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.     

The non-isothermal gravimetric method for study the thermal decomposition kinetic of HNBB and HNS explosives

The hexanitrostilben (HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl (HNBB). Therefore, the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS. The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method. The TG/DTG curves in non-isothermal method are obtained in range of 25°C–400 °C at heating rates of 3 °C/min, 5 °C/min, 8 °C/min, 10 °C/min and 12 °C/min. The data of weight-temperature are used for calculation of activation energy (E_a) of thermal decomposition reactions by methods of Ozawa, Kissinger, Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) as model-free methods and Strink's equation as model-fitting method. The compensation effect is used for prediction of mechanism and determination of pre-exponential factor (lnA) of the decomposition reaction. A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS. This result shows the lower thermal stability of HNBB in comparison to HNS. The Avrami equation (A_3/2) with function f(α) = 3/2(1-α)[-ln(1-α)]^1/3 indicates the predicted mechanism for thermal decomposition reaction both explosives.     

过氯酸铵 (AP) 爆燃的模拟

本文提出一个描述AP爆燃的物理化学模型,并计算了AP晶粒在10～800大气压下的爆燃速度、压力指数、燃面温度等参数值,计算结果和T.L. Boggs等人的实验结果相符文中提出AP爆燃过程中,在低压和高压下,可能存在着两种不同的凝聚相反应机理,并用以解释Boggs的实验现象。此外,本文还提出了一种描述绝热体系中,预混火焰燃烧时的化学反应速度表示式和计算方法,使气相温度梯度及热传导的计算简单合理,这也是本模拟研究取得成功的因素之一。     

Effect of particle gradation of aluminum on the explosion field pressure and temperature of RDX-based explosives in vacuum and air atmosphere

To optimize the energy output and improve the energy utilization efficiency of an aluminized explosive, an explosion device was developed and used to investigate the detonation pressure and temperature of R1 (Al6) aluminum powder and the aluminum powder particle gradation of R2 (Al6+Al13), R3 (Al6+Al24) and R4 (Al6+Al flake) in a confined space. By using gas chromatography, quantitative analysis and calculations were carried out to analyze the gaseous detonation products. Finally, the reaction ratios of the aluminum powder and the explosion reaction equations were calculated. The results show that in a confined space, the quasi-static pressures and equilibrium temperature of the aluminum powder in air are higher than in vacuum. In vacuum, the quasi-static pressures and equilibrium temperatures of the samples in descending order are R1>R3>R4>R2 and R3>R4>R1>R2, respectively. In air, the quasi-static pressures and equilibrium temperatures of the samples in descending order are R1>R2>R4>R3 and R1>R4>R2>R3, respectively. R4 (Al6+Al flake) and R3 (Al6+Al24) have relatively higher temperatures after detonation, which shows that the particle gradation method can enhance the reaction energy output of aluminum during the initial reaction stage of the explosion and increase the reaction ratio by 10.6% and 8.0%, respectively. In air, the reaction ratio of Al6 aluminum powder can reach as high as 78.16%, and the reaction ratio is slightly reduced after particle gradation. Finally, the reaction equations of the explosives in vacuum and in air were calculated by quantitative analysis of the explosion products, which provides a powerful basis for the study of RDX-based explosive reactions.     

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.     

基于敏感性分析的DF化学动力学模型的简化

基于两种燃料体系下的DF详细化学反应动力学模型,利用敏感性分析的方法,分别提出了相应的简化反应机理.简化过程中发现,仅考虑DF“冷反应”泵浦过程,忽略掉高振动激发态,忽略掉D2和DF分子的离解复合反应对整个系统影响不大.DF分子之间以及DF与D、D2、HF之间的能量转移反应具有较高的敏感性.简化机理在有效概括DF化学反...     

Vapor-phase decomposition of dimethyl methylphosphonate (DMMP), a sarin surrogate,in presence of metal oxides

Chemical warfare agents (CWA) are stockpiled in large quantities across the globe. Agents stored in inaccessible facilities need to be destroyed rapidly without dispersing the compounds to surrounding areas. Metal-based energetic formulations are used in such prompt defeat applications to rapidly decompose the CWA by generating a high temperature environment. An alternate, and possibly a more effective decomposition pathway could be provided by chemicidal action of aerosolized condensed combustion products, which typically consist of metal oxides. Toxic fumes that escape the high tem-perature blast zone can be neutralized by smoke generated during combustion, depending on the par-ticle size, surface characteristics, chemical properties, and concentration of this smoke. This review considers relevant experimental and modeling studies quantifying decomposition of CWA comprising organophosphorus compounds and their surrogates on the surface of various metal oxides. Dimethyl methylphosphonate (DMMP), a sarine surrogate, was used most commonly for such experiments. Many reported efforts focused on the mechanisms of adsorption of DMMP to various metal oxides and initial reaction steps cleaving various bonds from the chemisorbed molecules. For selected oxides, these ex-periments were supported by quantum-mechanical calculations. In other studies, the capacity of oxide surfaces to adsorb and decompose DMMP was quantified. In most cases, porous catalysts were used although limited experimental data are available for aerosolized nonporous oxide particles. The reported experimental data applicable to scenarios involving prompt decomposition of CWA are summarized. It is noted that information is lacking describing respective heterogeneous reaction kinetics. Preliminary estimates of aerosolized smoke particle concentrations required to destroy CWA are made considering gas phase diffusion rates and reported values of the oxide capacity to decompose CWA or their surrogates.     

甲基二氯硅烷甲醇醇解产物含量的红外与核磁共振分析

本文对二甲苯溶剂中ＭｅＳｉＨＣｌ２ 和甲醇的反应产物Ｍｅ （ＯＭｅ）２ＳｉＨ 及ＭｅＳｉ（ＯＭｅ）３ 作了红外和核磁共振分析， 结果表明： 以红外谱图中Ｓｉ－Ｈ 和苯环吸收带作为含量分析谱带， 采用比例法， 借助工作曲线，可确定反应产物的含量。亦可以通过对各组分处于不同化学位移下质子的核磁共振分析，采用归一化法，经过换算测定反应产物混合液中各组份含量。两种测定方法均简便快捷， 并对两法的测定结果作了分析比较。     

Sandwich structure for enhancing the interface reaction of hexanitrohexaazaisowurtzitane and nanoporous carbon scaffolds film to improve the thermal decomposition performance

Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane (CL-20) by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants. In this study, we synthesized a sandwich structure of CL-20 and nanoporous carbon scaffolds film (NCS) and emphatically studied the thermal decomposition performance of the composite structure. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal decomposition process of the composite structure. The kinetic parameters of thermal decomposition were calculated by the thermal dynamic analysis software AKTS. These results showed that the thermal decomposition performance of the sandwich structure of CL-20 and NCS was better than CL-20. Among the tested samples, NCS with a pore size of 15 nm had the best catalytic activity for the thermal decomposition of CL-20. Moreover, the thermal decomposition curve of the composite structure at the heating rate of 1 K/min was deconvoluted by mathematical method to study the thermal decomposition process. And a possible catalytic mechanism was proposed. The excellent thermal decomposition performance is due to the sandwich structure enhances the interface reaction of CL-20 and NCS. This work may promote the extensive use of CL-20 in the field of solid rocket propellant.     

A quasi-isentropic model of a cylinder driven by aluminized explosives based on characteristic line analysis

A quasi-isentropic study on the process of driving a cylinder with aluminized explosives was carried out to examine the influence of the aluminum (Al) reaction rate on cylinder expansion and the physical parameters of the detonation products. Based on the proposed quasi-isentropic hypothesis and relevant isentropic theories, the characteristic lines of aluminized explosives driving a cylinder were analyzed, and a quasi-isentropic model was established. This model includes the variation of the cylinder wall velocity and the physical parameters of the detonation products with the Al reaction degree. Using previously reported experimental results, the quasi-isentropic model was verified to be applicative and accurate. This model was used to calculate the physical parameters for cylinder experiments with aluminized cyclotrimethylenetrinitramine explosives with 15.0 % and 30.0 % Al content. The results show that this quasi-isentropic model can be used not only to calculate the cylinder expansion rule or Al reaction degree, but also to calculate the physical parameters of the detonation products in the process of cylinder expansion. For explosives with 15.0 % and 30.0 % Al, 24.3 % and 18.5 % of the Al was found to have reacted at 33.9 μs and 34.0 μs, respectively. The difference in Al content results in different reaction intensity, occurrence time, and duration of two forms of reaction (diffusion and kinetic) between the Al powder and the detonation products; the post-detonation burning reaction between the Al powder and the detonation products prolongs the positive pressure action time, resulting in a continuous rise in temperature after detonation.     

Decomposition algorithms for finding the shortest path between a source node and a sink node of a network

Decomposition algorithms for finding a shortest path between a source node and a sink node of an arbitrary distance network are developed. Different decomposition algorithms are proposed for different network topologies. Since Shier's algorithm compares very favorably with other decomposition algorithms in all the network topologies, we compare our algorithms against Shier's algorithm. It is shown that the efficiency of the proposed algorithms compares very favorably with Shier's algorithm. For special types of networks the computational requirements of the proposed algorithm is a polynomial of O(n²).     

Thermal hazard assessment of TKX-50-based melt-cast explosive

In the present study, thermal hazards of TNT and DNAN used as the molten binder in TKX-50-based melt-cast explosives were comparatively studied through accelerating rate calorimeter (ARC) and Cook-off experiments. Two kinds of ARC operation modes were performed to investigate the thermal safety performance under adiabatic conditions (HWS mode) and constant heating (CHR mode). The obtained results demonstrated that at both heating modes, DNAN/TKX-50 outperformed TNT/TKX-50 from the thermal safety point of view. However, the sensitivity to heat of the samples was reverse because of the different heating modes. In addition, the results of thermal hazard assessment obtained from the cook-off experiment complied with ARC analysis which indicated the molten binder TNT replaced by DNAN would reduce the hazard of the TKX-50 melt cast explosive. Furthermore, the results of cook-off experiments also showed that DNAN/TKX-50 outperformed TNT/TKX-50 from the aspect of thermal stability, which was consistent with the result of CHR mode because of the similar heating process.     

基于动力学和扩散分段控制的Mg/H2O反应模型及数值分析

为了数值研究宽广温度范围内Mg/H2O的反应特性,分别建立了考虑部分MgO在液滴表面凝聚的Mg/H2O扩散燃烧模型和基于Arrhenius公式的Mg/H2O反应动力学模型.数值研究了Mg/H2O反应速率在扩散控制和化学动力学控制下随反应条件变化的规律.研究结果表明,Mg液滴扩散燃烧时间计算结果与文献值相符;提高温度和水...     

气体化学反应速率的 DSMC 方法

为预报化学反应过程,应用ＤＳＭＣ方法研究了双原子分子的离解反应,讨论了高温情况下（Ｔ～Ｅａ／ｋ）采用由实验测定得到的反应速率与气体温度间Ａｒｒｈｅｎｉｕｓ经验关系式的可靠性问题,分析了振动热非平衡效应对于离解反应速率的影响,给出了由ＤＳＭＣ方法得到的离解反应速率与气体温度的关系曲线。     

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.     

子空间分解与淘汰优化方法

提出一种新的多学科设计优化方法,即子空间分解与淘汰优化方法.该方法通过子空间的分解和淘汰,提高剩余子空间的近似模型精度,基于子空间近似模型优化获取最优解.首先,基于设计空间近似模型获取最优解,如果近似模型达到满意精度,则终止优化;否则将设计空间分解为多个子空间.然后,各子空间基于近似模型优化,如果子空间没有可能获得优于...     

泰氟隆烧蚀产物对电子密度的影响

采用WNND格式,对有泰氟隆烧蚀产物引射的化学非平衡NS方程进行了数值模拟。采用7组元纯空气化学反应和19组元、28种反应的空气—泰氟隆化学反应系统,对照计算了壁面有泰氟隆烧蚀产物引射和纯空气绕流两种流场,研究了泰氟隆烧蚀产物对电子密度的影响。     

Numerical research on adverse effect of muzzle flow formed by muzzle brake considering secondary combustion

The simulation of the artillery interior and intermediate ballistics problem is performed to investigate the influence of a gas dynamics device, muzzle brake, on the muzzle hazard phenomena, such as flash and blast waves. The correlation of the chemical reactions with the characteristics of the muzzle flow field is analyzed by the simulation for a further understanding of the secondary combustion phenom-enon of the muzzle flow. The novel structure of muzzle flow caused by the muzzle brake is presented by the simultaneous solution of the interior ballistics model and multi-species Navier-Stokes equations in order to analyze the influence of the muzzle brake structure on the chemical reactions. The secondary combustion of the muzzle flow due to the oxygen-supplement chemical reactions is obtained by the chemical reaction kinetic model. The interaction of the blast waves released from the muzzle brake is illustrated in detail and the mechanism of the formation of muzzle flash is analyzed. This research provides a reference for the studies on the suppression of the muzzle flash.     

A new experimental way for the monitoring of the real/equivalent in-service-time of double base rocket propellant by coupling VST and PCA

The assessment of the real in-service-time(RIST)and the equivalent in-service-time(EIST)of double base rocket propellants(DBRPs)is of utmost importance for the safe storage and use of weapon systems as well as the efficiency of the accelerated aging plans.In this work,four DBRPs with similar chemical composition and different natural aging have been artificially aged at T = 338.65 K for 4 months with sampling every 30 days.The unaged and artificially aged samples have been investigated by vacuum stability test(VST)at five isothermal temperatures(T = 333.15 K,343.15 K,353.15 K,363.15 K,and 373.15 K).The volume of the evolved gases in VST was found to decrease with natural/artificial aging.Furthermore,the VST data were treated and subjected to principal component analysis(PCA).The results showed excellent discrimination of the DBRP samples according to their stability thermal properties.Most of the variance was described by the first principal component(PC1)whose scores were linearly correlated with the natural aging durations when PCA is applied on VST data obtained at T = 363.15 K.In light of the obtained results,a new experimental way for the estimation of the real/equivalent IST was proposed,which takes into account the impact of the natural aging of the sample.The approach predicts successfully the RIST of two similar DBRPs with a relative deviation of less than 2％.At the specific heating temperature T = 338.65 K,the developed model provides more conceivable EIST values,with asymptotic behavior against artificial aging duration evolution,thus overcoming some shortcomings of the common generalized van't Hoff formula(GvH).     

Study on energy release characteristics of reactive material casings under explosive loading

Reactive Materials (RMs), a new material with structural and energy release characteristics under shock-induced chemical reactions, are promising in extensive applications in national defense and military fields. They can increase the lethality of warheads due to their dual functionality. This paper focuses on the energy release characteristics of RM casings prepared by alloy melting and casting process under explosive loading. Explosion experiments of RM and conventional 2A12 aluminum alloy casings were conducted in free field to capture the explosive fireballs, temperature distribution, peak overpressure of the air shock wave and the fracture morphology of fragments of reactive material (RM) warhead casings by using high-speed camera, infrared thermal imager temperature and peak overpressure testing and scanning electron microscope. Results showed that an increase of both the fireball temperature and air shock wave were observed in all RM casings compared to conventional 2A12 aluminum ally casings. The RM casings can improve the peak overpressure of the air shock wave under explosion loading, though the results are different with different charge ratios. According to the energy release characteristics of the RM, increasing the thickness of RM casings will increase the peak overpressure of the near-field air shock wave, while reducing the thickness will increase the peak overpressure of the far-field air shock wave.