，respectively. The detonation velocity（8.3 km·s-1）and detonation pressure（31.3 GPa）of BNTF were estimated by Ka‐mlet‐Jacobs equation. Characteristic drop height of impact sensitivity（H50=43.0 cm）and friction sensitivity（36.0%）for BNTF were measured according to GJB772A-1997 methods 601.2 and 602.1，respectively.

Abstract:In order to develop a scale-up and continuous preparation method， the microchannel crystallization technology based on solvent/non-solvent method has been used to prepare hexanitrohexaazaisowurtzitane/octogen （CL-20/HMX） co-crystal. The field emission scanning electron microanalyzer （FE-SEM）， X-ray powder diffraction （XRD）， Raman spectroscopy， Fourier infrared spectroscopy （FT-IR）， thermal analysis and sensitivity test were applied to characterize and analyze the morphology， structure， thermal performance and sensitivity of samples. Results show that this method has successfully prepared CL-20/HMX co-crystal. Its apparent morphology is the flower clusters with a diameter of 20-30 μm， assembled by platelet crystals with thickness of 200-600 nm， accompanying individual flaky crystals （thickness of 200-600 nm）. The CL-20/HMX co-crystal prepared by microchannal crystallization has only one sharp exothermic decomposition peak during the exothermic process. Its exothermic peak temperature is at 243.4 ℃， which is lower than that of the raw materials CL-20 （250.2 ℃） and HMX （284.7 ℃）. Its temperature range of thermal decomposition is only from 242.7 to 246.0 ℃， much narrower than those of raw CL-20 （230.0-254.6 ℃） and HMX （281.0-290.7 ℃）， which means a higher energy release efficiency. Its apparent active energy is 470.75 kJ·mol^-1，falling between CL-20 （175.04 kJ·mol^-1） and HMX （481.45 kJ·mol^-1）， which is 297.29 kJ·mol^-1 hagher than that of raw CL-20，indicating a good thermal stability. Its impact sensitivity is 18 J， which is 8 J and 3.6 J higher than those of raw CL-20 （10 J） and HMX （14.4 J） respectively， and the friction sensitivity is 20% lower than that of raw CL-20. The sensitivity results show the safety of the CL-20/HMX co-crystal has been improved compared with the raw materials.

Abstract:In order to speed up the development of new energetic materials and reduce the time and resource consumption caused by a large number of experiments， a method for predicting enthalpy of formation of energetic materials is proposed based on the theory of material genetic engineering. Firstly， the collected atomic coordinate data representing the molecular structure of energetic materials were converted into a coulomb matrix representing the cartesian coordinate system in the molecule to eliminate the influence of translation， rotation， index order and other operations on the prediction of enthalpy of formation. Then， the enthalpy of formation of energetic materials was predicted according to the proposed fusion model of Convolutional Neural Network （CNN） and Bi-directional Long Short-term Memory Network （Bi-LSTM） based on Attention mechanism. In this way， not only can the characteristics of the data be extracted effectively， but also the correlation between the data and the lack of long-term dependence can be fully considered. Meanwhile， the influence of important characteristics on the prediction results can be highlighted. The comparison of experimental results shows that the proposed method based on deep learning has the lowest experimental error in the prediction of enthalpy of formation. Its Mean Absolute Error （MAE）， Mean Absolute Percentage Error （MAPE）， Root Mean Square Error （RMSE） and Root Mean Squared Logarithmic Error （RMSLE） are 0.0374， 1.32%， 0.0541 and 0.028， respectively. The prediction goal of "structure-performance" is realized， and a new method is provided for the prediction of enthalpy of formation of energetic materials.

Abstract:In order to understand the reaction characteristics of azide binder/non-isocyanate bonding system， curing processes of 3，3-bis（azidomethyl）oxetane-tetrahydrofuran copolymer（PBT）/bis-propargyl-succinate（BPS） binding system were investigated by microcalorimetry. The kinetic parameters and characteristic temperatures of PBT/BPS binding system were calculated through Kissinger method and Crane method. The equation between the complete curing time and the curing temperature was also fitted， demonstrating that the apparent activation energy， pre-exponential factor， reaction order and heat for curing reaction of PBT/BPS bonding system are 81.94 kJ·mol^-1， 10^8.48 s^-1， 0.93 and -926.88 J·g^-1， respectively. The values of gelation temperature， curing temperature and post-curing temperature were examined to 319.29 K， 344.52 K and 366.11 K， respectively. Besides， self-catalyzed phenomenon could be witnessed to exist in the curing reaction process of the PBT/BPS bonding system. The equation between the complete curing time and the curing temperature was y＝8.3345×10⁴e^-0.02309x-11.116.

Abstract:Six preparation methods of physical mixing， ball milling， vapor deposition， electrostatic spray/spinning， solvent/non-solvent and 3D printing for aluminum-fluoro reactive materials are summarized. Recent research progress of Al-fluoropolymer reactive materials are reviewed from the aspect of product performance and method advantages and disadvantages. The reaction process of aluminum-fluoropolymer reactive materials at slow heating rate and fast heating rate are introduced. The promising research directions in the future are pointed out， including design a new method that combines the advantages of various preparation methods and more attention should be paid to strengthen the research on the reaction mechanism of aluminum-fluoropolymer reactive materials when heated.

Abstract:In order to study the influence of stoichiometric ratio and oxygen content of oxidant on detonation process of gelled gasoline/gas-phase oxidant， a three-dimensional two-phase detonation model of gelled gasoline and gas-phase oxidant was established， and the internal detonation process of pulse detonation engine was simulated numerically using conservation element and solving element method. The effect of stoichiometric ratio and oxygen content of oxidant on the formation time， formation distance， peak pressure and propagation velocity of detonation wave were analyzed. The numerical results indicated that when the stoichiometric ratio is lower than 1.15， the formation distance and time of detonation wave decrease with increasing of stoichiometric ratio， and the pressure peak and propagation velocity of detonation wave increase at the same time. When the stoichiometric ratio is of 1.15， the formation distance and time of detonation wave are 0.288 m and 278 μs， and the pressure peak and propagation velocity of detonation wave are 1.85 MPa and 1437 m·s^-1， respectively. The pressure peak and propagation velocity of detonation wave increase with increasing oxygen content of oxidant， and when the oxygen content increases from 23% to 48%， the pressure peak and propagation velocity of detonation wave increase from 1.85MPa， 1437 m·s^-1 to 2.85MPa， 1868 m·s^-1， respectively.