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An aldehyde-group-containing energetic ZIF with unprecedented “negative” catalytic properties for seven different energetic materials

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Progress in Natural Science:materials International 2023年第6期33卷 924-934页

作者： Bojun Tan Xiong Yang Bo Wang Jinkang Dou Jing Zhang Wenjie Li Bozhou Wang Jiang Li Ning Liu Xi'an Modern Chemistry Research Institute School of materials Science and Engineering Chang'an University

energetic materials possessing high energy content, exceptional heat resistance, and insensitivity have long been recognized as a significant and prominent subject of academic debate. In this study, the necessity for high-energy explosives in both military and civilian domains prompted the introduction of the concept of an “energetic negative-burning rate catalyst” in heat-resistant and insensitive energetic materials. Therefore, a typical and effective catalyst(ZIF-90) was discovered. ZIF-90, which can be easily synthesized and features a large specific surface area and regular pore structure, contributes to molecular-scale changes in the pyrolysis process of energetic materials. Additionally, the presence of surface aldehyde groups facilitates the partial absorption of heat,thereby collectively contributing to the augmentation of pyrolysis peak temperatures for seven distinct energetic materials(RDX, HMX, CL-20, LLM-105, LLM-126, Al H3, and DAP-4). Specifically, the pyrolysis peak temperatures were elevated by 6.6°C, 1.7°C, 1.6°C, 6.4°C, 1.4°C, 13.1°C, and 7.0°C, respectively. Moreover, the highly stable ZIF-90, functioning as an intrinsically insensitive energetic Metal-Organic Framework(EMOF), not only effectively mitigates the sensitivity of energetic materials but also ensures minimal energy loss. Notably, the incorporation of a mere 5 wt% of ZIF-90 resulted in a significant enhancement of over one-fold in the heat resistance of LLM-105-based explosive cylinders, thereby validating the practical applicability of ZIF-90 in energetic materials. Moreover, the efficacy of ZIF-90 in solid propellant formulations was corroborated through flame experiments conducted on solid propellants. The development of such a pragmatic and universally applicable energetic negative-burning rate catalyst presents a promising strategy for the future advancement of highperformance, heat-resistant, and insensitive energetic materials.

关键词： energetic materials energetic negative-burning rate catalyst Heat resistance and insensitivity ZIF-90 Insensitive energetic metal-organic frameworks LLM-105-based explosive cylinder Solid propellant

The skeleton of 5,7-fused bicyclic imidazole-diazepine for heat-resistant energetic materials

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Defence Technology（防务技术） 2023年第9期27卷 193-199页

作者： Xiaoxiao Zheng Yubing Xue Changhao Dai Hongwei Yang Guangbin Cheng School of Chemistry and Chemical Engineering Nanjing University of Science and TechnologyNanjing210094China

In light of the low yields and complex reaction routes of some well-known 5,5-fused and 5,6-fused bicyclic compounds,a series of 5,7-fused bicyclic imidazole-diazepine compounds were developed with high yields by only two efficient ***,the seven-membered heterocyclic ring has a stable energetic skeleton with multiple modifiable ***,the 5,7-fused bicyclic energetic compounds were rarely reported in the area of energetic *** neutral compounds 1,2 and 4 were synthesized in this *** improve the detonation performances of the 5,7-fused neutral compounds,corresponding perchlorate 1a and 2a were further *** physicochemical and energetic performances of all newly developed compounds were experimentally *** newly prepared energetic compounds exhibit high decomposition temperatures(Td:243.8-336℃)and low mechanical sensitivities(IS:>15 J,FS:>280 N).Among them,the velocities performances of 1a(Dv=7651 m/s)and 4(Dv=7600 m/s)are comparable to that of typical heat-resistant energetic material HNS(Dv=7612 m/s).Meanwhile,the high decomposition temperature and low mechanical sensitivities(Td=336℃;IS=32 J;FS>353 N)of 4 are superior to that of HNS(Td=318℃;IS=5 J;FS=250 N).Hence,the 5,7-fused bicyclic compounds with high thermostability,low sensitivities and adjustable detonation performance have a clear tendency to open up a new space for the development of heat-resistant energetic materials.

关键词： Imidazole-diazepine Heat-resistant material 5,7-Fused skeleton energetic materials

Additive manufacturing of energetic materials:Tailoring energetic performance via printing

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Journal of materials Science & Technology 2022年第32期127卷 29-47页

作者： Nihan Chen Chunlin He Siping Pang Experimental Center of Advanced materials School of Materials Science&EngineeringBeijing Institute of TechnologyBeijing 100081China Yangtze Delta Region Academy of Beijing Institute of Technology Jiaxing 314019China Chongqing Innovation Center Beijing Institute of TechnologyChongqing 401120China State Key Laboratory of Explosion Science and Technology Beijing Institute of TechnologyBeijing 100081China

Additive manufacturing(AM),also called three-dimensional(3D)printing,has been developed to obtain energetic materials within the past decade.3D printing represents a family of flexible manufacturing techniques that enable fast and accurate fabrication of structures with complex 3D features and a broad range of sizes,from submicrometer to several *** methods have already been explored,including templating,melting extrusion,inkjet printing and electrospray *** was demonstrated that the structure achieved by AM could be used to manipulate the reactivity of energetic or reactive materials by changing the flow of gases and entrained particles via *** employing different AM techniques,energetic materials with controllable nanostructures and uniformly dispersed ingredients can be *** is exciting to tailor the energy release without defaulting to change the formulation of the conventional *** combustion and mechanical properties of conventional energetic materials can be retained at the same *** this review,the preparation and characterization of AM energetic materials that have been developed in the last decade are *** AM techniques used in the fabrication of energetic materials are compared and *** particular,formulations of energetic materials applied in AM,metallic fuels,binders and energetic fillers and their advantages in terms of combustion efficiency and other properties are proposed.

关键词： Additive manufacturing energetic materials Nanothermite Propellant

Dielectric constant predictions for energetic materials using quantum calculations

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Defence Technology（防务技术） 2021年第6期17卷 1988-1994页

作者： Pierre-Olivier Robitaille Hakima Abou-Rachid Josee Brisson RDDC-Valcartier 2459 Route de La BravoureQuebec CityQuebecG3J 1X5Canada Departement de Chimie and CERMA(Centre de Recherche sur Les Materiaux Avances) Universite Laval1045 Avenue de La MedecineQuebecG1V 0A6Canada

The dielectric constant(DC)is one of the key properties for detection of threat materials such as Improvised Explosive Devices(IEDs).In the present paper,the density functional theory(DFT)as well as ab-initio approaches are used to explore effective methods to predict dielectric constants of a series of 12 energetic materials(EMs)for which experimental data needed to experimentally determine the dielectric constant(refractive indices)are *** include military grades energetic materials,nitro and peroxide compounds,and the widely used ***-initio and DFT calculations are *** order to calculate dielectric constant values of materials,potential DFT functional combined with basis sets are considered for *** of the calculations are compared to experimental data listed in the scientific literature,and time required for calculations are both evaluated and *** best functional/basis set combinations among those tested are CAM-B3LYP and AUG-ccpVDZm,which provide great results,with accuracy deviations below 5%when calculated results are compared to experimental data.

关键词： DFT calculations energetic materials Dielectric constant Permittivity constant

Numerical simulation of radiated noise during combustion of energetic materials in a closed bomb

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Defence Technology（防务技术） 2022年第7期18卷 1167-1178页

作者： Shi-hui Xiong Tuo Yang Yu-jun Wu Jing-cheng Wang Yuan Li Yu-quan Wen State Key Laboratory of Explosion Science and Technology Beijing Institute of TechnologyBeijing100081China Xi'an Qinghua Cooperation North Special Energy Group Co.Ltd.Xi'an710025China Institute of Extreme Mechanics and School of Aeronautics Northwestern Polytechnical UniversityXi'an710072China

In this study,based on a closed bomb test combined with computational fluid dynamics,a structural finite element method,and an acoustic boundary element method,a fluid-solid acoustic one-way coupling calculation model is established for the combustion process of energetic materials in a closed bomb,and the effectiveness of the model is verified by *** is found that the maximum peak sound pressure increases exponentially with an increase in loading doses or gas ***,a change in the combustion coefficient of the energetic materials has little effect on the noise generated during the combustion process in the closed *** the combustion coefficient is reduced by a multiple of 16,the maximum transient sound pressure is reduced by 1.79 dB,and the sound pressure level in the frequency band is reduced by 1.75 *** an increase in shell thickness,the combustion noise of the energetic materials in the closed bomb decreases,and the reduction range of the combustion noise increases with the increase in shell thickness.

关键词： Pyrotechnics Noise energetic materials Fluid-structure interaction Acoustic boundary element

Recent advances on the nitrogen-rich 1,2,4-oxadiazole-azoles-based energetic materials

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Defence Technology（防务技术） 2022年第3期18卷 344-367页

作者： Wen-Li Cao Qamar-un-Nisa Tariq Zhi-Min Li Jun-Qing Yang Jian-Guo Zhang State Key Laboratory of Explosion Science and Technology Beijing Institute of TechnologyBeijing100081 PR China CAS Key Laboratory of Energy Regulation materials Shanghai200032China

This review covers recent advances in the synthesis and energetic performance of nitrogen-rich 1,2,4-oxadiazole-azoles-based energetic *** materials comprise of 1,2,4-oxadiazole subunit as a key structural motif linked to different nitrogen-rich or nitrogen-oxygen azoles:tetrazole,furazan,furoxan,1,3,4-oxadiazole,pyrazole,and *** attention is devoted to the introduction of various energetic groups including nitro,nitramino,azo,azoxy,dinitromethyl,trinitroethyl moieties,and their *** physicochemical and available performance parameters including density,decomposition temperature,heat of formation,detonation pressure,detonation velocity,impact sensitivity,and friction sensitivity of typical energetic compounds are also provided and ***,it was obtained that several screened compounds exhibit superior detonation properties and outstanding insensitivities,which can be classified as a new family of high-performance energetic ***,1,2,4-oxadiazole-azoles-based energetic materials still have many thorough works to further exploited and studied,expecting to get very promising insensitive high explosives for practical application and industrialization.

关键词： 1,2,4-Oxadiazole-azoles Triazole Tetrazole Furazan energetic materials Furoxan

Enhanced thermal- and impact-initiated reactions of PTFE/Al energetic materials through ultrasonic-assisted core-shell construction

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Defence Technology（防务技术） 2022年第8期18卷 1362-1368页

作者： Zhou-yang Wu Jin-xu Liu Song Zhang Xian-qing Liu Xiao Xu Wei-zhe Ma Shu-kui Li Chuan He School of materials Science and Engineering Beijing Institute of TechnologyBeijing100081China Science and Technology on Transient Impact Laboratory No.208 Research Institute of China Ordnance Industries102202China Department of materials Science and Engineering Shenzhen MSU-BIT UniversityShenzhen518172China

A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.

关键词： PTFE/Al Core-shell structure energetic materials Ultrasonic-assisted mixing

Progress on the application of graphene-based composites toward energetic materials:A review

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Defence Technology（防务技术） 2024年第1期31卷 95-116页

作者： Ting Zhang Xiaoming Gao Jiachen Li Libai Xiao Hongxu Gao Fengqi Zhao Haixia Ma College of Chemistry&Chemical Engineering Yan'an UniversityYan'an 716000ShaanxiPR China School of Chemical Engineering Northwest UniversityXi'an 710069ShaanxiPR China Xi'an Modern Chemistry Research Institute Xi'an 710065ShaanxiPR China

Carbon material is an important additive in energetic *** is a monolayer carbon material in which carbon atoms are arranged in two-dimensional honeycomb structure,who has special optical,electrical,and mechanical ***,the application of graphene-based composites in energetic materials has received extensive *** review mainly summarizes the applications of graphene and graphene-based nanomaterials in energetic *** effects of these materials on the thermal stability,sensitivity,mechanical property,ignition and combustion of energetic materials were ***,the progress of functionalized modification of graphene has been summarized,including covalent bonding modification and doping *** studies show that graphenebased materials exhibit excellent performances and might emerge as promising candidate for energetic materials.

关键词： Graphene Desensitization Thermal decomposition Catalytic combustion energetic materials

Modification of a ReaxFF potential at short range for energetic materials

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Defence Technology（防务技术） 2024年第12期42卷 176-182页

作者： Weiyi Li Tao Wang Wenhua Li Jintao Wang Wanxiao Guo Zexin Jiang Yilin Fang Xiyao Yun Ning Gao Rocket Force University of Engineering Xi'an710025China Institute of Frontier and Interdisciplinary Science and Key Laboratory of Particle Physics and Particle Irradiation(MOE) Shandong UniversityQingdao266237China

The ReaxFF can describe the properties of energetic materials(EMs)at equilibrium state,but does not work properly in simulating high-energy particle irradiation process because of its weak short-range *** this paper,a modification was made for such a potential by connecting ZieglerBiersack-Littmark(ZBL)potential to ReaxFF-lg through comparing to Density Functional Theory(DFT)results to accurately describe short-range *** modification,the newly fitted ReaxFF-lg/ZBL potential predicts better the equation of state for EMs In displacement cascade simulations,comparing to results from ab initio molecular dynamics(AIMD),ReaxFF-lg/ZBL presented the similar transferred energy from a primary knock-on atom to surrounding atoms,better than the original ReaxFF-lg *** large-scale displacement cascade simulations indicated ReaxFF-lg/ZBL could be applied for cascade simulations with PKA energy from less than 1 keV to high energy(e.g.35 keV)cases,which is suitable for effectively simulating high-energy displacement cascades in EMs using molecular dynamics method.

关键词： Molecular dynamics Potential modification energetic materials Displacement cascade Density functional theory Ab initio molecular dynamics