为探究主体炸药HMX的粒度对PBX(HMX)/AP复合含能材料的热分解和激光点火性能的影响,通过溶剂-非溶剂法对原料HMX和AP进行重结晶并筛分得到不同粒径分布的HMX_R和细粒度AP_R(5～20μm),进而制备含不同HMX粒度的PBX(HMX)/AP,对所得晶体和复合物分别进行SEM、DSC、DSC-IR及热分解动力学和1064nm激光点火测试。结果表明,HMX_R和AP_R的热分解表观活化能E_a和热爆炸临界温度T_b随着晶体粒度减小而减小; PBX(HMX)/AP中,HMX_RC的粒径范围为30～140μm、d₅₀为68μm、按HMX与AP零氧平衡配比的PBX(HMX_RC)/AP热性能最优,其热分解表观活化能E_a为212.78kJ/mol,比HMX_RC降低约274.44kJ/mol; 其热爆炸临界温度为197.45℃,比HMX_RC降低约76.25℃,比AP_R降低约81.63℃; 含不同HMX粒度的PBX(HMX)/AP的点火延迟时间随着HMX粒度的减小而减小,质量燃烧速率相应增大,其中零氧平衡配比的PBX(HMX_RC)/AP的激光点火性能最佳,其激光点火延迟时间为8200ms,质量燃烧速率为0.718g/(cm²·s)。表明HMX粒度范围影响传热、传质和物质间相互作用效率,进而影响点火、传火性能; 细粒度和零氧平衡及良好的黏结复合最有利于PBX(HMX)/AP中HMX与AP的协同热分解。

To improve the accuracy of crystal density prediction in the development process of new nitrogen/oxygen heterocyclic energetic materials, by using quantum chemical method, the quantitative structural parameters such as dipole moment, quadrupole moment, polarizability, the highest occupied orbital energy and the lowest empty orbital energy of the synthesized heterocyclic compounds were calculated under three functions. The numbers of hydrogen bond donor, hydrogen bond acceptor, and rotatable bond were obtained from the PubChem database. By using the stepwise regression method, the parameters closely related to density were selected, and the multiple linear regression(MLR)and back propagation(BP)neural network models were established, respectively. The results show that under the three function levels, the model established by B3PW91 function has the best prediction accuracy, and the BP neural network model has the higher precision accuracy in density predicting of heterocyclic energetic materials than the MLR model. Compared with the existing methods, at the B3PW91/6-31G(d,p)level, the average absolute percentage error and correlation coefficient of BP neural network model are 3.1% and 0.956, respectively,showing that the established model can be used to predict the density of heterocyclic energetic materials accurately.

The review starts from the research of ReaxFF molecular dynamics in the field of energetic materials and focuses on the composition and development of the ReaxFF force field, optimization methods, and applications. Among the development methods, local and global optimization methods are highlighted, including multiple objective evolutionary strategies, enhanced particle swarm optimization algorithm, and neural network reactive force field. The application of the ReaxFF force field in energetic material simulations has mainly focused on exploring microstructural reactivity, dynamic evolution, initial chemical decomposition pathways, and intermediate and stable product distributions. Depending on the different external conditions, the application fields are heating and pressurization, shock loading, laser, and electric field. The main research concerns single component/mixture/co-crystal explosives, defective explosives, and metal composite explosives. Finally, there are some suggestions for the accuracy and transferability of ReaxFF. ReaxFF reactive force field trained with the artificial intelligence framework can significantly increase its accuracy in complex reactions. If reaction laws based on ReaxFF replace phenomenological laws for critical indicators such as local reactivity in continuum simulation models, this would be a crucial step towards realizing the multi-scale full-process simulations with mechanical and chemical kinetic response couplings. The 134 references are attached.

A comprehensive review was conducted on the historical development, construction scheme, and training strategy of the machine learning potential. This novel technique approximates the potential energy surface of molecular system at the level of first-principle calculations and has been successfully applied in the molecular modelling of combustion and explosion for energetic materials, including nitramine compounds(RDX, CL-20, and ICM-102), oxidizers(AP)and high-energy particles(Al, B). In addition, the representative applications of machine learning potential on the combustion of hydrocarbon fuels were also introduced. Furthermore, the challenges and future development perspectives of machine learning potential in energetic materials were discussed. It is well demonstrated that machine learning potentials, particularly deep potential models, are highly accurate and efficient. The data-driven approach makes it feasible to empower the simulation of million atoms with a great accuracy as first-principle calculations. In the final remark, the key challenges for the further development of machine learning potentials are discussed:(1)sampling issue for a complex potential energy surface under extreme conditions;(2)accuracy problem in the training dataset. With 91 references.

To provide guidance for reasonable use of the attachment energy model and the development of crystal morphology prediction in energetic materials, the applications of the attachment energy model in the crystal morphology prediction of energetic materials in the last decade were reviewed, and the crystal shape prediction results of the same systems were compared. The calculation protocol of attachment energy in vacuum and in solvent, as well as the structural model construction, were described in detail. The influence factors on the accurate calculation of the attachment energy, such as force field, model size, crystal-solvent interaction, and so on, were discussed. The recent development of the attachment energy model was also introduced, including the correction of solvent effect, the exploration of supersaturation, and the new strategy of crystal shape prediction. The aim of this review is to promote the crystal morphology prediction method of energetic materials to a more accurate mechanism model.With 82 references.

To identify the optimal preparation process of perovskite energetic material DAP-4, triethylenediamine hexahydrate, ammonium perchlorate, and perchloric acid as raw materials were used. Firstly, it was determined that the factors including perchloric acid, deionized water, and the discharge temperature had a greater effect on the yield of DAP-4 through single-factor experiments, and the less influential factors were the reaction time and reaction temperature. Then, the optimal preparation process was determined by designing three-factor and three-level orthogonal experiments, and the particle diameter, thermal decomposition performance, and sensitivity of DAP-4 under each experimental condition were also measured. The results showed that the influence of each factor on the yield of DAP-4 was as follows: perchloric acid=discharge temperature > deionized water, and the best preparation process was: the volume of perchloric acid(the mass fraction is 35%)was 32.6mL(n₁:n₂:n₃=1:1:7.5), and the deionized water was 125mL and the discharge temperature was 20℃. Under these conditions, the yield of DAP-4 can reach 95.9%, and changing the amount of perchloric acid, deionized water, and discharge temperature had little effect on the morphology and particle diameter of DAP-4, and the particle diameter distribution was between 50—90μm, the apparent activation energy of DAP-4 samples synthesized under different process conditions ranged from 175 to 217kJ/mol, and the impact sensitivity and electrostatic sensitivity were both insensitive.

The research progress in the synthesis of energetic materials with nitrogen-rich N-oxide skeletons was reviewed. The compounds were classified by monocyclic, tandemed and fused molecular skeletons. Focusing on the comparison of the introduction strategies of N-oxide fragments, it is proved that the skeleton synthesis of fused nitrogen-rich aromatic N-oxides is more difficult, but often gives denser structures than tandem and monocyclic nitrogen-rich N-oxides. The direct nitrogen oxidation introduction strategy and the cyclic nitrogen oxidation introduction strategy were analyzed and discussed, providing a reference for the design of nitrogen-rich N-oxides with different skeleton structures. In addition, the synthesis methods of related compounds were further compared and the properties of representative compounds were evaluated. With 61 references.

Nano-energetic compounds were widely applied to realize the efficient energy release and controllable reaction of weapons and ammunition, which had also been studied by many countries as an important key material to improve the level of national defense technology. In order to give full play to the potential of energetic materials and meet the high-performance needs of weapons, the preparation methods of nano-energetic materials and their applications in the field of explosives were reviewed based on the related research work, which was aimed to provide a reference for the research in the field of nano-explosive. First, the preparation methods were summarized and classified by high-energy fuel, single-compound explosive, strong oxidant and hydrogen storage materials, and the process characteristics and refining effect were also introduced. Second, the interrelationship between the nano-energetic materials and other components was investigated in detail, as well as the application advantages were described. At last, the main factors limiting the further development of nano-energetic materials were explored from the perspectives of particle dispersion, oxidative deactivation and moisture absorption. With 197 references.

In view of the current problems that energetic materials cannot meet the urgent needs of high-tech weapons and equipment for multi-mode, special-shaped and gradient charging, additive manufacturing technology for energetic materials is developed. Firstly, the concept, basic principle and technical characteristics of additive manufacturing technology were introduced. Then,the research progress of additive manufacturing technology in energetic materials, including initiating explosive devices, gun propellants, rocket propellants, mixed explosives and thermites, was described respectively based on the related research at home and abroad. The basic problems, such as adaptive formula design, special device/software development, online monitoring of safety/quality, etc. which limited the development of additive manufacturing technology of energetic materials were furtherly analyzed. Finally, the future development of additive manufacturing technology for energetic materials was prospected, and it was pointed out that it was necessary to take the gradient structure-function combining design idea as the starting point, and develop a new mechanism of 4D printing for energetic materials under intelligent, cross-scale and extreme conditions, so as to provide technical support for the development of weapons and equipment with adjustable power and controllable motion. With 135 references.

The direct ink writing(DIW)technology and its application in energetic materials was systematically introduced. Recent research progresses and applications of DIW technology were emphasized, including metastable intermolecular composites(thermite, aluminum-fluorine polymer), propellants and explosives grains with complex structure, and pyrotechnics. The main relevant challenges and the opportunities of DIW technology were also proposed. DIW technology covers the deficiency of traditional charge technology to a certain extent, and it has great application potential in the research and development of new porous charge/charge with special structure and explosive charge with variable energy density. In the future, it is proposed that the research on additive manufacturing explosive formula for application, the photothermal co-curing matrix, and the integrated manufacturing of ammunition with cased and charge should be enhanced. Thus, new ideas and technical approaches for the development of new and high-precision strategic weapons and equipment in China will be provided.

To improve the combustion performance of Al based composite energetic materials, multilayer graphene was prepared by oxidation and reduction heat treatment. Al-C, Al-B and Al-B-C composites were prepared by high energy ball milling method. The structure of the composites were characterized by SEM, EDS mapping and XRD. The heat of combustion of the composites were measured by oxygen bomb calorimeter. The ignition delay time of composites were measured by CO₂ laser igniter. The results show that the prepared multilayer graphene has a specific surface area of 85.5m²/g and a pore diameter of 15—200nm. The Al-C material heat treated at 600℃ and 700℃ has the highest combustion calorific value, and the ignition delay time increases with an increase in heat treatment temperature; Al-B is easy to produce AlB₂ at high temperature, which leads to the highest heat of combustion without heat treatment and the minimum ignition delay time of treatment at 750℃. The heat of combustion of Al-B-C composites after heat treatment at 600℃ and 700℃ is the highest. The addition of too much of B inhibits the combustion of the materials, but it will shorten the ignition delay time of the materials.

Owing to the rapid release of multi-component gas during the reaction process of energetic materials, the technical issues in sampling and transmission, spectral analysis, and quantitative analysis are elaborated by using the continuous real-time and full-component scanning detection method of mass spectrometry. The technical difficulties of the reliability and distortion mechanism of different mass spectrometry sampling interfaces, the overlap of spectra due to the synchronous coupling of reaction process and ionization, and quantitative analysis of multi-component gas are analyzed. Three representative reaction processes are selected to illustrate the secondary reaction of crystallization of the evolved gas from boiler slags, nonlinear analysis of the mass spectrum signal in CaS gasification, and quantitative analysis of the mass spectra of the evolved gas from the typical energetic material Fx. The results show that the quantitative mass spectrometry method, equivalent characteristic spectrum analysis(ECSA^), can be used to determine the sampling distortion and accurately analyze the mass change rate of multi-component gas. Based on the continuous dynamic information for the mass changes of the multi-component gas and the mass balance of materials, components, and elements, the ECSA^ method enables accurate identification of multiple reaction processes.

Due to the sponge-like pore structure of nanoporous silicon, it is difficult to fill with oxidants. This is the reason why the porous silicon composite energetic materials are mostly in a fuel-rich state. Meanwhile, adjusting the porosity of nanoporous silicon efficiently remains a challenge, so the oxygen-fuel ratio cannot be precisely controlled. In order to solve these above problems, the closely-arranged monolayer polystyrene microspheres were used as the template, and the nanoporous silicon nanowires with controllable morphologies and structures are obtained through reactive ion etching(RIE)technology and metal-assisted chemical etching(MACE). Porous silicon nanowires can precisely adjust the oxygen-fuel ratio of the composite systems by controlling the RIE time. At the same time, the two-dimensional linear structure is very beneficial to promote the filling ratio efficiently. The results show that the composite energetic system achieves the best stoichiometric reaction equilibrium and the energy output when the RIE time is 80s(the diameter of silicon nanowire of about 150nm). Moreover, the silicon nanowires with different structures and morphologies were prepared by using silicon wafers with different resistivity. The structure of silicon nanowires prepared by silicon wafers with lower resistivity is looser and more porous. The silicon nanowires prepared by silicon wafers with low resistivity can not only effectively shorten the heat transfer distance and reduce the activation energy of the reaction but also enhance the heat release of the reaction. It is beneficial to improve the combustion performance and facilitate the ignition of the nanocomposite energetic systems. The work could provide a new idea for the development of silicon-based energetic materials.

Several commonly used detection methods in the pyrolysis study of energetic materials with their advantages and disadvantages were briefly introduced. The "soft" ionization characteristics of photoionization mass spectrometry(PIMS)and its advantages in the analysis of pyrolysis products were described. “Soft” ionization can make the products ionize without generation of ionization fragments, which is convenient for the rapid analysis of complex systems. It is conductive to online detection of the rapidly evolving intermediates generated from the pyrolysis process of energetic materials. Recent application progress of PIMS in study of pyrolysis of energetic materials, such as NTO, FOX-7, FOX-12 and CL-20, were summarized emphatically. The PIMS methods used in these studies include single photon ionization mass spectrometry and atmospheric pressure photoionization high resolution mass spectrometry based on vacuum ultraviolet(VUV)light generated from discharge lamp or synchrotron radiation sources. The new pyrolysis products and intermediates detected by online PIMS were also summarized. Finally, the future opportunities of PIMS in study of energetic materials were prospected. For characterization of fast reactions, by optimizing the mass spectrometer and developing high-brightness photoionization sources, it is expected to achieve time-resolved measurement at millisecond or sub-millisecond. It will help to study the pyrolysis and combustion process of energetic materials under high temperature and high pressure. For quantitative measurement, it is necessary to establish and improve the photoionization cross section database of energetic materials and main products. 61 References were attached.

In order to fully utilize the performance advantage of fullerene and expand the application of fullerene and its derivatives in the field of high-energy materials, the updated preparation methods and specific research direction of the functional fullerene derivatives used in energetic materials were reviewed. The effects of fullerene and its derivatives on the thermal decomposition, combustion performance and stability of energetic materials were discussed in detail. It shows that fullerene and its derivatives can be used as energetic components, combustion catalysts, desensitizers and stabilizer. As energetic components, they show good thermal performances. As combustion catalysts, the activation energy of energetic materials can be significantly reduced. As desensitizer, the friction sensitivity and impact sensitivity of HMX can be reduced to 48% and 50%, respectively. As stabilizer, they have high scavenging rate of nitrogen oxide radicals. Finally, the preparation methods and application fields of different fullerene derivatives were summarized, and the future development direction and research focus were prospected. 85 References were attached.

To explore the effect of graphdiyne(GDY)on the thermal decomposition characteristics of HMX, the GDY/HMX(mass ratio of 1:4)composite energetic materials was prepared, and the differential scanning calorimetry(DSC)and the thermogravimetry coupled with Fourier transform infrared spectrometry and mass spectrometry(TG/DTG-FTIR-MS)technique were employed to investigate the pyrolysis processes of the HMX and GDY/HMX comparatively. The apparent activation energies of HMX and GDY/HMX were calculated by Kissinger, FWO, KAS, Starink, Kissinger-iterative, and Ozawa-iterative methods, and the modified esták-Berggren empirical equation was used to reconstruct the kinetic models of their thermal decomposition reactions. The results show that the apparent activation energy of HMX is reduced by 73.6kJ/mol in the presence of GDY. The pyrolysis process of the GDY/HMX composite follows the n-order kinetic equation f(α)=3.04α^0.39(1-α)^1.17. GDY plays a crucial role in promoting the C—N bond cleavage during HMX decomposition, leading to the release firstly of the C₂HO and N₂O. And the gaseous products including NO, NO₂, HCN, CO, N₂, HCNO, CO₂, and H₂O are also detected.

Based on the current research on microfluidic technology at home and abroad, the research progress of microfluidic technology in the synthesis of energetic compounds, modification of energetic materials, and preparation of composite energetic materials is reviewed from the perspective of equipment and material performance regulation. According to the development needs, several priorities for subsequent development are proposed: overcome the problem of microchannel blockage and expanding the application of solid-containing systems; combine with flow field simulation for accurate selection of process parameters; further combine on-line detection technology to establish an automatic feedback adjustment system to realize intelligent preparation of energetic materials; give full play to the advantages of high throughput and promote the application of microfluidic technology in the industrial production of energetic materials. 102 References are attached.

为了研究铝粉含量对含铝炸药作功能力的影响，同时获得含铝炸药中铝粉的反应规律，对5种不同配方的炸药（RDX、RDX/Al、RDX/LiF）开展了Φ25 mm圆筒试验，利用光子多普勒测速技术（PDV）获得了圆筒的速度历程，在JWL状态方程的基础上提出了一种考虑铝粉二次反应速率的含铝炸药状态方程拟合方法。结果表明，对于粒径2 μm的铝粉，结合光子多普勒测速技术，Φ25 mm圆筒试验能够较好地表征铝粉的二次反应过程，铝粉反应的起始时间小于3 μs，铝粉在10~15 μs时间内已经反应完毕；新方法拟合得到的炸药状态方程较好地再现了圆筒膨胀过程，并能够对炸药中铝粉的反应情况进行半定量计算；3种铝粉含量的RDX/Al炸药中，质量分数15%的铝粉炸药作功能力最强；得出在炸药配方设计时，应综合考虑爆热和产物比容，单纯追求高爆热，不能获得最佳的毁伤效果。

为了测试新研制的CO₂相变爆炸激发药剂的安全性,依据GJB5891.22-2006 火工品药剂试验方法的第二十二部分“机械撞击感度试验”和第二十四部分“摩擦感度试验”方法,对其进行了撞击感度和摩擦感度测试,按照《危险货物运输 爆炸品的认可和分项试验方法》,开展了12m跌落试验、75℃热稳定性试验和外部火烧试验。结果表明,在1.2kg钢锤、500mm落高条件下,25发撞击感度试验爆炸概率为0; 在1.5kg钢锤、摆角100°、表压2.45MPa条件下,25发摩擦感度试验爆炸概率为0; 12m跌落试验和75℃热稳定性试验中激发药剂试样均未出现燃烧或爆炸现象,75℃热稳定性试验结束时激发药剂的温度仅比试验温度75℃高出0.5℃,表明激发药剂为热稳定性物质; 外部火烧试验结果表明,144kg激发药剂在露天敞开的条件下,仅用1min左右时间就燃烧完全,但未发生爆炸,也没有危险的迸射物射出。各试验结果均表明,激发药剂的危险感度低、安全性好,其原因在于激发药剂组分中C₂H₈N₂O₄对燃烧反应具有一定的抑制作用,精确控制其含量,可使激发药剂具有良好的燃烧性能和较高的安全性。

In order to research the influence of MgH₂ on ignition and combustion performance for typical energetic materials, the ignition delay time and flame propagation velocity of the mixture of MgH₂ and five kinds energetic materials were measured and calculated by laser ignition and high-speed photography visualization technology. The results show that 50.0% and 11.1% MgH₂ have the best effect on improving the ignition and combustion performance of RDX. 11.1% MgH₂ is the best for HMX. Meanwhile, 20.0%-33.3% MgH₂ can significantly improve the flame propagation speed of CL-20. However, the ignition delay time of mixture is shorter when the addition of MgH₂ is 50.0% and 11.1%. Furthermore, the ignition delay time of the mixture of FOX-7 and ADN with MgH₂ are less than that of energetic components and MgH₂ respectively, which means that the ignition process of these energetic materials and MgH₂ can promote each other. Considering the improvement of ignition performance and flame combustion performance of FOX-7, the addition of 11.1% MgH₂ is the most favorable. The improvement of ignition and combustion performance of ADN by using MgH₂ is proportional to the amount of MgH₂ added. The reason why MgH₂ promotes the ignition and combustion performance of energetic materials is that the decomposition products of MgH₂ benefit the phase transition of energetic materials, and finally enhance the ignition and combustion properties.

The developments of amplification methods of nitrogen chains in energetic material synthesis were reviewed. The common reactions such as substitution reactions of N—X bonds by azido groups, electro-catalytic oxidation reactions of azide ions, diazo transfer reactions of primary amines, dimerization reactions of diimine, N-amination and nitration reactions, oxidative coupling reactions of amine groups, and diazo-coupling reactions of amine groups were summarized. The mechanisms of typical amplification reactions of nitrogen chains were also introduced. The structural evolution processes of ionic nitrogen chains such as N⁺₅, [N₇O]⁺, N^-₈, and organic compounds with all-nitrogen fragments such as N₃/N₄/N₅/N₆/N₇/N₈/N₁₀/N₁₁ chains were emphatically discussed. The possible synthetic routes of N^-₇, N₁₀ and N₁₂ chains and the development trends of this research field were pointed out. With 65 references.

The research status and prospect of using metal hydride as additives in energetic materials(EMs)are summarized in this study through three aspects: thermodynamics, energy and combustion performance of metal hydride in EMs. The results show that the combustion heat, energy level and some other performance indices of system are improved effectively, while opportune percentages of metal hydride are added in EMs. Despite huge potentials exist for the addition of metal hydride in EMs, some practical difficulties hinder the general application of them. Among them, the appropriate thermal stability of metal hydride should be developed and payed attention. Doping and nanocrystallization are two useful ways to improve the thermodynamics performance of metal hydride.

In order to study the thermal decomposition properties of 5,5'-bistetrazole-1,1'-diolate(TKX-50)/graphene oxide(GO)nano-composite energetic materials, liquid nitrogen-assisted spray freeze-drying method was used to prepare TKX-50/GO composite materials. The morphology, structure and surface element of the samples were characterized and analyzed by using the scanning electron microscopy-energy spectroscopy(SEM-EDS)and X-ray diffraction(XRD). The thermal decomposition properties of composites were analyzed by using the thermogravimetry-differential scanning calorimetry(TG-DSC). The apparent activation energy was calculated by using the Kissinger method. The results show that the TKX-50/GO composite prepared by liquid nitrogen-assisted freeze spray drying method has nano-scale layered network structure. Compared to the TKX-50, the first stage decomposition peak temperature of TKX-50/GO composite energetic material decreases by 12.0, 12.5 and 12.2℃, and the second stage decomposition peak temperature decreases by 12.5℃ and 16.4℃. With the increase of GO content, the decomposition peak in the second stage is not obvious, and the two decomposition stages of TKX-50/GO₅ are overlapped. The apparent activation energy of the nano-composite materials increases from 146.2kJ/mol to 163.3, 168.5 and 172.9kJ/mol compared to the TKX-50, respectively. GO improves the activation energy barrier of the composite energetic material, decreases the decomposition peak temperature and shortens the reaction interval time, so the GO improves the energy release rates and promotes the thermal decomposition of TKX-50/GO composite materials.

The working mechanism of electrospinning apparatus and the effects of main process parameters on the composition and morphology of fibers are introduced in detail. The basic principle is that charged droplet in the high-voltage electric field overcomes the surface tension of the polymer solution as a function of electrostatic force and then undergoes a stretching and whipping process, leading to finally the formation of long and thin nanofibers on a grounded collector. In addition, the recent progress of the application of electrospinning technique in the field of superthermites, nanocrystallization of single energetic materials and solid fuels, and the ultrasensitive fluorescence detection of explosives is reviewed.The results show that the electrospinning technique is an effective method to control the morphology of nanofibers and achieve the nano-crystallization of energetic materials. It can effectively inhibit the surface oxidation and pre-reaction sintering of nano aluminum particles for the thermite-type energetic materials. Also, it can increase the dispersion of particles and improve the reaction efficiency and the heat release of reaction.Meanwhile, the nano-crystallization of energetic materials by the electrospinning technique has remarkable effects on improving the combustion decomposition characteristics, increasing the energy density, reducing the sensitivity, and enhancing the mechanical properties of energetic materials. Finally, the future research trends and application of electrospinning functionalized nano-energetic composites are also prospected.

In order to obtain the influence rule of the plasma initiation voltage and the contact area between plasma and insensitive energetic materials on the response intensity of the insensitive energetic materials,the typical molecular insensitive energetic materials 1,1-diamino-2,2-dinitroethylene(FOX-7), 2,6-diamino-3,5-dinitropyrazine-1-oxide(LLM-105)and 1,3,5-triamino-2,4,6-trinitrobenzene(TATB)as well as ionic insensitive energetic materials N-guanylurea-dinitramide(FOX-12)and dihydroxylammonium 5,5’-bistetrazole-1,1-diolate(HATO)were selected, and a series of initiation experiments were carried out, with plasma generated by exploding bridge wire at different initiation voltages of 15, 20 and 25kV, and with straight wire(Z)and spiral wire(W). Detonation response intensity was evaluated by morphology and maximum deformation of witness plates. The results show that the initiation response are different with types of insensitive energetic materials. Increasing the plasma initiation voltage can significantly increase the response intensity of molecular insensitive energetic materials, and the order of response intensity of molecular energetic materials FOX-7, LLM-105 and TATB is W/25kV>Z/20kV>W/20kV, the ionic insensitive energetic materials FOX-12 and HATO have no significant rule for plasma initiation conditions. Compared with ionic insensitive energetic materials, molecular insensitive energetic materials are more sensitive to plasma detonation voltages and contact area between plasma and insensitive energetic materials.

In order to have an intuitive understanding of the transition in different molecular configurations of energetic materials at the molecular level the transition state structures of β-RDX→α-RDX,γ-HMX→β-HMX,ε-CL-20→β-CL-20 and β-FOX-7→α-FOX-7 during molecular configuration transformation were searched by Gaussian 09 software with density functional theory(DFT)and TS algorithm,and their conformational transformation processes were determined. The difficulty of molecular configuration transition of polymorphic energetic materials was estimated by calculating the change of Gibbs free energy along the configuration transition path. The results show that the transition from the metastable crystal form to the stable crystal form will first cross the transition state and overcome the free energy barrier to transform into a metastable state structure. The free energy barriers to be overcome for the β-RDX→α-RDX, γ-HMX→β-HMX, ε-CL-20→β-CL-20 and β-FOX-7→α-FOX-7 molecular configuration transitions were 5.25, 22.21, 9.69 and 10.24 kJ/mol, respectively. Therefore, the difficulty level of transformations for β-RDX→α-RDX, γ-HMX→β-HMX, ε-CL-20→ β-CL-20 and β-FOX-7→α-FOX-7 under normal temperature and pressure is HMXFOX-7>CL-20>RDX.

The principles and characteristics of the atomic layer deposition (ALD) technology are briefly described. In comparison with the traditional vapor deposition technologies, ALD boasts its unique capabilities in precise film thickness control, low temperature deposition, large area and three-dimensional uniformity. These features make ALD a promising technology for preparing the energetic composites and fabricating the surfaces of energetic materials. The latest research progresses on the applications of ALD in the preparation and modification of energetic materials are summarized, including synthesis of metastable intermolecular composites (MIC), de-sensitization of metal fuels and explosives, and stability improvement of aluminum, aluminum hydride and ammonium dinitramide (ADN). The importance and prospects of ALD in precise synthesis and surface fabrication of energetic materials are evaluated. With 29 references.

Based on fractal theory and heat conduction theory, the correlation among sensitivity, heat conduction, and fractal dimension of energetic materials were analyzed. Meanwhile, the fractal heat conduction models of micro and nano energetic materials were established. To verify the correctness of the model, the size fractal dimension and surface fractal dimension of two kinds of nitroamine explosives with different particle size were calculated, and the thermal conductivity was calculated by the model. The results show that the tangential effective thermal conductivity (k_t) and radial effective thermal conductivity (k_r) of nano RDX were higher by 0.204 and 0.059 W/mk than k_t and k_r of raw RDX, respectively. The k_t and k_r of nano HMX were higher by 0.079 and 0.426 W/mK than k_t and k_r of raw HMX, respectively. This meant that nano energetic materials were of higher effective thermal conductivity than micron energetic materials, which quite benefited to dissipating of the heat and decreasing of temperature of hot spots. Thus, nano energetic materials exhibited lower sensitivities. It is also concluded that the sensitivity of energetic materials can be assessed by means of the models.

With glycidyl azide polymer (GAP) as energetic gel matrix and hexamethylene diisocyanate (HDI) as cross-linking agent, GAP-HDI/CL-20 nano-composite energetic materials containing 25%, 45% and 60% CL-20 in mass ratio were prepared by the sol-gel method and vacuum freezing-drying technology. Their structure and morphology were characterized by SEM, Raman and FT-IR,and the thermal decomposition characteristics were studied by DTA. According to the test results of DTA curves at different heating rates, the thermal decomposition kinetic parameters, thermodynamic parameters and critical temperature of thermal explosion of the prepared samples were calculated. The results show that CL-20 particles were successfully loaded into GAP-HDI gel skeleton. The morphologies of CL-20 particles are changed from prism to spheroid and the particle sizes are nano-scale. The initial thermal decomposition temperature of GAP-HDI/CL-20 is earlier than that of raw material CL-20. The apparent activation energies of GAP-HDI/CL-20 nano-composite energetic materials with CL-20 mass fraction of 25%,45% and 60% are 224.9, 228.9 and 231.7 kJ/mol, respectively, which are decreased by 28.4, 24.4 and 21.6 kJ/mol compared with that of raw material CL-20, indicating that the thermal decomposition activity of GAP-HDI/CL-20 is improved, the thermodynamic parameters and the critical temperature of thermal explosion increase with the increase of CL-20 content.

To adjust the oxygen balance of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20),and further improve its energy utilization efficiency,the CL-20/ammonium perchlorate (AP) composite energetic material with zero oxygen balance was prepared by emulsion method.The factors affecting the emulsion stability were studied.The morphology,structure and properties of the material were characterized by scanning electron microscope (SEM),X-ray diffraction (XRD),differential scanning calorimeter and impact sensitivity test.The results show that when the dosage of the surfactant tween-80 is 0.56% of the total mass of AP and CL-20,the stable O/W structure can be formed and the emulsion can keep good stability within 48 h.The micron scale hollow spherical α-CL-20 crystals are attached to the AP crystal surface and both can be full contacted.The CL-20/AP composite energetic materials have only one exothermic peak at 243.38℃,and the heat released reaches 1 538.83 J/g.Compared with the raw material CL-20,the heat released increases by 60.7%.The characteristic drop height H₅₀ of impact sensitivity of CL-20/AP composite energetic materials is 45 cm,and increases by 32 cm compared with the raw material CL-20,revealing that the safety performance of CL-20 is significantly improved.

Embarked from the recent development of metal-fluoropolymer mechanical activation energetic composites (MAECs), the energy properties of metal-fluoropolymer were introduced, the energy advantages and release mechanism were analyzed.The typical defects of metal-fluoropolymer were summarized as the low energy release rate caused by the large diffusion distance between two components. The method of adjusting the energy release rate was compared, such as the use of nano aluminum powder, design of the micro device of reaction materials and the mechanical activation treatment. The superiority of mechanical activation was also analyzed. The research status of the mechanical activation process, reaction mechanism, detonation performance and application of MAECs was reviewed. The present status and problems of the research on MAECs of metal-fluorine polymer were evaluated, and the future development trend was also discussed.

The compatibility of sodium and guanidinium salts of bis(3-(5-nitro-1,2,4-triazole))(Na₂·cis-BNT, G₂·trans-BNT) with cyclotrimethylenetrinitramine(RDX), cyclotetramethyle-netetranitroamine(HMX) and 3,3-diazidomethyl oxetane-glycidyl azide polymer(BAMO-GAP),and the thermal behaviors of the mixture system were investigated by differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG). The effect of sample preparation methods (grinding method or solvent method) on the compatibility of mixed system was preliminarily explored. The results show that there are some differences in compatibility results of the mixed system obtained by dry method and wet method for Na₂·cis-BNT and G₂·trans-BNT, When the binary systems are prepared by grinding method, the Na₂·cis-BNT/RDX system is compatible, Na₂·cis-BNT/HMX system is slightly sensitive, which is suitable for short-term use, while G₂·trans-BNT/RDX system is sensitive and G₂·trans-BNT/HMX system is incompatible. When the binary systems are prepared by solvent method, the mixtures of Na₂·cis-BNT with RDX, HMX, BAMO-GAP and G₂·trans-BNT with BAMO-GAP are compatible, but the mixtures of G₂·trans-BNT/RDX and G₂·trans-BNT/HMX are sensitive, which are not suitable for use. The sample preparation methods have an influence on the compatibilities of HMX based mixtures for its heterogeneous thermal decomposition process. Therefore, when the compatibility is determined by DSC, the mixing method of the sample prearation needs to be clearly explained and the final judgment shall be combined with other methods.

The hexanitrohexaazaisowurtzitane(CL-20)/split multi-walled carbon nanotubes (SMWNTs) nano-composite energetic material was prepared by an ultrasound inhalation method using SMWNTs as raw material and CL-20 as filler.It was characterized by TEM, DSC-TG and XRD and laser ignition test was conducted. The results show that CL-20 grains are filled into the SWMNTs, and the filling position is at the port of SWMNTs, which is arranged with granular. Compared with pure CL-20, the initial decomposition temperature of CL-20/SMWNTs decreases from 239.6℃ to 229.6℃,and the peak temperature reduces from 221.4℃ to 173.6℃. CL-20/SMWNTs nano-composite energetic material has high photosensitivity and can be ignited under laser energy of 50W.

The molecular structures of energetic materials of nine aza-bicyclic nitramine with different functional groups and parent ring structure were calculated and studied under B3LYP 6-31++G (d, p) calculation accuracy using density fuctional theory (DFT) with Gassian03 software. The relationship between the structure and properties was analyzed. Their geometry configurations were optimized. The molecular volume and energy etc. were obtained via. calculation. Based on this, the density, detonation properties and sensitivities of the materials were calculated. Through comparison of the molecular structure, the effects of different functional groups and structure of rings on the properties of this kind of energetic materials were studied from the aspects of density, heat of formation, detonation properties and stability etc. The functional groups and structure of bicyclic nitramine compounds were obtained via. comparison. The results show that bicyclic nitramine structure is conducive for stable structure, formation of a compact space layout and improvement of impact sensitivity and density. At the same time, the introduction of carbonyl group and approaching zero oxygen balance are good technology process to improve the performance of such kind of energetic materials.

The advantages of self-assembly method are highlighted by analyzing and comparing the energy properties of the nanostructured energetic materials fabricated by different approaches. The self-assembly strategy can effectively control the arrangement of component nanoparticles, improve the dispersity of ingredients, and increase the intimacy between the reactants. Therefore, the burning rate and reactivity, as well as energy efficiency, of the assembled nanostructured energetic materials are enhanced, due to that the length of mass and heat transport during reaction are reduced. Recent advances reported in previous publications related to the self-assembly of aluminum-based nanostructured energetic materials are summarized and classified into two categories: direct and indirect methods. Accordingly, the development direction of the self-assembly to prepare nanostructured energetic materials is proposed.

Starting from the related achievements of recent development in the field of energetic materials, the main research direction in this field was discussed, and the latest achievements of theoretical prediction of the physicochemical properties of energetic materials were described in particular, mainly including quantum chemistry, molecular dynamics or semi empirical QSPR modeling approaches to predict the research progress in sensitivity, combustion and detonation performances,reaction activity, curing mechanism and mechanical properties of energetic materials.The main technical barriers existed at present were summarized, including the lack of complete and unified standard experimental database on performances of energetic materials, no commercial software with independent intellectual property rights to calculate the energetic material properties, and international commercial software with reliable predictors of physical and chemical properties of energetic materials is limited to the detonation performance and combustion performance. Literature research shows that China needs to further strengthen the research in this field, and finally build a comprehensive software platform that can evaluate the performance and security of energetic materials.With 90 references.

The common kinetic mechanism functions were derived, which include the diffusion mechanism function, the random nucleation and the subsequent growth mechanism function, the power law mechanism function, the phase boundary reaction mechanism function and the chemical reaction mechanism function. The technical approach for logical selection and determination of the most probable mechanism function was presented. The function mechanisms of decomposition reaction of some energetic materials were collected and expatiated. The mechanism function and rate equation of the exothermic decomposition reaction process of 6b-nitrohexahydro-2H-1,3,5-trioxacyclopenta-［cd］-pentalene-2,4,6-triyl trinitrate (NHTPN) are reported with 79 references.

According to the difference of chemical structure, Mg-based hydrogen storage materials were divided into three categories: Mg-based hydrogen storage alloy hydrides, MgH₂ and Mg-based metal complex hydrides. The research progress in the application of the three categories of Mg-based hydrogen storage materials in energetic materials was introduced. The application prospects and existing problems of Mg-based hydrogen storage materials in energetic materials were analyzed. The application situation of computer simulation technology in the study of Mg-based hydrogen storage materials affecting the thermal decomposition of propellant was introduced. The results reveal that Mg-based hydrogen storage materials can promote the thermal decomposition process of energetic materials to improve their energy level and the relatively higher thermal stability of Mg-based hydrogen storage materials enhances the compatibility and stability of energetic materials. Mg-based hydrogen storage alloy hydrides, MgH₂ and Mg-based metal complex hydrides can significantly improve the application performance of solid propellants and explosives. Therefore, the Mg-based hydrogen storage materials have broad application prospects in the field of energetic materials. With 47 references.

Energetic Polymer/Nitroguanidine composite energetic material was prepared by solvent/nonsolvent method using energetic polymer (EP) and nitroguanidine (NQ) as raw materials. Its morphology and structure were characterized by scanning electron microscope (SEM), BET method and X-ray diffraction (XRD). The thermal properties of EP/NQ composite energetic material and its physical blends were compared and analyzed by thermogravimetry differential scanning calorimetry (TG-DSC). Results show that the EP/NQ composite energetic material has a three-dimensional nano-network structure. The NQ particles with mean particle size of 49-62nm are deposited on EP and the long needle like form of NQ is eliminated. The surface area of EP/NQ composite energetic material is smaller than that of EP, and the surface area decreases from 54.599m²/g to 25.02m²/g with increasing the mass fraction of NQ from 40% to 60%. EP/NQ composite energetic material has the characteristic of a single thermal decomposition peak, its thermal decomposition peak temperature is 55-59℃ lower than that of NQ and its peak temperature rises from 200.1℃ to 203.7℃ with increasing the mass fraction of NQ from 40% to 60%. The decomposition heat of EP/NQ composite energetic material is much higher than that of the physical blends.

Taking oxalic acid and aminoguanidine bicarbonate as raw materials, a new insensitive energetic material, dihydroxylammonium 3,3′-dinitro-5,5′-bis-1,2,4-triazole-1,1′-diolate(MAD-X1) was synthesized by cyclodehydration, diazotizationsubstitution, oxidation and neutralization reactions with a total yield of 41.2%. Its structure was characterized by IR, ¹HNMR,¹³C NMR and elemental analyses. The synthetic mechanism for the synthesis of  3,3′-diamino-5,5′-bi-1,2,4-triazole(DABT) by onepot method was dissussed. The effect of mole ratio of sodium nitrite and sulfuric acid on the yield of diazotizationsubstitution reaction was investigated. The thermal behavior of MAD-X1 was analyzed. The energy properties of MAD-X1-CMDB propellant were calculated by NASA-CEA program. Results show that the onepot method for synthesis of DABT has the advantages of short cycle and high yield(75.1%). The best mole ratio of sodium nitrite and sulfuric acid is 2.4∶1 and the acidification reagent is hydrochloric acid. The thermal decomposition peak temperature of MAD-X1 is 248.7°C. The theory specific impulse and [JP]characteristic velocity of MAD-X1-CMDB propellant are2449.6N·s/kg and 1540.7m/s,respectively.