The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development...The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.展开更多
Finding energetic materials with tailored properties is always a significant challenge due to low research efficiency in trial and error.Herein,a methodology combining domain knowledge,a machine learning algorithm,and...Finding energetic materials with tailored properties is always a significant challenge due to low research efficiency in trial and error.Herein,a methodology combining domain knowledge,a machine learning algorithm,and experiments is presented for accelerating the discovery of novel energetic materials.A high-throughput virtual screening(HTVS)system integrating on-demand molecular generation and machine learning models covering the prediction of molecular properties and crystal packing mode scoring is established.With the proposed HTVS system,candidate molecules with promising properties and a desirable crystal packing mode are rapidly targeted from the generated molecular space containing 25112 molecules.Furthermore,a study of the crystal structure and properties shows that the good comprehensive performances of the target molecule are in agreement with the predicted results,thus verifying the effectiveness of the proposed methodology.This work demonstrates a new research paradigm for discovering novel energetic materials and can be extended to other organic materials without manifest obstacles.展开更多
As a typical energetic composite,polytetrafluoroethylene(PTFE)/aluminum(Al)has been widely applied in explosives,pyrotechnics,and propellants due to its ultra-high energy density and intense exothermic reaction.In thi...As a typical energetic composite,polytetrafluoroethylene(PTFE)/aluminum(Al)has been widely applied in explosives,pyrotechnics,and propellants due to its ultra-high energy density and intense exothermic reaction.In this work,the radial gradient(RG)structure of PTFE/Al cylinders with three different PTFE morphologies(200 nm and 5μm particles and 5μm fiber)and content changes are prepared by 3D printing technology.The effect of radial gradient structure on the pressure output of PTFE/Al has been studied.Compared with the morphology change of PTFE,the change of component content in the gradient structure has an obvious effect on the pressure output of the PTFE/Al cylinder.Furthermore,the relationships of the morphology,content of PTFE and the combustion reaction of the PTFE/Al cylinder reveal that the cylinder shows a more complex flame propagation process than others.These results could provide a strategy to improve the combustion and pressure output of PTFE/Al.展开更多
Heat-resistant energetic materials refer to a type of energetic materials that possess a high melting point,high stability and operational safety. By studying the structures of these energetic materials has showed tha...Heat-resistant energetic materials refer to a type of energetic materials that possess a high melting point,high stability and operational safety. By studying the structures of these energetic materials has showed that the thermal stability can be enhanced by introducing amino groups to form intra/inter-molecular hydrogen bonds, constructing conjugate systems and designing symmetrical structures. This article aims to review the physical and chemical properties of ultra-high temperature heat-resistant energetic compounds and provide valuable theoretical insights for the preparation of ultra-high temperature heatresistant energetic materials. We also analyze the selected 20 heat-resistant energetic materials with decomposition temperatures higher than 350℃, serving as templates for the synthesis of various highperformance heat-resistant energetic materials.展开更多
The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the ...The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge.In this work,HMX-PEI/rGO/g-C_(3)N_(4)(HPrGC)composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C_(3)N_(4).The g-C_(3)N_(4) used for desensitization has a richπ-conjugated system and shows outstanding ability in reducing friction sensitivity.The hierarchical structure of HPrGC formed by electrostatic self-assembly andπ-πstacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution,thus exhibiting a prominent synergistic desensitization effect on HMX.The results show that rGO/gC_(3)N_(4) coating has no effect on the crystal structure and chemical structure of HMX.More importantly,the perfect combination of g-C_(3)N_(4) and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity(IS:21 J,FS:216 N).Obviously,the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings.展开更多
The molecular geometries,heats of formation and electronic structures of three trinitrobenzenes(1,2,3TNB,1,2,4TNB and 1,3,5TNB)and their chloro derivatives were studied by using the quantum chemical MO AM1 method at t...The molecular geometries,heats of formation and electronic structures of three trinitrobenzenes(1,2,3TNB,1,2,4TNB and 1,3,5TNB)and their chloro derivatives were studied by using the quantum chemical MO AM1 method at the RHF level and ab initio method at the HF/321G level.The decompositions of the title compounds were investigated by using the AM1 method at the UHF level.The decomposition activation energies were obtained and the order of the relative stabilities of the title compounds is found.The substituent effects on the structures and properties and on the decompositions of the title compounds are discussed in the present paper.展开更多
Silicone rubber(SR) composites are most widely used as thermal interface materials(TIMs) for electronics heat dissipation. Thermal impedance as the main bottleneck limiting the performance of TIMs is usually neglected...Silicone rubber(SR) composites are most widely used as thermal interface materials(TIMs) for electronics heat dissipation. Thermal impedance as the main bottleneck limiting the performance of TIMs is usually neglected. Herein, the thermal impedance of SR composites loaded with different levels of hexagonal boron nitride(h-BN) as TIMs was elaborated for the first time by the ASTM D 5470 standard test and finite element analysis. It was found that elastic modulus and surface roughness of SR composites increased with the increase of h-BN content, indicating that the conformity was reduced. When the assembly pressure was 0.69 MPa, there existed an optimal h-BN content at which the contact resistance was minimum(0.39 K·cm^(2)·W^(-1)). Although the decreased bond line thickness(BLT) by increasing the assembly pressure was beneficial to reduce the thermal impedance, the proper assembly pressure should be selected to prevent the warpage of the contact surfaces and the increase in contact resistance, according to the compression properties of the SR composites. This study provides valuable insights into fabrication of high-performance TIMs for modern electronic device applications.展开更多
This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, empha...This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.展开更多
Detonation performance is crucial for evaluating the power of high explosives(HEs),and the equation of state(EOS)that accurately describes the high-temperature,high-pressure,and high-temperature,medium-pressure states...Detonation performance is crucial for evaluating the power of high explosives(HEs),and the equation of state(EOS)that accurately describes the high-temperature,high-pressure,and high-temperature,medium-pressure states of detonation products is key to assessing the damage efficiency of these energetic materials.This article examines the limitations of the VLW EOS in representing the thermodynamic states of explosive detonation gas products under high-temperature and medium-to high-pressure conditions.A new gas EOS for detonation products,called VHL(Virial-Han-Long),is proposed.The accuracy of VHL in describing gas states under high-temperature and medium-to high-pressure conditions is verified,and its performance in evaluating explosive detonation and working capabilities is explored.The results demonstrate that VHL exhibits high precision in calculating detonation performance.Subsequently,the detonation performance of three new HEs(ICM-101,ONC,and TNAZ)was calculated and compared to traditional HEs(TATB,CL-20,and HMX).The results indicate that ONC has superior detonation performance compared to the other explosives,while ICM-101 shows a detonation velocity similar to CL-20 but with slightly lower detonation pressure.The detonation characteristics of TNAZ are comparable to those of the standard HE HMX.From the perspective of products,considering the comprehensive work performance(mechanical work and detonation heat),both ONC and ICM-101demonstrate relatively superior performance.展开更多
The energy release of energetic composites is severely limited by the inert alumina(Al_(2)O_(3))layer on the surface of aluminum(Al).Polytetrafluoroethylene(PTFE)could eliminate Al_(2)O_(3)layer due to its highly elec...The energy release of energetic composites is severely limited by the inert alumina(Al_(2)O_(3))layer on the surface of aluminum(Al).Polytetrafluoroethylene(PTFE)could eliminate Al_(2)O_(3)layer due to its highly electronegativity and oxidability of fluorine.However,adding PTFE particles would weaken interfacial interactions resulted in poor mechanical properties and interfacial exothermic reaction.Herein,a bridging Al-PTFE as fuel and interfacial reinforcing agent was added and used to prepare LLM-105/AlPTFE microspheres,achieving both high energy output and excellent mechanical properties.The energy release and combustion reaction performance of LLM-105/Al-PTFE microspheres are significantly improved due to high reaction heat and increased interfacial reaction area of Al-PTFE.The maximum pressure and pressurization rate of LLM-105/Al-PTFE microspheres are 164.06 kPa and 29.88 kPa/s,respectively,which are 40.11%and 16.67%higher than those of physical mixed samples.Furthermore,the tensile strength and compressive strength of LLM-105/Al-PTFE microspheres are 100.40%and 26.47%higher than those of LLM-105/Al.This work provides a new approach to improve the energy release and mechanical properties for energetic composites.展开更多
Nowadays, ultrafine explosives are widely used in military fields. Ultrafine 2,2',4,4',6,6'-hexanitrostilbene(HNS) has emerged as an optimal primer for explosion foil initiators due to its excellent therma...Nowadays, ultrafine explosives are widely used in military fields. Ultrafine 2,2',4,4',6,6'-hexanitrostilbene(HNS) has emerged as an optimal primer for explosion foil initiators due to its excellent thermal stability and high-voltage short-pulse initiation performance. However, the solid phase ripening of ultrafine HNS leads to a degradation in its impact detonation performance. Previous studies have indicated that residual dimethyl formamide(DMF), which is present in ultrafine HNS prepared using the recrystallization method, affects ultrafine HNS ripening. The mechanism of residual solvent effects on solid phase ripening of ultrafine HNS is unclear. In this work, the specific surface area(SSA) derived from small angle X-ray scattering(SAXS) was utilized for kinetic fitting analysis to explore the mechanism by which residual solvents enhance the solid phase ripening of ultrafine HNS. The results of the SSA measured by insitu SAXS under conditions of 150℃ for 40 h revealed that the sample with 0.2% residual DMF exhibited a 21.51% decrease in SSA, whereas the sample with only 0.04% residual DMF showed a decrease of 15.66%.Furthermore, the higher amounts of residual DMF accelerated the reduction in SSA with time. Kinetic fitting analysis demonstrated that reducing residual DMF would lower both the activation energy and the pre-exponential factor, consequently decreasing the rate constant of solid phase ripening. The mechanism was speculated that it primarily facilitated the Ostwald ripening(OR). Additionally, contrast variation small angle X-ray scattering(CV-SAXS) confirmed that coating of ultrafine HNS particles is an effective method for inhibiting ripening, significantly reducing both the rate and extent of ripening of ultrafine HNS. This study predicts how residual solvents impact the solid phase ripening process of ultrafine HNS and proposes strategies for enhancing the long-term stability of ultrafine explosives.展开更多
Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and ...Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.展开更多
This study investigates the paradoxical detonation behavior of TKX-50,a nitrogen-rich energetic material,exhibiting higher detonation velocities but lower metal acceleration ability compared to HMX.Through experimenta...This study investigates the paradoxical detonation behavior of TKX-50,a nitrogen-rich energetic material,exhibiting higher detonation velocities but lower metal acceleration ability compared to HMX.Through experimental measurements and theoretical calculations,we propose a novel three-factor competition mechanism to explain this phenomenon.TKX-50-based PBX formulations achieved detonation velocities up to 9100 m/s,surpassing HMX-based counterparts.However,cylinder expansion tests revealed a 15%reduction in metal acceleration ability.Thermochemical measurements showed lower detonation heat for TKX-50(4900 J/g)versus HMX(5645 J/g).Our mechanism involves:(1)compositional effects prevailing at high pressures;(2)Energy release becoming essential as pressure drops;(3)Pressure-dependent product composition evolution functioning at low pressure.VLW code calculations unveiled a"crossover"in Hugoniot curves,lending support to this mechanism.This study furnishes a new framework for comprehending the performance of nitrogen-rich energetic materials,with significant implications for the design and optimization of future high-energy density materials.展开更多
Realizing effective enhancement in the thermally conductive performance of polymer bonded explosives(PBXs) is vital for improving the resultant environmental adaptabilities of the PBXs composites. Herein, a kind of pr...Realizing effective enhancement in the thermally conductive performance of polymer bonded explosives(PBXs) is vital for improving the resultant environmental adaptabilities of the PBXs composites. Herein, a kind of primary-secondary thermally conductive network was designed by water-suspension granulation, surface coating, and hot-pressing procedures in the graphene-based PBXs composites to greatly increase the thermal conductive performance of the composites. The primary network with a threedimensional structure provided the heat-conducting skeleton, while the secondary network in the polymer matrix bridged the primary network to increase the network density. The enhancement efficiency in the thermally conductive performance of the composites reached the highest value of 59.70% at a primary-secondary network ratio of 3:1. Finite element analysis confirmed the synergistic enhancement effect of the primary and secondary thermally conductive networks. This study introduces an innovative approach to designing network structures for PBX composites, significantly enhancing their thermal conductivity.展开更多
The precise characterization of interfacial structure for polymer-bonded explosive(PBX) modification is challenging due to the complexity of the interface. The inherent properties between explosive and binders affect ...The precise characterization of interfacial structure for polymer-bonded explosive(PBX) modification is challenging due to the complexity of the interface. The inherent properties between explosive and binders affect interface bonding, lowering the interfacial strength in unpredicted ways. Surface modification is an effective method to balance multi-utility in materials engineering, which has been carried out to design of high-performance composites with improved interfacial properties. Experimental methods may determine the coating shell for capturing the PBX structures. Various approaches were applied to characterize the structure and properties of PBX interface, including molecular dynamicsbased computational models to predict bonding properties. In this review, systematic organization were provided and summarized with detective methods on the surface and interface of explosives. Meanwhile, the usage scenarios and limitations of each measurement were proposed. Conclusions from the review yield useful guidelines and references for systematical characterization on the modification of explosive and can be extended to other materials.展开更多
The incorporation of graphene fillers into polymer matrices has been recognized for its potential to enhance thermal conductivity,which is particularly beneficial for applications in thermal management.The uniformity ...The incorporation of graphene fillers into polymer matrices has been recognized for its potential to enhance thermal conductivity,which is particularly beneficial for applications in thermal management.The uniformity of graphene dispersion is pivotal to achieving optimal thermal conductivity,thereby directly influencing the effectiveness of thermal management,including the mitigation of local hot-spot temperatures.This research employs a quantitative approach to assess the distribution of graphene fillers within a PBX(plastic-bonded explosive)matrix,focusing specifically on the thermal management of hot spots.Through finite element method(FEM)simulations,we have explored the impact of graphene filler orientation,proximity to the central heat source,and spatial clustering on heat transfer.Our findings indicate that the strategic distribution of graphene fillers can create efficient thermal conduction channels,which significantly reduce the temperatures at local hot spots.In a model containing 0.336%graphene by volume,the central hot-spot temperature was reduced by approximately 60 K compared to a pure PBX material,under a heat flux of 600 W/m^(2).This study offers valuable insights into the optimization of the spatial arrangement of low-concentration graphene fillers,aiming to improve the thermal management capabilities of HMX-based PBX explosives.展开更多
The current work addresses the challenge of elucidating the performance of fluoroelastomers within the HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)based polymer-bonded explosives(PBXs).To simulate the confine...The current work addresses the challenge of elucidating the performance of fluoroelastomers within the HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)based polymer-bonded explosives(PBXs).To simulate the confined interface in PBXs,bilayer films of F2314/HMX and F2311/HMX were designed.Neutron reflectivity(NR),nanoindentation,and X-ray reflectivity(XRR)were employed to examine the layer thickness,interface characteristics,diffusion behavior,and surface morphology of the bilayers.NR measurements revealed interface thicknesses of 45Å and 98Å for F2314/HMX and F2311/HMX,respectively,indicating deeper penetration of F2311 into the HMX matrix.NR also suggested a denser polymer network with a higher scattering length density(SLD)near the HMX interface for both fluoroelastomers,while the bound layer of F2311 was notably thicker.Nanoindentation cross-checks and confirms the presence of a bound layer,highlighting the differences in stiffness and diffusion ability between the two polymers.The consistency between the NR and nanoindentation results suggests that F2311 demonstrates better flexibility and elasticity,whereas F2314 is stiffer and more plastic.Accordingly,the structures and performances of different fluoroelastomers at the HMX interface are discussed,which can provide valuable insights into the selection of binders for PBX formulations tailored to specific applications.展开更多
Herein,a first example of energetic-energetic cocrystal polymorphs with a 1:1 M ratio was discovered by cocrystallizing CL-20(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane)with 1,3-DNP(1,3-dinitropyrazole...Herein,a first example of energetic-energetic cocrystal polymorphs with a 1:1 M ratio was discovered by cocrystallizing CL-20(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane)with 1,3-DNP(1,3-dinitropyrazole).These two energetic cocrystal polymorphs(cocrystal 1 and cocrystal 2)exhibit distinct crystal packing styles,which lead to significant variations in their physicochemical properties.Notably,cocrystal 2 has a high density of 1.963 g·cm^(-3)at 170 K,exhibiting high detonation performances(9187 m·s^(-1);38.68 GPa)comparable to HMX(1,3,5,7-tetranitro-1,3,5,7-tetrazocane)meanwhile displaying an improved safety(10 J)relative to RDX(1,3,5-trinitro-1,3,5-triazinane),making it a potential high-energy,low-sensitivity energetic material.This work opens up a new strategy to deeply tune properties of energetic materials by constructing energetic-energetic cocrystal polymorphs.These energetic cocrystal polymorphs represent a new field of energetic materials that has not yet been studied.展开更多
As one of the important components of high-effi-ciency perovskite/silicon series devices,wide-bandgap(WBG)perovskite solar cells(PSCs)have been suffering from serious carrier transport barriers and huge open-circuit v...As one of the important components of high-effi-ciency perovskite/silicon series devices,wide-bandgap(WBG)perovskite solar cells(PSCs)have been suffering from serious carrier transport barriers and huge open-circuit voltage deficit de-rived from non-radiative recombination,especial-ly at the buried interface that are often overlooked.Herein,we combined cationic and anion passiva-tion strategies via ammonium tetra-n-butyl tetrafluoroborate(TBABF_(4))pre-treating the buried interface.Theoretical calculation predicts that the tetrabutylammonium(TBA^(+))organic cations and(tetrafluoroborate)BF_(4)^(−)anions can easily interact with charged interfacial defect.Characterizations further confirm the enhance-ment of carrier transport performance and decrease in defect density upon TBABF4 pre-treat-ment.Consequently,a power conversion efficiency of 21.35%with an ultrahigh filling factor of 84.12%is obtained for 1.68 eV-WBG inverted PSCs.In addition,the device with TBABF4 pre-treatment demonstrates excellent shelf,thermal,and operational stability.展开更多
Interaction of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)/ammonium perchlorate(AP) and its effect on mechanical sensitivity may result in some restrictions for the application of AP/HMX system in high energetic weapo...Interaction of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)/ammonium perchlorate(AP) and its effect on mechanical sensitivity may result in some restrictions for the application of AP/HMX system in high energetic weapon system. In this work, impact sensitivity test is used to study the effects of wax coating of HMX, AP and aluminum(Al) powder on sensitivity properties of HMX/AP/Al mixtures.Thermogravimetry-differential scanning calorimetry(TG-DSC) analysis has been developed to investigate the mechanism of interaction between HMX and AP during the course of thermal decomposition of HMX/AP/AI mixtures. The results show that severe interaction effect exists between AP and HMX, which causes the impact sensitivity(H_(50)) to become smaller. The impact energy(E_(50)) of mixture can be improved under the circumstances of effective separating HMX from AP by surface coating with Wax. AP may firstly engender low-temperature decomposition under the circumstance of external heat or mechanical impact, which causes the exothermic peak of HMX forward shift about 28 C. The gaseous product releasing from thermal decomposition of HMX accelerates further decomposition of AP. For HMX/AP composite system, the interactive catalysis effect between AP and HMX can be eliminated mostly by adding a great deal of Al powder(i.e. above 30%).展开更多
基金Sponsored by National Natural Science Foundation of China (21231002,21276026,21271023,21173021,91022006,11202193,11172276,and 11072225)the 111 Project ( B07012)+1 种基金the Program of Cooperation of the Beijing Education Commission ( 20091739006)Specialized Research Fund for the Doctoral Program of Higher Education ( 20101101110031)
文摘The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.
基金the Science Challenge Project(TZ2018004)the National Natural Science Foundation of China(21875228 and 21702195)for financial support。
文摘Finding energetic materials with tailored properties is always a significant challenge due to low research efficiency in trial and error.Herein,a methodology combining domain knowledge,a machine learning algorithm,and experiments is presented for accelerating the discovery of novel energetic materials.A high-throughput virtual screening(HTVS)system integrating on-demand molecular generation and machine learning models covering the prediction of molecular properties and crystal packing mode scoring is established.With the proposed HTVS system,candidate molecules with promising properties and a desirable crystal packing mode are rapidly targeted from the generated molecular space containing 25112 molecules.Furthermore,a study of the crystal structure and properties shows that the good comprehensive performances of the target molecule are in agreement with the predicted results,thus verifying the effectiveness of the proposed methodology.This work demonstrates a new research paradigm for discovering novel energetic materials and can be extended to other organic materials without manifest obstacles.
基金supported by the National Natural Science Foundation of China(Grant Nos.11872341 and 22075261)。
文摘As a typical energetic composite,polytetrafluoroethylene(PTFE)/aluminum(Al)has been widely applied in explosives,pyrotechnics,and propellants due to its ultra-high energy density and intense exothermic reaction.In this work,the radial gradient(RG)structure of PTFE/Al cylinders with three different PTFE morphologies(200 nm and 5μm particles and 5μm fiber)and content changes are prepared by 3D printing technology.The effect of radial gradient structure on the pressure output of PTFE/Al has been studied.Compared with the morphology change of PTFE,the change of component content in the gradient structure has an obvious effect on the pressure output of the PTFE/Al cylinder.Furthermore,the relationships of the morphology,content of PTFE and the combustion reaction of the PTFE/Al cylinder reveal that the cylinder shows a more complex flame propagation process than others.These results could provide a strategy to improve the combustion and pressure output of PTFE/Al.
基金supported by the National Natural Science Foundation of China(Grant Nos.21975127,22105102,and 22135003)Young Elite Scientist Sponsorship Program by CAST(Grant No.YESS20210074)the Fundamental Research Funds for the Central Universities(Grant No.30921011204)。
文摘Heat-resistant energetic materials refer to a type of energetic materials that possess a high melting point,high stability and operational safety. By studying the structures of these energetic materials has showed that the thermal stability can be enhanced by introducing amino groups to form intra/inter-molecular hydrogen bonds, constructing conjugate systems and designing symmetrical structures. This article aims to review the physical and chemical properties of ultra-high temperature heat-resistant energetic compounds and provide valuable theoretical insights for the preparation of ultra-high temperature heatresistant energetic materials. We also analyze the selected 20 heat-resistant energetic materials with decomposition temperatures higher than 350℃, serving as templates for the synthesis of various highperformance heat-resistant energetic materials.
基金the financial support from the National Natural Science Foundation of China (Grant No.51972278)the Open Project of the State Key Laboratory of Environment-friendly Energy Materials (Southwest University of Science and Technology,Grant No.20fksy16)。
文摘The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge.In this work,HMX-PEI/rGO/g-C_(3)N_(4)(HPrGC)composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C_(3)N_(4).The g-C_(3)N_(4) used for desensitization has a richπ-conjugated system and shows outstanding ability in reducing friction sensitivity.The hierarchical structure of HPrGC formed by electrostatic self-assembly andπ-πstacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution,thus exhibiting a prominent synergistic desensitization effect on HMX.The results show that rGO/gC_(3)N_(4) coating has no effect on the crystal structure and chemical structure of HMX.More importantly,the perfect combination of g-C_(3)N_(4) and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity(IS:21 J,FS:216 N).Obviously,the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings.
文摘The molecular geometries,heats of formation and electronic structures of three trinitrobenzenes(1,2,3TNB,1,2,4TNB and 1,3,5TNB)and their chloro derivatives were studied by using the quantum chemical MO AM1 method at the RHF level and ab initio method at the HF/321G level.The decompositions of the title compounds were investigated by using the AM1 method at the UHF level.The decomposition activation energies were obtained and the order of the relative stabilities of the title compounds is found.The substituent effects on the structures and properties and on the decompositions of the title compounds are discussed in the present paper.
基金financially supported by Sichuan Science and Technology Program (No.2022YFH0090)the Fundamental Research Funds for the Central Universities。
文摘Silicone rubber(SR) composites are most widely used as thermal interface materials(TIMs) for electronics heat dissipation. Thermal impedance as the main bottleneck limiting the performance of TIMs is usually neglected. Herein, the thermal impedance of SR composites loaded with different levels of hexagonal boron nitride(h-BN) as TIMs was elaborated for the first time by the ASTM D 5470 standard test and finite element analysis. It was found that elastic modulus and surface roughness of SR composites increased with the increase of h-BN content, indicating that the conformity was reduced. When the assembly pressure was 0.69 MPa, there existed an optimal h-BN content at which the contact resistance was minimum(0.39 K·cm^(2)·W^(-1)). Although the decreased bond line thickness(BLT) by increasing the assembly pressure was beneficial to reduce the thermal impedance, the proper assembly pressure should be selected to prevent the warpage of the contact surfaces and the increase in contact resistance, according to the compression properties of the SR composites. This study provides valuable insights into fabrication of high-performance TIMs for modern electronic device applications.
基金financial support from the National Natural Science Foundation of China (Grant No.22375190)。
文摘This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.
基金supported by the National Natural Science Foundation of China(Gant Nos.11372291 and 11902298)。
文摘Detonation performance is crucial for evaluating the power of high explosives(HEs),and the equation of state(EOS)that accurately describes the high-temperature,high-pressure,and high-temperature,medium-pressure states of detonation products is key to assessing the damage efficiency of these energetic materials.This article examines the limitations of the VLW EOS in representing the thermodynamic states of explosive detonation gas products under high-temperature and medium-to high-pressure conditions.A new gas EOS for detonation products,called VHL(Virial-Han-Long),is proposed.The accuracy of VHL in describing gas states under high-temperature and medium-to high-pressure conditions is verified,and its performance in evaluating explosive detonation and working capabilities is explored.The results demonstrate that VHL exhibits high precision in calculating detonation performance.Subsequently,the detonation performance of three new HEs(ICM-101,ONC,and TNAZ)was calculated and compared to traditional HEs(TATB,CL-20,and HMX).The results indicate that ONC has superior detonation performance compared to the other explosives,while ICM-101 shows a detonation velocity similar to CL-20 but with slightly lower detonation pressure.The detonation characteristics of TNAZ are comparable to those of the standard HE HMX.From the perspective of products,considering the comprehensive work performance(mechanical work and detonation heat),both ONC and ICM-101demonstrate relatively superior performance.
基金supported by the National Natural Science Foundation of China(Grant Nos.T2222027 and 12202416)。
文摘The energy release of energetic composites is severely limited by the inert alumina(Al_(2)O_(3))layer on the surface of aluminum(Al).Polytetrafluoroethylene(PTFE)could eliminate Al_(2)O_(3)layer due to its highly electronegativity and oxidability of fluorine.However,adding PTFE particles would weaken interfacial interactions resulted in poor mechanical properties and interfacial exothermic reaction.Herein,a bridging Al-PTFE as fuel and interfacial reinforcing agent was added and used to prepare LLM-105/AlPTFE microspheres,achieving both high energy output and excellent mechanical properties.The energy release and combustion reaction performance of LLM-105/Al-PTFE microspheres are significantly improved due to high reaction heat and increased interfacial reaction area of Al-PTFE.The maximum pressure and pressurization rate of LLM-105/Al-PTFE microspheres are 164.06 kPa and 29.88 kPa/s,respectively,which are 40.11%and 16.67%higher than those of physical mixed samples.Furthermore,the tensile strength and compressive strength of LLM-105/Al-PTFE microspheres are 100.40%and 26.47%higher than those of LLM-105/Al.This work provides a new approach to improve the energy release and mechanical properties for energetic composites.
基金the Presidential Foundation of CAEP(Grant No.YZJJZQ2023005)the National Natural Science Foundation of China(Grant No.22375191).
文摘Nowadays, ultrafine explosives are widely used in military fields. Ultrafine 2,2',4,4',6,6'-hexanitrostilbene(HNS) has emerged as an optimal primer for explosion foil initiators due to its excellent thermal stability and high-voltage short-pulse initiation performance. However, the solid phase ripening of ultrafine HNS leads to a degradation in its impact detonation performance. Previous studies have indicated that residual dimethyl formamide(DMF), which is present in ultrafine HNS prepared using the recrystallization method, affects ultrafine HNS ripening. The mechanism of residual solvent effects on solid phase ripening of ultrafine HNS is unclear. In this work, the specific surface area(SSA) derived from small angle X-ray scattering(SAXS) was utilized for kinetic fitting analysis to explore the mechanism by which residual solvents enhance the solid phase ripening of ultrafine HNS. The results of the SSA measured by insitu SAXS under conditions of 150℃ for 40 h revealed that the sample with 0.2% residual DMF exhibited a 21.51% decrease in SSA, whereas the sample with only 0.04% residual DMF showed a decrease of 15.66%.Furthermore, the higher amounts of residual DMF accelerated the reduction in SSA with time. Kinetic fitting analysis demonstrated that reducing residual DMF would lower both the activation energy and the pre-exponential factor, consequently decreasing the rate constant of solid phase ripening. The mechanism was speculated that it primarily facilitated the Ostwald ripening(OR). Additionally, contrast variation small angle X-ray scattering(CV-SAXS) confirmed that coating of ultrafine HNS particles is an effective method for inhibiting ripening, significantly reducing both the rate and extent of ripening of ultrafine HNS. This study predicts how residual solvents impact the solid phase ripening process of ultrafine HNS and proposes strategies for enhancing the long-term stability of ultrafine explosives.
基金supported by the National Natural Science Foundation of China(Grant Nos.T2222027 and 12202416)。
文摘Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.
基金support provided by the National Natural Science Foundation of China(Grant No.12102405)the Presidential Foundation of CAEP(Grant No.YZJJZQ2023008).
文摘This study investigates the paradoxical detonation behavior of TKX-50,a nitrogen-rich energetic material,exhibiting higher detonation velocities but lower metal acceleration ability compared to HMX.Through experimental measurements and theoretical calculations,we propose a novel three-factor competition mechanism to explain this phenomenon.TKX-50-based PBX formulations achieved detonation velocities up to 9100 m/s,surpassing HMX-based counterparts.However,cylinder expansion tests revealed a 15%reduction in metal acceleration ability.Thermochemical measurements showed lower detonation heat for TKX-50(4900 J/g)versus HMX(5645 J/g).Our mechanism involves:(1)compositional effects prevailing at high pressures;(2)Energy release becoming essential as pressure drops;(3)Pressure-dependent product composition evolution functioning at low pressure.VLW code calculations unveiled a"crossover"in Hugoniot curves,lending support to this mechanism.This study furnishes a new framework for comprehending the performance of nitrogen-rich energetic materials,with significant implications for the design and optimization of future high-energy density materials.
基金supported by the National Natural Science Foundation of China (Grant Nos. 22475179 and 22275173)。
文摘Realizing effective enhancement in the thermally conductive performance of polymer bonded explosives(PBXs) is vital for improving the resultant environmental adaptabilities of the PBXs composites. Herein, a kind of primary-secondary thermally conductive network was designed by water-suspension granulation, surface coating, and hot-pressing procedures in the graphene-based PBXs composites to greatly increase the thermal conductive performance of the composites. The primary network with a threedimensional structure provided the heat-conducting skeleton, while the secondary network in the polymer matrix bridged the primary network to increase the network density. The enhancement efficiency in the thermally conductive performance of the composites reached the highest value of 59.70% at a primary-secondary network ratio of 3:1. Finite element analysis confirmed the synergistic enhancement effect of the primary and secondary thermally conductive networks. This study introduces an innovative approach to designing network structures for PBX composites, significantly enhancing their thermal conductivity.
基金financial support from the National Natural Science Foundation of China (Grant Nos.U2130207,22275173)presidential foundation of China Academy of Engineering Physics (Grant No.YZJJZQ2023008)。
文摘The precise characterization of interfacial structure for polymer-bonded explosive(PBX) modification is challenging due to the complexity of the interface. The inherent properties between explosive and binders affect interface bonding, lowering the interfacial strength in unpredicted ways. Surface modification is an effective method to balance multi-utility in materials engineering, which has been carried out to design of high-performance composites with improved interfacial properties. Experimental methods may determine the coating shell for capturing the PBX structures. Various approaches were applied to characterize the structure and properties of PBX interface, including molecular dynamicsbased computational models to predict bonding properties. In this review, systematic organization were provided and summarized with detective methods on the surface and interface of explosives. Meanwhile, the usage scenarios and limitations of each measurement were proposed. Conclusions from the review yield useful guidelines and references for systematical characterization on the modification of explosive and can be extended to other materials.
基金supported by the National Natural Science Foundation of China(Grant No.U2330208).
文摘The incorporation of graphene fillers into polymer matrices has been recognized for its potential to enhance thermal conductivity,which is particularly beneficial for applications in thermal management.The uniformity of graphene dispersion is pivotal to achieving optimal thermal conductivity,thereby directly influencing the effectiveness of thermal management,including the mitigation of local hot-spot temperatures.This research employs a quantitative approach to assess the distribution of graphene fillers within a PBX(plastic-bonded explosive)matrix,focusing specifically on the thermal management of hot spots.Through finite element method(FEM)simulations,we have explored the impact of graphene filler orientation,proximity to the central heat source,and spatial clustering on heat transfer.Our findings indicate that the strategic distribution of graphene fillers can create efficient thermal conduction channels,which significantly reduce the temperatures at local hot spots.In a model containing 0.336%graphene by volume,the central hot-spot temperature was reduced by approximately 60 K compared to a pure PBX material,under a heat flux of 600 W/m^(2).This study offers valuable insights into the optimization of the spatial arrangement of low-concentration graphene fillers,aiming to improve the thermal management capabilities of HMX-based PBX explosives.
基金supported in part by the National Natural Science Foundation of China(Nos.12335018,12105264,and 12275248)NSAF Joint Fund Project(Nos.U2230107,U1730244,U2130207)+1 种基金Innovation and Development Fund of China Academy of Engineering Physics(No.CXKS20240052)Central Guidance for Local Science and Technology Development Fund Project(No.2023ZYDF075).
文摘The current work addresses the challenge of elucidating the performance of fluoroelastomers within the HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)based polymer-bonded explosives(PBXs).To simulate the confined interface in PBXs,bilayer films of F2314/HMX and F2311/HMX were designed.Neutron reflectivity(NR),nanoindentation,and X-ray reflectivity(XRR)were employed to examine the layer thickness,interface characteristics,diffusion behavior,and surface morphology of the bilayers.NR measurements revealed interface thicknesses of 45Å and 98Å for F2314/HMX and F2311/HMX,respectively,indicating deeper penetration of F2311 into the HMX matrix.NR also suggested a denser polymer network with a higher scattering length density(SLD)near the HMX interface for both fluoroelastomers,while the bound layer of F2311 was notably thicker.Nanoindentation cross-checks and confirms the presence of a bound layer,highlighting the differences in stiffness and diffusion ability between the two polymers.The consistency between the NR and nanoindentation results suggests that F2311 demonstrates better flexibility and elasticity,whereas F2314 is stiffer and more plastic.Accordingly,the structures and performances of different fluoroelastomers at the HMX interface are discussed,which can provide valuable insights into the selection of binders for PBX formulations tailored to specific applications.
基金support for this study by the National Natural Science Foundation of China(Grant No.22275175)。
文摘Herein,a first example of energetic-energetic cocrystal polymorphs with a 1:1 M ratio was discovered by cocrystallizing CL-20(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane)with 1,3-DNP(1,3-dinitropyrazole).These two energetic cocrystal polymorphs(cocrystal 1 and cocrystal 2)exhibit distinct crystal packing styles,which lead to significant variations in their physicochemical properties.Notably,cocrystal 2 has a high density of 1.963 g·cm^(-3)at 170 K,exhibiting high detonation performances(9187 m·s^(-1);38.68 GPa)comparable to HMX(1,3,5,7-tetranitro-1,3,5,7-tetrazocane)meanwhile displaying an improved safety(10 J)relative to RDX(1,3,5-trinitro-1,3,5-triazinane),making it a potential high-energy,low-sensitivity energetic material.This work opens up a new strategy to deeply tune properties of energetic materials by constructing energetic-energetic cocrystal polymorphs.These energetic cocrystal polymorphs represent a new field of energetic materials that has not yet been studied.
文摘As one of the important components of high-effi-ciency perovskite/silicon series devices,wide-bandgap(WBG)perovskite solar cells(PSCs)have been suffering from serious carrier transport barriers and huge open-circuit voltage deficit de-rived from non-radiative recombination,especial-ly at the buried interface that are often overlooked.Herein,we combined cationic and anion passiva-tion strategies via ammonium tetra-n-butyl tetrafluoroborate(TBABF_(4))pre-treating the buried interface.Theoretical calculation predicts that the tetrabutylammonium(TBA^(+))organic cations and(tetrafluoroborate)BF_(4)^(−)anions can easily interact with charged interfacial defect.Characterizations further confirm the enhance-ment of carrier transport performance and decrease in defect density upon TBABF4 pre-treat-ment.Consequently,a power conversion efficiency of 21.35%with an ultrahigh filling factor of 84.12%is obtained for 1.68 eV-WBG inverted PSCs.In addition,the device with TBABF4 pre-treatment demonstrates excellent shelf,thermal,and operational stability.
基金supported by the National Nature Science Foundation of China(Nos.11402238,11502243 and 11502245)
文摘Interaction of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)/ammonium perchlorate(AP) and its effect on mechanical sensitivity may result in some restrictions for the application of AP/HMX system in high energetic weapon system. In this work, impact sensitivity test is used to study the effects of wax coating of HMX, AP and aluminum(Al) powder on sensitivity properties of HMX/AP/Al mixtures.Thermogravimetry-differential scanning calorimetry(TG-DSC) analysis has been developed to investigate the mechanism of interaction between HMX and AP during the course of thermal decomposition of HMX/AP/AI mixtures. The results show that severe interaction effect exists between AP and HMX, which causes the impact sensitivity(H_(50)) to become smaller. The impact energy(E_(50)) of mixture can be improved under the circumstances of effective separating HMX from AP by surface coating with Wax. AP may firstly engender low-temperature decomposition under the circumstance of external heat or mechanical impact, which causes the exothermic peak of HMX forward shift about 28 C. The gaseous product releasing from thermal decomposition of HMX accelerates further decomposition of AP. For HMX/AP composite system, the interactive catalysis effect between AP and HMX can be eliminated mostly by adding a great deal of Al powder(i.e. above 30%).
