Preparation and characterization of HMX/EVA/hBNNSs micro-composites with improved thermal stability and reduced sensitivity

Hexagonal boron nitride nanosheets(HBNNSs)have huge potential in the field of coating materials owing to their remarkable chemical stability,mechanical strength and thermal conductivity.Thin-layer hBNNSs were obtained by a liquid-phase exfoliation of h-BN powders and incorporated into EVA coatings for improving the safety performance of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX).HBNNSs and ethylene-vinyl acetate copolymer(EVA)were introduced to HMX by a solvent-slurry process.For com-parison,the HMX/EVA and HMX/EVA/graphene(HMX/EVA/G)composites were also prepared by a similar process.The morphology,crystal form,surface element distribution,thermal decomposition property and impact sensitivity of HMX/EVA/hBNNSs composites were contrastively investigated.Results showed that as prepared HMX/EVA/hBNNSs composites were well coated with hBNNSs and EVA,and exhibited better thermal stability and lower impact sensitivity than that of HMX/EVA and HMX/EVA/G composites,suggesting superior performance of desensitization of hBNNSs in explosives.     

Theoretical design of new bridge-ring insensitive high energy compounds by selected normal Diels-Alder reactions between NH2-substituted oxazoles and NO2/NF2/NHNO2-substituted ethylenes/acetylenes

In this work, NH₂-substituted oxazoles and NO₂/NF₂/NHNO₂-substituted ethylenes/acetylenes were designed and used as dienes and dienophiles, respectively, in order to develop new bridge-ring insensitive high energy compounds through the Diels-Alder reaction between them. The reaction type, reaction feasibility and performance of reaction products were investigated in detail theoretically. The results showed that dienes most possibly react with dienophiles through the HOMO-diene controlled normal Diels-Alder reaction at relatively low energy barrier. Tetranitroethylene could react with the designed dienes much more easily than other dienophiles, and was employed to further design 29 new bridge-ring energetic compounds. Due to high heat of formation, density and oxygen balance, all designed bridge-ring energetic compounds have outstanding detonation performance, 16 of them have higher energy than HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and 2 others even possess comparative energy with the representative of high energy compounds CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane). The predicted average h₅₀ value of these bridge-ring energetic compounds is 83 cm, showing their low impact sensitivity. The NH₂ groups could obviously impel the proceeding of Diels-Alder reactions, but would slightly decrease the energy and sensitivity performance. In all, the new designed bridge-ring compounds have both high energy and low sensitivity, and may be produced through Diels-Alder reactions at relatively low energy barrier. This paper may be helpful for the theoretical design and experiment synthesis of new advanced insensitive high energy compounds.     

Formation and characterization of core-shell CL-20/TNT composite prepared by spray-drying technique

The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene (CL-20/TNT) composite was prepared by spray-drying method in which sensitive high energy explosive (CL-20) was coated with insensitive explosive (TNT). The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Laser particle size analyzer, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impact sensitivity test and detonation performance. The results of SEM, TEM, XPS and XRD show that ϵ-CL-20 particles are coated by TNT. When the ratio of CL-20/TNT is 75/25, core-shell structure is well formed, and thickness of the shell is about 20–30 nm. And the analysis of heat and impact show that with the increase of TNT content, the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material (CL-20), but also greatly reduce the impact sensitivity. Compared with the CL-20/TNT mixture (75/25) at the same ratio, the characteristic drop height of core-shell CL-20/TNT composite (75/25) increased by 47.6% and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites. Therefore, the preparation of the core-shell composites can be regarded as a unique means, by which the composites are characterized by controllable decomposition rate, high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.     

Burning rate and other characteristics of strontium titanate (SrTiO3) supplemented AP/HTPB/Al composite propellants

In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO₃), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other catalytic applications. Initially, SrTiO₃ was characterized for particle size, morphology and material/phase identification (using XRD). By varying SrTiO₃ content in a standard composite propellant, different compositions were prepared and their performance and processing parameters like the end of mix (EOM) viscosity, mechanical properties, density, burning rate, pressure exponent (n-value), etc. were measured. The results reveal that 2% SrTiO₃ causes more than 12% enhancement in propellant burning rate (at 70 ksc pressure) in comparison to the standard propellant composition. The pressure exponent also increases to 0.46, whereas the standard composition was having its value as 0.35.     

Structure design and property adjustment of new cage rich-nitrogen pentazolyltetraazacubanes as potential high energy density compounds

In this study, based on two attractive energetic compounds pentazole (PZ) and tetraazacubane (TAC), a new family of high energy and high nitrogen compounds pentazolyltetraazacubanes were designed. Then, a different number of NH₂ or NO₂ groups were introduced into the system to further adjust the property. The structures, properties, and the structure-property relationship of designed molecules were investigated theoretically. The results showed that all nine designed compounds have extremely high heat of formation (HOF, 1226-2734 kJ/mol), good density (1.73–1.88 g/cm³), high detonation velocity (8.30–9.35 km/s), high detonation pressure (29.8–39.7 GPa) and acceptable sensitivity (ΔV: 41-87 ų). These properties could be effectively positive adjusted by replacing one or two PZ rings by NH₂ or/and NO₂ groups, especially for the energy and sensitivity performance, which were increased and decreased obviously, respectively. As a result, two designed pentazolyltetraazacubanes were predicted to have higher energy and lower sensitivity than the famous high energy compound in use 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while two others have better combination property than 1,3,5-Trinitro-1,3,5-triazacyclohexane. In all, four new pentazolyltetraazacubanes with good combination performance were successfully designed by combining PZ with TAC, and the further property adjustment strategy of introducing a suitable amount of NH₂/NO₂ groups into the system. This work may help develop new cage energetic compounds.     

Effect of nano powder (Al2O3-CaO) addition on the mechanical properties of the polymer blend matrix composite

This work describes the preparation and study of the properties of composite nanoparticles prepared by the sol-gel method which consists of two materials (Al₂O₃-CaO), and study the effect of these nanoparticles on the mechanical behavior of a polymer blend (EP 4% + 96% UPE). The powder was evaluated by X-ray diffraction analysis, scanning electron microscopy analysis (SEM), particle size analysis, and energy dispersive X-ray analysis (EDX). The mechanical behavior of the composite material was assessed by tensile test, bending test and hardness test. The evaluation results of the composite nanoparticles showed good distribution of the chemical composition between aluminum oxide and calcium oxide, smoothness in particles' size at calcination in high and low temperatures, formation of different shapes of nanoparticles and different (kappa and gamma) phases of the Al₂O₃ particles. The results of mechanical behavior tests showed marked improvement in the mechanical properties of the resulted composite material, especially at 1.5%, compared with polymer blend material without nano powder addition. The tensile properties improved about (24 and 14.9) % and bending resistance about (23.5 and 16.8) % and hardness by (25 and 22) % when adding particles of size (63.8 and 68.6) respectively. Therefore, this reflects the efficiency of the proposed method to manufacture the nanocomposite powder and the possibility of using this powder as a strengthening material for the composite materials and using these composite materials in bio applications, especially in the fabrication of artificial limbs.     

Study of nano-nitramine explosives: preparation,sensitivity and application

Nano-nitramine explosives (RDX, HMX, CL-20) are produced on a bi-directional grinding mill. The scanning electron microscope (SEM) observations show that the prepared particles are semi-spherical, and the narrow size distributions are characterized using the laser particle size analyzer. Compared with the micron-sized samples, the nano-products show obvious decrease in friction and impact sensitivities. In the case of shock sensitivities, nano-products have lower values by 59.9% (RDX), 56.4% (HMX), and 58.1% (CL-20), respectively. When nano-RDX and nano-HMX are used in plastic bonded explosives (PBX) as alternative materials of micron-sized particles, their shock sensitivities are significantly decreased by 24.5% (RDX) and 22.9% (HMX), and their detonation velocities are increased by about 1.7%. Therefore, it is expected to promote the application of nano-nitramine explosives in PBXs and composite modified double-based propellants (CMDBs) so that some of their properties would be improved.     

Shock-induced reaction behaviors of functionally graded reactive material

In this paper, the ballistic impact experiments, including impact test chamber and impact double-spaced plates, were conducted to study the reaction behaviors of a novel functionally graded reactive material (FGRM), which was composed of polytetrafluoroethylene/aluminum (PTFE/Al) and PTFE/Al/bismuth trioxide (Bi₂O₃). The experiments showed that the impact direction of the FGRM had a significant effect on the reaction. With the same impact velocity, when the first impact material was PTFE/Al/Bi₂O₃, compared with first impact material PTFE/Al, the FGRM induced higher overpressure in the test chamber and larger damaged area of double-spaced plates. The theoretical model, which considered the shock wave generation and propagation, the effect of the shock wave on reaction efficiency, and penetration behaviors, was developed to analyze the reaction behaviors of the FGRM. The model predicted first impact material of the FGRM with a higher shock impedance was conducive to the reaction of reactive materials. The conclusion of this study provides significant information about the design and application of reactive materials.     

Ni-Zn铁氧体粉末的溶胶-凝胶合成及微波性能

以硝酸铁、硝酸镍、硝酸锌、柠檬酸和氨水为原料,用溶胶-凝胶法合成了不同组成的Ni-Zn铁氧体粉末。利用热分析、X射线衍射等手段研究了干凝胶热分解行为。利用网络分析仪对铁氧体粉末的电磁性能进行了表征,考察了铁氧体的组成与其电磁性能之间的关系。结果表明,溶胶-凝胶法合成的铁氧体粉末的μ″值随测试频率的提高和Ni-Zn铁氧体中锌含量的增加而减小。     

The mechanical performance and a rate-dependent constitutive model for Al3Ti compound

The Al₃Ti compound has potential application in the high temperature structure materials due to its low density, high strength and stiffness. The mechanical behaviors of the material under different loading rates were studied using compression tests. The results indicate that Al₃Ti is a typical brittle material and its compressive strength is dependent on the strain rate. Therefore, a series of rate-dependent constitutive equations are needed to describe its mechanical behaviors accurately. However, it is still short of professional research on the material model for Al₃Ti. In this study, the material model was developed on the basis of JH-2 constitutive equations using the experimental data. The model was then applied in simulating the impact process of Ti/Al₃Ti metal-intermetallic laminate composites so as to validate the established model. Good agreement between simulation and experiment results shows the constitutive model predict the material responses under high rate and large deformation accurately. This work provides more support for the theoretical and numerical research on the intermetallic.     

纳米二氧化硅增强硬质聚氨酯泡沫塑料的制备

采用功率超声,将纳米二氧化硅颗粒分散到多次甲基多苯基多异氰酸酯体系内,然后与聚醚多元醇聚合制得了纳米二氧化硅增强的硬质聚氨酯泡沫塑料。SEM分析表明,纳米二氧化硅均匀分散在聚氨酯泡沫中。在较低添加量时,纳米二氧化硅使压缩强度和冲击强度有一定提高,但会引起多次甲基多苯基多异氰酸酯粘度迅速增加,从而导致发泡反应困难,当添加量为7wt%时,压缩强度和冲击强度开始下降。     

Performances and direct writing of CL-20 based ultraviolet curing explosive ink

A new type of explosive ink formulation that can be quickly cured was prepared with unsaturated polyester as binder,styrene as active monomer,2,4,6-trimethylbenzoyl-diphenylphosphine oxide as photoinitiator,and hexanitrohexaazaisowurtzitane (CL-20) as the main explosive.Then the explosive ink direct writing technology was used to charge the micro-sized energetic devices,the curing mechanism of the explosive ink was discussed,and the microstructure,safety performance and explosive transfer performance of the explosive ink molded samples were tested and analyzed.Results indicate that the composite material has a fast curing molding speed,its hardness can reach 2H within 8 min.The crystal form of CL-20 in the molded sample is still ε type.The CL-20 based W-curing explosive ink formulation has good compatibility,its apparent activation energy is increased by about 3.5 kJ/mol.The composite presents a significant reduction in impact sensitivity and its characteristic drop height can reach 39.8 cm,which is about 3 times higher than the raw material.When the line width of charge is 1.0 mm,the critical thickness of the explosion can reach 0.015 mm,and the explosion velocity is 7129 m/s when the charge density is 1.612 g/cm3.     

Experimental study on ceramic balls impact composite armor

Ceramic balls represent a new type of damaging element, and studies on their damaging power of composite armor are required for a comprehensive evaluation of the effectiveness of various types of weapons. The goal of this study was to determine the impact of ϕ7 mm toughened Al₂O₃ ceramic balls on a composite ceramic/metal armor. The influences of the ceramic panel and the thickness of the metal backing material on the destroying power of the ceramic balls were first determined. Based on the agreement between numerical simulation, experimental results, and calculation models of the target plate resistance, the response mechanism of the ceramic balls was further analyzed. The results indicate that for a back plate of Q235 steel, with an increasing thickness of the ceramic panel, the piercing speed limit of the ceramic balls gradually increases and the diameter of the out-going hole on the metal back decreases. Different conditions were tested to assess the effects on the piercing speed, the diameter of the out-going hole, the micro-element stress, and the integrity of the recovered ceramic bowl.     

Studies on the flame propagation characteristic and thermal hazard of the premixed N2O/fuel mixtures

An experimental study was carried out to investigate the flame propagation and thermal hazard of the premixed N₂O/fuel mixtures, including NH₃, C₃H₈ and C₂H₄. The study provided the high speed video images and data about the flame locations, propagation patterns, overpressures and the quenching diameters during the course of combustion in different channels to elucidate the dynamics of various combustion processes. The onset decomposition temperature was determined using high-performance adiabatic calorimetry. It was shown that the order of the flame acceleration rate and thermal hazard was N₂O/C₂H₄>N₂O/C₃H₈>N₂O/NH₃.     

Enhancing the explosive characteristics of a Semtex explosive by involving admixtures of BCHMX and HMX

A well-known ternary plastic explosive, Czech Semtex 1H, contains a mixture of PETN and RDX softened by SBR. In this work, BCHMX was used to replace PETN in Semtex 1H to form Sem-BC+RDX. In addition, another mixture based on BCHMX and HMX as energetic fillers bonded by the polymeric matrix of Semtex 1H (Sem-BC+HMX) was studied. The particle size distribution of each individual explosive was determined to obtain the optimum mixing conditions. Friction and impact sensitivities were determined. The velocity of detonation was reported practically and the detonation properties were calculated by EXPLO5 code. The explosive strength of each sample was measured by the ballistic mortar test. The conclusion confirms that the velocity of detonation of Sem-BC+HMX was the highest in comparison with the prepared samples. Sem-BC+RDX has the least impact and frictions sensitivities. Sem-BC+RDX has higher detonation velocity, detonation properties and explosive strength than Semtex 1H. Addition of BCHMX in Semtex 1H as a replacement for PETN is the candidate to produce a high performance advanced Czech plastic explosive.     

Theoretical calculation and experimental study on the interaction mechanism between TKX-50 and AP

The combination of 5,5′-bistetrazole-1,1′-diolate (TKX-50) and ammonium perchlorate (AP) can make greater use of the chemical energy of TKX-50 based energetic materials. The research on the interaction mechanism between TKX-50 and AP is very important for designing TKX-50-AP compounds and judging the formation feasibility of composite particles, which can lay a theoretical foundation for the preparation of TKX-50-AP mixed crystals and the application of TKX-50 in propellant, propellant and explosive. Herein, in order to research the interaction mechanism between TKX-50 and AP, density-functional theory calculation was applied to optimize three configurations of TKX-50-AP compounds. The geometry structure, electrostatic potential and binding energy of the compounds were predicted, and the electronic density topological analysis was also carried out. Then TKX-50-AP mixed crystals structures were constructed, and the radial distribution function of H–O and H–N in mixed crystals was calculated. Finally, solvent/non-solvent method was applied to prepare TKX-50-AP composites, and the infrared spectroscopy and the non-isothermal decomposition performance of the composites were characterized. Results show that the superposition of positive charges in TKX-50 molecule and negative charges in AP makes the electrostatic potential distributions of TKX-50-AP compounds different from that of TKX-50 and AP. The interaction energies of TKX-50-AP 1, TKX-50-AP 2 and TKX-50-AP 3 are 39.743 kJ/mol, 61.206 kJ/mol and 27.702 kJ/mol, respectively. The interaction between TKX-50 molecules and AP molecules in TKX-50-AP mixed crystals both depends on hydrogen bonds and van der Waals force, and the number and strength of hydrogen bonds are significantly greater than that of van der Waals force. The composition of AP and TKX-50 makes the absorption peak of the five-membered rings and NH₃OH⁺ of TKX-50 shift to low wavenumber in the infrared spectroscopy. In general, TKX-50 interacts with AP via hydrogen bonds and van der Waals force, and the calculated results are in good agreement with the experimental results. The composition of TKX-50 and AP can also prolong the decomposition process.     

Preparation of reduced sensitivity co-crystals of cyclic nitramines using spray flash evaporation

The present day weapon technology demands novel energetic materials that exhibit simultaneous high explosive yield and reduced sensitivity. This article demonstrates application of spray evaporation to prepare reduced sensitive co-crystals of high performance nitramine explosives like HMX and CL-20 with a relatively less insensitive explosive 1,1-diamino-2,2-dinitroethylene or FOX-7. Stronger intermolecular hydrogen bonding in FOX-7 is responsible for limited solubility in most of organic solvents. Large solubility differences of FOX-7 with HMX and CL-20 restricts it's co-crystallization through classical methods that yields thermodynamically favorable product. Spray flash evaporation, a kinetic crystallization method, has been therefore adopted and could successfully produce CL-20/FOX-7 (2:1) and HMX/FOX-7 (4:1) co-crystals. The fine powdered materials obtained were characterized by SEM, powder XRD, Raman spectroscopy, DSC-TGA etc. Multipoint Raman spectra showed consistent occurrence of spectral features indicating stoichiometric co-existence of ingredients in the crystal lattices. DSC analysis showed absence of all thermally assisted solid-solid phase transformation in the co-crystals as they were observed in pristine materials. The thermal stability calculated in terms of activation barrier for decomposition, revealed the CL-20/FOX-7 co-crystal to be intermediately stable on comparison to their constituents while, the HMX/FOX-7 co-crystal is more stable. Compared to pure HMX and CL-20, both the co-crystals have shown higher insensitivity to impact force, suggesting them to be suitable for future generation insensitive munitions.     

Liquid phase in-situ synthesis of LiF coated boron powder composite and performance study

Among practical metal additives, boron (B) has a high volumetric heating value, making it a promising choice as a fuel additive. Although B can theoretically yield a large amount of energy upon complete combustion, its combustion is retarded by the initial presence of B oxide, which coats the surfaces of B particle. To improve the ignition and combustion properties of B powder, LiOH and NH₄F were used as precursors to synthesize uniformly LiF-coated B composites (LiF-B) in situ. The LiF-B mixture was also prepared for comparison using a physical method. X-ray diffraction (XRD), Fourier-transform infrared (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDS) were used to characterize the morphologies and compositions of the products. The thermal and combustion properties of the samples were characterized by thermal gravity-differential thermal gravity (TG-DTG), differential scanning calorimetry (DSC) and closed bomb experiment. The XRD, FTIR, SEM and EDS results demonstrated the successful preparation of the coated LiF-B sample. The TG-DTG and closed bomb experiment results indicated that the addition of LiF decreased the ignition temperature of B powder, and increasing its reaction efficiency. DSC results show that when LiF-B was added, the released heat of underwater explosive increased by 6727.2, 7280.4 and 3109.6 J/g at heating rates of 5, 10, and 15 °C/min, respectively. Moreover, LiF-B decreased the activation energy of secondary combustion reaction of explosive system as calculated through Kissinger's method by 28.9%, which indicated an excellent catalytic effect for the thermal decomposition of underwater explosive. The results reveal that LiF can improve the combustion efficiency of B powder, thereby increasing the total energy of explosives. The mechanical sensitivity increased slightly after adding LiF-B to the underwater explosive. Compared to the underwater explosive with added B, the mechanical sensitivity of the explosive with added LiF-B was significantly lower.     

An investigation on anti-impact and penetration performance of basalt fiber composites with different weave and lay-up modes

The woven basalt fiber composites (WBFC) and the unidirectional [0°/90°/45°/-45°]_s basalt fiber composites (UBFC) were prepared by hot-pressing. Three-point bending test, low velocity impact test, and ballistic test were performed to the prepared composites. After the tests, the specimens were recovered and analyzed for micromorphology. Three-point bending tests show that both the bending strength and stiffness of the WBFC surpass those of the UBFC. Low velocity impact test results show that the low velocity impact resistance to hemispherical impactor of the UBFC is higher than that of the WBFC, but the low velocity impact resistance to sharp impactor of the UBFC is lower than that of the WBFC. For the ballistic test, it can be found that the ballistic property of the UBFC is higher than that of the WBFC. After the tests, microscopic analysis of the specimens was applied, and their failure mechanism was discussed. The main failure modes of the UBFC are delamination and fibers breakage under the above loading conditions while the main failure mode of the WBFC is fibers breakage. Although delamination damage can be found in the WBFC under the above loading conditions, the degree of delamination is far less than that of the UBFC.     

用溶胶-凝胶法制备碳纤维三维编织物增强氧化铝基复合材料的研究

本文研究了溶胶－凝胶（Ｓｏｌ－ｇｅｌ）法制备碳纤维三维编织物增强氧化铝（Ａｌ２Ｏ３）基复合材料的成型工艺及其力学性能，研究了两种主要起始物Ａｌ（ＮＯ３）３、ＡｌＣｌ３配制的氧化铝溶胶对复合材料成型工艺和力学性能的影响。分别以Ａｌ（ＮＯ３）３和ＡｌＣｌ３为起始物，制备得到Ⅰ＃、Ｉ＃复合材料。研究表明，以Ａｌ（ＮＯ３）３为起始物配制的溶胶粘度较小，利于材料的致密化。经过溶胶浸渍、凝胶、裂解１３个周期后，Ⅰ＃材料的密度和室温三点弯曲强度分别为１．８６ｇ／ｃｍ３和１４５．２ＭＰａ，而ＩＩ＃材料的密度和室温三点弯曲强度分别为１．６３ｇ／ｃｍ３和１０４．１ＭＰａ，材料均呈典型的韧性断裂模式。用扫描电子显微镜（ＳＥＭ）观察试样的断口形貌，发现断口表面有大量的纤维拔出，纤维表现了较好的增韧效果。