Combustion of B4C/KNO3 binary pyrotechnic system

Presented herein is an experimental study on the combustion of B4C/KNO3 binary pyrotechnic system.Combustion products were tested using X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometer(EDS).According to the results of tests and CEA calculation,the combustion reaction equation was established.The flames and burning rates were recorded by a high speed camera and a spectrophotometer.The effect of B4C particle size on the thermal sensitivity of B4C/KNO3 was investigated by differential scanning calorimetry(DSC)techniques.In addition,a reliable method for calculating the flame temperature was proposed.Based on the results of experiments,the combustion reaction mechanism was briefly analyzed.The burning rate,flame temperature and thermal sensitivity of B4C/KNC3 increase with the decrease of B4C particle size.The mass ratio of B4C/KNO3 has a great effect on combustion properties.Oxidizer-rich compositions have low flame temperatures,low burning rates,and provide green light emission.The combustion reactions of fuel-rich compositions are vigorous,and the B4C/KNO3 with mass ratio of 25:75 has the highest burning rate and the highest flame temperature.     

固冲补燃室团聚硼颗粒燃烧试验

研究团聚硼颗粒在补燃室中的点火燃烧对提高固冲发动机性能具有重要意义。通过试验模拟固冲发动机工作过程的方法,开展了补燃室流场条件下的团聚硼颗粒点火燃烧试验。结合高速火焰图像处理技术和流场参数测量结果,对试验中团聚硼颗粒的点火燃烧状态、火焰结构以及颗粒尺寸变化等进行了分析,获得了补燃室燃气温度和氧气含量等因素对团聚硼颗粒点火燃烧过程的影响机制。对燃烧残渣进行了分析,发现燃烧前后颗粒尺寸变化不大,燃烧过程中高温气流可能进入了颗粒内部并与硼颗粒发生反应。     

Thermal and combustion behavior of Al-MnO2 nanothermite with poly(vinylidene fluoride -co- hexafluoropropylene) energetic binder

Fluoropolymers get increasing attention in energetic materials application due to the high fluorine content. To explore the effect of poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) on Al/MnO2 nanothermite, the samples with different contents are prepared and characterized by SEM, TG-DSC, XRD, and their ignition and combustion behavior are tested and recorded. The results show that P(VDF-HFP) as an energetic binder can combine the nanothermite components together, even exist in the gaps. The integrity of energetic materials has been improved. Thermal analysis shows that the addition of P(VDF-HFP) greatly changes the thermal reaction processes, and the exothermic peaks appear early, but the utilization of fuel and oxidizer is not efficient from the XRD results. Furthermore, the appropriate addition of P(VDF-HFP) can directly reduce the ignition energy threshold and increase the combustion time, which is necessary for the potential ignition charge application. The possible reasons for above phenomena are discussed and analyzed. This research provides a reference for improvement of thermite-based ignition charge formulation.     

Thermodynamics and performance of Al/CuO nanothermite with different storage time

The storage stability of energetic materials is important for its application. Here, the storage stability of Al/CuO nanothermite, which was prepared by electrospray method and stored with different storage time, was systematically researched. The activation energy of Al/CuO nanothermite was calculated by differential scanning calorimetry (DSC). The ignition temperature and the curve pressure history of Al/CuO nanothermite was measured using ignition temperature measuring device and constant-volume pressurization tests, respectively. Further, the thermites were characterized by X-ray Diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The results show that the morphology of the thermites did not change significantly. The activation energy was decreased from 254.1 kJ/mol to 181.8 kJ/mol after storage for 13 months. When stored for 0, 7 and 13 months, the peak pressures of Al/CuO nanothermite were 685.8 kPa, 626.3 kPa and 625.5 kPa, respectively. In addition to the ignition temperature, it was 775 ℃, 739 ℃ and 754 ℃, respectively. This result indicated that the ignition and combustion properties of Al/CuO nano-thermite are obviously reduced when stored for a long time, at room temperature.     

Hazard evaluation of ignition sensitivity and explosion severity for three typical MH2 (M＝Mg,Ti, Zr) of energetic materials

MgH2, TiH2, and ZrH2 are three typical metal hydrides that have been gradually applied to composite explosives and propellants as additives in recent years. To evaluate ignition sensitivity and explosion severity, the Hartmann device and spherical pressure vessel were used to test ignition energy and ex-plosion pressure, respectively. The results showed that the ignition sensitivity of ZrH2, TiH2 and MgH2 gradually increased. When the concentration of MgH2 is 83.0 g/m3 in Hartmann device, the ignition energy attained a minimum of 10.0 mJ. The explosion pressure of MgH2 were 1.44 times and 1.76 times that of TiH2 and ZrH2, respectively, and the explosion pressure rising rate were 3.97 times and 9.96 times that of TiH2 and ZrH2, respectively, through the spherical pressure vessel. It indicated that the reaction reactivity and reaction rate of MgH2 were higher than that of TiH2 and ZrH2. In addition, to conduct in-depth theoretical analysis of ignition sensitivity and explosion severity, gas production and combus-tion heat per unit mass of ZrH2, TiH2 and MgH2 were tested by mercury manometer and oxygen bomb calorimetry. The experimental results revealed that MgH2 had a relatively high gas production per unit mass (5.15 mL/g), while TiH2 and ZrH2 both had a gas production of less than 2.0 mL/g. Their thermal stability gradually increased, leading to a gradual increase in ignition energy. Furthermore, compared with theoretical combustion heat, the combustion ratio of MgH2, TiH2 and ZrH2 was more than 96.0%, with combustion heat value of 29.96, 20.94 and 12.22 MJ/kg, respectively, which was consistent with the explosion pressure and explosion severity test results.     

Effect of metal powders on explosion of fuel-air explosives with delayed secondary igniters

In order to improve the energy level of fuel air explosive(FAE) with delayed secondary igniters, high energetic metal powders were added to liquid fuels mainly composed of ether and isopropyl nitrate. Metal powders' explosive properties and reaction mechanisms in FAE were studied by high-speed video, pressure test system, and infrared thermal imager. The results show that compared with pure liquid fuels, the shock wave overpressure, maximum surface fireball temperature and high temperature duration of the mixture were significantly increased after adding high energetic metal powder. The overpressure values of the liquid-solid mixture at all measuring points were higher than that of the pure liquid fuels. And the maximum temperature of the fireball was up to 1700 ℃, which was higher than that of the pure liquid fuels. After replacing 30％of aluminum powder with boron or magnesium hydride, the shock wave pressure of the mixture was further increased. The high heat of combustion of boron and the hydrogen released by magnesium hydride could effectively increase the blast effect of the mixture. The improvement of the explosion performance of boron was better than magnesium hydride. It shows that adding high energetic metal powder to liquid fuels can effectively improve the explosion performance of FAE.     

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.     

Deconsolidation and combustion performance of thermally consolidated propellants deterred by multi-layers coating

Both heating and solvent-spray methods are used to consolidate the standard grains of double-base oblate sphere propellants plasticized with triethyleneglycol dinitrate (TEGDN) (TEGDN propellants) to high density propellants. The obtained consolidated propellants are deterred and coated with the slow burning multi-layer coating. The maximum compaction density of deterred and coated consolidated propellants can reach up to 1.39 g/cm³. Their mechanic, deconsolidation and combustion performances are tested by the materials test machine, interrupted burning set-up and closed vessel, respectively. The static compression strength of consolidated propellants deterred by multi-layer coating increases significantly to 18 MPa, indicating that they can be applied in most circumstances of charge service. And the samples are easy to deconsolidate in the interrupted burning test. Furthermore, the closed bomb burning curves of the samples indicate a two-stage combustion phenomenon under the condition of certain thickness of coated multi-layers. After the outer deterred multi-layer coating of consolidated samples is finished burning, the inner consolidated propellants continue to burn and breakup into aggregates and grains. The high burning progressivity can be carefully obtained by the smart control of deconsolidation process and duration of consolidated propellants. The preliminary results of consolidated propellants show that a rapid deconsolidation process at higher deconsolidation pressure is presented in the dynamic vivacity curves of closed bomb test. Higher density and higher macro progressivity of consolidated propellants can be obtained by the techniques in this paper.     

Shock initiation performance of NTO-based polymer bonded explosive

3-nitro-1,2,4-tri-azol-5-one (NTO) is a high energy insensitive explosive. To study the shock initiation process of NTO-based polymer bonded explosive JEOL-1 (32%octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 32% NTO, 28% Al and 8% binder system), the cylinder test, the gap experiments and numerical simulation were carried out. Firstly, we got the detonation velocity (7746 m/s) and the parameters of Jones-Wilkins-Lee (JWL) equation of state (EOS) for detonation product by cylinder test and numerical simulation. Secondly, the Hugoniot curve of unreacted explosive for JEOL-1 was obtained calculating the data of pressure and time at different Lagrangian positions. Then the JWL EOS of unreacted explosive was obtained by utilizing the Hugoniot curve as the reference curve. Finally, we got the pressure growth history of JEOL-1 under shock wave stimulation and the parameters of the ignition and growth reaction rate equation were obtained by the pressure-time curves measured by the shock-initiation gap experiment and numerical simulation. The determined trinomial ignition and growth model (IG model) parameters can be applied to subsequently simulation analysis and design of insensitive ammunition with NTO-based polymer bonded explosive.     

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.     

The surface activation of boron to improve ignition and combustion characteristic

Boron is a very promising and highly attractive fuel because of high calorific value. However, the practical applications in explosives and propellants of boron have been limited by long ignition delay time and low combustion efficiency. Herein, nano-Al and graphene fluoride (GF) as surface activated materials are employed to coat boron (B) particles to improve ignition and combustion performance. The reaction heat of nano-Al coated B/KNO₃ and GF coated B/KNO₃ are 1116.83 J/g and 862.69 J/g, respectively, which are higher than that of pure B/KNO₃ (823.39 J/g). The ignition delay time of B/KNO₃ could be reduced through nano-Al coating. The shortest ignition delay time is only 75 ms for B coated with nano-Al of 8 wt%, which is much shorter than that of pure B/KNO₃ (109 ms). However, the ignition delay time of B/KNO₃ coated with GF has been increased from 109 to 187 ms. B coated with GF and nano-Al shown significantly influence on the pressure output and flame structure of B/KNO₃. Furthermore, the effects of B/O ratios on the pressure output and ignition delay time have been further fully studied. For B/KNO₃ coated with nano-Al and GF, the highest pressures are 88 KPa and 59 KPa for B/O ratio of 4:6, and the minimum ignition delay time are 94 ms and 148 ms for B/O ratio of 7:3. Based on the above results, the reaction process of boron coated with GF and nano-Al has been proposed to understand combustion mechanism.     

Formulation development and characterization of cellulose acetate nitrate based propellants for improved insensitive munitions properties

Cellulose acetate nitrate (CAN) was used as an insensitive energetic binder to improve the insensitive munitions (IM) properties of gun propellants to replace the M1 propellant used in 105 mm artillery charges. CAN contains the energetic nitro groups found in nitrocellulose (NC), but also acetyl functionalities, which lowered the polymer's sensitivity to heat and shock, and therefore improved its IM properties relative to NC. The formulation, development and small-scale characterization testing of several CAN-based propellants were done. The formulations, using insensitive energetic solid fillers and high-nitrogen modifiers in place of nitramine were completed. The small scale characterization testing, such as closed bomb testing, small scale sensitivity, thermal stability, and chemical compatibility were done. The mechanical response of the propellants under high-rate uni-axial compression at, hot, cold, and ambient temperatures were also completed. Critical diameter testing, hot fragment conductive ignition (HFCI) tests were done to evaluate the propellants' responses to thermal and shock stimuli. Utilizing the propellant chemical composition, theoretical predictions of erosivity were completed. All the small scale test results were utilized to down-select the promising CAN based formulations for large scale demonstration testing such as the ballistic performance and fragment impact testing in the 105 mm M67 artillery charge configurations. The test results completed in the small and large scale testing are discussed.     

Numerical study on the case effect of a bomb air explosion

When considering the bomb explosion damage effect, the air shock wave and high-speed fragments of the bomb case are two major threats. In experiments, the air shock wave was studied by the bare ex-plosives superseding the real cased bomb; in contrast, the bomb case influence was ignored to reduce risk. The air explosion simulations of the MK84 warhead with and without the case were conducted. The numerical simulation results showed that the bomb case significantly influenced the shock wave generated by the bomb: the spatial distribution of shock wave in the near field changed, and the peak value of shock wave was reduced. Breakage of the case and kinetic energy of the fragmentation consumed 3 and 38% of the explosion energy, respectively. The increasing factors of the peak over-pressure induced by the bare explosive on the ground and in the air were 1.43-3.04 and 1.37-1.57, respectively. Four typical stages of case breakage were defined. The mass distribution of the fragments follows the Mott distribution. The initial velocity distribution of the fragments agreed well with the Gurney equation.     

A melt-cast Duan-Zhang-Kim mesoscopic reaction rate model and experiment for shock initiation of melt-cast explosives

A melt-cast Duan-Zhang-Kim (DZK) mesoscopic reaction rate model is developed for the shock initiation of melt-cast explosives based on the pore collapse hot-spot ignition mechanism. A series of shock initiation experiments was performed for the Comp B melt-cast explosive to estimate effects of the loading pressure and the particle size of granular explosive component, and the mesoscopic model is validated against the experimental data. Further numerical simulations indicate that the initial density and formula proportion greatly affect the hot-spot ignition of melt-cast explosives.     

炸药热安定性的快速评定方法

本文分析了量气法和热分析法评定炸药热安定性的问题,提出把由一条DSC曲线测得的热分解动力学参数引入热平衡方程,以数值模拟方法计算出炸药在一定环境温度下的热爆炸延滞期,并据此判别炸药热安定性的观点和方法。经实验验证,该方法快速、准确。     

火箭弹防静电作用研究

针对电发火弹药静电放电问题,以某型130 mm火箭弹为例,采用真实静电感度测试系统测试了电火工品在有、无绝缘层时50%的静电点火能量,并在试验程序及数据处理中使用真实静电感度数据处理方法统计了50%静电发火能量的估计值。通过比较发现二者的差值在误差范围内,这表明静电放电研究中可以将弹体所接受的能量视作全部作用于火工品上,绝缘层不吸收静电放电的能量。在电发火弹药的防护中,必须采用静电防护措施杜绝电发火弹药的意外发火。     

无电焊接中厚度钢板焊接接头的组织结构与性能研究

采用无电焊接方法对12mm厚度钢板进行了焊接。分析了满足中厚度钢板焊接能量要求的技术途径;利用SEM,EDS,XRD等手段观察、分析了焊缝的组织成分与显微结构;测试了焊接接头的拉伸强度、弯曲强度、显微硬度等力学性能。结果表明:在选择高放热体系基础上,通过增大焊接笔直径、减小反应物料粒径、提高压坯密度等方法,可以有效增大焊接热效率,从而满足中厚度钢板焊接能量需求;焊缝组织分为热影响区、熔合区与合金区,焊缝合金与母材间通过熔合区形成了冶金结合;焊接接头因固溶强化和析晶强化的作用,具有良好的力学性能,拉伸强度、平均显微硬度与弯曲强度分别为357MPa、186HV0.2与644MPa,达到了野战应急抢修技术要求。     

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the param-eters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0％to 15％,every 5％increase of aluminum resulted in about a 1.3％decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14％and 8％higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 μs throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12％and 2.9 μs higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80％of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.     

Microcrack- and microvoid-related impact damage and ignition responses for HMX-based polymer-bonded explosives at high temperature

Investigating the damage and ignition behaviors of polymer-bonded explosive (PBX) under a coupled impact and high-temperature loading condition is required for the safe use of charged PBXs. An improved combined microcrack and microvoid model (CMM) was developed for better describing the thermal effects of deformation, damage, and ignition responses of PBXs. The main features of the model under typical dynamic loadings (i.e. uniaxial tension and compression, and lateral confinement) at different initial temperature were first studied. And then the effects of temperature on impact-shear sensitivity of HMX-based PBXs were investigated. The results showed that the ignition threshold velocity of shear-crack hotspots exhibits an increase from 260 to 270 to 315–325 m/s when initial temperature increases from 301 to 348 K; and then the threshold velocity decreases to 290–300 m/s with the initial temperature continually increasing to 378 K. The predicted ignition threshold velocity level of the explosives under coupled impact and high temperature loading conditions were consistent with the experimental data.     

Burning characteristics of high density foamed GAP/CL-20 propellants

The monolithic foamed propellants with high densities were prepared by casting and two-step foaming processes. Glycidyl azide polymer (GAP) and isocyanate were used as the binder system and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW, CL-20) was employed as the energetic component. The newly designed formulation containing 60 % CL-20 produced a force constant of 1077 J/g and low flame temperature of 2817 K. Two foamed propellants with densities of 1.32 g/cm³ and 1.53 g/cm³ were fabricated by a confined foaming process and examined by closed bomb tests. The results revealed that porosity significantly affects burning performance. A size effect on combustion behaviors was observed for the foamed propellant with 5.56 % porosity, and a double-hump progressive dynamic vivacity curve was obtained. At last, the 30 mm gun test was carried out to demonstrate the interior ballistic performance, and the muzzle velocity increased by 120 m/s at the same maximum chamber pressure when monolithic propellant was added in the charge.